01892nas a2200169 4500008004100000022001400041245012200055210006900177260007100246300001400317490000800331520118500339100002401524700002601548700001601574856013201590 2009 eng d a1932-744700aDensity functional investigation of relativistic effects on the structure and reactivity of tetrahedral gold clusters0 aDensity functional investigation of relativistic effects on the  a1155 16TH ST, NW, WASHINGTON, DC 20036 USAbAMER CHEMICAL SOCcAPR a7101-71060 v1133 a

The influence of relativistic effects on the structure, vibrational modes, and reactivity of recently discovered tertrahedral gold clusters (Au(19) and Au(20)) are investigated using density functional methods. The intramolecular reactivity of the clusters was analyzed using density functional-based reactivity descriptors. The work shows that whereas the structural properties and vibrational modes are considerably affected by the relativistic effects, the reactivity trends based on Fukui function calculation on various atoms within this cluster remain unaffected by the absence or presence of relativistic effects. The reactivity descriptors reveal that the vertex atoms are the most reactive ones in Au(20) toward a nucleophilic attack. On the other hand, atoms connecting the missing vertex edge with the pyramid base along with the vertex atom are the most reactive for a nucleophilic attack in Au(19). The atoms lying at the center of each face are favorable for an electrophilic attack in both cases. Interestingly, the atoms with a missing cap in Aulg are highly favorable for electrophilic attack, and Au(20) has more sites for a favorable nucleophilic attack.

1 aDe, Himadri, Sekhar1 aKrishnamurty, Sailaja1 aPal, Sourav uhttps://library.ncl.res.in/content/density-functional-investigation-relativistic-effects-structure-and-reactivity-tetrahedral-001450nas a2200169 4500008004100000022001400041245013200055210006900187260007300256300001200329490000800341520073500349100002501084700002601109700001601135856012901151 2010 eng d a0009-261400aInfluence of plane wave cut-off on structural and electronic properties in Sn-BEA and Ti-BEA zeolite water molecule interaction0 aInfluence of plane wave cutoff on structural and electronic prop aPO BOX 211, 1000 AE AMSTERDAM, NETHERLANDSbELSEVIER SCIENCE BVcJAN a374-3790 v4843 a

Periodic systems are best described by the pseudo-potential methods. However, the accuracy of its description depends on the cut-off of plane wave basis. This is much more critical in the case of weak interactions, where a clear understanding on the influence of plane wave cut-off on the structural and electronic properties is not readily available in the literature. In the present work, we have taken a metal substituted beta zeolite-H2O complex for understanding this objective. Our studies show that while a lower cut-off of 500 eV is sufficient for the convergence of the structural parameters, description of energy-dependent properties necessitates a high cut-off value. (C) 2009 Elsevier B.V. All rights reserved.

1 aKulkarni, Bhakti, S.1 aKrishnamurty, Sailaja1 aPal, Sourav uhttps://library.ncl.res.in/content/influence-plane-wave-cut-structural-and-electronic-properties-sn-bea-and-ti-bea-zeolite-002926nas a2200229 4500008004100000022001400041245014300055210006900198260007300267300001000340490000800350520203500358653001702393653001802410653002702428653001702455653002702472100002502499700002602524700001602550856013002566 2010 eng d a1381-116900aProbing lewis acidity and reactivity of Sn- and Ti-beta zeolite using industrially important moieties: a periodic density functional study0 aProbing lewis acidity and reactivity of Sn and Tibeta zeolite us aPO BOX 211, 1000 AE AMSTERDAM, NETHERLANDSbELSEVIER SCIENCE BVcAUG a36-430 v3293 a

The Lewis acidic nature and reactivity of two industrially important catalysts, viz.. Sn and Ti substituted beta zeolite (T-BEA) are analyzed using a unique combination of structural parameters, energetics and reactivity descriptors. To achieve this purpose, we adsorb the industrially important moieties (L) namely NH(3), H(2)O, CH(3)OH, CH(3)CN on the active sites of T-BEA. The calculations were performed using a periodic density functional method where the valence electrons are described using a plane wave basis set in conjunction with pseudo-potentials for the core electrons. The analysis of the structural properties of these complexes reveals that TO(4) shows typical characteristic splitting 120 degrees/90 degrees, close to bipyramidal geometry as compared to tetrahedral symmetry observed in the bare T-BEA. This is associated with small variations in the framework bond lengths (>= 0.08 angstrom) and a substantially large variation of bond angles (<= 10 degrees) in all the ligand-zeolite complexes. Further in both cases of Sn and Ti substituted beta zeolite, ligand interacts at optimum inter-atomic bond distance. Our interaction energies show that adsorption of all ligand moieties is stronger at Sn center than that of Ti. In general, the order of stability of the different T-BEA adducts is NH(3) > H(2)O > CH(3)OH > CH(3)CN. The ligand interaction is associated with the corresponding bond elongation and bond reduction of the adsorbed molecules on catalyst active site, which can be taken as measure of red or blue shifted frequencies. Finally, the global descriptors of reactivity justify the fact that soft acid, Sn-BEA, interacts strongly with soft bases following the Pearson's HSAB principle. However, hard acid, Ti-BEA interacts with soft bases to form a stable Lewis adduct. Furthermore, the HOMO-LUMO gap of all Sn-BEA-L adducts is lower than that of Ti-BEA-L adducts indicating to its higher Lewis acidic nature compared to Ti-BEA. (C) 2010 Elsevier B.V. All rights reserved.

10aBeta zeolite10aLewis acidity10aLigand-zeolite complex10aPeriodic-DFT10aReactivity descriptors1 aKulkarni, Bhakti, S.1 aKrishnamurty, Sailaja1 aPal, Sourav uhttps://library.ncl.res.in/content/probing-lewis-acidity-and-reactivity-sn-and-ti-beta-zeolite-using-industrially-important-000820nas a2200169 4500008004100000022001400041245013700055210006900192260007100261300001400332490000800346520014600354100002400500700002600524700001600550856008400566 2010 eng d a1932-744700aUnderstanding the reactivity properties of Au-n (6 <= n <= 13) clusters using density functional theory based reactivity descriptors0 aUnderstanding the reactivity properties of Aun 6 n 13 clusters u a1155 16TH ST, NW, WASHINGTON, DC 20036 USAbAMER CHEMICAL SOCcAPR a6690-67030 v1143 a

{Relativistic density functional theory (DFT) based calculations have been performed on gold clusters with six to thirteen atoms (Au-n

1 aDe, Himadri, Sekhar1 aKrishnamurty, Sailaja1 aPal, Sourav uhttps://library.ncl.res.in/content/understanding-reactivity-properties-au-n-6-000844nas a2200181 4500008004100000022001400041245011600055210006900171260007100240300001600311490000800327520014800335100002400483700002600507700001900533700001600552856009400568 2011 eng d a1932-744700aFinite temperature behavior of gas phase neutral Au-n (3 <= n <= 10) clusters: a first principles investigation0 aFinite temperature behavior of gas phase neutral Aun 3 n 10 clus a1155 16TH ST, NW, WASHINGTON, DC 20036 USAbAMER CHEMICAL SOCcSEP a17278-172850 v1153 a

{Relativistic density functional theory (DFT) based molecular dynamical simulations are performed on gold clusters with 3-10 atoms (Au-n

1 aDe, Himadri, Sekhar1 aKrishnamurty, Sailaja1 aMishra, Deepti1 aPal, Sourav uhttps://library.ncl.res.in/content/finite-temperature-behavior-gas-phase-neutral-au-n-3-001981nas a2200169 4500008004100000022001400041245014900055210006900204260007100273300001600344490000800360520124700368100002501615700002601640700001601666856012901682 2011 eng d a1932-744700aSize- and shape-sensitive reactivity behavior of Al-n(n=2-5, 13, 30, and 100) clusters toward the N-2 molecule: a first-principles investigation0 aSize and shapesensitive reactivity behavior of Alnn25 13 30 and  a1155 16TH ST, NW, WASHINGTON, DC 20036 USAbAMER CHEMICAL SOCcAUG a14615-146230 v1153 a

Reactivity of aluminum clusters has been found to exhibit size-sensitive variations. N-2 reduction is a hard process, and its dissociation on the Al surface is one of the few chemical methods available under nonhazardous conditions. In this context, we attempt to understand the adsorption behavior of N-2 molecules as a function of varying size and shape of Al clusters using a Density Functional Theory (DFT) based method. During the complex formation, various N-2 adsorption modes are examined. The results clearly demonstrate that, while the interaction energy does not vary with respect to the cluster size, shape of the cluster is highly contributive toward the chemisorption (a prerequisite for the reactivity) of the N-2 molecule. The underlying electronic and structural factors influencing the adsorption of N-2 molecules on the Al clusters are analyzed with the help of the Electron Localization Function (ELF) and Frontier Molecular Orbitals. As an illustration, the activation barrier calculations on various Al-13 conformations are calculated, and results confirm the experimental propositions that high-energy structures (depending upon their geometrical and electronic orientation) are more favorable for N-2 reduction.

1 aKulkarni, Bhakti, S.1 aKrishnamurty, Sailaja1 aPal, Sourav uhttps://library.ncl.res.in/content/size-and-shape-sensitive-reactivity-behavior-al-nn2-5-13-30-and-100-clusters-toward-n-2-002601nas a2200217 4500008004100000022001400041245011400055210006900169260009200238300001200330490000700342520176600349653000802115653000902123653002802132653003302160100001902193700001602212700002602228856012902254 2011 eng d a0892-702200aUnderstanding the molecular conformations of Na-dimyristoylphosphatidylglycerol (DMPG) using DFT-based method0 aUnderstanding the molecular conformations of Nadimyristoylphosph a4 PARK SQUARE, MILTON PARK, ABINGDON OX14 4RN, OXON, ENGLANDbTAYLOR & FRANCIS LTDcAUG a953-9630 v373 a

The molecular conformations of phospholipids comprising a lipid bilayer determine the physico-chemical properties of the latter. In this study, we attempt to understand the various possible conformations available for an anionic lipid molecule dimyristoylphosphatidylglycerol (DMPG) with Na as its charge-compensating cation. The various possible molecular orientations available for lipid molecule are analysed using a density functional theory-based method. Our study reveals a rich conformational space with two different types of glycerol body orientations, more commonly known as rotamers. Interestingly, this is in agreement with the molecular conformations proposed earlier by NMR studies on lipid monomer solutions. We demonstrate that these conformations are an outcome of delicate balance of electrostatic and van der Waals forces along with intra-molecular hydrogen bonds achieved by a critical combination of torsion angles. Na(+) ions are seen to interact predominantly with the oxygen atoms of the glycerol groups in tail and head along with that of phosphate oxygen atoms leading to a cage-like orientation of lipid molecule around the Na(+). Following the conformational analysis, we attempt to evaluate the electronic properties of few low-lying conformations. This study shows that though the water molecules screen the Na-O(lipid) interactions, they do not dramatically modify the Na-O(lipid) bond distances. The lipid conformation retains the cage-like structure around the Na(+) in the presence of water molecules. Some amount of charge transfer from the water molecules to Na ion is noted. The water molecules modify the phosphate-tail glycerol group interactions leading to a more stable Na-DMPG-H(2)O and Na-DMPG-4H(2)O complexes.

10aDFT10aDMPG10amolecular conformations10arotamer and hydration energy1 aMishra, Deepti1 aPal, Sourav1 aKrishnamurty, Sailaja uhttps://library.ncl.res.in/content/understanding-molecular-conformations-na-dimyristoylphosphatidylglycerol-dmpg-using-dft-001859nas a2200229 4500008004100000022001400041245010400055210006900159260007300228300001200301490000800313520098400321653001801305653004001323653003001363653002201393653002501415100002401440700002601464700001601490856012301506 2012 eng d a0920-586100aFirst principle investigation on the thermal stability of a golden fullerene: a case study of Au-320 aFirst principle investigation on the thermal stability of a gold aPO BOX 211, 1000 AE AMSTERDAM, NETHERLANDSbELSEVIER SCIENCE BVcDEC a106-1090 v1983 a

Structural and electronic properties of Au-32 cluster are analyzed using relativistic density functional theory (DFT) based methods. Further, DFT based molecular dynamical (MD) simulations are performed on Au-32 golden fullerene with an aim of understanding its thermal stability at various working temperatures. Various conformations being populated at different temperatures of a cluster are analyzed. The study shows that the ground state icosahedral conformation is stable only up to 300 K and structure remains in a hollow conformation only up to 400 K. This clearly explains the reasons for failure by experimentalists in trapping the unique fullerene conformation in spite of the theoretical predictions of it being a very stable one. The above MD study also indicates that the bare fullerene Au-32 cluster (without any stabilizing ligands) can be used for potential catalytic applications only around room temperatures. (C) 2012 Elsevier B. V. All rights reserved.

10aAu-32 cluster10aBorn-Oppenheimer molecular dynamics10aDensity functional theory10aGolden fullerenes10aRelativistic effects1 aDe, Himadri, Sekhar1 aKrishnamurty, Sailaja1 aPal, Sourav uhttps://library.ncl.res.in/content/first-principle-investigation-thermal-stability-golden-fullerene-case-study-au-32-002344nas a2200169 4500008004100000022001400041245011700055210006900172260007100241300001600312490000800328520165200336100001701988700001602005700002602021856012702047 2013 eng d a1932-744700aInfluence of charge and ligand on the finite temperature behavior of gold clusters: a BOMD study on Au-6 cluster0 aInfluence of charge and ligand on the finite temperature behavio a1155 16TH ST, NW, WASHINGTON, DC 20036 USAbAMER CHEMICAL SOCcOCT a20982-209900 v1173 a

Conformation and electronic charge on a gold cluster are known to determine its catalytic property. However, little is known on the finite temperature behavior of various gold cluster conformations. Much less is known on the role of charge or a ligand in stabilizing a conformation at finite temperatures. In this work, we have carried out relativistic density functional theory (DFT) based molecular dynamical simulations on neutral and charged Au-6 clusters with an aim of understanding the stability of ground state conformations as a function of charge on the cluster. Our simulations reveal that cationic and anionic Au-6 clusters undergo conformational transitions at 500 K where as neutral Au-6 cluster retains its ground state conformation up to a temperature of 1100 K. In order to look into the factors leading to the stabilization of neutral Au-6 cluster (or destabilization of cationic and anionic Au-6 clusters), structural and electronic properties are analyzed. Factors such as charge redistribution within the atoms and composition of molecular orbitals are seen to contribute towards stronger Au-Au bonds in Au-6(0) thereby stabilizing it considerably. Following the analysis, simulations are also extended to neutral, cationic, and anionic Au-6-COn (n = 1,2) complexes. In the case of CO chemisorbed Au-6 clusters, neutral and negatively charged ground state conformations are stable up to nearly 800 K, while the positively charged Au-6 ground state conformation collapses at room temperature. This work, in short demonstrates how charge or even a ligand can be used to moderate the physical properties of a gold cluster.

1 aManzoor, Dar1 aPal, Sourav1 aKrishnamurty, Sailaja uhttps://library.ncl.res.in/content/influence-charge-and-ligand-finite-temperature-behavior-gold-clusters-bomd-study-au-6-001795nas a2200169 4500008004100000022001400041245021300055210006900268260007100337300001400408490000800422520102600430100001701456700001601473700002601489856011001515 2013 eng d a1089-563900aUnderstanding the site selectivity in small-sized neutral and charged AI(n) (4 <= n <= 7) clusters using density functional theory based reactivity descriptors: a validation study on water molecule adsorption0 aUnderstanding the site selectivity in smallsized neutral and cha a1155 16TH ST, NW, WASHINGTON, DC 20036 USAbAMER CHEMICAL SOCcSEP a8691-87020 v1173 a

Aluminum clusters are now technologically important due to their high catalytic activity. Our present study on the small-sized aluminum clusters applies density functional theory (DFT)-based reactivity descriptors to identify potential sites for adsorption and eventual chemical reaction. Depending on symmetry, susceptibility of various type of reactive sites within a cluster toward an impending electrophilic and/or nucleophilic attack is predicted using the reactivity descriptors. In addition, the study devises general rules as to how the size, shape, and charge of the cluster influences the number of available sites for an electrophilic and/or nucleophilic attack. The predictions by reactivity descriptors are validated by performing an explicit adsorption of water molecule on Al clusters with four atoms. The adsorption studies demonstrate that the most stable water-luster complex is obtained when the molecule is adsorbed through an oxygen atom on the site with the highest relative electrophilicity.

1 aDas, Susanta1 aPal, Sourav1 aKrishnamurty, Sailaja uhttps://library.ncl.res.in/content/understanding-site-selectivity-small-sized-neutral-and-charged-ain-4-001941nas a2200241 4500008004100000022001400041245011400055210006900169260005700238300000900295490000800304520105600312653002401368653003601392653001101428653002401439653002101463100002101484700002201505700002601527700001601553856013001569 2014 eng d a1432-881X00aComputational investigation on the catalytic activity of Rh-6 and Rh4Ru2 clusters towards methanol activation0 aComputational investigation on the catalytic activity of Rh6 and a233 SPRING ST, NEW YORK, NY 10013 USAbSPRINGERcDEC a15970 v1343 a

Catalysis of molecular activation of small molecules through scission of strong chemical bonds is one of the major challenges faced by chemists. More specifically, activation of the strong C-H and O-H bonds of various alcohols, especially methanol, is one of the various important intermediate steps of key organic reactions. Our present work explores a suitable metal cluster catalyst towards methanol dissociation. In particular, we have examined the effect of ruthenium doping (Rh:Ru = 2:1) on the catalytic activity of Rh-6 cluster towards methanol dissociation. Density functional theory-based calculations illustrate two competitive pathways for methanol dissociation, which are via O-H and C-H bond breaking. Both the pathways are found to be energetically favourable in the presence of bimetallic and mono-metallic clusters. Importantly, energy barrier for O-H bond dissociation reduces considerably in doped cluster as compared to pure Rh-6 cluster and is smaller than the values reported for a number of other small metallic clusters.

10aBimetallic Clusters10aDensity Functional Theory (DFT)10aDoping10aMethanol Activation10aRhodium Clusters1 aGhatak, Kamalika1 aSengupta, Turbasu1 aKrishnamurty, Sailaja1 aPal, Sourav uhttps://library.ncl.res.in/content/computational-investigation-catalytic-activity-rh-6-and-rh4ru2-clusters-towards-methanol-002012nas a2200169 4500008004100000022001400041245007600055210006900131260007100200300001600271490000800287520137800295100001701673700001601690700002601706856011001732 2014 eng d a1932-744700aDinitrogen activation by silicon and phosphorus doped aluminum clusters0 aDinitrogen activation by silicon and phosphorus doped aluminum c a1155 16TH ST, NW, WASHINGTON, DC 20036 USAbAMER CHEMICAL SOCcAUG a19869-198780 v1183 a

N-2 reduction is crucial for life, and very few catalysts are currently available to carry out this process at ambient temperature and pressure. In the present work, density functional theory based calculations reveal doped aluminum clusters to be highly reactive toward molecular nitrogen and hence are prospective materials for its activation at low temperatures. Calculations on silicon and phosphorus doped aluminum clusters with 5-8 atoms demonstrate an enhanced N-2 activation with respect to their pristine ground state and high energy counterparts. This increased efficiency of N-2 activation by doped ground state Al clusters is corroborated by an increment of the N N bond length, a red shift in N N bond stretching frequency, and adsorption energy (E-ad). Ab initio molecular-dynamics simulations demonstrate consequential efficiency of doped clusters toward dinitrogen activation at finite temperature. The ability of doped clusters toward activation of molecular nitrogen is site and shape sensitive. In short, this theoretical study highlights the critical role of doping foreign impurities for future endeavors in the design of cost-effective and efficient catalysts for N-2 activation at ambient temperatures. This observation may spur further studies in the field of aluminum nanocatalysis by doping silicon and phosphorus atom in aluminum clusters.

1 aDas, Susanta1 aPal, Sourav1 aKrishnamurty, Sailaja uhttps://library.ncl.res.in/content/dinitrogen-activation-silicon-and-phosphorus-doped-aluminum-clusters-002006nas a2200169 4500008004100000022001400041245008700055210006900142260000900211300001400220490000800234520142600242100001701668700002601685700001601711856010901727 2014 eng d a1932-744700aEffect of silicon doping on the reactivity and catalytic activity of gold clusters0 aEffect of silicon doping on the reactivity and catalytic activit cAPR  a7501-75070 v1183 a

Doping is known to be an excellent and simple way of catalyst design. Although notable progress has been made in understanding the reactivity and catalytic activity of gas-phase and supported gold clusters, very few studies have been carried out on the doped gold clusters. In the present work, we have carried out density functional theory calculations to investigate the effect of silicon doping on the reactivity and catalytic activity of gold nanoclusters. The present work particularly focuses on the adsorption and activation of molecular oxygen on the pristine and silicon-doped gold clusters. The results confirm that the silicon-doped Au7Si cluster shows considerable binding and activation of the O-2 molecule in comparison to the pristine Au-8 cluster as reflected in the relevant geometrical parameters (O-O and Au-O bond lengths) and O-O stretching frequency. However, silicon doping has no contrasting effect on the reactivity and catalytic activity of the Au-7 cluster. In addition to the stronger binding and activation of the O-2 molecule, the doped Au7Si cluster leads to a significant reduction in the activation barrier (0.57 eV) for the environmentally important CO oxidation reaction in contrast to the catalytically inactive pristine Au-8 cluster (1.22 eV). Thus, our results highlight the critical role of doping foreign impurities for future endeavors in the field of gold nanocatalysis.

1 aManzoor, Dar1 aKrishnamurty, Sailaja1 aPal, Sourav uhttps://library.ncl.res.in/content/effect-silicon-doping-reactivity-and-catalytic-activity-gold-clusters01930nas a2200157 4500008004100000245016500041210006900206260000800275300001600283490000800299520127400307100001701581700002601598700001601624856013201640 2016 eng d00aContriving a catalytically active structure from an inert conformation: a density functionalinvestigation of Al, Hf, and Ge doping of Au-20 tetrahedral clusters0 aContriving a catalytically active structure from an inert confor cSEP a19636-196410 v1203 a

The transformation of an inert structure into a catalytically active conformation has immense potential from a structural engineering point of view. In the present work, we explored methods of achieving such a transformation through a density-functional-based study. Au-20 is known be one of the most stable and catalytically inert gold clusters, with a well-known tetrahedral structure. We demonstrate the transformation of the inert Au-20 conformation into a highly active catalytic cluster through selective doping with Hf and Ge atoms. Depending on the dopant, the inert tetrahedral Au-20 cluster evolves into either an endohedral or a hollow-cage-like conformation. The structural changes are manifested in the catalytic properties as well, with the result that the transformed doped cages exhibit extremely low activation barriers for the environmentally important CO oxidation reaction as compared to reported inert Au-20 cluster. The activation barriers for CO oxidation are particularly low (<0.12 eV) when germanium is directly involved in the CO oxidation. Thus, the current work highlights the importance of engineering structural properties of metal nanoclusters with the help of heteroatom dopants for future applications in efficient catalysis.

1 aManzoor, Dar1 aKrishnamurty, Sailaja1 aPal, Sourav uhttps://library.ncl.res.in/content/contriving-catalytically-active-structure-inert-conformation-density-functionalinvestigation03075nas a2200265 4500008004100000022001400041245008500055210006900140260009200209300001200301490000700313520211500320653001902435653002602454653003002480653002202510653002802532653003002560653001602590100001702606700002602623700001702649700002702666856011602693 2016 eng d a0892-702200aDFT based assay for tailor-made terpyridine ligand-metal complexation properties0 aDFT based assay for tailormade terpyridine ligandmetal complexat a4 PARK SQUARE, MILTON PARK, ABINGDON OX14 4RN, OXON, ENGLANDbTAYLOR & FRANCIS LTDcMAY a618-6270 v423 a

Electron-rich terpyridine ligand and its metal complexes have a potential to grow as responsive surfaces by adapting their physicochemical properties as a function of environment. The responsiveness is brought about by judicious molecular level designing that is currently hindered due to lack of information and control on terpyridine (TPy)-metal (M) interactions at single molecule level. So far there is no organised understanding on the binding of different metals with TPy ligand and ways to modulate it. Being a large conjugated [GRAPHICS] system, TPy has a large scope to be functionalised with electron exchanging groups to alter its electronic structure and consequently its binding with metal atoms. In first report of such a kind, using density functional theory (DFT), we demonstrate that convenient modulation of TPy-M binding is possible through functionalisation of TPy for [GRAPHICS] , Ru, Fe, Mo and Au. Electron donating groups viz., CH [GRAPHICS] , OCH [GRAPHICS] , C [GRAPHICS] H [GRAPHICS] , NH [GRAPHICS] and electron withdrawing groups viz., CF [GRAPHICS] , COOH, CN and NO [GRAPHICS] are considered for functionalisation of TPy ligand. Significantly, the present work focuses on the functionalisation at 4 and 4 [GRAPHICS] positions of TPy molecule. The role of such a functionalisation in influencing the ligands structure-property correlation is missing in the literature to the best of our knowledge. The present investigation quantifies that by pertinent functionalisation of TPy, TPy-M binding energies can be modified up to [GRAPHICS] 60kcal/mol. Our results reveal that functionalisation leads to a considerable charge redistribution within the TPy-M complex with carbon atoms in pyridine rings functioning as major electron sink/source with a corresponding red/blue shift of [GRAPHICS] stretching frequency. This modifies the red-ox, optical and other chemical properties of TPy-M complexes. In brief, the present report illustrates a way to design ligands such as TPy for diverse applications through tailor-made functionalisation using electronic structure methodology.

10aBinding energy10acharge redistribution10aDensity functional theory10afunctionalisation10aMetal organic complexes10ametal-ligand interactions10aterpyridine1 aJoshi, Krati1 aKrishnamurty, Sailaja1 aSingh, Iksha1 aSelvaraj, Kaliaperumal uhttps://library.ncl.res.in/content/dft-based-assay-tailor-made-terpyridine-ligand-metal-complexation-properties02379nas a2200169 4500008004100000022001400041245009500055210006900150260011000219300001400329490000700343520167300350100001702023700002602040700001602066856012702082 2016 eng d a1463-907600aEndohedrally doped gold nanocages: efficient catalysts for O-2 activation and CO oxidation0 aEndohedrally doped gold nanocages efficient catalysts for O2 act aTHOMAS GRAHAM HOUSE, SCIENCE PARK, MILTON RD, CAMBRIDGE CB4 0WF, CAMBS, ENGLANDbROYAL SOC CHEMISTRYcMAR a7068-70740 v183 a

Gold nanocages are the most attractive catalytic materials as all the atoms in the cage type clusters reside on the surface, making them available for chemisorption by reacting molecules. Due to a hollow space at the center, their chemical and catalytic properties can be tuned effectively and easily by endohedral doping. While a significant experimental and theoretical understanding is currently available on the structural and electronic properties of doped gold cages, very little information is available on their reactivity and catalytic behavior. In the present work, with the help of density functional theory calculations we demonstrate that endohedral doping leads to a notable increase in the binding energy of molecular oxygen on the gold nanocages. The enhancement in the O-2 binding energy on the doped gold cages is also confirmed by a significant decrease in the Au-O and an increase in the O-O bond lengths, corroborated by a red shift (similar to 250 cm(-1)) in the O-O stretching frequency as compared to the pristine cage. Furthermore, interestingly, the doped gold cages show very low activation barriers for the environmentally important CO oxidation reaction as compared to the pristine gold cage. Importantly, the decrease in the barrier height is comparatively greater for the rate limiting step of O-O-C-O intermediate formation and as a result the CO oxidation is expected to be more facile on the doped gold cages. Thus, the current study highlights the role of heteroatom doping in imparting new chemical and catalytic properties to gold cages and is expected to spur further research in the design of efficient gold nanocatalysts.

1 aManzoor, Dar1 aKrishnamurty, Sailaja1 aPal, Sourav uhttps://library.ncl.res.in/content/endohedrally-doped-gold-nanocages-efficient-catalysts-o-2-activation-and-co-oxidation-001360nas a2200157 4500008004100000245008600041210006900127260000800196300001600204490000700220520080100227100001801028700001601046700002601062856011401088 2016 eng d00aN-2 activation on Al metal clusters: catalyzing role of BN-doped graphene support0 aN2 activation on Al metal clusters catalyzing role of BNdoped gr cOCT a27721-277270 v183 aThe successful sustenance of life demands an ambient abiotic process for N-2 activation and dissociation. The Bosch-Haber process remains the only abiotic and synthetic means for N-2 activation and its fixation. Metal nanoclusters have been recently reported for activating molecular nitrogen. Interestingly, the metal clusters explored so far for N-2 activation are free clusters and, hence, are practically not applicable by experimental chemists. Using density functional theory (DFT) based methodology, we propose a potential catalytic system for di-nitrogen activation, viz. supported Al clusters. Al clusters supported on BN doped graphene sheets are seen to activate N-2 molecule with a red shift in the N-N stretching frequency up to 874 cm(-1) with activation barriers as low as 1.14 eV.1 aKumar, Deepak1 aPal, Sourav1 aKrishnamurty, Sailaja uhttps://library.ncl.res.in/content/n-2-activation-al-metal-clusters-catalyzing-role-bn-doped-graphene-support01246nas a2200157 4500008004100000245009900041210006900140260000800209300001600217490000800233520065900241100001800900700002600918700001600944856012800960 2017 eng d00aDissociative adsorption of molecular hydrogen on BN-doped graphene-supported aluminum clusters0 aDissociative adsorption of molecular hydrogen on BNdoped graphen cNOV a26493-264980 v1213 aThe present work demonstrates dissociative adsorption of molecular hydrogen on supported and unsupported aluminum Wclusters (Al-n, n = 4-8, 13) using density functional theory based calculations. The studies reveal that the presence of a BN-doped graphene surface support reduces the dissociative adsorption barrier of the bond in molecular hydrogen on even atom clusters. In particular, supported Al-6 demonstrates a barrier-less dissociative adsorption toward the H-2 molecule. These results demonstrate the excellent potential of supported Al nanoparticles for hydrogen storage and also the potential of doped graphene systems are catalyzing supports.1 aKumar, Deepak1 aKrishnamurty, Sailaja1 aPal, Sourav uhttps://library.ncl.res.in/content/dissociative-adsorption-molecular-hydrogen-bn-doped-graphene-supported-aluminum-clusters01895nas a2200157 4500008004100000022001400041245004600055210004300101260000800144300001400152490000700166520144700173100001701620700002601637856007401663 2018 eng d a1463-907600aAu26: a case of fluxionality/co-existence0 aAu26 a case of fluxionalitycoexistence cAPR a8616-86230 v203 a

The Au26 cluster is one of the widely studied gold clusters in the size range of n = 21–30. It has been proposed in a more recent combined experimental and theoretical study that the neutral Au26 cluster is fluxional. The fluxionality of a cluster is relevant to its catalytic applications. In this context, to explore the extent of fluxionality, Born Oppenheimer Molecular Dynamical (BOMD) simulations are carried out on experimentally and theoretically proposed fluxional Au26 conformations (three compact or core–shell structures and a high symmetry cage structure). The simulations reveal that the high energy golden tube outperforms the ground state structure (compact C2v conformation) as well as the other two low-symmetry compact conformations in terms of thermal stability. The enhancement in the thermal stability is explained on the basis of structural integrity imposed by the open skeleton of shortest bond distances within Au26-Tube. In addition to this, the homogeneous distribution of charges and the strong s–d hybridization exhibited by FMOs are seen to play a pivotal role in increasing the stability of Au26-Tube. The present investigation also reveals that the characteristic fluxionality proposed to exist in the Au26 system is noted only above 400 K and it is missing at room temperature. The simulations also bring forth the question of how relevant a ground state conformation is at working temperatures.

1 aJoshi, Krati1 aKrishnamurty, Sailaja uhttps://library.ncl.res.in/content/au26-case-fluxionalityco-existence01431nas a2200193 4500008004100000022001500041245012700056210006900183260000800252300001600260490000700276520071800283100001801001700002501019700002601044700002701070700001601097856012401113 2018 eng d a 1463-907600aDissociative chemisorption of hydrogen molecules on defective graphene-supported aluminium clusters: a computational study0 aDissociative chemisorption of hydrogen molecules on defective gr cNOV a26506-265120 v203 a

Using periodic density functional theory-based calculations, in the present study, we address the chemical bonding between aluminium clusters (Al-n, n = 4-8 and 13) and monovacant defective graphene. The adsorption strength of the above-mentioned aluminium clusters is fivefold (approximate to 3 to 5 eV) higher on defective graphene as compared to the earlier reported values on non-defective graphene and BN-doped graphene. The Bader charge analysis and different charge densities reveal that this adsorption is driven by significant charge transfer from the Al clusters to defective graphene. Thus, chemisorbed Al clusters demonstrate high activity towards dissociative adsorption of molecular hydrogen.

1 aKumar, Deepak1 aGovindaraja, Thillai1 aKrishnamurty, Sailaja1 aKaliaperumal, Selvaraj1 aPal, Sourav uhttps://library.ncl.res.in/content/dissociative-chemisorption-hydrogen-molecules-defective-graphene-supported-aluminium02781nas a2200181 4500008004100000022001400041245011100055210006900166260000800235300001600243490000800259520210000267100002202367700002502389700002702414700002602441856013202467 2019 eng d a1932-744700aDinitrogen activation on graphene anchored single atom catalysts: local site activity or surface phenomena0 aDinitrogen activation on graphene anchored single atom catalysts cNOV a27492-275000 v1233 a

Catalysis on two-dimensional (2D) substrates with metal clusters or centers is generally dealt with as a surface phenomenon under the conjecture that the delocalized electron density is the driving force. When single atom catalysts (SACs) are anchored on such materials with delocalized electron density, for instance graphene, the stimulant for catalysis may be either the d-electrons on the metal or the system altogether. To understand the contributing factors of catalysis on such systems, a case study of dinitrogen (N-2) activation on Mo anchored graphene has been made by employing periodic and finite models of graphene. The periodic model represents a continuum of SACs anchored periodically on graphene, while the finite models are graphene nanoflakes of varying sizes and edge orientations. In addition to the physical aspects, such as size/finiteness of graphene, the influence of varying chemical compositions of the substrate on the activity is also evaluated by doping graphene with different B and N concentrations. This study, while clearly bringing out the connotation of regulating atomic composition of graphene substrate for dinitrogen activation, also surprisingly unveils the relative insignificance of varying the size and edge effects of the substrate. These features are highlighted through an analysis of red shift in the N-N stretching frequency, charge transfer to dinitrogen from the catalytic system, and structural and electronic characteristics of the catalytic system. The total and projected density of states plots reveal hybridization between the metal d orbitals and the p orbitals of carbon and nitrogen in the valence band. On the other hand, the frontier molecular orbital analysis also depicts a strong chemisorption of dinitrogen with the metal-graphene supports on account of direct hybridization between the d orbitals of the supported metal atom and the p orbitals of dinitrogen. The Bader and Lowdin charge distribution on the adsorbed dinitrogen in periodic and finite models shows the preeminence of local site over the surface activity.

1 aMaibam, Ashakiran1 aGovindaraja, Thillai1 aSelvaraj, Kaliaperumal1 aKrishnamurty, Sailaja uhttps://library.ncl.res.in/content/dinitrogen-activation-graphene-anchored-single-atom-catalysts-local-site-activity-or-surface02973nas a2200193 4500008004100000022001400041245008100055210006900136260000900205300001600214490000600230520229300236100002502529700002502554700003402579700002602613700002802639856011202667 2019 eng d a2050-748800aEffective polysulfide trapping polar interlayer for high rate Li-S batteries0 aEffective polysulfide trapping polar interlayer for high rate Li cAPR  a10067-100760 v73 a

A microporous and polymeric C3N4 framework (CNF), when exploited as an interlayer and as a cathode host in Li-S batteries, demonstrates significantly improved electrochemical behavior with a special relevance to high rate applications up to 5C. A CNF obtained through a template free synthesis approach and activated with KOH is endowed with a high specific surface area of 1000 m(2) g(-1), a desirable nitrogen content (13%) to ensure polarity and a microporous architecture, required to increase the accommodation capability of discharge products. The difference in electronegativity between C and N in CNFs combats in a major way the shuttling of lithium polysulfides (LIPSs) and ensures the realization of increased LIPS binding sites due to the presence of pyridinic nitrogen. Furthermore, a CNF driven change in the molecular configuration of adsorbed LIPSs leads to the uniform distribution and sequestration of discharge products. Similarly, micropores and the polymeric nature of CNFs facilitate the effective confinement of LIPSs and ably accommodate the volume changes (through the formation of Li2S upon discharge) respectively, especially when a microporous CNF interlayer is involved in the Li-S assembly. In particular, a CNF with 60 wt% sulfur loading, otherwise represented as CNFS-60, when exploited as a cathode in combination with the deployment of a CNF interlayer exhibits appreciable capacity values of 500 and 400 mA h g(-1) at 3 and 5C respectively. Furthermore, the combination of the CNF interlayer and cathode demonstrates a steady state discharge capacity of 437 mA h g(-1) at 1C rate up to 300 cycles, without any significant capacity loss. The involvement of chemical interaction of the CNF with lithium polysulfides is demonstrated using density functional theory calculations. Hence, the effective trapping and the subsequent localization of migrating LIPSs arising from the strong chemical interaction of the CNF with soluble LIPSs and the advantages of high concentration of accessible pyridinic nitrogen sites to the LIPS adsorption in improving the electrochemical behavior of the Li-S system could be understood. This new CNF based interlayer provides a promising approach and ample scope for its implementation in futuristic Li-S batteries.

1 aKaruppiah, Saravanan1 aKalimuthu, Balakumar1 aNazrulla, Mohammed, Azeezulla1 aKrishnamurty, Sailaja1 aNallathamby, Kalaiselvi uhttps://library.ncl.res.in/content/effective-polysulfide-trapping-polar-interlayer-high-rate-li-s-batteries02518nas a2200145 4500008004100000245013200041210006900173260000900242300001600251490000600267520191800273100002402191700002602215856013102241 2019 eng d00aMolecular and dissociative adsorption of oxygen on au-pd bimetallic clusters: role of composition and spin state of the cluster0 aMolecular and dissociative adsorption of oxygen on aupd bimetall cJULY a12687-126950 v43 a

Utilization of molecular oxygen as an oxidizing agent in industrially important reactions is the ultimate goal to design environmentally benign processes under ambient conditions. However, the high thermal stability and a large O-O dissociation barrier in O-2 molecule pose a great challenge toward its successful application in the oxidative chemistry. To achieve this goal, different catalysts based on monometallic and bimetallic clusters have been developed over the years to promote binding and dissociation of molecular oxygen. The successful design of efficient metal cluster catalysis needs an in-depth knowledge of synergistic effects between different metal atoms and intrinsic catalytic mechanisms for O-2 adsorption and dissociation. Here, we present a systematic theoretical investigation of reaction pathways for O-2 adsorption and dissociation on Au-8, Pd-8, and Au8-nPdn (n = 1-7) nanoclusters in different spin states. The density functional calculations point out that the O-2 dissociation barriers can be significantly reduced with the help of certain bimetallic clusters along specific spin channels. Our results particularly indicate that Au5Pd3 and Au1Pd7 show very large O-2 binding energies of 1.76 and 1.69 eV, respectively. The enhanced O-2 binding subsequently leads to low activation barriers of 0.98 and 1.19 eV along the doublet and quartet spin channels, respectively, without the involvement of any spin flip-over for O-2 dissociation. Furthermore, the computed O-2 dissociation barriers are significantly low as compared to the already reported barriers (1.95-3.65 eV) on monometallic and bimetallic Au-Ag clusters. The results provide key mechanistic insights into the interaction and dissociation of molecular oxygen with Au-Pd clusters, which can prove informative for the design of efficient catalysts for oxidative chemistry involving molecular oxygen as a reactant.

1 aDar, Manzoor, Ahmad1 aKrishnamurty, Sailaja uhttps://library.ncl.res.in/content/molecular-and-dissociative-adsorption-oxygen-au-pd-bimetallic-clusters-role-composition-and02277nas a2200253 4500008004100000022001400041245010300055210006900158260000900227300001100236490000900247520140000256653002301656653001601679653001901695653001601714653004201730653002101772100002901793700001701822700002701839700002601866856013101892 2019 eng d a2210-271X00aProbing the catalytic activity of pristine and doped Pd and Ni metal clusters towards H2O molecule0 aProbing the catalytic activity of pristine and doped Pd and Ni m cDEC  a1126240 v11703 a

Electrolysis of H2O to produce molecular hydrogen, the most environment friendly and energy efficient fuel, using cost effective catalysts is one of the major global research challenges. To date, Pt remains the best suitable and yet highly expensive electro-catalyst for hydrogen evolution reaction. Design of an alternative cost-effective catalyst requires a fundamental molecular level understanding of the water molecule adsorption and its activation. In that context, we examine the adsorption and activation of water molecule on model alternative catalysts namely, Ni-6 and Pd-6 clusters using density functional theory based methodology. Ni-6 and Pd-6 clusters and their singly doped counterparts are used for this study. Mo, W, Fe, Co and Cu are used as doping elements. To quantify the influence of medium (neutral and alkaline) on the activation of the water molecule, Ni based clusters are considered in neutral and anionic states, respectively. The activity of these clusters towards H2O molecule is evaluated in terms of the adsorption energy, charge transfer, bandgap, red shift in O-H stretching frequency and dissociation barriers for H2O. The studies demonstrate that doping with Co in all the studied clusters (Pd-6, Ni-6 and anionic Ni-6) increases their activity. Best activity is noted for Fe doped neutral Ni b clusters with a dissociation barrier of 5.76 kcal/mol.

10aActivation barrier10aNi clusters10aO-H activation10aPd clusters10aRed shift of O-H stretching frequency10aWater adsorption1 aSamal, Pragnya, Paramita1 aJoshi, Krati1 aKaliaperumal, Selvaraj1 aKrishnamurty, Sailaja uhttps://library.ncl.res.in/content/probing-catalytic-activity-pristine-and-doped-pd-and-ni-metal-clusters-towards-h2o-molecule02123nas a2200265 4500008004100000022001400041245013800055210006900193260000900262300001400271490000700285520121800292653002001510653001501530653001901545653002501564653001401589653000901603100002201612700002901634700001801663700002601681700002001707856013001727 2020 eng d a2155-543500aIron-catalyzed C(sp(2))-H alkylation of indolines and benzo[h]quinoline with unactivated alkyl chlorides through chelation assistance0 aIroncatalyzed Csp2H alkylation of indolines and benzohquinoline  cJUL  a7312-73210 v103 a

Regioselective C-H bond alkylation of indolines and benzo[h]quinoline with a wide range of unactivated and highly demanded primary and secondary alkyl chlorides is accomplished using a low-cost iron catalyst. This reaction tolerates diverse functionalities, such as C(sp(2))-Cl, fluoro, alkenyl, silyl, ether, thioether, pyrrolyl, and carbazolyl groups including cyclic and acyclic alkyls as well as alkyl-bearing fatty-alcohol and polycyclic-steroid moieties. The demonstrated iron-catalyzed protocol proceeded via either a five-membered or a six-membered metallacycle. Intriguingly, the C-7-alkylated indolines can be readily functionalized into free-NH indolines/indoles and tryptamine derivatives. A detailed mechanistic investigation highlights the participation of an active Fe(I) catalyst and the involvement of a halogen-atom transfer process via a single-electron-based mechanism. Deuterium labeling and kinetics analysis indicate that the C-H metalation of indoline is the probable turnover-limiting step. Overall, the experimental and theoretical studies supported an Fe(I)/Fe(III) pathway for the alkylation reaction comprising the two-step, one-electron oxidative addition of alkyl chloride.

10aalkyl chlorides10aAlkylation10aC-H activation10achelation assistance10aindolines10airon1 aJagtap, Rahul, A.1 aSamal, Pragnya, Paramita1 aVinod, C., P.1 aKrishnamurty, Sailaja1 aPunji, Benudhar uhttps://library.ncl.res.in/content/iron-catalyzed-csp2-h-alkylation-indolines-and-benzohquinoline-unactivated-alkyl-chlorides01232nas a2200169 4500008004100000022001400041245012300055210006900178260000900247300001600256490000700272520058700279100001700866700002600883700002400909856012900933 2020 eng d a1463-907600aSurface functionalization: an efficient alternative for promoting the catalytic activity of closed shell gold clusters0 aSurface functionalization an efficient alternative for promoting cOCT  a23351-233590 v223 a

{Surface functionalization through adsorption of ligands or non-metal atoms is considered to be an interesting and viable approach for tuning the physicochemical properties of gold clusters. Highly stable and magic numbered electronic configurations of thiolate protected gold clusters such as Au-25(SR)(18), Au-38(SR)(24)etc. with intriguing properties are the direct manifestation of the rich chemistry of the Au-S interface. The present investigation discerns the CO oxidation activity of structurally well characterized sulphur functionalized gold cluster anions AumS4-

1 aJoshi, Krati1 aKrishnamurty, Sailaja1 aDar, Manzoor, Ahmad uhttps://library.ncl.res.in/content/surface-functionalization-efficient-alternative-promoting-catalytic-activity-closed-shell02701nas a2200265 4500008004100000022001400041245016000055210006900215260000800284300001100292490000800303520172400311653003002035653003202065653001702097653001902114653003702133100002202170700001902192700001702211700002502228700002602253700002702279856012902306 2020 eng d a0304-389400aUnravelling the distinct surface interactions of modified graphene nanostructures with methylene blue dye through experimental and computational approaches0 aUnravelling the distinct surface interactions of modified graphe cAPR a1217550 v3883 a

Nanoscopic modifications leading to multi-dimensional graphene structures are known to significantly influence their candidature for several applications including catalysis, energy storage, molecular sensing and most significantly adsorption and remediation of harmful materials such as dyes. The present work attempts to identify the key trajectories that connect the structural qualification with a chosen application, viz., the interactive forces in dye remediation. Various physico-chemically Modified Graphene Nanostructures (MGNs) such as 2 dimensional Graphite, Graphene Oxide (GO), reduced GO (rGO), holey rGO, and 3 dimensional GO hydrogel and Holey GO hydrogel are chosen and synthesised herein. These represent varieties of physicochemical features with respect to their dimensionality, surface features such as oxygen functionality, nanoscopic holes etc., that contribute to their characteristic overall surface interactions. Methylene Blue (MB), a popular industrial effluent posing major environmental concern is chosen to be a probe adsorbate in this case study. An exclusive real time in-situ UV visible spectral experiment provides the revealing reasons behind the outstanding performance of 2D GO sheets with an adsorption capacity of greater than 92 % even at high MB concentrations (>2000 ppm). A complex dependency of various factors such as surface oxygen, morphology, nanoporosity etc. on the unique overall interaction with an adsorbent such as MB by all these adsorbates is demonstrated using experimental and DFT based computational studies. Electrostatics and hydrogen bonding are understood to be the two dominant forces driving the MB adsorption on the best performing GO here.

10aDensity functional theory10aIn-situ UV-vis spectroscopy10aInteractions10aMethylene blue10aModified Graphene Nanostructures1 aManappadan, Zinoy1 aKumar, Shubham1 aJoshi, Krati1 aGovindaraja, Thillai1 aKrishnamurty, Sailaja1 aSelvaraj, Kaliaperumal uhttps://library.ncl.res.in/content/unravelling-distinct-surface-interactions-modified-graphene-nanostructures-methylene-blue03405nas a2200229 4500008004100000022001400041245021300055210006900268260000800337300001600345490000800361520247400369100002702843700002202870700003402892700001802926700001902944700002602963700003002989700002703019856012903046 2020 eng d a1932-744700aUnsymmetrical squaraine dyes for dye-sensitized solar cells: position of the anchoring group controls the orientation and self-assembly of sensitizers on the TiO2 surface and modulates its flat band potential0 aUnsymmetrical squaraine dyes for dyesensitized solar cells posit cAUG a18436-184510 v1243 a

The position of the anchoring group is systematically changed with a series of alkyl group wrapped donor-acceptor-donor (D-A-D) based squaraine dyes, 4-SQ to 7-SQ, for the use in dye-sensitized solar cells (DSSCs). By this approach, the orientation as well as the self-assembly of the sensitizers can be controlled on the semiconducting TiO2 surface. All of the dyes functionalized with hydrophobic alkyl groups at sp(3)-C and N atoms of the indoline units that is far away from the TiO2 surface to control the self-assembly of dyes and passivate the surface. Controlling both the orientation as well as the self-assembly of the sensitizers synergistically enhances the V-oc of the DSSC device by imparting the dipole moment on the TiO2 surface and minimizing the interfacial charge recombination process of electrons from TiO2 to the oxidized electrolyte, respectively. Further, the presence of a meta-carboxyl group with respect to the N atom of the indoline donor unit for the dyes 4-SQ and 6-SQ makes them nonconductive for the charge injection process, which sheds light on the importance of through-space electron transfer for the device performance. Emission from the relaxed twisted state was found to be a deactivation pathway for 4-SQ on TiO2 and ZrO2, which revealed the importance of structural factors that promote spatial interaction between the sensitizer and metal oxide surface. Computational studies showed the systematic changes in the dipole moment for the sensitizers 4-SQ, 5-SQ, and 6-SQ upon anchoring to the TiO2 surface. The DSSC device performance varied with the position of anchoring groups in the sensitizers. The DSSC device performance of 5-SQ indicates a J(sc) value of 11.35 mA cm(-2), V-oc of 0.698 V, and ff of 77% corresponding to a power conversion efficiency of 6.08% in the presence of 3 equiv of coadsorbent CDCA, which is nearly 1.5 times higher than 6-SQ (V-oc 0.7 V, J(sc) 7.76 mA cm(-2), ff 76%, and eta 4.14%) and 2.6 times higher than 4-SQ (V-oc 0.658 V, J(sc) 4.42 mA cm(-2), ff 78%, and eta 2.28%). IPCE studies revealed the importance of orientation for the charge injection and self-assembly of dyes, as devices with 5-SQ and 6-SQ as a sensitizer showed 94 and 77% response at 578 nm, respectively, which correspond to the aggregated structure of the dye. Mott-Schottky and IPCE experiments showed that the orientation of sensitizers could modulate the V-oc due to the shift in the flat band potential of TiO2.

1 aSingh, Ambarish, Kumar1 aMaibam, Ashakiran1 aJavaregowda, Bharathkumar, H.1 aBisht, Rajesh1 aKudlu, Ashwath1 aKrishnamurty, Sailaja1 aKrishnamoorthy, Kothandam1 aNithyanandhan, Jayaraj uhttps://library.ncl.res.in/content/unsymmetrical-squaraine-dyes-dye-sensitized-solar-cells-position-anchoring-group-controls01964nas a2200253 4500008004100000022001400041245011500055210006900170260000800239300001400247490000700261520109300268653001501361653001801376653001401394653001801408653002001426100003801446700001801484700002201502700002601524700003001550856013001580 2021 eng d a1867-388000aDurable metalloporphyrin 2D-polymer for photocatalytic hydrogen and oxygen evolution from river and sea waters0 aDurable metalloporphyrin 2Dpolymer for photocatalytic hydrogen a cAPR a1717-17210 v133 a

It is highly imaginary that the outcome of a combination of two complementary resources leads to answer an alarming global issue. One such possible example is the solar seawater splitting for `clean fuel' H-2 generation. Since the catalytic activity and stability of the photocatalysts are substantially challenged in seawater, the design of an efficient and stable photocatalyst is highly desirable. Herein, we demonstrate the solar seawater splitting by a two-dimensional polymer catalyst derived from metalloporphyrin bearing multi-hydroxyl groups. A bimetallic (Co and Ni) porphyrin 2D-polymer exhibits excellent long-term durability of 15 cycles of H-2 and O-2 generation in 200 days from pure water without a considerable decrease in efficiency. Detailed studies using river and seawaters also show the reliable performance of the catalyst over repeated cycles. Here the deactivation modes of catalytic activity have been nullified by the layered metalloporphyrin polymer structure through stable pi-pi stacking, signifying the molecular design of 2D-polymer photocatalyst.

10a2D-polymer10aPhotocatalyst10aporphyrin10aSelf-assembly10awater splitting1 aRanjeesh, Kayaramkodath, Chandran1 aGeorge, Leena1 aMaibam, Ashakiran1 aKrishnamurty, Sailaja1 aBabu, Sukumaran, Santhosh uhttps://library.ncl.res.in/content/durable-metalloporphyrin-2d-polymer-photocatalytic-hydrogen-and-oxygen-evolution-river-and01430nas a2200133 4500008004100000245009700041210006900138260000800207520088800215100002201103700002601125700002401151856012101175 2021 eng d00aElectrocatalytic nitrogen reduction directed through the p-band center of boron on BSAC@Mo2C0 aElectrocatalytic nitrogen reduction directed through the pband c cNOV3 aGreener modes of ammonia synthesis via the electrocatalytic route have been investigated on pristine and defective Mo2C based monolayers anchored with metal-free boron atom catalysts. Boron single atom catalysts (SACs) on the defective Mo2C monolayer has been found to activate N2 strongly with an adsorption energy of −1.92 eV and reduce it to NH3 efficiently with a significantly low overpotential of 0.41 eV. The exothermic adsorption of N2 and low overpotential for the nitrogen reduction reduction (NRR) appertain to the p-band center of the boron atom catalyst and charge transfer between the adsorbed N2 and the catalyst, respectively. This work brings forth the correlation between electron occupancy on the boron center and NRR catalytic efficiency on a metal-free SACs@Mo2C monolayer couple, thereby serving as a lead in designing metal free electrocatalysts for the NRR.1 aMaibam, Ashakiran1 aKrishnamurty, Sailaja1 aDar, Manzoor, Ahmad uhttps://library.ncl.res.in/content/electrocatalytic-nitrogen-reduction-directed-through-p-band-center-boron-bsacmo2c02037nas a2200169 4500008004100000245008100041210006900122260000900191300001600200490000700216520143400223100002201657700002201679700002901701700002601730856011101756 2021 eng d00aEnhanced photocatalytic properties of a chemically modified blue phosphorene0 aEnhanced photocatalytic properties of a chemically modified blue cAPR  a13348-133580 v113 a

It is high time to placate the peak demand for an efficient, economic and green fuel in the form of H-2 through photocatalytic water splitting. Several low dimensional materials have been explored for their photocatalytic properties on account of their surface to volume ratio. The present study illustrates the excellent photocatalytic potential of a two-dimensional material, viz. a chemically tempered blue-phosphorene sheet, with single atom thickness and high carrier mobility. Metal-free element, sulphur, is explored as a dopant in a 32-atom blue-phosphorene sheet. The dopant is inserted at three locations viz. central, edge and central edge positions with varying concentrations from 3.125% to 18.75% (corresponding to n = 1 to 6 sulphur atoms within a 32-atom blue-phosphorene sheet, P32-nSn). The cohesive energy studies predict the higher stability of even number S doped sheets as compared to their odd counterparts. Photocatalytic activity is studied in terms of band gap and band alignment for different concentrations of the former. Studies reveal that edge doping demonstrates better water molecule activation independent of S atom concentration. The edge doped systems not only provide the chemical activity to activate water, but also show feasible HER overpotentials of 1.24-1.29 eV at neutral medium. Finally, this work opens up a driving lead of non-corrosive catalysts for water molecule splitting.

1 aMaibam, Ashakiran1 aDas, Sawan, Kumar1 aSamal, Pragnya, Paramita1 aKrishnamurty, Sailaja uhttps://library.ncl.res.in/content/enhanced-photocatalytic-properties-chemically-modified-blue-phosphorene02151nas a2200181 4500008004100000022001400041245010700055210006900162260000800231300001400239490000700253520149300260100002201753700002601775700001701801700002601818856012501844 2021 eng d a1144-054600aExploring edge functionalised blue phosphorene nanoribbons as novel photocatalysts for water splitting0 aExploring edge functionalised blue phosphorene nanoribbons as no cFEB a3570-35800 v453 a

Hydrogen gas, a highly combustible and eco-friendly fuel is stealing the limelight and its production is one of the major areas of research. An efficient and green method for producing clean hydrogen gas with no harmful by-product is water splitting. With the introduction of low dimensional materials, water splitting has become an easier and cost-effective process. The present work demonstrates the application of one such low dimensional material viz., edge functionalised Blue Phosphorene Nano-Ribbons (BPNRs) as potential photocatalysts. With a carrier mobility of 10(3) cm(2) V-1 s(-1) and a band gap of 1.5-3.0 eV, BPNRs are an attractive candidate for photocatalysis. BPNRs with different edge oreintations, viz. zigzag and armchair are functionalised with CH3O, COOCH3, CHO, COOH, OH, NH2, CONH2, SH, C6H5, and NO2 groups. Their performance towards activating water molecules at different sites on the nanoribbon is studied. The functionalised edges of the BPNRs are the active sites showing similar to 1.2% to 3.2% efficiency in activating the O-H bond of the water molecule. Among the different groups explored, CONH2 functionalised zigzag BPNR clearly exhibits a higher potential towards the adsorption of water molecules (-0.98 eV) and activation of O-H bonds with an elongation of 3.2% and a red shift of 500.6 cm(-1). This is attributed to the lone pair of electrons on the nitrogen atom contributing to the electron donating nature of the CONH2 functional group.

1 aMaibam, Ashakiran1 aChakraborty, Debalina1 aJoshi, Krati1 aKrishnamurty, Sailaja uhttps://library.ncl.res.in/content/exploring-edge-functionalised-blue-phosphorene-nanoribbons-novel-photocatalysts-water02725nas a2200169 4500008004100000022001400041245017900055210006900234260000800303300001400311490000700325520202600332100001702358700002202375700002602397856013202423 2021 eng d a1144-054600aFinite temperature behavior of carbon atom-doped silicon clusters: depressed thermal stabilities, coexisting isomers, reversible dynamical pathways and fragmentation channels0 aFinite temperature behavior of carbon atomdoped silicon clusters cMAY a8217-82270 v453 a

Silicon carbide clusters are significant due to their predominant occurrence in meteoric star dust, particularly in carbon-rich asymptotic giant branch stars. Of late, they have also been recognized as nanoclusters with potential applications in technology. Them both being elements of the same group, there is excellent potential for precise control over the physico-chemical properties of such molecular length-scale materials through atomic engineering and this has been explored recently by various experimentalists. This report simulates one of the significant physical properties, viz. conformational stability, of various carbon-doped silicon clusters as a function of temperature using Born-Oppenheimer molecular dynamics methodology. Single carbon atom-doped silicon clusters with 4-9 atoms (i.e., Si3C-Si8C) are chosen for this study as the gas phase geometries of these clusters have been characterized using a combination of experimental and theoretical methods in the recent past. The simulations ratify that various conformations do not interconvert among themselves at 300 K. The interconversion occurs at 500 K or above, thereby ratifying the possibility of the coexistence of multiple conformations of a given cluster, which are generally synthesized under subroom temperature conditions. Furthermore, the above single carbon atom-doped silicon clusters: (a) have depressed thermal stabilities as compared to their pristine counterparts with the exception of a Si5C conformation; (b) undergo multifarious evolution of the cluster, through the reversible dynamical and fragmentation pathways as a function of temperature and (c) single carbon atom-doped silicon clusters with 7 atoms (starting from Si6C) and above undergo a fragmentation at nearly 2000 K. The underlying electronic and structural properties of various clusters are discussed to explain the above observations with a note on critical fragmentation energy barriers required for the segmentation of clusters with seven or more atoms.

1 aJoshi, Krati1 aMaibam, Ashakiran1 aKrishnamurty, Sailaja uhttps://library.ncl.res.in/content/finite-temperature-behavior-carbon-atom-doped-silicon-clusters-depressed-thermal-stabilities02265nas a2200169 4500008004100000022001400041245018100055210006900236260000900305300001400314490000700328520153700335100004301872700002601915700002701941856012701968 2021 eng d a1144-054600aGraphene-based frustrated Lewis pairs as bifunctional catalysts for CO2 reduction via the dissociative chemisorption of molecular H-2: a periodic density functional perspective0 aGraphenebased frustrated Lewis pairs as bifunctional catalysts f cJUN  a9959-99660 v453 a

Nanocarbon-based frustrated Lewis pair (FLP) bifunctional catalysts, on account of their unquenched electron transfer property, are becoming increasingly attractive as catalysts for the CO2 reduction reaction via the dissociative chemisorption of H-2. In the present study, we propose a nanocarbon-based FLP catalyst. The pair comprises nitrogen doped/phosphorus doped graphene as Lewis bases and M(C6F5)(3) (M = B, Al, Ga, and In) as Lewis acids. The computational investigation reveals that the carbon atoms adjacent to the doped N and P atoms are the active sites towards the dissociative chemisorption of hydrogen molecule. The analyses of the Bader charges and difference charge densities validate the dissociative chemisorption of H-2 molecule and the fact that a significant electron redistribution promotes the polarization of the hydrogen molecule. Density of states confirms the hybridization between the p-states of the nitrogen/phosphorus atom and the s-state of hydrogen atom in all FLPs. The dissociative chemisorption of hydrogen is noted in all FLP complexes, thereby facilitating a low barrier reaction path for CO2 reduction. Between P-doped and N-doped FLPs, N-doped FLP catalysts prove to be a more promising counterpart with considerably low activation barriers, ranging between 0.01 and 0.11 eV, towards CO2 reduction. Thus, the present study demonstrates the great potential of doped carbon-based FLPs as novel nanostructure catalysts for CO2 reduction via the direct utilization of molecular hydrogen.

1 aSenthamaraikannan, Thillai, Govindaraj1 aKrishnamurty, Sailaja1 aKaliaperumal, Selvaraj uhttps://library.ncl.res.in/content/graphene-based-frustrated-lewis-pairs-bifunctional-catalysts-co2-reduction-dissociative01902nas a2200193 4500008004100000022001400041245018300055210006900238260000800307300001400315490000700329520113700336100001901473700002901492700002601521700001501547700002001562856012601582 2021 eng d a1463-926200aAn innovative light assisted production of acetic acid from CO2 and methanol: a first photocatalytic approach using a reusable cobalt(ii) molecular hybrid at atmospheric pressure0 ainnovative light assisted production of acetic acid from CO2 and cNOV a9048-90600 v233 aAcetic acid is an important commodity chemical that is produced either by fermentation processes, or more commonly, through chemical routes such as methanol carbonylation with CO and H-2, acetaldehyde oxidation, or hydrocarbon oxidation. More recently, methanol hydrocarboxylation with CO2 and H-2 under thermal catalytic conditions has attracted interest. The synthesis of acetic acid from easily available CO2 is of great significance yet rarely reported. The present paper describes the first photocatalytic approach for the synthesis of acetic acid from methanol and CO2 under ambient reaction conditions without using molecular hydrogen. The maximum conversion of methanol achieved is 60% with a selectivity of 81% towards acetic acid using an octa-sulfur bound cobalt phthalocyanine (CoPc/S8) photocatalyst without an additional sacrificial electron donor. Product analysis, controlled experiments and DFT calculations suggest the formation of methylene carbene as a reactive intermediate. The developed methodology represents a potentially exciting approach for synthesizing acetic acid utilizing CO2 in a sustainable manner.1 aSaini, Sandhya1 aSamal, Pragnya, Paramita1 aKrishnamurty, Sailaja1 aRay, Anjan1 aJain, Suman, L. uhttps://library.ncl.res.in/content/innovative-light-assisted-production-acetic-acid-co2-and-methanol-first-photocatalytic02878nas a2200277 4500008004100000022001400041245014900055210006900204260000800273300001600281490000600297520188700303653003702190653001702227653000802244653002302252653001302275653002002288653003002308100002502338700002202363700002902385700002602414700002902440856013102469 2021 eng d a2168-048500aMechanistic investigations on the catalytic transfer hydrogenation of lignin-derived monomers over Ru catalysts: theoretical and kinetic studies0 aMechanistic investigations on the catalytic transfer hydrogenati cOCT a14040-140500 v93 aThe hydrodeoxygenation (HDO) reaction of oxygenated compounds such as lignin-derived phenolics is well studied using molecular H-2 as a hydrogen source, yet the use of high pressures discourages its use on an industrial scale. As an alternative, the catalytic transfer hydrogenation (CTH) pathway provides in situ hydrogenation species, which reduces the need for the high-pressure infrastructure required when molecular hydrogen is used. Nevertheless, this strategy is scantly studied, and in lieu with this, herein we report the kinetic and mechanistic investigations of the CTH strategy for the HDO of guaiacol, phenol, anisole veratrole, and eugenol to their respective products. For potential commercialization purposes, low loading of metal, milder reaction conditions, and high selectivity toward desired products with a high H/C ratio were considered while designing catalysts (0.5 wt % Ru on SiO2-Al2O3, SiO2, Al2O3-acidic, Al2O3-basic, and Al2O3-neutral) for these reactions. As high as 74% cyclohexanol yield from guaiacol was achieved at 225 degrees C in the presence of isopropyl alcohol (IPA) as the hydrogen source and over the Ru/Al2O3-acidic catalyst reduced at 150 degrees C. A detailed kinetic study is carried out to understand the interaction of the substrate and intermediates with the catalyst and the influence of reaction parameters on the product formation. It was observed that the cisisomer of 2-methoxycyclohexanol rapidly undergoes further conversion than the trans-isomer. The experimental observations are substantiated through density functional theory (DFT) studies on Ru(0001) and guaiacol molecule complexes. DFT studies indicate that the adsorption of the cis-isomer is more exothermic as compared to that of the trans counterpart, and the underlying electronic factors are elucidated using charge density difference and density of states plots.10acatalytic transfer hydrogenation10aCyclohexanol10aDFT10aHydrodeoxygenation10akinetics10alignin monomers10aSupported metal catalysts1 aKhan, Tufeil, Sartaj1 aSingh, Dheerendra1 aSamal, Pragnya, Paramita1 aKrishnamurty, Sailaja1 aDhepe, Paresh, Laxmikant uhttps://library.ncl.res.in/content/mechanistic-investigations-catalytic-transfer-hydrogenation-lignin-derived-monomers-over-ru01871nas a2200289 4500008004100000022001400041245013600055210006900191260000900260300001600269490000700285520090000292653001901192653001901211653002001230653001201250653001401262653001101276653002301287100002801310700002901338700001801367700002401385700002601409700002001435856012601455 2021 eng d a2155-543500aNi(II)-catalyzed intramolecular C-H/C-H oxidative coupling: an efficient route to functionalized cycloindolones and indenoindolones0 aNiIIcatalyzed intramolecular CHCH oxidative coupling an efficien cOCT  a12384-123930 v113 aNickel(II)-catalyzed intramolecular C(sp(2))-H/C(sp(3))-H and C(sp(2))-H/C(sp(2))-H oxidative couplings in indoles are achieved via chelation assistance. These reactions provide access to biologically relevant five- and six-membered substituted cyclopentaindolones, carbazolones, and indenoindolones in high yields and good chemoselectivity employing an air-stable and defined nickel catalyst, (bpy)Ni(OAc)(2). The oxidative cyclizations proceeded either through a six-membered or an unconventional seven-membered nickelacycle. An extensive mechanistic investigation by experiments and theoretical calculations revealed a facile indole's C(2)-H nickelation and a rate-limiting reductive elimination process. This intramolecular oxidative cyclization operates via a probable Ni(II)/Ni(III) pathway involving single-electron oxidation of nickel without the participation of a carbon-based radical.10aC-H activation10acycloindolones10aindenoindolones10aindoles10aMechanism10aNickel10aoxidative coupling1 aAnkade, Shidheshwar, B.1 aSamal, Pragnya, Paramita1 aSoni, Vineeta1 aGonnade, Rajesh, G.1 aKrishnamurty, Sailaja1 aPunji, Benudhar uhttps://library.ncl.res.in/content/niii-catalyzed-intramolecular-c-hc-h-oxidative-coupling-efficient-route-functionalized02742nas a2200145 4500008004100000245013400041210006900175260000800244300001200252490000800264520214400272100002202416700002602438856013202464 2021 eng d00aNitrogen activation to reduction on a recyclable V-SAC/BN-graphene heterocatalyst sifted through dual and multiphilic descriptors0 aNitrogen activation to reduction on a recyclable VSACBNgraphene  cMAY a480-4910 v6003 a

Efficient reduction of nitrogen to ammonia at a minimal cost would require a recherche catalyst tailored by assimilating the inherent electronic and reactive nature of Single Atom Catalysts (SACs) on heteroatom doped-graphene. A full-scale DFT study accounting for disparate descriptions of atomic orbitals and representation of support, has been carried out to identify the most active and recyclable SAC/B-graphene composite as catalyst for Nitrogen Reduction Reaction (NRR). Dual and Multiphilic descriptors derived reactivity pattern of six different metal SACs V, Fe, Ni, Ru, W and Re on periodic and non-periodic paradigms of pristine and BN-pair doped graphene supports, align with the calculated chemisorption efficacy and activation of N2. The enzymatic route of nitrogen reduction on three most ideal metal SACs (V, W and Re) culminates Vanadium SAC, a relatively cheaper metal, anchored on BNring-graphene with an energy barrier of ⩽1.24 eV as a highly active and recyclable catalyst for NRR.

1 aMaibam, Ashakiran1 aKrishnamurty, Sailaja uhttps://library.ncl.res.in/content/nitrogen-activation-reduction-recyclable-v-sacbn-graphene-heterocatalyst-sifted-through-dual01934nas a2200157 4500008004100000022001400041245013800055210006900193260000800262490000600270520127200276100004301548700002701591700002601618856013201644 2021 eng d a2296-264600aRole of chemical structure of support in enhancing the catalytic activity of a single atom catalyst toward NRR: a computational study0 aRole of chemical structure of support in enhancing the catalytic cSEP0 v93 aUsing the periodic density functional theory–based methodology, we propose a potential catalytic system for dinitrogen activation, viz., single metal atoms (Mo, Fe, and V) supported on graphene-based sheets. Graphene-based sheets show an excellent potential toward the anchoring of single atoms on them (Mo, Fe, and V) with adsorption energies ranging between 1.048 and 10.893 eV. Factors such as defects and BN doping are noted to enhance the adsorption energies of single metal atoms on the support. The adsorption of a dinitrogen molecule on metal atom–anchored graphene-based supports is seen to be highly favorable, ranging between 0.620 and 2.278 eV. The adsorption is driven through a direct hybridization between the d orbitals of the metal atom (Mo, Fe, and V) on the support and the p orbital of the molecular nitrogen. Noticeably, BN-doped graphene supporting a single metal atom (Mo, Fe, and V) activates the N2 molecule with a red shift in the N–N stretching frequency (1,597 cm−1 as compared to 2,330 cm−1 in the free N2 molecule). This red shift is corroborated by an increase in the N–N bond length (1.23 Å from 1.09 Å) and charge transfer to an N2 molecule from the catalyst.1 aSenthamaraikannan, Thillai, Govindaraj1 aKaliaperumal, Selvaraj1 aKrishnamurty, Sailaja uhttps://library.ncl.res.in/content/role-chemical-structure-support-enhancing-catalytic-activity-single-atom-catalyst-toward-nrr01879nas a2200253 4500008004100000022001400041245011500055210006900170260000800239300001100247490000800258520105200266653001601318653001101334653002701345653000801372653001401380653001901394653001401413100002901427700001101456700002601467856013201493 2021 eng d a0169-433200aSubstrate augmented catalytic activity towards NRR: a case study of Li doped Al clusters on defective graphene0 aSubstrate augmented catalytic activity towards NRR a case study  cNOV a1505860 v5663 aDensity Functional Theory (DFT) based methods are applied to examine the potential of lithium doped aluminium clusters consisting of 3-13 atoms for dinitmgen molecule activation in terms of N N bond length, redshift in N N bond stretching frequency, nitrogen interaction energy and frontier molecular orbitals analysis. The present work highlights the role of monovacant C-3 defective graphene as a support in fine tuning the catalytic activity of Li doped Al clusters for reduction of N-2. Fundamental insights to synergic binding of clusters with defective graphene is brought out and its role in enhancing activation of dinitmgen molecule is explained. Supported Aln-1Li clusters with six or more atoms are noted to be more active towards N-2 molecule activation as compared to the clusters without support. Dinitrogen molecule undergoes a maximum bond elongation of 1.56 angstrom corresponding to redshift of 1690 cm(-1) on Al7Li@graphene and Al12Li@graphene. This is maximum value reported in context of activation for N-2 molecule till date.10aAl clusters10aAl12Li10aC-3 defective graphene10aDFT10aLi Doping10aN-2 activation10aRed-shift1 aSamal, Pragnya, Paramita1 aPoonam1 aKrishnamurty, Sailaja uhttps://library.ncl.res.in/content/substrate-augmented-catalytic-activity-towards-nrr-case-study-li-doped-al-clusters-defective01363nas a2200241 4500008004100000022001400041245008300055210006900138260000800207300000800215490000800223520055400231653000900785653002900794653002200823653004300845653001700888653002200905100003000927700002900957700002600986856010901012 2021 eng d a1432-881X00aThermal stability of an endohedrally doped aluminum nanoclusters: a BOMD study0 aThermal stability of an endohedrally doped aluminum nanoclusters cSEP a1320 v1403 aIn this article, thermal stability of doped Al-13 nanoclusters has been systematically investigated within the framework of density functional theory (DFT). To explain thermal stability, simulations have been carried out over a temperature range from 300 to 1100 K using Born-Oppenheimer molecular dynamics (BOMD). The atomic displacements have been quantified by calculating delta(rms,) MSD and epsilon(pro.) The thermal stability of different clusters is explained using underlined electronic properties such as HOMO-LUMO, charges and bond length.10aBOMD10aBond length fluctuations10aEndohedral doping10aMean squared ionic displacements (MSD)10aNanoclusters10aRoot mean squared1 aSingh, Chandrodai, Pratap1 aSamal, Pragnya, Paramita1 aKrishnamurty, Sailaja uhttps://library.ncl.res.in/content/thermal-stability-endohedrally-doped-aluminum-nanoclusters-bomd-study02873nas a2200265 4500008004100000022001400041245015900055210006900214260000800283300001100291490000800302520192200310653002202232653003002254653002102284653002302305653001802328653002002346100002002366700002002386700003002406700002602436700002102462856012402483 2022 eng d a0925-838800aFacile fabrication of nano silver phosphate on B-doped g-C3N4: an excellent p-n heterojunction photocatalyst towards water oxidation and Cr (VI) reduction0 aFacile fabrication of nano silver phosphate on Bdoped gC3N4 an e cMAR a1628530 v8983 aA photostable Ag3PO4/BCN type-II p-n heterojunction has been demonstrated by loading nano Ag3PO4 on B-doped g-C3N4 nanosheet (BCN). The photocatalysts were successfully characterized by various physicochemical techniques and their photocatalytic activities were tested towards the water oxidation reaction to produce oxygen and Cr (VI) reduction under visible light. The HRTEM confirms Ag3PO4 with a particle size of 15 nm has been deposited on BCN to construct a p-n heterojunction. The BCNS-50 absorbs more visible light in the solar spectrum as compared to other catalyst, demonstrating the ability to generate 587 mu mol h(-1)g(-1) O-2 and reduces 98% of 20 ppm Cr (VI) solution in 1 h. The lower PL intensity as well as lower arc value in case of BCNS-50 suggests the maximum e-h separation and lower charge transfer resistance across the semiconductor/electrolyte interface. The BCN sheet provides a compact heterojunction where the oxidation peak of Ag3PO4 decreases gradually and disappear in case of BCNS-50 suggesting the enhance stability of Ag3PO4 in the heterojunction. BCNS-50 could able to produce -139 and 3087.5 mu A photocurrent both in cathodic and anodic direction which is approximately 7 and 2.4 folds higher as compared to nano Ag3PO4. The generation of photocurrent in both cathodic and anodic direction confirms the formation of p-n heterojunction which further supported by Mott-Schottky analysis. Furthermore the construction of the p-n heterojunction is verified via Mott-Schottky study. DFT calculation explains the contribution of various atomic orbital of Ag3PO4 and BCN towards the formation of hybrid orbital in the heterojunction and the path for charge delocalization between them. This work may provide a limelight and alternative pathway for enhanced photocatalytic performance on construction of the p-n heterojunction in a simple way. (C) 2021 Elsevier B.V. All rights reserved.10aCr (VI) reduction10aDensity functional theory10aInterfacial zone10ap-n heterojunction10aPhotocatalyst10aWater oxidation1 aSahoo, Mitarani1 aBabu, Pradeepta1 aSingh, Chandrodai, Pratap1 aKrishnamurty, Sailaja1 aParida, Kulamani uhttps://library.ncl.res.in/content/facile-fabrication-nano-silver-phosphate-b-doped-g-c3n4-excellent-p-n-heterojunction02821nas a2200313 4500008004100000245018800041210006900229260000800298300001600306490000600322520168400328653002302012653001802035653003302053653003202086653002002118653003302138653002202171100002002193700001602213700001702229700001702246700002002263700001902283700002402302700002602326700002402352856013102376 2022 eng d00aFirst-principles investigation of the electrocatalytic reduction of CO2 on zirconium-based single-, double-, and triple-atom catalysts anchored on a graphitic carbon nitride monolayer0 aFirstprinciples investigation of the electrocatalytic reduction  cOCT a15409-154170 v53 a

Conversion of carbon dioxide (CO2) with the help of an appropriate electrocatalyst with high stability, low onset potential, and exceptional selectivity is still one of the great tasks in the electrocatalytic reduction of CO2 to valuable chemicals. Herein, by means of systematic first-principles simulations, we investigate the CO2 reduction reaction (CO2RR) activity of zirconium-based single-, double-, and triple-atom (Zrn@C2N; n = 1-3) catalysts anchored on a graphitic carbon-nitride monolayer. In tune with the Sabatier principle, our results reveal that a moderate CO2 binding is vital for a low onset potential for the CO2RR. Consequently, based on rigorous free energy calculations, the Zr-based single-atom catalyst (SAC) is found to be most effective to convert CO2 to valuable products such as HCOOH and CH3OH. It is worth noting that CO2 reduction to HCOOH is spontaneous via the *HCOO intermediate on Zr1@C2N and involves a low onset potential of -0.23 V with respect to the reversible hydrogen electrode from the *COOH intermediate. Among all the catalysts evaluated computationally, the Zr SAC further reveals the lowest onset potential of -0.89 V for CH3OH formation. The results show that the Zr-based catalysts especially Zr1@C2N are found to effectively suppress the competitive hydrogen evolution reaction and promote the CO2RR. Moreover, all three catalysts exhibit high kinetic and thermal stability with negligible distortion due to which their structures can be retained very well up to 600 K. Thus, the current work may provide effective catalyst-design strategies for enhancing the electrocatalytic CO2RR performance of Zr-based materials.

10aC1 and C2 products10aCO2 reduction10afirst-principles simulations10ahydrogen evolution reaction10aonset potential10asingle-atom catalysts (SACs)10aZrn@C2N catalysts1 aHassan, Afshana1 aAnis, Insha1 aShafi, Sadaf1 aAssad, Assif1 aRasool, Anjumun1 aKhanam, Romana1 aBhat, Gulzar, Ahmad1 aKrishnamurty, Sailaja1 aDar, Manzoor, Ahmad uhttps://library.ncl.res.in/content/first-principles-investigation-electrocatalytic-reduction-co2-zirconium-based-single-double02608nas a2200253 4500008004100000022001400041245013800055210006900193260000900262300001100271490000800282520169600290653001901986653002502005653001602030653001402046653002802060100002902088700002902117700002702146700002902173700002602202856012602228 2022 eng d a0927-775700aFree base phthalocyanine coating as a superior corrosion inhibitor for copper surfaces: a combined experimental and theoretical study0 aFree base phthalocyanine coating as a superior corrosion inhibit cSEP  a1291380 v6483 a

In the quest of novel, eco-benign copper corrosion inhibitors, free base and a set of six metal Phthalocyanine (Pc) coatings (where metal is Zn, Cu, Fe, Co, Ni, Mn) are systematically evaluated for their corrosion inhibition efficiency. The study demonstrates that the free base Phthalocyanine coatings are superior corrosion inhibitors for Cu surface in HCl with a corrosion inhibition efficiency of 88% as compared to its metal counterparts. A detailed and indepth study involving concerted electrochemical polarisation, impedance measurements at various concentrations of HCl assert the superior corrosion inhibition efficiency of free base Pc coatings as compared to its metal counterparts. Underlying factors/interface chemistry contributing to it is brought out using first principle based studies. First principles based computational studies establish that superior corrosion inhibition ability of free base phthalocyanine molecule is attributed to its innate binding ability with copper surface and its better inter-molecular packing. Thus, the theoretical adsorption trends of various studied phthalocyanine molecules while clearly following the experimental corrosion inhibition efficiency trends undermine the importance of contribution of chelating factors for the formation of a stable and efficient corrosion inhibition coating on a surface and that the adhesion/adsorption strength of a molecule correlates directly to its corrosion inhibition efficiency. The experimental observations are further substantiated through FE-SEM, EDAX and XPS studies. The corrosion inhibition efficiency of free base phthalocyanine is followed by its zinc based counterpart at 85%.

10aCopper surface10aCorrosion inhibitors10aDFT studies10aImpedance10aPhthalocyanine coatings1 aSamal, Pragnya, Paramita1 aDekshinamoorthy, Amuthan1 aArunachalam, Shivakami1 aVijayaraghavan, Saranyan1 aKrishnamurty, Sailaja uhttps://library.ncl.res.in/content/free-base-phthalocyanine-coating-superior-corrosion-inhibitor-copper-surfaces-combined00902nas a2200229 4500008004100000022001400041245012500055210006900180260000800249300001100257490000700268653001900275653005600294653002600350653004300376653003000419653002600449100001900475700002600494700002700520856012500547 2022 eng d a2296-264600aFrom ``Cosmic Cooking'' to chemistry of the future: a collective dialogue on chemistry as a tribute to Prof. Sourav Pal.0 aFrom Cosmic Cooking to chemistry of the future a collective dial cAPR a9081650 v1010acosmic cooking10acoupled cluster and density functional calculations10adialogue on chemistry10apincers porphyrinoids and oxometalates10asmall molecule activation10aTheoretical chemistry1 aRoy, Soumyajit1 aKrishnamurty, Sailaja1 aSchoefberger, Wolfgang uhttps://library.ncl.res.in/content/cosmic-cooking-chemistry-future-collective-dialogue-chemistry-tribute-prof-sourav-pal01549nas a2200193 4500008004100000022001400041245011000055210006900165260000900234300001600243490000700259520084100266100002301107700002901130700002101159700002601180700002801206856012101234 2022 eng d a0022-326300aLewis acid-catalyzed chemodivergent and regiospecific reaction of phenols with quaternary peroxyoxindoles0 aLewis acidcatalyzed chemodivergent and regiospecific reaction of cNOV  a14155-141670 v873 a

The indium-catalyzed regiospecific coupling of substituted phenol derivatives and quaternary peroxyoxindoles for the synthesis of C2 or C4 benzoxazin-3-one-substituted phenols via skeletal rearrangement is described. This reaction is demonstrated with 17 examples with good yields and diverse aryl substituents. In contrast to the indium-catalyzed reaction, the Cu(OTf)2- catalyzed reaction of the phenol with quaternary peroxyoxindoles afforded C2 or C4 2-oxindole-substituted phenol derivatives. This diverse catalytic reaction generated various biologically important phenol-substituted 2-oxindole derivatives directly without any skeleton rearrangement and was demonstrated with 19 examples in high yield. The regiospecificity and the reaction pathways were explained with the support of density functional theory (DFT).

1 aShaikh, Moseen, A.1 aSamal, Pragnya, Paramita1 aUbale, Akash, S.1 aKrishnamurty, Sailaja1 aGnanaprakasam, Boopathy uhttps://library.ncl.res.in/content/lewis-acid-catalyzed-chemodivergent-and-regiospecific-reaction-phenols-quaternary01582nas a2200193 4500008004100000022001400041245013600055210006900191260000900260300001400269490000600283520085800289100002101147700003001168700001601198700002201214700002601236856012601262 2022 eng d a2470-134300aMapping the finite-temperature behavior of conformations to their potential energy barriers: case studies on Si6B and Si5B clusters0 aMapping the finitetemperature behavior of conformations to their cFEB  a6167-61730 v73 a

Dynamical simulations of molecules and materials have been the route to understand the rearrangement of atoms within them at different temperatures. Born-Oppenheimer molecular dynamical simulations have further helped to comprehend the reaction dynamics at various finite temperatures. We take a case study of Si6B and Si5B clusters and demonstrate that their finite-temperature behavior is rather mapped to the potential energy surface. The study further brings forth the fact that an accurate description of the dynamics is rather coupled with the accuracy of the method in defining the potential energy surface. A more precise potential energy surface generated through the coupled cluster method is finally used to identify the most accurate description of the potential energy surface and the interconnected finite-temperature behavior.

1 aManeri, Asma, H.1 aSingh, Chandrodai, Pratap1 aKumar, Ravi1 aMaibam, Ashakiran1 aKrishnamurty, Sailaja uhttps://library.ncl.res.in/content/mapping-finite-temperature-behavior-conformations-their-potential-energy-barriers-case02499nas a2200241 4500008004100000022001400041245010600055210006900161260000900230300001100239490000800250520167900258653001101937653000801948653004201956653002301998653002102021100002402042700003002066700002602096700001702122856011802139 2022 eng d a0014-305700aStructure-property insights into chiral thiophene copolymers by direct heteroarylation polymerization0 aStructureproperty insights into chiral thiophene copolymers by d cDEC  a1116760 v1813 a

Chiral thiophene copolymers with fluorene as co monomer are designed having N-Boc-L-glutamic acid-1-tert-butyl ester as a chiral substituent located either on the thiophene unit or the fluorene unit with varying spacer length. The atom-economic direct heteroarylation polymerization (DHAP) method is utilized for the polymerization. Gibb's free energy (delta G) for polymerization determined using DFT calculations indicate difficulty in achieving high molar mass when the bulky chiral substituents are attached through short spacer to the backbone. The experimental observations are in agreement with the theoretical calculations with no polymer-ization or very low molar mass sticky compounds obtained for reactions with predicted + & UDelta;G values. Structure -property relationship are compared for two chiral polymers -P4 and P5 having the chiral substitution on thiophene and fluorene units respectively. No CD signal is observed in THF-a good solvent where the polymers are molecularly dissolved. Intense bisignated CD signal is observed for both polymers upon addition of methanol - a poor solvent, to their THF solution. The bisignate CD signal with maxima at lower wavelength and inflection point associated with the pi-pi* absorption band is characteristic of exciton coupling between polymer chains in a left handed helical orientation. Small differences are observed in the intensity of the CD signal for the polymers P4 and P5 highlighting the impact of steric hindrance of bulky pendant groups on polymer conformation. DHAP is an atom economic polymerization procedure that can be gainfully utilized for developing chiral conjugated polymers.

10achiral10aDFT10aDirect heteroarylation polymerization10aGibb?s free energy10aSteric Hindrance1 aNikam, Shrikant, B.1 aSingh, Chandrodai, Pratap1 aKrishnamurty, Sailaja1 aAsha, S., K. uhttps://library.ncl.res.in/content/structure-property-insights-chiral-thiophene-copolymers-direct-heteroarylation01803nas a2200205 4500008004100000022001400041245011200055210006900167260000900236300001600245490000700261520105300268653002601321653002301347653002201370653002001392100003001412700002601442856012901468 2022 eng d a0360-319900aSynergetic storage of ammonia over Al quantum dots embedded graphene sheets: a first principles perspective0 aSynergetic storage of ammonia over Al quantum dots embedded grap cOCT  a36873-368850 v473 a

In view of the increasing energy demand and global warming, it is imperative to search for a renewable and environmental friendly fuel in lieu of non-renewable energy resources. Hydrogen stands out to be the best fuel as both, renewable and clean. Concerning the use of hydrogen as a fuel, its production as well as storage are current global challenges being worked on. In this article, a density functional theory based study is performed to identify the potential of supported Al cluster cages for ammonia storage. In this context, initially, stability of pristine and doped aluminum nanoclusters anchored on graphene sheet is evaluated following which thus supported stable nanoclusters are studied for the adsorption of NH3 to identify their storage capacity. For both, complexes and NH3 adsorbed complexes, Density of States (DOS), Charge Density Difference (CDD) and Bader charge analysis is done to understand their electronic properties.(c) 2022 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.

10aAluminum nanoclusters10aDefective graphene10aEndohedral doping10aNH 3 adsorption1 aSingh, Chandrodai, Pratap1 aKrishnamurty, Sailaja uhttps://library.ncl.res.in/content/synergetic-storage-ammonia-over-al-quantum-dots-embedded-graphene-sheets-first-principles02241nas a2200217 4500008004100000022001400041245016500055210006900220260000900289300001200298490000700310520143100317100002001748700001601768700001701784700002201801700002001823700002601843700002401869856013001893 2022 eng d a2044-475300aTantalum based single, double, and triple atom catalysts supported on g-C2N monolayer for effective nitrogen reduction reaction: a comparative DFT investigation0 aTantalum based single double and triple atom catalysts supported cJAN  a310-3190 v123 aDesign of efficient and low cost electrocatalysts for the reduction of N-2 molecule to NH3 in a green manner remains a great challenge in the 21st century. Herein, we have used density functional theory based first principle simulations to systematically investigate the nitrogen reduction reaction (NRR) ability of single, double, and triple Ta-atom catalysts anchored to C2N monolayer. Our results demonstrate that the single and triple Ta-atom catalysts anchored to C2N monolayer act as superior catalysts for the NRR via alternating and distal pathways as compared to the Ru(0001) stepped surface. In particular, the triple Ta-atom catalyst anchored to C2N shows enhanced NRR performance with a limiting potential of -0.72 V which is comparable to the experimentally reported Ru based single atom catalyst. Further, all the three catalysts were found to be highly selective for NRR with an enhanced ability to suppress the competitive hydrogen evolution reaction. Electronic structure analysis revealed that the enhanced ability of Ta-3@C2N catalyst to effectively capture and reduce N-2 molecule could be attributed to the built up of localized d states near the fermi level, thereby aiding in strong electron transfer into the antibonding orbitals of N-2. Thus, our findings propose a highly active catalyst for the NRR with an emphasis on the importance of triple atom-based catalysts for electrocatalytic applications.1 aRasool, Anjumun1 aAnis, Insha1 aDixit, Mudit1 aMaibam, Ashakiran1 aHassan, Afshana1 aKrishnamurty, Sailaja1 aDar, Manzoor, Ahmad uhttps://library.ncl.res.in/content/tantalum-based-single-double-and-triple-atom-catalysts-supported-g-c2n-monolayer-effective02689nas a2200337 4500008004100000022001400041245014200055210006900197260000800266490000700274520145100281653004201732653003801774653002701812653003601839653003601875653002801911653002301939100002001962700003001982700002702012700003002039700002702069700002402096700002102120700001802141700001802159700002602177700002402203856012402227 2023 eng d a1613-681000aActive site engineering and theoretical aspects of ``Superhydrophilic'' nanostructure array enabling efficient overall water electrolysis0 aActive site engineering and theoretical aspects of Superhydrophi cDEC0 v193 a

The rational design of noble metal-free electrocatalysts holds great promise for cost-effective green hydrogen generation through water electrolysis. In this context, here, the development of a superhydrophilic bifunctional electrocatalyst that facilitates both oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) in alkaline conditions is demonstrated. This is achieved through the in situ growth of hierarchical NiMoO4@CoMoO4 center dot xH(2)O nanostructure on nickel foam (NF) via a two-step hydrothermal synthesis method. NiMoO4@CoMoO4 center dot xH(2)O/NF facilitates OER and HER at the overpotentials of 180 and 220 mV, respectively, at the current density of 10 mA cm(-2). The NiMoO4@CoMoO4 center dot xH(2)O/NF parallel to NiMoO4@CoMoO4 center dot xH(2)O/NF cell can be operated at a potential of 1.60 V compared to 1.63 V displayed by the system based on the Pt/C@NF parallel to RuO2@NF standard electrode pair configuration at 10 mA cm(-2) for overall water splitting. The density functional theory calculations for the OER process elucidate that the lowest Delta G of NiMoO4@CoMoO4 compared to both Ni and NiMoO4 is due to the presence of Co in the OER catalytic site and its synergistic interaction with NiMoO4. The preparative strategy and mechanistic understanding make the windows open for the large-scale production of the robust and less expensive electrode material for the overall water electrolysis.

10adensity functional theory (DFT) study10ahydrogen evolution reaction (HER)10aHydrothermal synthesis10aoxygen evolution reaction (OER)10asuperhydrophilic nanostructures10asynergistic interaction10awater electrolysis1 aBarik, Sidharth1 aKharabe, Geeta, Pandurang1 aIllathvalappil, Rajith1 aSingh, Chandrodai, Pratap1 aKanheerampockil, Fayis1 aWalko, Priyanka, S.1 aBhat, Suresh, K.1 aDevi, Nandini1 aVinod, C., P.1 aKrishnamurty, Sailaja1 aKurungot, Sreekumar uhttps://library.ncl.res.in/content/active-site-engineering-and-theoretical-aspects-superhydrophilic-nanostructure-array02343nas a2200229 4500008004100000022001400041245011800055210006900173260000800242490000700250520149600257653002801753653001901781653002801800653002101828653003201849100002501881700002901906700002701935700002601962856012501988 2023 eng d a1439-423500aCan Li atoms anchored on boron- and nitrogen-doped graphene catalyze dinitrogen molecules to ammonia? a DFT study0 aCan Li atoms anchored on boron and nitrogendoped graphene cataly cJUN0 v243 a

The most successful electrochemical conversion of ammonia from dinitrogen molecule reported to date is through a Li mediated mechanism. In the framework of the above fact and that Li anchored graphene is an experimentally feasible system, the present work is a computational experiment to identify the potential of Li anchored graphene as a catalyst for N-2 to NH3 conversion as a function of (a) minimum number of Li atoms needed for anchoring on graphene sheets and (b) the role of chemical modification of graphene surfaces. The studies bring forth an understanding that Li anchored graphene sheets are potential catalysts for ammonia conversion with preferential adsorption of N-2 through end-on configuration on Li atoms anchored on doped and pristine graphene surfaces. This mode of adsorption being characteristic of Nitrogen Reduction Reaction (NRR) through enzymatic pathway, examination of the same followed by analysis of electronic properties demonstrates that tri-Li atoms (Tri Atom Catalysts, TACs) are more efficient as catalysts for NRR as compared to two Li atoms (Di Atom Catalysts, DACs). Either way, the rate determining step was found to be *NH2 ->*NH3 step (mixed pathway) with Delta G(max)=1.02 eV and *NH2-*NH3 ->*NH2 step (enzymatic pathway) with Delta G(max)=1.11 eV for 1B doped TAC and DAC on graphene sheet, respectively. Consequently, this work identifies the viability of Li anchored graphene based 2-D sheets as hetero-atom catalyst for NRR.

10acomputational chemistry10aGraphene Sheet10aheterogeneous catalysis10aLi Nanoparticles10aNitrogen Reduction Reaction1 aVerma, Tushar, Singh1 aSamal, Pragnya, Paramita1 aSelvaraj, Kaliaperumal1 aKrishnamurty, Sailaja uhttps://library.ncl.res.in/content/can-li-atoms-anchored-boron-and-nitrogen-doped-graphene-catalyze-dinitrogen-molecules01682nas a2200205 4500008004100000022001400041245011900055210006900174260000800243300001400251490000700265520092200272100002101194700002901215700002501244700002301269700002601292700002801318856013001346 2023 eng d a0022-326300aCatalyst-assisted selective vinylation and methylallylation of a quaternary carbon center using tert-butyl acetate0 aCatalystassisted selective vinylation and methylallylation of a  cJUL a9686-97030 v883 a

The In-(OTf)(3)-catalyzed & alpha;-vinylationof varioushydroxy-functionalized quaternary carbon centers using in situ generatedisobutylene from tert-butyl acetate is presentedas a novel synthetic methodology. Moreover, tert-butylacetate is a nonflammable feed stock and is a readily available sourcefor the in situ production of vinyl substituents, as demonstratedby the vinylation reaction with quaternary hydroxy/methoxy compounds.Moreover, an excellent selectivity for methylallylation over vinylationwas obtained with Ni-(OTf)(2) as a catalyst. In the case ofperoxyoxindole, methylallyl-functionalized 1,4-benzoxazin-3-one derivativeswere formed through the sequential rearrangement of peroxyoxindolefollowed by the nucleophilic attack by isobutylene. The detailed mechanismfor this reaction and rationalization for the selectivity are providedusing kinetics and density functional theory studies.

1 aMohanta, Nirmala1 aSamal, Pragnya, Paramita1 aPandey, Akanksha, M.1 aMondal, Shankhajit1 aKrishnamurty, Sailaja1 aGnanaprakasam, Boopathy uhttps://library.ncl.res.in/content/catalyst-assisted-selective-vinylation-and-methylallylation-quaternary-carbon-center-using02388nas a2200301 4500008004100000022001400041245012100055210006900176260000800245300001600253490000700269520134900276653002001625653002001645653002901665653003601694653002701730653003201757100001901789700002201808700002401830700002601854700001901880700002601899700001901925700001601944856012601960 2023 eng d a1944-824400aChemical bridge-mediated heterojunction electron transport layers enable efficient and stable perovskite solar cells0 aChemical bridgemediated heterojunction electron transport layers cJUN a29597-296080 v153 a

Perovskite solar cells (PSCs) emerged as potential photovoltaicenergy-generating devices developing in recent years because of theirexcellent photovoltaic properties and ease of processing. However,PSCs are still reporting efficiencies much lower than their theoreticallimits owing to various losses caused by the charge transport layerand the perovskite. In this regard, herein, an interface engineeringstrategy using functional molecules and chemical bridges was appliedto reduce the loss of the heterojunction electron transport layer.As a functional interface layer, ethylenediaminetetraacetic acid (EDTA)was introduced between PCBM and the ZnO layer, and as a result, EDTAsimultaneously formed chemical bonds with PCBM and ZnO to serve asa chemical bridge connecting the two. DFT and chemical analyses revealedthat EDTA can act as a chemical bridge between PCBM and ZnO, passivatedefect sites, and improve charge transfer. Optoelectrical analysisproved that EDTA chemical bridge-mediated charge transfer (CBM-CT)provides more efficient interfacial charge transport by reducing trap-assistedrecombination losses at ETL interfaces, thereby improving device performance.The PSC with EDTA chemical bridge-mediated heterojunction ETL exhibiteda high PCE of 21.21%, almost no hysteresis, and excellent stabilityto both air and light.

10acharge transfer10achemical bridge10aelectron transport layer10aethylenediaminetetraacetic acid10aPerovskite solar cells10atrap-assisted recombination1 aPatil, Pramila1 aMaibam, Ashakiran1 aSangale, Sushil, S.1 aMann, Dilpreet, Singh1 aLee, Hyun-Jung1 aKrishnamurty, Sailaja1 aKwon, Sung-Nam1 aNa, Seok-In uhttps://library.ncl.res.in/content/chemical-bridge-mediated-heterojunction-electron-transport-layers-enable-efficient-and02219nas a2200229 4500008004100000022001400041245011500055210006900170260000800239300001100247490000800258520137100266653001501637653003101652653003001683653003001713653003101743100002701774700003001801700002601831856013201857 2023 eng d a0169-433200aChemically modified graphene sheets as potential sensors for organophosphate compounds(pesticide): A DFT study0 aChemically modified graphene sheets as potential sensors for org cMAY a1567450 v6193 a

Owing to the extensive use of pesticides in agriculture and the threat posed to the environment and humankind, attention is drawn toward the need for its remediation from various sources, in particular from water. The adsorption characteristics of hydrophobic graphene and its BN doped counterparts are evaluated using DFT methodology, to assess their sensing potential towards notable pesticide molecules (Organophosphate pesticides (OPs) such as chlorpyriphos, parathion, methyl-parathion, and fenitrothion). To accomplish this, various elec-tronic properties such as band structure, DOS, Bader charge analysis, and CDD have been calculated. Interest-ingly, exothermic interactions (-0.1 eV to-2 eV) have been noted for all the OPs with NB doped single vacancy defect induced graphene surfaces. With an exception of FTN, all the other OPs showed significant changes in the electronic properties of surfaces as apparent from the change in band gap and nature of the band from indirect to direct. The appreciable adsorption energy, higher charge transfer, and notable variation in the band gap are the decisive factors behind the strong interaction exhibited by NB doped surfaces especially dg-(NB-2)2 (except FTN). These findings demonstrate the suitability of NB doped single vacancy defect induced graphene sheets for the detection of the studied OPs.

10aAdsorption10aBN doped graphene surfaces10aCharge density difference10aDensity functional theory10aOrganophosphate pesticides1 aShivankar, Bhavana, R.1 aSingh, Chandrodai, Pratap1 aKrishnamurty, Sailaja uhttps://library.ncl.res.in/content/chemically-modified-graphene-sheets-potential-sensors-organophosphate-compoundspesticide-dft02065nas a2200205 4500008004100000022001400041245009100055210006900146260000800215300001200223490000700235520134700242100002401589700002701613700002201640700002601662700003001688700002701718856011401745 2023 eng d a0031-865500aD-A-D-based unsymmetrical thiosquaraine dye for the dye-sensitized solar cells(dagger)0 aDADbased unsymmetrical thiosquaraine dye for the dyesensitized s cMAR a529-5370 v993 a

In dye-sensitized solar cell, modulating the electronic properties of the sensitizer by varying the donor, pi-spacer, acceptor and anchoring groups help optimizing the structure of the dye for better device performance. Here, a donor-acceptor-donor-based unsymmetrical thiosquaraine sensitizer (SQ5S) has been designed and synthesized. Photophysical, electrochemical, theoretical and photovoltaic characterizations of SQ5S dye have been compared with its oxygen analog, SQ5. The incorporation of the sulfur atom in the acceptor unit of SQ5S dye showed an intense peak at 688 nm, which was 38 nm of red-shifted and showed the panchromatic light harvesting response with the onset of 850 nm compared with SQ5 dye. The LUMO and HOMO energy levels are well aligned with the conduction band of TiO2 and the redox potential of electrolyte for the charge injection and the dye-regeneration processes, respectively. Photovoltaic efficiency of 1.51% (V-OC 610 mV, J(SC) 3.07 mA cm(-2), ff 81%) has been achieved for SQ5S dye, whereas SQ5 showed the device performance of 5.43% (V-OC 723 mV, J(SC) 9.3 mA cm(-2), ff 80%). The decreased device performance for the dye SQ5S has been attributed to the favorable intersystem crossing process associated with the photoexcited SQ5S that reduces the driving force for the charge injection process.

1 aJadhav, Avinash, P.1 aSingh, Ambarish, Kumar1 aMaibam, Ashakiran1 aKrishnamurty, Sailaja1 aKrishnamoorthy, Kothandam1 aNithyanandhan, Jayaraj uhttps://library.ncl.res.in/content/d-d-based-unsymmetrical-thiosquaraine-dye-dye-sensitized-solar-cellsdagger01835nas a2200169 4500008004100000022001400041245012000055210006900175260000900244300001100253490000800264520119500272100002201467700002601489700002501515856012501540 2023 eng d a0169-433200aElectrocatalytic nitrogen reduction on defective graphene modulated from single atom catalyst to aluminium clusters0 aElectrocatalytic nitrogen reduction on defective graphene modula cJUN  a1570240 v6233 a

Density Functional Theory (DFT) investigation on the most earth-abundant Al-based catalysts, has been conducted detailing its electronic properties and catalytic efficacy for nitrogen reduction at ambient condition. The Al-based catalysts have been modulated to perform as par a highly performing, but rare, Ru-single atom catalytic center by varying number of Al atoms, shape, and size. The coalesce of band-center, work function and electronic properties in metal atom catalysts along with N-N bond activation has been demonstrated to be responsible for an efficient nitrogen reduction reaction (NRR) with Delta Gmax of 0.78 eV in Al5 supported on N-doped double vacancy graphene (Al5@N4-DVG) catalyst. Electron localization function analysis has shown a weak physisorption of N2 in the Al-based catalysts. Projected Density of States (PDOS) illustrates the enhancement of aluminium electron density in Al5@N4-DVG led to enhanced orbital densities overlap of Alp and Np electrons. The Bader charge analysis and electronic analysis of the intermediates show efficient electron gain on the N atoms, leading to formation of NH3 from the NxHy intermediates in Al5@N4-DVG catalyst.

1 aMaibam, Ashakiran1 aKrishnamurty, Sailaja1 aBabaRao, Ravichandar uhttps://library.ncl.res.in/content/electrocatalytic-nitrogen-reduction-defective-graphene-modulated-single-atom-catalyst02281nas a2200241 4500008004100000022001400041245009800055210006900153260000800222300001100230490000800241520142300249653001901672653003601691653003101727653002401758653002301782653002301805100002901828700003001857700002601887856012601913 2023 eng d a0169-433200aExpounding lemonal terpenoids as corrosion inhibitors for copper using DFT based calculations0 aExpounding lemonal terpenoids as corrosion inhibitors for copper cMAR a1560660 v6143 a

The most important bottleneck in identifying an innovative and yet viable corrosion inhibitor for copper surfaces is discerning the chemical interactions at the interface of adsorbate and adsorbent. The present work, primarily, discerns the interface chemistry of green corrosion inhibitors, viz., lemonal terpenoids, with the copper surfaces for the first time. The interface chemistry is evaluated for distinct facets of copper, modelled by periodic surfaces to finite sized aggregates, with two stereoisomers viz., citral and neral through density functional calculations. The adsorption/ interaction properties between the surface and the corrosion inhibiting molecule are analysed through the electronic properties such as density of states, charge density difference plots and Bader charges where in distinct bonding mechanisms are identified as a function of varying facets. Apart from the adsorption properties, molecular packing properties are of paramount importance towards the design of an efficient corrosion inhibitor for a surface. Hence, we also analyse the intermolecular stacking energies between the inhibitors when packed among themselves in vacuum and when adhered on to metal surfaces. The studies bring forth an understanding that lemon terpenoids are highly potential corrosion inhibitors for copper surfaces, particularly, for Cu (110) surfaces both in neutral and protonated form.

10aCopper surface10aDensity Functional Theory (DFT)10aGreen corrosion inhibitors10aInterface chemistry10aLemonal terpenoids10aMolecular stacking1 aSamal, Pragnya, Paramita1 aSingh, Chandrodai, Pratap1 aKrishnamurty, Sailaja uhttps://library.ncl.res.in/content/expounding-lemonal-terpenoids-corrosion-inhibitors-copper-using-dft-based-calculations01178nas a2200253 4500008004100000022001400041245008400055210006900139260000800208300001200216490000800228520038000236653000600616653002400622653001000646653001900656653001800675653001900693100002100712700002700733700002600760700002800786856011000814 2023 eng d a1615-415000aFeCl2-catalyzed rearrangement of aryl peroxyoxindole into 1,3-benzooxazin-4-One0 aFeCl2catalyzed rearrangement of aryl peroxyoxindole into 13benzo cFEB a515-5210 v3653 a

We report an FeCl2-catalyzed radical rearrangement of aryl peroxyoxindoles into 1,3-benzooxazin-2-ones to obtain a variety of aryl substituted 1,3-benzooxazin-4-ones in moderate to good yields. Mechanistically, this skeletal rearrangement of peroxyoxindoles proceeded via radical pathway and was well supported with a series of experimental findings and DFT studies.

10a110a3-Benzooxazin-4-one10aFeCl210aPeroxyoxindole10arearrangement10aRing expansion1 aMohanta, Nirmala1 aSamal, PragnyaParamita1 aKrishnamurty, Sailaja1 aGnanaprakasam, Boopathy uhttps://library.ncl.res.in/content/fecl2-catalyzed-rearrangement-aryl-peroxyoxindole-13-benzooxazin-4-one02388nas a2200229 4500008004100000022001400041245016600055210006900221260000900290300001100299490000800310520155500318653002201873653002701895653002201922653001601944653001101960100001801971700001901989700002602008856012402034 2023 eng d a0169-433200aFunctionalized Mo2BX2 (X = H, OH, O) MBenes as a promising sensor, capturer and storage material for environmentally toxic gases: A case study of 1T and 2H phase0 aFunctionalized Mo2BX2 X H OH O MBenes as a promising sensor capt cAPR  a1562990 v6153 a

MBenes analogous to MXenes, exfoliated from the bulk MAB phase (M = transition metal, A = IIIA and IVA group, and B = boron) have appeared as promising two dimensional (2D) materials due to their intriguing properties. Here, we report the 2D 1T-2H-phase of Mo2B with their functionalized derivatives Mo2BX2 (X= H, OH, O) and investigate their structural, electronic, and adsorption behavior of toxic gases using the first-principles calculations. This study finds that pristine and functionalized MBenes have dynamic and thermal stability and possess metallic nature in both phases. Based on adsorption behavior and comparison with other 2D materials, we find that pristine MBenes are a desirable adsorbent for NO2, SO2, and CO2 capture. In contrast, the moderate adsorption energies for functionalized MBenes-NH3 systems reveal good sensitivity for NH3 gas detection in both phases. In particular, 2H-Mo2BH2 has higher CT (-0.11e) and appropriate adsorption energy (-0.30 eV), leads a shorter recovery time. Further, DOS calculations reveal that the electrical conducting behavior of MBenes makes them suitable for NH3 detection with a short recovery time. Our results would provide the first insight into the surface-functionalized effect on the structural and electronic properties of the MBenes, and shed light on the application of MBenes for the sensing and catalyst of typical toxic and greenhouse gases, respectively.

10aAdsorption energy10aFirst-principles study10aFunctionalization10aGas sensing10aMBenes1 aShukla, Aarti1 aSharma, Gautam1 aKrishnamurty, Sailaja uhttps://library.ncl.res.in/content/functionalized-mo2bx2-x-h-oh-o-mbenes-promising-sensor-capturer-and-storage-material02738nas a2200289 4500008004100000022001400041245016500055210006900220260000800289300001100297490000700308520168400315653002501999653003302024653002402057653004502081653003402126653002702160100002002187700002202207700001902229700001702248700002202265700002602287700000502313856013002318 2023 eng d a2352-152X00aHigh rate, high temperature, dendrite free plating/stripping of Li in 3-dimensional honeycomb boron carbon nitride to realize an ultrastable lithium metal anode0 aHigh rate high temperature dendrite free platingstripping of Li  cSEP a1075470 v683 a

Lithium (Li) metal could be the anode of choice for energy dense Li-batteries owing to its high theoretical specific capacity. However, low coulombic efficiency and poor safety on account of the occurrence of the Li-dendrites during charging-discharging pose a bottleneck for practical applications. In this work, we report a high-rate plating and stripping of Li through host engineering to realize ultrastable Li metal anode (LMA). Benchmark plating/stripping efficiency could be achieved via uniquely structured, highly ordered honeycomb boron carbon nitride (HBCN) as a functional scaffold. Boron and nitrogen doping, large surface area and ordered mesoporous structure induce homogeneous solid electrolyte interface (SEI) layer formation and provide numerous nucleation sites with subsequent dendrite-free growth with 99.98 % coulombic efficiency at 8 mA cm(-2) high current and 10 mAh cm(-2) capacity over 3000 cycles. Via post-cycling advanced characterizations techniques of Ex-situ XPS, 3D X-ray micro-tomography analyses and FESEM, we demonstrate the formation of a stable SEI layer and morphological changes that occurred during Li plating cycles in the HBCN structure. Computational studies validate the high lithium plating-stripping efficacy of HBCN to its highly ordered porous nature, exothermic Li-binding and upshift in the Fermi levels. When tested at elevated temperature (50 degrees C), a stable Li plating-stripping in HBCN is realised at 4 mA cm(-2) current and 10 mAh cm(-2) capacity values with similar to 100 % C.E. Furthermore, we report the results of testing a Li metal cell comprised of Li deposited HBCN anode and LiFePO4 (LFP) cathode.

10aBoron carbon nitride10aDendrite-free Li metal anode10aFunctional scaffold10aHigh temperature plating/stripping of Li10aMolecular planarity parameter10aX-ray micro-tomography1 aPatrike, Apurva1 aKarbhal, Indrapal1 aWasnik, Kundan1 aTorris, Arun1 aMaibam, Ashakiran1 aKrishnamurty, Sailaja1 a uhttps://library.ncl.res.in/content/high-rate-high-temperature-dendrite-free-platingstripping-li-3-dimensional-honeycomb-boron02601nas a2200241 4500008004100000022001400041245018300055210006900238260000800307300001100315490000800326520170900334653002002043653002502063653002702088653002102115653001302136100002002149700001602169700001802185700002602203856013002229 2023 eng d a1387-181100aInsights into adsorption of various gases on extra-framework cations of zeolite: a dispersion corrected DFT study on zeolite cluster models with Li plus , Na plus and K plus ions0 aInsights into adsorption of various gases on extraframework cati cNov a1127390 v3613 a

Design of an economical and sustainable gas separation material is relevant in several industrial processes. Zeolites with tunable pore sizes are ideal molecular sieves of many gases. The adsorption centers of these molecular sieves are extra-framework Lewis acid centers. In this study, we attempt to delineate the electronic properties of such centers (Li+, Na+ and K+) and their sorption properties towards N2, O2, CO, CO2 and H2. Negative framework of zeolites are modeled using different cluster models that present distinct electronic environment and role of this environment on the Lewis acidity of the cation. The sorption property towards different gases is evaluated using dispersion corrected DFT studies. The results obtained are benchmarked for one of the studied model using CCSD calculations. The results indicate that while the local environment modulates the adsorption properties, the relative adsorption properties between different ions follow the same order irrespective of the type of negative framework modeled. This reveals that intrinsic atomic properties of the charge compensating cations drive the sorption properties of the zeolites. Adsorption energies compounded with the analysis of IR stretching frequencies of the adsorbed gases reveals that Li centers shows molecular adsorption (charge donation to the cationic centers) towards N2 as compared to O2 and towards CO2/CO as compared to H2, demonstrating the applicability of Li-Zeolites as ideal membranes for oxygen concentrators and syngas separation. These adsorption studies are ratified by the BOMD simulations at 300 K, where H2 and O2 desorbs while N2, CO and CO2 remains adsorbed to the cationic site.

10aBOMD simulation10aCO/CO2/H2 separation10aExtra-framework cation10aN2/O2 separation10azeolites1 aDevasia, George1 aKumar, Ravi1 aVaval, Nayana1 aKrishnamurty, Sailaja uhttps://library.ncl.res.in/content/insights-adsorption-various-gases-extra-framework-cations-zeolite-dispersion-corrected-dft02031nas a2200217 4500008004100000022001400041245018000055210006900235260000900304490000700313520118900320653002901509653001601538653002001554653001301574100002501587700003001612700002601642700002001668856012501688 2023 eng d a1861-472800aInvestigation of the effect of zeolite supports and the role of W-species for one-pot catalytic conversion of cellulose to ethylene glycol: theoretical & experimental studies.0 aInvestigation of the effect of zeolite supports and the role of  cFEB 0 v183 a

Endeavors were made to study the influence of various zeolite (HY, NaY, NaZSM-5 and HZSM-5) supports with (Al)-Ni-W metal combination catalysts for the ethylene glycol (EG) production, selectively from cellulose. From the experimental results ZSM-5 (NaZSM-5/73.3% & HZSM-5/67.7%) support is superior over HY & NaY support in selective EG production from cellulose. It was understood that W- species with oxygen vacancies (WO3-x, XPS analysis) plays an important role in producing the glycolaldehyde (GA) intermediate (via C-C cleavages), which on hydrogenation over Ni- sites selectively produce EG. Further, the studies based on the Density Functional Theory (DFT) were conducted to substantiate the involvement of the WO3-x species in the reaction. The adsorption energies and structural changes establish that the C-2-C-3 bond of the glucose elongates and thereby activates on adsorbing to WO3-x sites supporting the formation of GA. Activation of GA on Ni- sites is distinguished by an increase of 0.1 angstrom in C=O bond length, which facilitates the hydrogenation of C=O resulting in EG. The reaction pathway is explained through an analysis of CDD and DOS.

10aCellulose hydrogenolysis10aDFT studies10aethylene glycol10azeolites1 aSreekantan, Sreejith1 aSingh, Chandrodai, Pratap1 aKrishnamurty, Sailaja1 aMarimuthu, Banu uhttps://library.ncl.res.in/content/investigation-effect-zeolite-supports-and-role-w-species-one-pot-catalytic-conversion02048nas a2200229 4500008004100000022001400041245010800055210006900163260000900232300001400241490000700255520125900262653002101521653001001542653002201552100002201574700002201596700002901618700002601647700002001673856012501693 2023 eng d a1463-926200aIron-catalyzed regioselective C-H alkylation of indoles: an additive-free approach in renewable solvent0 aIroncatalyzed regioselective CH alkylation of indoles an additiv cNOV  a9733-97430 v253 a

Alkylated indoles are important motifs in various biologically active molecules and drug candidates. Herein, we report a mild and efficient iron-catalyzed protocol for synthesizing alkylated indoles via C-H bond alkylation of indoles with unactivated alkenes, demonstrating a high level of regioselectivity. The reaction occurs under additive-free, solvent-free (or trace green solvent, 2-MeTHF) and less energy-intensive conditions using a sustainable metal catalyst and provides easy access to privileged alkylated indoles with anti-Markovnikov selectivity. Alkylation is compatible with important functionalities, such as fluoro, chloro, trifluoromethyl, alkenyl, ether, thioether, silyl, and siloxane, including heteroaryl, pyridinyl, carbazolyl, and indolyl moieties (45 examples, up to 96% yield). The developed protocol is very simple, straightforward, and fully accords with the principles of green chemistry. A detailed mechanistic investigation manifests the facile indole's C-H activation at the Fe(0) center, reversible 1,2-insertion of the alkene into the Fe-H bond of a metallacycle, and a turnover-limiting reductive elimination. Alkylated indoles are important motifs in various biologically active molecules and drug candidates.

10aAromatic Ketones10aGreen10aorganic synthesis1 aPradhan, Chandini1 aJagtap, Rahul, A.1 aSamal, Pragnya, Paramita1 aKrishnamurty, Sailaja1 aPunji, Benudhar uhttps://library.ncl.res.in/content/iron-catalyzed-regioselective-c-h-alkylation-indoles-additive-free-approach-renewable02480nas a2200325 4500008004100000245010800041210006900149260000800218300001400226490000600240520139800246653001601644653002401660653002601684653002301710653001501733653001701748100002101765700002601786700002901812700002901841700002501870700002601895700002101921700002201942700001601964700002601980700002602006856012202032 2023 eng d00aMnXWO4 nanostructure-based catalysts for single-step oxidation of cyclohexane and methane to oxygenates0 aMnXWO4 nanostructurebased catalysts for singlestep oxidation of  cAPR a7245-72580 v63 a

Activation of the C-H bond in cyclohexane (CYH) and methane is a crucial step to obtain desirable oxygenated products using nanostructured catalyst and is a great challenge and an efficient route to mitigate the inauspicious effects of climate change. The active sites were identified using XRD, HR-TEM, SEM, N2 sorption analysis, TPR, Raman, XPS, TGA, in situ DRIFT, XAS, etc. In optimal reaction conditions, 46% of CYH was converted into adipic acid (AA) on MnxWO4 nanostructures within 6 h. The recyclability test confirmed the catalyst heterogeneity, which revealed no appreciable loss of catalytic activity even after three consecutive reactions. In situ DRIFT study reveals that CYH is oxidized to cyclohexanone and cyclohexanol (KA oil) and is further oxidized to AA via carboxylate intermediates. DFT studies disclosed that MnOx species are responsible for the C-H activation of CYH, and the Mn2+/Mn3+ redox centers play a vital role in the absorption of KA oil to form AA. Herein, we demonstrated the significant role of the ``MnOx'' species and that adequate Lewis and Bronsted acidic sites, redox centers of (Mn2+/Mn3+), and lattice oxygen are accountable for the CYH conversion toward the AA. Additionally, we have reported the oxidation of methane to methanol (146 mu mole per gram of catalyst) in the presence of water at 75 degrees C without over-oxidation products.

10aAdipic Acid10aC-H bond activation10aCyclohexane oxidation10amethane activation10aMnOx chain10aRedox center1 aPrabu, Marimuthu1 aManikandan, Marimuthu1 aSamal, Pragnya, Paramita1 aGurrala, Lakshmi, Prasad1 aMekala, Siva, Prasad1 aArchana, Ramakrishnan1 aNayak, Chandrani1 aBhattacharyya, D.1 aJha, S., N.1 aKrishnamurty, Sailaja1 aRaja, Thirumalaiswamy uhttps://library.ncl.res.in/content/mnxwo4-nanostructure-based-catalysts-single-step-oxidation-cyclohexane-and-methane02862nas a2200205 4500008004100000022001400041245009900055210006900154260000800223300001600231490000700247520213700254100002402391700002602415700002202441700002202463700002602485700001702511856012802528 2023 eng d a1463-907600aQuantum dot (Aun/Agn, n=3-8) capped single lipids: interactions and physicochemical properties0 aQuantum dot AunAgn n38 capped single lipids interactions and phy cAUG a22294-223030 v253 a

Realizing the potential of nano-hybrid biomaterials in various applications (nanoprobes to drug delivery), special attention has been devoted towards their synthesis and development. Nonetheless, several questions pertaining to the interface chemistry between the constituent entities (biomolecules and organic/inorganic part) of these hybrids, still remain unresolved. Keeping these unsolved issues in mind, the present theoretical investigation focuses on determining the electronic/physicochemical properties and interactions within gold and silver quantum dot-capped single lipid molecules. Quantum dots of varying sizes and shapes have been chosen and then coupled with lipid molecules (1,2-dimyristoyl-sn-glycero-3-phosphocholine (DMPC), 1,2-dimyristoyl-sn-glycero-3-phosphoethanolamine (DMPE), 1,2-dimyristoyl-sn-glycero-3-phosphoglycerol, sodium salt (DMPG)), at the choline/glycerol, carboxylate and phosphate site. It has been identified that Au Qds interact strongly as compared to Ag clusters. In addition to the type, the shape and size of the Qd also influences their attachment with lipids. Among various sites, the phosphate site provides a considerably stronger platform for the coupling of Qds. On the other hand, attachment at the choline site leads to significantly lower interaction energies. The trend noted in interaction energies coincides with the structure-electronic property analysis (interatomic bond distances, charge transfer, PO2- stretching frequencies), which further helps in deducing the nature of interactions. The molecular dynamics simulations performed on selected Qd-lipid complexes established that the Qd interacting with lipids at the phosphate site remains fairly stable at room temperature without undergoing fragmentation into individual components. On the other hand, at the choline site, the Qd-to-lipid coupling is unstable and therefore they experience disintegration at 300 K temperature. Additionally, a unique glycerol-to-phosphate site crossover is evidenced, which reaffirms that the phosphate site is selectively preferred by Qds for binding with lipid molecules.

1 aManeri, Asma, H. H.1 aVarode, Shruti, Suhas1 aMaibam, Ashakiran1 aRanjan, Priyatosh1 aKrishnamurty, Sailaja1 aJoshi, Krati uhttps://library.ncl.res.in/content/quantum-dot-aunagn-n3-8-capped-single-lipids-interactions-and-physicochemical-properties02511nas a2200289 4500008004100000245010800041210006900149260000900218300001600227490000600243520146800249653003101717653001601748653003301764653004401797653003501841100001801876700002401894700003001918700002901948700002401977700002602001700002202027700001902049700002202068856013102090 2023 eng d00aShape-controlled MoO3/MnO x nanocatalyst for the selective synthesis of 2-phenylquinoxaline drug motifs0 aShapecontrolled MoO3MnO x nanocatalyst for the selective synthes cDEC  a23442-234530 v63 a

We have developed a highly effective shape-controlled MoO3/MnOx nanocatalyst for the selective synthesis of 2-phenylquinoxaline drug motifs at room temperature without any external oxidant. Electron microscopy images reveal that the MnOx material contains rod-shaped particles (length: 500-1000 nm and width: 150-200 nm) and the MoO3 species are uniformly dispersed in the MoO3/MnOx material. The MoO3/MnOx nanocatalyst calcined at 500 degrees C (MoO3/MnOx-5) contains abundant strong acid sites and an optimum ratio of Mn4+/Mn3+, which are responsible for the C-N cross-coupling reaction between 2-phenylethylamine and o-phenylenediamine, giving higher yields (>96%) of 2-phenylquinoxaline at mild conditions. The broad scope of this catalytic strategy at room temperature and without an external oxidant was confirmed by achieving >90% yields of functional 2-phenylquinoxalines from C-N cross-coupling of various o-phenylenediamines and 2-phenylethylamines. The outstanding reusability efficiency of the MoO3/MnOx-5 nanocatalyst up to five cycles without the need for a regeneration step as well as the effective scalability highlighted the practicability of the MoO3/MnOx-based catalytic protocol for carbon-heteroatom coupling reactions at room temperature and without an external oxidant. Using computational studies, the possible reasons for the selective synthesis of 2-phenylquinoxaline over the MoO3/MnOx-5 nanocatalyst were elucidated.

10acascade C-N cross-coupling10aDFT studies10aroom temperature andopen air10ashape-controlled MoO3/MnOx nanocatalyst10astructure-activity correlation1 aSingh, Nittan1 aPutla, Suresh, Babu1 aSingh, Chandrodai, Pratap1 aKalbande, Pavan, Narayan1 aChoudhary, Priyanka1 aKrishnamurty, Sailaja1 aKrishnan, Venkata1 aBhatte, Kushal1 aSudarsanam, Putla uhttps://library.ncl.res.in/content/shape-controlled-moo3mno-x-nanocatalyst-selective-synthesis-2-phenylquinoxaline-drug-motifs03453nas a2200253 4500008004100000022001400041245009600055210006900151260000800220300001600228490000800244520261200252653001102864653001002875653001302885653001702898100002802915700002702943700002202970700002602992700003003018700002703048856012403075 2023 eng d a1932-744700aSteric and electronic effect in unsymmetrical squaraine dyes for dye-sensitized solar cells0 aSteric and electronic effect in unsymmetrical squaraine dyes for cNOV a22473-224880 v1273 a

Functionalizing the light harvesting sensitizers with additional electron-donating or -withdrawing groups is a potential approach to modulate the photophysical and electrochemical properties which in-turn optimizes the driving force associated with the charge injection and dye-regeneration processes at the dye-TiO2/electrolyte interface and the photovoltaic device performance in dye-sensitized solar cells (DSSCs). Furthermore, modulated electronic levels of the dyes provide an opportunity to reduce the overpotential associated with the dye-regeneration process and make the dye-TiO2 interface compatible with various electrolytes. Furthermore, an in-built steric feature by means of introducing linear/branched alkyl groups in the sensitizer is important in controlling the aggregation of dyes on the TiO2 surface. Hence, to integrate both steric and electronic properties, a series of alkyl group-wrapped unsymmetrical squaraine dyes (SQ-X) with electron-donating and -withdrawing groups have been designed, synthesized, and utilized for DSSC device fabrication. These dyes are functionalized with alkyl groups at both sp(3)-C and N-atoms of the indoline donor moiety at the nonanchoring side to have a similar steric feature. Photophysical and electrochemical studies revealed that the HOMO and LUMO energy levels of the SQ-X series of dyes have been modulated systematically with sufficient driving forces for both charge injection and dye-regeneration processes with iodolyte (I-/I-3(-)) electrolyte. In the presence of electron-donating groups in SQ-X (where X = -NPh2 and -OMe), the HOMO energy levels are less positive than SQ-H, whereas the presence of electron-withdrawing groups such as -CO2Me, -CN, and -NO2 pushed the HOMO energy levels toward more positive potentials. Enhanced photovoltaic performances have been obtained for the dyes containing electron-donating groups, where the dye with the -NPh2 group showed a maximum of eta 7.03% (V-OC 708 mV, J(SC) 13.16 mA cm(-2), and ff 78%). The dye with the strong electron-withdrawing group -NO2 showed an efficiency of 1.49% (V-OC = 634 mV, J(SC) = 3.13 mA cm(-2), and ff 75%). As the dyes with the electron-withdrawing group possess deep positive HOMO energy levels, the DSSC device characterization has been investigated with the Cu+/2+ redox shuttle. The reduced device performance of electron-withdrawing-group-containing dyes is due to the unfavored charge distribution in the LUMO compared to the presence of electron-donating-group-containing dyes, and it was supported by the difference in the charge injection efficiency.

10acobalt10aDonor10aDynamics10aOrganic dyes1 aNawghare, Indrajeet, S.1 aSingh, Ambarish, Kumar1 aMaibam, Ashakiran1 aKrishnamurty, Sailaja1 aKrishnamoorthy, Kothandam1 aNithyanandhan, Jayaraj uhttps://library.ncl.res.in/content/steric-and-electronic-effect-unsymmetrical-squaraine-dyes-dye-sensitized-solar-cells01988nas a2200217 4500008004100000022001400041245017200055210006900227260000900296300001600305490000700321520113700328100002901465700002901494700002601523700002401549700002201573700001501595700002901610856013101639 2023 eng d a0743-746300aSulfonated zinc phthalocyanine coating as an efficient and ecofriendly corrosion inhibitor for copper surfaces: an in silico led design and its experimental validation0 aSulfonated zinc phthalocyanine coating as an efficient and ecofr cNOV  a17295-173070 v393 a

The current study highlights the successful integration of an in silico design with experimental validation to create a highly effective corrosion inhibitor for copper (Cu) surfaces. The synthesized sulfonated zinc phthalocyanine (Zn-Pc) is electrochemically characterized and demonstrates an impressive 97% inhibition efficiency, comparable to the widely used industrial corrosion inhibitor, BTA, for Cu surfaces. The corrosion inhibition is comprehensively analyzed through potentiodynamic polarization and impedance spectroscopy techniques, supported by their respective equivalent circuits. Furthermore, the sample undergoes thorough characterization using scanning electron microscopy, energy-dispersive X-ray analysis, X-ray photoelectron spectroscopy, contact angle measurements, and atomic force microscopy. Density functional theory calculations reveal that sulfonated Zn-Pc exhibits the highest interaction energy, underscoring its exceptional inhibition properties. These results open possibilities for utilizing computational methods to design and optimize corrosion inhibitors for protection of Cu surfaces.

1 aDekshinamoorthy, Amuthan1 aSamal, Pragnya, Paramita1 aKrishnamurty, Sailaja1 aKhatri, Praveen, K.1 aJain, Suman, Lata1 aRay, Anjan1 aVijayaraghavan, Saranyan uhttps://library.ncl.res.in/content/sulfonated-zinc-phthalocyanine-coating-efficient-and-ecofriendly-corrosion-inhibitor-copper01927nas a2200169 4500008004100000022001400041245009000055210006900145260000800214300001600222490000600238520133100244100002401575700002601599700001701625856011501642 2023 eng d a2470-134300aUnderstanding the stability of an unprecedented Si-Be bond within quantum confinement0 aUnderstanding the stability of an unprecedented SiBe bond within cAPR a14814-148220 v83 a

As of today, the Si-Be bond remains underexplored in the literature, and therefore its anomalous behavior continues to be an unsolved puzzle to date. Therefore, the present study aims at evaluating the integrity of an unprecedented Si-Be bond within quantum confinement. To accomplish this, first-principles-based calculation are performed on Be-doped silicon clusters with atomic sizes 6, 7, and 10. Silicon clusters are sequentially doped with one, two, and three Be atoms, and their thermal response is registered in the temperature range of 200-1500 K, which discloses several research findings. During the course of the simulations, the clusters face various thermal events such as solid cluster phase, rapid structural metamorphosis, and fragmentation. Si-Be nanoalloy clusters are noted to be thermally stable at lower temperatures (200-700 K); however, they begins to disintegrate earlier at a temperature as low as 800 K. This lower stability is attributed to the weak nature of Si and Be heteroatomic interactions, which is corroborated from the structural and electronic property analysis of the doped clusters. In addition to this, the performance of Be-doped clusters at finite temperatures is also compared with the thermal response of two other popular systems, viz., C-and B-doped silicon clusters.

1 aManeri, Asma, Harun1 aKrishnamurty, Sailaja1 aJoshi, Krati uhttps://library.ncl.res.in/content/understanding-stability-unprecedented-si-be-bond-within-quantum-confinement02182nas a2200229 4500008004100000022001400041245012100055210006900176260000800245300001200253490000700265520138100272653002501653653002101678653000801699653002201707653001501729100002401744700003001768700002601798856012801824 2023 eng d a0892-702200aUnderstanding the thermal stability of a 3d, 4d, and 5d element doped aluminium nanocluster through BOMD simulations0 aUnderstanding the thermal stability of a 3d 4d and 5d element do cFEB a245-2500 v493 a

Endohedrally doped atomic clusters have generated considerable interest among computational chemists on account of their tunable chemical properties that mimic a super atom. Such endohedrally doped clusters have also been experimentally realised in the more recent past. The present work explores the practical existence of 3d, 4d and 5d doped aluminium clusters, more specifically doped Al13 cluster, by evaluating systematically their structural stability through the first principle molecular dynamical simulations. Born-Oppenheimer Molecular Dynamics (BOMD) simulations have been carried out on Al12X atomic clusters where X = Ti, V, Fe, Co, Ni, Cu, Zn, Y, Mo, Ru, Rh and W are in endohedral position. The thermal stability of such endohedrally doped clusters is quantified through parameters such as delta(rms), MSD and is an element of(pro). Electronic structure calculations reveal that endohedral doping of only Rh, Cu and Zn is preferred in the Al-13 cluster. Other dopants prefer to remain on the surface positions. However, finite temperature calculations reveal that the Al12Zn cluster undergoes surface modifications from 300K leading to a distorted icosahedral structure. Al12Cu cluster in quartet spin state is the only thermally stable cluster with Cu remaining in the endohedral position and structure retaining icosahedral confirmation till 700K.

10aAl-13 atomic cluster10aBOMD simulations10aDFT10aEndohedral doping10asuper atom1 aSamudre, Nikhil, S.1 aSingh, Chandrodai, Pratap1 aKrishnamurty, Sailaja uhttps://library.ncl.res.in/content/understanding-thermal-stability-3d-4d-and-5d-element-doped-aluminium-nanocluster-through03156nas a2200277 4500008004100000022001400041245011500055210006900170260000900239300001200248490000700260520223500267653002102502653001102523653001302534653002102547653002002568653001602588653000902604100003102613700002202644700002602666700003002692700002702722856012902749 2023 eng d a0743-746300aVisible-light-active unsymmetrical squaraine dyes with pyridyl anchoring groups for dye-sensitized solar cells0 aVisiblelightactive unsymmetrical squaraine dyes with pyridyl anc cDEC  a251-2630 v403 a

Visible-light-active alkyl group-wrapped unsymmetrical squaraine dyes SD1-SD3 were synthesized, featuring an indoline donor and pyridine and carboxylic acid anchoring groups. Their photophysical, electrochemical, and photovoltaic characteristics were examined by fabricating a dye-sensitized solar cell (DSSC) device. Both carboxylic acid and pyridine anchoring groups containing squaraine dyes SD3 and SD2 possess similar photophysical and electrochemical characteristics. However, their photovoltaic performances were completely different. The SD3 dye with the carboxylic acid anchoring group displayed a DSSC device efficiency of 7.20% (V-OC 0.81 V; J(SC) 12.29 mA/cm(2)) using iodolyte (I-/I-3(-)) electrolyte, compared to SD1 (V-OC 0.659 V; J(SC) 4.97 mA/cm(2); and eta - 2.34%) and SD2 (V-OC 0.629 V; J(SC) 1.68 mA/cm(2); and eta - 0.84%), which were featured with pyridyl anchoring groups. These results were attributed to dye loading on the Lewis and Br & oslash;nsted acidic sites of TiO2 and the importance of aggregated structures for photocurrent generation. In the incident photon-to-current efficiency (IPCE) analysis, SD1 dye-sensitized devices exhibited photocurrent generation from both monomeric and aggregated dyes on the TiO2 surface. In contrast, SD2 showed photocurrent generation solely from aggregated states. Despite the introduction of long alkyl chains to reduce dye aggregation and charge recombination, the results indicated preferential charge injection from only the aggregated SD2 dye on TiO2. Fluorescence-quenching experiments indicated an efficient charge transfer from the aggregated SD2 dye to TiO2 compared to that of the monomeric dye. Cosensitization, a method to enhance the light-harvesting efficiency and photocurrent generation in DSSCs, was explored by simultaneously cosensitizing pyridyl-based dyes (SD1 and SD2) with a blue-colored carboxylic acid-based squaraine dye SD4. IPCE analysis demonstrated that both SD1 and SD4 contributed to generating a photocurrent of 9.11 mA/cm(2). The sequential cosensitization of SD1 and SD4 with the coadsorbent CDCA showed the highest performance, with a V-OC of 0.663 V, a J(SC) of 11.43 mA/cm(2), and an efficiency (eta) of 5.20%.

10aco-sensitization10aDesign10aEmmision10aFluorescent Dyes10aHigh-Efficiency10aOrganic Dye10aRing1 aDeshmukh, Shivdeep, Suresh1 aMaibam, Ashakiran1 aKrishnamurty, Sailaja1 aKrishnamoorthy, Kothandam1 aNithyanandhan, Jayaraj uhttps://library.ncl.res.in/content/visible-light-active-unsymmetrical-squaraine-dyes-pyridyl-anchoring-groups-dye-sensitized02596nas a2200253 4500008004100000022001400041245011300055210006900168260000800237490000600245520168400251653002101935653003001956653002601986653002402012653001802036100002402054700002702078700002202105700002602127700003002153700002702183856013202210 2024 eng d a2367-093200aAniline and indoline donors based far-red active unsymmetrical squaraine dyes for dye sensitized solar cells0 aAniline and indoline donors based farred active unsymmetrical sq cFEB0 v83 a

In dye-sensitized solar cells (DSSC), controlling the dye-aggregation on the metal-oxide surface by appending the alkyl groups around the donor or pi-spacer unit of the dye is a potential approach to enhance DSSC efficiency. Further, rigidification of the dye structures by cyclization modulates the photophysical properties of the sensitizer. Here a series of donor-acceptor-donor (D-A-D) type far-red active unsymmetrical squaraine dyes (SQA) have been designed and synthesized, where N,N-dimethylaniline, methylated- and branched-indoline have been used as donor units. These dyes showed absorption between 629-654 nm (lambda max) with the molar extinction coefficient of 1.49-1.94x105 M-1 cm-1. Systematic enhancements in DSSC device efficiency have been observed due to the cyclization and alkyl-groups incorporation in this set of dyes which were further enhanced with the addition of chenodeoxycholic acid (CDCA). The highest DSSC device efficiency of 4.78 % (Jsc of 8.77 mA/cm2 and Voc of 692 mV) has been achieved for SQA3. The IPCE profile of SQA dyes indicates the contribution of aggregated structures for the photocurrent generation. Further, co-sensitization of SQA3 dye with a complementary visible light active dye AK4 showed the enhanced device efficiency of 6.27 % with panchromatic IPCE response. Dye rigidification, and controlled aggregation of dyes on TiO2 by means of cyclization of donor unit and introducing the alkyl groups in the dye structure synergistically improve the dye-sensitized solar cell (DSSC) device performance. Donor-Acceptor-Donor (D-A-D) based unsymmetrical squaraine dye SQA3 showed the DSSC device performance of 4.78 %.image

10aco-sensitization10adye-sensitized solar cell10aeffect of alkyl chain10amolecular planarity10asquaraine dye1 aJadhav, Avinash, P.1 aSingh, Ambarish, Kumar1 aMaibam, Ashakiran1 aKrishnamurty, Sailaja1 aKrishnamoorthy, Kothandam1 aNithyanandhan, Jayaraj uhttps://library.ncl.res.in/content/aniline-and-indoline-donors-based-far-red-active-unsymmetrical-squaraine-dyes-dye-sensitized02936nas a2200301 4500008004100000022001400041245013700055210006900192260000800261490000700269520184900276653003702125653001802162653004202180653003002222653003002252653001702282100002002299700003002319700002902349700002502378700001802403700002002421700001802441700002602459700002402485856012502509 2024 eng d a1613-681000aBreaking the Pt electron symmetry and OH spillover towards ptir active center for performance modulation in direct ammonia fuel cell0 aBreaking the Pt electron symmetry and OH spillover towards ptir  cDEC0 v203 a

The growing interest in low-temperature direct ammonia fuel cells (DAFCs) arises from the utilization of a carbon-neutral ammonia source; however, DAFCs encounter significant electrode overpotentials due to the substantial energy barrier of the *NH2 to *NH dehydrogenation, compounded by the facile deactivation by *N on the Pt surface. In this work, a unique catalyst, Pt4Ir@AlOOH/NGr i.e., Pt4Ir/ANGr, is introduced composed of PtIr alloy nanoparticles controllably decorated on the pseudo-boehmite phase of AlOOH-supported nitrogen-doped reduced graphene (AlOOH/NGr) composite, synthesized via the polyol reduction method. The detailed studies on the structural and electronic properties of the catalyst by XAS and VB-XPS reveal the possible electronic modulations. The optimized Pt4Ir/ANGr composition exhibits a significantly improved onset potential and mass activity for AOR. The DFT study confirms the OHad species spillover by AlOOH and Pt4Ir (100) facilitates the conversion of the *NH2 to *NH with minimal energy barriers. Finally, testing of DAFC at the system level using a membrane electrode assembly (MEA) with Pt4Ir/ANGr as the anode catalyst, demonstrating the suitability of the catalyst for its practical applications. This study thus uncovers the potential of the Pt4Ir catalyst in synergy with ANGr, largely addressing the challenges in hydrogen transportation, storage, and safety within DAFCs. In this article, a versatile catalyst, Pt4Ir/ANGr, is introduced composed of PtIr alloy nanoparticles decorated on AlOOH/NGr composite. The AlOOH provides an -OH-rich surface conducive to the facile adsorption and decoration of the PtIr alloy nanoparticles and OHad species spillover from AlOOH to the Pt4Ir active center during AOR, further validating the higher experimental activity obtained in Pt4Ir/ANGr. image

10aammonia oxidation reaction (AOR)10ad-band center10adensity functional theory (DFT) study10adirect ammonia fuel cells10ahydroxyl spillover effect10aXAS analysis1 aBarik, Sidharth1 aKharabe, Geeta, Pandurang1 aSamal, Pragnya, Paramita1 aUrkude, Rajashri, R.1 aKumar, Sachin1 aYoyakki, Athira1 aVinod, C., P.1 aKrishnamurty, Sailaja1 aKurungot, Sreekumar uhttps://library.ncl.res.in/content/breaking-pt-electron-symmetry-and-oh-spillover-towards-ptir-active-center-performance02052nas a2200265 4500008004100000022001400041245015000055210006900205260000900274300001400283490000700297520102600304653002401330653003601354653005501390653003801445653003001483653002001513100002501533700002501558700002401583700002701607700002601634856012601660 2024 eng d a0360-319900aComputational identification of most potent atom pair catalysts for electrocatalytic nitrogen reduction reaction over hydrogen evolution reaction0 aComputational identification of most potent atom pair catalysts  cMAR  a1345-13580 v583 a

Robust electrocatalytic atom pair compositions (APCs) where Nitrogen Reduction Reaction (NRR) is more enhanced over competing Hydrogen Evolution Reaction (HER) is searched for using computational studies based on Density Functional Theory based methods. Atomic pairs are anchored on mechanically and thermally stable graphene surfaces. A wide range of transition metal based atom pair compositions from 3d, 4d, and 5d groups are systematically investigated for reduction of dinitrogen molecule with lower reduction barrier as compared to HER. APR compositions of Ni-Rh with an overall limiting potential of -0.22 V, Fe-W with an overall limiting potential of -0.26 V and Co-Pt with an overall limiting potential of -0.28 V are identified as the most potent atomic pairs for enhanced nitrogen reduction reaction over the HER. Finally, the performance of most potent composition, viz., Ni-Rh is validated to be consistent with respect to their thermodynamic stability and performance within the solvent effects.

10aAtom pair catalysts10aDensity Functional Theory (DFT)10aElectrochemical nitrogen reduction reaction (eNRR)10ahydrogen evolution reaction (HER)10aIR stretching frequencies10aN-N bond length1 aVerma, Tushar, Singh1 aDar, Afshana, Hassan1 aDar, Manzoor, Ahmad1 aSelvaraj, Kaliaperumal1 aKrishnamurty, Sailaja uhttps://library.ncl.res.in/content/computational-identification-most-potent-atom-pair-catalysts-electrocatalytic-nitrogen02491nas a2200157 4500008004100000022001400041245012700055210006900182260000900251300001600260490000800276520186900284100002902153700002602182856012502208 2024 eng d a1932-744700aFirst-principles simulation of active site selectivity for CO2 and H2 adsorption on Mg(OH)+/Mg2+ and Ca(OH)+/Ca2+ zeolites0 aFirstprinciples simulation of active site selectivity for CO2 an cDEC  a21659-216710 v1283 a

One very effective strategy for addressing global warming and transitioning to sustainable energy sources is selective CO2 separation over H-2. Porous materials, particularly zeolites, have demonstrated enormous potential for energy-efficient separation techniques combined with storage. By altering interactions at cation-binding sites, zeolite's gas adsorption characteristics toward carbon capture can be improved. In this study, Mg and Ca are assessed as extra-framework cations in divalent (Ca2+, Mg2+) and monovalent states (Ca(OH)(+), Mg(OH)(+)) in faujasite and chabazite zeolites for CO2 capture over H-2. The study also explores the impact of mixed cations, viz., a combination of both Ca2+ and Mg2+ in the framework, on their selective adsorption potential. This study uses DFT with dispersion corrections to calculate adsorption energies, enthalpies, and Gibb's free energies of adsorbed CO2 and H-2 molecules. Among the dispersion parameters evaluated, viz., D4, TS/HI, and MBD, D4 approaches experimental accuracy. In general, the adsorption trend obtained for CO2 is Mg FAU > Ca FAU > Mg CHA > Ca CHA > Mg(OH)(+) FAU > Ca(OH)(+) FAU > Mg(OH)(+) CHA > Ca(OH)(+) CHA. The heats of adsorption using PBE+D4 for CO2 are -46 kJ/mol for Ca FAU and -10 kJ/mol for Ca(OH)(+) FAU, respectively. These values closely align with the experimental results of -45 and -6 kJ/mol, respectively, within a chemical accuracy limit of +/- 4 kJ/mol. The relative adsorption energies suggest that for both FAU and CHA, there exists a minimum difference of 26 kJ/mol in adsorption energies between CO2 and H-2. Hence, this piece of work highlights that FAU with Ca and Mg as extra-framework cations in a six-membered cage can be a viable substitute to replace, the current best candidate in literature, viz., Li+, for selective CO2 capture.

1 aSamal, Pragnya, Paramita1 aKrishnamurty, Sailaja uhttps://library.ncl.res.in/content/first-principles-simulation-active-site-selectivity-co2-and-h2-adsorption-mgohmg2-and02215nas a2200253 4500008004100000022001400041245013200055210006900187260000800256300001100264490000900275520129000284653001501574653004001589653002501629653003001654653002501684100002901709700003001738700002001768700001901788700002601807856012801833 2024 eng d a2210-271X00aIndazole-5-amine (AIA) as competing corrosion coating to Benzotriazole (BTAH) at the interface of Cu: A DFT and BOMD case study0 aIndazole5amine AIA as competing corrosion coating to Benzotriazo cSEP a1147620 v12393 a

This study compares three organic compounds-benzotriazole (BTAH), imidazole (IM), and indazole-5-amine (AIA)-as corrosion inhibitors for copper substrates. Using Density Functional Theory (DFT) and Born-Oppenheimer Molecular Dynamics (BOMD) calculations, it identifies AIA as a promising and cost-effective alternative to the toxic BTAH. The adsorption strength on Cu(1 0 0) surfaces is ranked AIA>BTAH>IM for both neutral and deprotonated forms. These findings are supported by electronic parameter studies, including Bader charge analysis, density of states (DOS), charge density differences (CDD), and frontier molecular orbital analysis. AIA shows the best adsorption in a parallel orientation at the top site. Packing studies reveal that hydrogen bonding stabilizes the interaction energies within self-assembled AIA aggregates. Organometallic complexation studies reveal that deprotonated BTAH exhibits higher interaction energy with a single Cu atom compared to AIA when bonded through the carbon end, consistent with the findings from BOMD studies. However, on periodic Cu surfaces, AIA outperforms BTAH molecules as seen from adsorption energies. This investigation highlights AIA's potential as a superior and more economical corrosion inhibitor for copper.

10aAdsorption10aBorn-Oppenheimer molecular dynamics10aCorrosion inhibition10aDensity functional theory10aIndazole derivatives1 aSamal, Pragnya, Paramita1 aSingh, Chandrodai, Pratap1 aTiwari, Shivani1 aShah, Vaishali1 aKrishnamurty, Sailaja uhttps://library.ncl.res.in/content/indazole-5-amine-aia-competing-corrosion-coating-benzotriazole-btah-interface-cu-dft-and02741nas a2200181 4500008004100000245010100041210006900142260000800211520202500219100002702244700003402271700001702305700002302322700003202345700003202377700002602409856012402435 2024 eng d00aInvestigation of cathinone analogs targeting human dopamine transporter using molecular modeling0 aInvestigation of cathinone analogs targeting human dopamine tran cMAY3 a

In a step towards understanding the structure–property relationship among Synthetic Cathinones (SCs), a combined methodology based on Density Functional Theory (DFT), Administration, Distribution, Metabolism, Excretion, and Toxicity (ADMET) predictions, docking and molecular dynamics simulations have been applied to correlate physicochemical descriptors of various SCs to their biological activity. The results from DFT and molecular docking studies correlate well with each other explaining the biological activity trends of the studied SCs. Quantum mechanical descriptors viz. polarizability, electron affinity, ionization potential, chemical hardness, electronegativity, molecular electrostatic potential, and ion interaction studies unravel the distinguishingly reactive nature of Group D (pyrrolidine substituted) and Group E (methylenedioxy and pyrrolidine substituted) compounds. According to ADMET analysis, Group D and Group E molecules have a higher probability of permeating through the blood–brain barrier. Molecular docking results indicate that Phe76, Ala77, Asp79, Val152, Tyr156, Phe320, and Phe326 constitute the binding pocket residues of hDAT in which the most active ligands MDPV, MDPBP, and MDPPP are bound. Finally, to validate the derived quantum chemical descriptors and docking results, Molecular Dynamics (MD) simulations are performed with homology-modelled hDAT (human dopamine transporter). The MD simulation results revealed that the majority of SCs remain stable within the hDAT protein’s active sites via non-bonded interactions after 100 ns long simulations. The findings from DFT, ADMET analysis, molecular docking, and molecular dynamics simulation studies complement each other suggesting that pyrrolidine-substituted SCs (Group D and E), specifically, MPBP and PVN are proven potent SCs along with MDPV, validating various experimental observations.

1 aShivankar, Bhavana, R.1 aBhandare, Vishwambhar, Vishnu1 aJoshi, Krati1 aS., Patil., Vishal1 aDhotare, Priyanka, Shrikant1 aSonawane, Kailas, Dasharath1 aKrishnamurty, Sailaja uhttps://library.ncl.res.in/content/investigation-cathinone-analogs-targeting-human-dopamine-transporter-using-molecular01844nas a2200265 4500008004100000022001400041245012400055210006900179260000900248300001400257490000800271520093200279653001401211653000901225653001101234653002101245653004101266100002801307700002201335700002901357700002401386700002601410700002001436856012201456 2024 eng d a1615-415000aIron-catalyzed C-C and C-N bond-forming tandem amidation offering access to 3-amino-3-aminomethyl-2-oxindole frameworks0 aIroncatalyzed CC and CN bondforming tandem amidation offering ac cJUN  a2801-28100 v3663 a

An iron-catalyzed protocol for the synthesis of 3-amino-3-aminomethyl-2-oxindole heterocyclic structures is disclosed employing isatins and non-nucleophilic N-methoxybenzamides. This reaction class is associated with broad scope and tolerates numerous functionalities, such as fluoro, chloro, bromo, iodo, trifluoromethyl, nitrile, ester, ether, and alkenyl, including heteroaryl - thiophene, benzothiophene, carbazolyl, indolyl, eugenol, and polycyclic cholesterol moieties. Detailed mechanistic investigations reveal that the reaction proceeds via iron-catalyzed N-O bond cleavage in N-methoxybenzamides, generating formaldehyde and benzamide, and through the intermediacy of isatin-ketimines and N-(hydroxymethyl)benzamides. Overall, this amidation reaction involves one C-C and two C-N bond-forming tandem processes, providing a range of beta-amino-aminomethyl-oxindoles (45 examples) in up to 88% yields. image

10abenzamide10airon10aIsatin10atandem amidation10atetrasubstituted carbon stereocenter1 aAnkade, Shidheshwar, B.1 aPradhan, Chandini1 aSamal, Pragnya, Paramita1 aGonnade, Rajesh, G.1 aKrishnamurty, Sailaja1 aPunji, Benudhar uhttps://library.ncl.res.in/content/iron-catalyzed-c-c-and-c-n-bond-forming-tandem-amidation-offering-access-3-amino-300812nas a2200217 4500008004100000022001400041245011200055210006900167260000800236490000700244653001900251653001900270653001800289653004200307653001100349100002700360700003000387700002600417700002500443856012600468 2024 eng d a2192-650600aMetal-organic frameworks for enhanced hydrogen generation from syngas: a density functional theory approach0 aMetalorganic frameworks for enhanced hydrogen generation from sy cNOV0 v8910acarbon capture10aH-2 separation10aMetal organic10aPorous coordination network (PCN-250)10aSyngas1 aGopalsamy, Karuppasamy1 aSingh, Chandrodai, Pratap1 aKrishnamurty, Sailaja1 aBabaRao, Ravichandar uhttps://library.ncl.res.in/content/metal-organic-frameworks-enhanced-hydrogen-generation-syngas-density-functional-theory00847nas a2200241 4500008004100000022001400041245010800055210006900163260000900232300001400241490000700255653002100262653001800283653001400301653001900315100002500334700002700359700002600386700001700412700002300429700003000452856012300482 2024 eng d a2044-475300aPolyvalent interaction and confinement to suppress polysulfide dissolution and improve electrocatalysis0 aPolyvalent interaction and confinement to suppress polysulfide d cJUN  a3416-34230 v1410acathode material10aHIGH-CAPACITY10aParticles10aSULFUR CATHODE1 aBharathkumar, H., J.1 aShivankar, Bhavana, R.1 aKrishnamurty, Sailaja1 aChen, Dehong1 aCaruso, Rachel, A.1 aKrishnamoorthy, Kothandam uhttps://library.ncl.res.in/content/polyvalent-interaction-and-confinement-suppress-polysulfide-dissolution-and-improve02297nas a2200229 4500008004100000022001400041245010500055210006900160260000900229490000700238520147700245653003001722653002601752653002101778653002201799653003201821653001401853100002201867700002401889700002601913856012801939 2024 eng d a2352-152X00aQuasi-molecular hydrogen storage capacity of graphene quantum dots: A dispersion corrected DFT study0 aQuasimolecular hydrogen storage capacity of graphene quantum dot cAPR 0 v843 a

Efficient storage of hydrogen, green fuel with the highest energy density, remains a pressing challenge. Among the several materials investigated for their potential hydrogen storage, 2D materials, like graphene, have advantages such as mechanical strength and large surface area but fail to store hydrogen reversibly. In this context, the present computational experiment demonstrates the potential of Graphene Quantum Dots (GQDs) with 24, 40 and 42 carbon atoms for their hydrogen storage capacity in quasi-molecular mode. Factors such as edge terminations, heteroatom doping, and anchoring of metal atoms are evaluated as a function of their storage capacity. The study clearly demonstrates an enhanced storage capacity of quantum dots, particularly, when a single Ti adatom is anchored on a 24 carbon atom GQD with a storage weight % of 2.24 % w/w. The storage weight % is further noted to increase as a function of the number of Ti atoms anchored on the GQD with the highest hydrogen storage weight % of 6.1 % w/w. Importantly, the adsorption of hydrogen molecule on the Ti atom is through a quasi-molecular mode and is driven by Kubas interaction. This type of interactions makes GQDs as viable storage materials at room temperature. Secondly, the work demonstrates that GQDs offer higher storage capacities of hydrogen molecules as compared to their 2D counterparts viz., graphene sheets, making them attractive candidates to be explored experimentally.

10aDensity functional theory10agraphene quantum dots10aHydrogen storage10aKubas interaction10aQuasi -molecular adsorption10aTi adatom1 aKhadilkar, Pranav1 aSamudre, Nikhil, S.1 aKrishnamurty, Sailaja uhttps://library.ncl.res.in/content/quasi-molecular-hydrogen-storage-capacity-graphene-quantum-dots-dispersion-corrected-dft00913nas a2200241 4500008004100000022001400041245014900055210006900204260001100273300001600284490000700300100001800307700002300325700002000348700002600368700001700394700001600411700002900427700002500456700002800481700003000509856013200539 2024 eng d a2041-652000aScalable approach using a gC3N4 -covalent organic framework hybrid catalyst towards sustainable hydrogen production from seawater and wastewater0 aScalable approach using a gC3N4 covalent organic framework hybri cAUG 22 a13381-133880 v151 aAsokan, Kiran1 aBhagyasree, T., M.1 aDevasia, George1 aKrishnamurty, Sailaja1 aSolim, Sabah1 aRueda, Lina1 aAl-Mohannadi, Dhabia, M.1 aAl-Hashimi, Mohammed1 aKakosimos, Konstantinos1 aBabu, Sukumaran, Santhosh uhttps://library.ncl.res.in/content/scalable-approach-using-gc3n4-covalent-organic-framework-hybrid-catalyst-towards-sustainable02302nas a2200229 4500008004100000022001400041245012500055210006900180260000800249490000700257520147900264653001901743653002201762653002001784653003601804653002301840100001701863700002601880700002401906700001701930856012501947 2024 eng d a1439-423500aSize and morphology dependent activity of Cu clusters for CO2 activation and reduction: a first principles investigation0 aSize and morphology dependent activity of Cu clusters for CO2 ac cDEC0 v253 a

Various Cu-based materials in diverse forms have been investigated as efficient catalysts for electrochemical reduction of CO2; however, they suffer from issues such as higher over potential and poor selectivity. The activity and selectivity of CO2 electro reduction have been shown to change significantly when the surface morphology (steps, kinks, and edges) of these catalysts is altered. In light of this, size and morphology dependent activity of selected copper clusters, Cun (n=2-20) have been evaluated for the activation and reduction of CO2 molecule. The phase-space of these copper clusters is rich in conformations of distinct morphologies starting from planar, 2D geometries to prolate-shaped geometries and also high-symmetry structures. The binding efficiency and the activation of CO2 are highest for medium sized clusters (n=9-17) with prolate-morphologies as compared to small or larger sized CunCO(2) clusters that are existing mainly as planar (triangular, tetragonal etc.) or highly-symmetric geometries (icosahedron, capped-icosahedron etc.), respectively. The best performing (prolate-shaped) CunCO2 conformations are quite fluxional and also they are thermally stable, as demonstrated by the molecular dynamics simulations. Furthermore, on these CunCO(2) conformations, the step-by-step hydrogenation pathways of CO2 to produce value-added products like methanol, formic acid, and methane are exceptionally favorable and energy-efficient.

10aCO2 activation10aCO2 hydrogenation10aCopper clusters10aDensity Functional Theory (DFT)10amolecular dynamics1 aAmin, Seerat1 aKrishnamurty, Sailaja1 aDar, Manzoor, Ahmad1 aJoshi, Krati uhttps://library.ncl.res.in/content/size-and-morphology-dependent-activity-cu-clusters-co2-activation-and-reduction-first02159nas a2200265 4500008004100000022001400041245011500055210006900170260000900239300001400248490000700262520120400269653003601473653004801509653002701557653002201584653002101606653002001627100002201647700002301669700002601692700002101718700002501739856012901764 2024 eng d a1944-824400aSurface electronic properties-driven electrocatalytic nitrogen reduction on metal-conjugated porphyrin 2D-MOFs0 aSurface electronic propertiesdriven electrocatalytic nitrogen re cFEB  a8707-87160 v163 a

Two-dimensional (2D) metal organic framework (MOF) or metalloporphyrin nanosheets with a stable metal-N-4 complex unit present the metal as a single-atom catalyst dispersed in the 2D porphyrin framework. First-principles calculations on the 3d-transition metals in M-TCPP are investigated in this study for their surface-dependent electronic properties including work function and d-band center. Crystal orbital Hamiltonian population (-pCOHP) analysis highlights a higher contribution of the bonding state in the M-N bond and antibonding state in the N-N bond to be essential for N-N bond activation. A linear relationship between Delta G(max) and surface electronic properties, N-N bond strength, and Bader charge has been found to influence the rate-determining potential for nitrogen reduction reaction (NRR) in M-TCPP MOFs. 2D Ti-TCPP MOF, with a kinetic energy barrier of 1.43 eV in the final protonation step of enzymatic NRR, shows exclusive NRR selectivity over competing hydrogen reduction (HER) and nitrogenous compounds (NO and NO2). Thus, Ti-TCPP MOF with an NRR limiting potential of -0.35 V in water solvent is proposed as an attractive candidate for electrocatalytic NRR.

10aDensity Functional Theory (DFT)10aelectrocatalytic nitrogen reductionreaction10akinetic energy barrier10alimitingpotential10aMetalloporphyrin10aNRR selectivity1 aMaibam, Ashakiran1 aOrhan, Ibrahim, B.1 aKrishnamurty, Sailaja1 aRusso, Salvy, P.1 aBabaRao, Ravichandar uhttps://library.ncl.res.in/content/surface-electronic-properties-driven-electrocatalytic-nitrogen-reduction-metal-conjugated03587nas a2200181 4500008004100000245015100041210006900192260000800261300001600269490000600285520287600291100001603167700001803183700002903201700002603230700002003256856012903276 2024 eng d00aSynergistic combination of ZnCl2/Cu-BTC MOF for the photocatalytic oxidative deamination of benzylamines using CO2 under visible-light irradiation0 aSynergistic combination of ZnCl2CuBTC MOF for the photocatalytic cJUL a2095–21010 v23 a

This paper demonstrates the first CO2-mediated oxidative deamination of benzylamines to benzaldehydes using a combination of ZnCl2 and Cu-BTC MOF as photocatalysts in a carbon tetrachloride solvent under visible-light irradiation. Interestingly, the synergistic combination of ZnCl2 and Cu-BTC afforded the targeted oxidation of benzylamine to benzaldehyde, wherein CO2 acted as an oxidant. The individual components yielded the corresponding imine as the main product, resulting from the oxidative coupling of the benzylamine. DFT calculations and computational studies supported the proposed reaction pathways involving the formation of an intermediate imine from benzylamine via dehydrogenation followed by hydrolysis to produce benzaldehyde. This work, demonstrating the use of CO2 as an oxidant, may open up new avenues for CO2 utilization in chemical production by using sustainable light energy.

1 aKumar, Amod1 aBhatt, Sakshi1 aSamal, Pragnya, Paramita1 aKrishnamurty, Sailaja1 aJain, Suman, L. uhttps://library.ncl.res.in/content/synergistic-combination-zncl2cu-btc-mof-photocatalytic-oxidative-deamination-benzylamines00945nas a2200253 4500008004100000022001400041245013300055210006900188260000900257300001600266490000700282653001700289653003200306653003400338100003400372700002400406700002100430700002300451700002600474700002100500700002300521700003000544856011700574 2024 eng d a1944-824400aSynergistic effect of lactam and pyridine nitrogen on polysulfide chemisorption and electrocatalysis in lithium sulfur batteries0 aSynergistic effect of lactam and pyridine nitrogen on polysulfid cAUG  a42059-420680 v1610aLi-S battery10aphenyl-diketopyrrolopyrrole10apyridine-diketopyrrolopyrrole1 aJavaregowda, Bharathkumar, H.1 aKargude, Radhakisan1 aBirajdar, Sarika1 aShivankar, Bhavana1 aKrishnamurty, Sailaja1 aJones, Lathe, A.1 aCaruso, Rachel, A.1 aKrishnamoorthy, Kothandam uhttps://library.ncl.res.in/content/synergistic-effect-lactam-and-pyridine-nitrogen-polysulfide-chemisorption-and02525nas a2200277 4500008004100000022001400041245012100055210006900176260000800245300001400253490000600267520153600273653002301809653003101832653002801863653002501891653001901916653001801935100002601953700003101979700002502010700002602035700003002061700002702091856012902118 2024 eng d a2574-096200aTriazatruxene amine donor-based visible-light-responsive unsymmetrical squaraine dyes for dye-sensitized solar cells0 aTriazatruxene amine donorbased visiblelightresponsive unsymmetri cSEP a7982-79910 v73 a

Optimized charge-transfer dynamics at the dye-TiO2/electrolyte interface are required for an enhanced dye-sensitized solar cell (DSSC) device performance. Such an optimized interface enhances the charge-injection, dye-regeneration, and diminished charge-recombination processes, synergistically enhancing the device efficiency. In this study, octupolar-structured sensitizers are designed to improve the interaction between the dye and the redox electrolyte for increasing the dye-regeneration process upon photoexcitation. Accordingly, a set of unsymmetrical squaraine dyes with indoline and triazatruxene amine donor-based D-A-D dyes are designed (KV1-KV3), synthesized, and sensitized with a semiconducting metal oxide (TiO2) film. The sensitizer forms a monolayer on the TiO2 surface, leading to a dye-dye interaction, which broadens the absorption spectrum. The N atom of the triazatruxene amine donor was left unsubstituted in KV1, whereas a hexyl chain was installed in KV2 and KV3 and a branched alkyl chain was installed on the core N atoms in KV3 to control the self-assembly of dyes on the TiO2 surface. Self-assembly of alkyl groups wrapped in KV1-KV3 dyes on the TiO2 surface aids surface passivation and broadens the absorption profile, improving the light-harvesting capabilities. The DSSC devices based on KV2 exhibited a high power conversion efficiency of 7.85% (V-oc = 794 mV, J(sc) = 14.76 mA/cm(2), and FF = 67%), with an onset incident photon-to-current conversion efficiency response from 680 nm.

10aaggregationof dyes10aDye-sensitized solar cells10ametal-free organic dyes10aself-assembly of dye10asquaraine dyes10atriazatruxene1 aIngole, Kiran, Balaso1 aDeshmukh, Shivdeep, Suresh1 aVerma, Tushar, Singh1 aKrishnamurty, Sailaja1 aKrishnamoorthy, Kothandam1 aNithyanandhan, Jayaraj uhttps://library.ncl.res.in/content/triazatruxene-amine-donor-based-visible-light-responsive-unsymmetrical-squaraine-dyes-dye01317nas a2200277 4500008004100000022001400041245010500055210006900160260000800229300001500237490000600252520041000258653001900668653002500687653000800712653001600720653001400736100002300750700002200773700002400795700002500819700002200844700002600866700002300892856012400915 2024 eng d a2365-654900a`Turning on' to glutathione: a rhodamine-based fluorescent chemodosimeter with nanomolar sensitivity0 aTurning on to glutathione a rhodaminebased fluorescent chemodosi cOCT ae2024029430 v93 a

A new colorimetric and fluorescence turn-on chemodosimeter for selective detection of GSH over Cys and Hcy with 34-fold enhancement in emission intensity is reported. Probe 1 exhibited ultra-sensitivity toward GSH with 0.125 nM detection limit and successfully displayed GSH detection in MCF-7 live cells. The mechanism of sensing is established by density functional theoretical calculations.

10aChemodosimeter10aFluorescence turn-on10aGSH10aMCF-7 cells10aRhodamine1 aBadekar, Pooja, S.1 aDeo, Harshada, S.1 aVarma, Mokshada, E.1 aKulkarni, Prasad, P.1 aMaibam, Ashakiran1 aKrishnamurty, Sailaja1 aKumbhar, Anupa, A. uhttps://library.ncl.res.in/content/turning-glutathione-rhodamine-based-fluorescent-chemodosimeter-nanomolar-sensitivity02578nas a2200217 4500008004100000022001400041245015200055210006900207260000800276490000700284520173800291653003002029653003702059653003002096653001702126100002502143700002202168700002602190700001802216856012602234 2024 eng d a0934-086600aUltra-small Au nanoclusters with tailored photoluminescence properties using modified thiol ligands: a computational and experimental demonstration0 aUltrasmall Au nanoclusters with tailored photoluminescence prope cOCT0 v413 a

Au nanoclusters with tailored photoluminescence can be obtained through controlled nanoparticle ligand interface chemistry. The present work reports molecular gold nanoclusters with tuneable photoluminescence emission from 600 to 700 nm using N,N `,N `'-trialkyl (11-mercaptoundecyl)ammonium chloride ligands as capping-agents. The tunability within red spectral region is regulated through specific interface chemistry between gold nanoclusters of molecular range and functional groups of the quaternary ammonium head over N,N `,N `'-trialkyl(11-mercaptoundecyl)ammonium chloride. Combined understanding obtained from the spectroscopy, microscopy, and density functional theory studies demonstrate that the functional group specific electronic interactions at the interfaces steer the emission characteristics of ``molecular'' Au nanoparticles. The study clearly identifies that bulkier functional groups, i.e., triethyl, tripropyl, tributyl, and dimethyl benzene over N+ (of thiol ligand) through their steric effects minimize the particle size giving rise to tunable photoluminescence emission in red spectral region. However, the red shift seen in the emission Au nanoclusters with N-(11-mercaptoundecyl)-N,N `-dimethylbenzenammonium chloride ligand in contradiction to particle size effect is computationally proved to be due to the delocalization of electron density from benzene aromatic ring to N+ of ammonium head leading to a reduction in the HOMO-LUMO energy gap. Fluorescence properties of water dispersible Au nanoclusters are tuned by varying the ammonium head group. Density Functional Theory studies correlate the distinction in emission when head group is phenyl to charge transfer characteristics. image

10aDensity functional theory10aphotoluminescent Au nanoclusters10asurface plasmon resonance10athiol ligand1 aChahande, Anurag, M.1 aMaibam, Ashakiran1 aKrishnamurty, Sailaja1 aDevi, Nandini uhttps://library.ncl.res.in/content/ultra-small-au-nanoclusters-tailored-photoluminescence-properties-using-modified-thiol02358nas a2200313 4500008004100000022001400041245014700055210006900202260000900271300001200280490000800292520132300300653001501623653001101638653001601649653001201665653000801677653001501685100002201700700002401722700002301746700002001769700002801789700002101817700002601838700002201864700002601886856013201912 2025 eng d a1226-086X00aBinderless low silica X zeolite for methane separation from binary CO2/CH4 biogas stream: A comprehensive experimental and computational study0 aBinderless low silica X zeolite for methane separation from bina cSEP  a705-7190 v1493 a

This study presents the synthesis of binderless Na-LSX (B-Na-LSX) and binderless NaK-LSX (B-NaK-LSX). XRD, SEM, EDS, and N-2 physisorption were used for characterization of samples. Computational modelling of prepared sorbent was performed for the fundamental understanding of zeolite topology and adsorption behaviour. The breakthrough experiments are used to evaluate the adsorption capacities on CO2/CH4 (40/60 vol%) binary biogas stream. The results were compared with commercial Na-LSX (C-Na-LSX). The breakthrough adsorption capacity of B-Na-LSX was 3.08 mmol g(-1) and 0.29 mmol g(-1) of CO2 and CH4, respectively, at 300 K and 1 bar. CO2 sorption capacity of B-Na-LSX was similar to 11 % and similar to 17 % higher than B-NaK-LSX (2.77 mmol g(-1)) and C-Na-LSX (2.56 mmol g(-1)), respectively. DFT study reveals that the higher adsorption of CO2 over CH4 was attributed to higher charge transfer from CO2 to zeolite framework. Dual-bed six-step Pressure Swing Adsorption (PSA) was performed on B-Na-LSX at 6 bar. similar to 232 cycles were run with above 98 % of CH4 purity and similar to 74 % of recovery. The life-cycle test of sorbent was studied. It was implied that the designed sorbent is effective to produce the high purity of CH4 and can be utilized for a longer period for CH4 production.

10aBinderless10aBiogas10aLSX zeolite10amethane10aPSA10aSeparation1 aYadav, Tushar, R.1 aShrotri, Aadesh, R.1 aKate, Pranjali, N.1 aDevasia, George1 aNiphadkar, Prashant, S.1 aMali, Nilesh, A.1 aKrishnamurty, Sailaja1 aBokade, Vijay, V.1 aNandanwar, Sachin, U. uhttps://library.ncl.res.in/content/binderless-low-silica-x-zeolite-methane-separation-binary-co2ch4-biogas-stream-comprehensive03165nas a2200157 4500008004100000022001400041245011300055210006900168260000800237490000600245520256000251100001702811700002602828700002402854856012902878 2025 eng d a2398-490200aBoosting the CO2 reduction activity of Cu double-atom catalysts through coordination environment engineering0 aBoosting the CO2 reduction activity of Cu doubleatom catalysts t cOCT0 v93 a

Double-atom catalysts (DACs) offer a reasonable and scalable route towards carbon neutrality owing to their efficient catalytic features. However, the challenges associated with the flexibility of their coordination structure usually restrict their full potential as efficient catalysts. Herein, we comprehensively examined the impact of coordination environment regulation on the CO2R activity of Cu2-DACs supported on C, N, or B co-doped graphene using ab initio simulations. We highlighted the marked role of the local coordination sphere of Cu2-DACs in modulating their structural stability and charge transfer characteristics, thereby regulating the adsorption of CO2 and various reaction characteristics. Notably, boron- and carbon-coordinated Cu2 centres (Cu2-BxCy) resulted in remarkably strong CO2 adsorption (-0.65 to -2.31 eV), attributed to their amplified electronic interactions with the CO2 molecule. The weak CO2 binding observed on the carbon-nitrogen- and nitrogen-boron-coordinated Cu2 centres (Cu2-NxCy and Cu2-NxBy) further highlighted the role of the coordination environment in facilitating the versatile binding modes of the key reaction species. The varying CO2 interactions in these systems were further comprehended and supported by a multilevel descriptor () combining both geometric and electronic parameters. This descriptor closely mirrored the DFT results, thereby accentuating its effectiveness as a predictive tool to perfectly model the CO2 interactions on these catalysts. Moreover, the dynamic behaviour in the adsorption modes led to partial breakdown of the conventional linear scaling relations between the key CO2 reduction intermediates (*COOH, *CO, and *HCO). Among the numerous types of investigated electrocatalysts, Cu2-B5C1 emerged as a highly active and selective catalyst for methanol production, with a remarkably low limiting potential of -0.54 V, surpassing the performance of several reported Cu-based systems. Besides, our findings underscored the often-overlooked yet crucial role of explicit solvation, which significantly altered both the potential-determining step and product selectivity. These outcomes emphasized the necessity of including solvation effects in realistic electrochemical modelling. Collectively, this study provides a critical mechanistic insight into better understanding the coordination effect on the CO2R and a robust design strategy for next-generation Cu-based DACs, guiding the development of highly efficient and selective catalysts for CO2 electroreduction.

1 aAmin, Seerat1 aKrishnamurty, Sailaja1 aDar, Manzoor, Ahmad uhttps://library.ncl.res.in/content/boosting-co2-reduction-activity-cu-double-atom-catalysts-through-coordination-environment02825nas a2200253 4500008004100000245019400041210006900235260000800304300001100312490000700323520181000330653002102140653002402161653005202185653002902237653003802266100001702304700002702321700002602348700002802374700001902402700002002421856013002441 2025 eng d00aClove essential oil-supported disposable in-tip cellulose paper (DICP) device for facile extraction of anesthetic drugs from postmortem samples: a white analytical toxicology (WAT) approach0 aClove essential oilsupported disposable intip cellulose paper DI cJUN a1020100 v453 a

A novel disposable in-tip cellulose paper (DICP) device, enhanced with clove essential oil (CEO), was developed for the extraction of four anesthetic drugs (lidocaine, prilocaine, ropivacaine, and bupivacaine) from postmortem blood and urine samples. The DICP device, equipped with 1 x 3 cm CEO-impregnated cellulose paper (CP) strips (prepared via a simple dip-coating process), is attached to a 1000 mu L micropipette. The findings from density functional theory (DFT) study reveals that CEO-impregnated cellulose demonstrates stronger and more diverse interactions with anesthetic drugs, as evidenced by more negative adsorption energy (-0.62 eV) and enhanced non-covalent interactions compared to cellulose alone. The procedure involves aspirating and dispensing diluted biological samples through the DICP device for 30 cycles, adsorbing the analytes onto the CEO-impregnated CP strips. The adsorbed analytes are subsequently eluted with 0.5 mL of ethyl acetate through 40 aspirating-dispensing cycles and analyzed by GC-MS. The method achieved limits of quantification as low as 0.01 mu g/mL, with intra-day and inter-day precisions below 10.2 % and 14.6 %, respectively, and accuracy ranging from 90.5 % to 110.7 %. Relative recoveries ranged from 66 % to 87.6 %, while matrix effects remained consistently below 11.9 %. The DICP-GC-MS method demonstrated exceptional sustainability, achieving a whiteness score of 97.2 %, underscoring its alignment with green analytical chemistry principles and operational simplicity. Applicability was demonstrated through the successful analysis of postmortem cardiac blood in a suspected anesthetic drug overdose case, highlighting its potential as a robust, high-throughput, and eco-friendly approach for routine forensic toxicological screening.

10aAnesthetic drugs10aClove essential oil10aDisposable in-tip cellulose paper (DICP) device10aGreen sample preparation10aWhite analytical toxicology (WAT)1 aJain, Rajeev1 aShivankar, Bhavana, R.1 aKrishnamurty, Sailaja1 aAl-Khateeb, Lateefa, A.1 aSheetal, Sarah1 aAlharthi, Sarah uhttps://library.ncl.res.in/content/clove-essential-oil-supported-disposable-tip-cellulose-paper-dicp-device-facile-extraction02212nas a2200277 4500008004100000022001400041245008600055210006900141260000800210300001200218490000700230520131600237653001601553653001401569653002201583653002101605653001101626100001801637700003401655700002001689700002201709700002601731700003001757700003001787856011701817 2025 eng d a1613-681000aDiamondoid all-carbon porous aromatic framework host for lithium-sulfur batteries0 aDiamondoid allcarbon porous aromatic framework host for lithiums cJUN a25003880 v213 a

Lithium-sulfur batteries (LSBs) hold incredible potential as next-generation energy storage systems. However, practical applications of LSBs are significantly hindered by several critical challenges. For the first time, scalable all-carbon porous 3D polymers (3DPs) that do not contain heteroatoms or functional groups and do not require post-functionalization are investigated as hosts in lithium-sulfur batteries, demonstrating enhanced cycling stability and overall battery performance. The pyrene-containing 3DP exhibits 75% capacity retention after 600 cycles at 1 C and 52% capacity retention after 1300 cycles at 0.2 C, better than phenyl comprising 3DP. Furthermore, even at higher sulfur loading (4.1 mg cm(-2)) with an electrolyte/sulfur ratio of 5 mu L mg(-1), pyrene 3DP displayed a high capacity of 600 mA h g(-1) and stable performance over 250 cycles with negligible capacity fade. The defined pore structure of 3DPs prevents the migration of polysulfides through physical confinement and the large pi -clouds of 3DPs interact with the negative charge-bearing polysulfides generated in charge-discharge cycles through anion-pi interaction. In this way, The design ensures that the host 3DPs interact with neutral sulfur and anionic polysulfides, resulting in an excellent performance.

10a3D polymers10aBatteries10aLi-Sulfur battery10aporous materials10apyrene1 aKumar, Viksit1 aJavaregowda, Bharathkumar, H.1 aDevasia, George1 aNarayanan, Aswini1 aKrishnamurty, Sailaja1 aKrishnamoorthy, Kothandam1 aBabu, Sukumaran, Santhosh uhttps://library.ncl.res.in/content/diamondoid-all-carbon-porous-aromatic-framework-host-lithium-sulfur-batteries03071nas a2200277 4500008004100000022001400041245013500055210006900190260000900259300001400268490000600282520203300288653002402321653002502345653003102370653003502401653005202436100002402488700002702512700002702539700001602566700002602582700003002608700002702638856012802665 2025 eng d a2574-096200aEffect of cyclization and alkyl group wrapping in visible-light-active unsymmetrical squaraine dyes for dye-sensitized solar cells0 aEffect of cyclization and alkyl group wrapping in visiblelightac cAPR  a5017-50300 v83 a

A series of alkyl group-appended indoline- and carboxylic acid-functionalized indolenine-based visible-light-active unsymmetrical squaraine dyes, SQA7-10, were designed, synthesized, and utilized for the dye-sensitized solar cells device fabrication. The number of alkyl group has been increased systematically on the indoline moiety to control the self-assembly of dyes on TiO2 and to passivate the photoanode that helps in improving the open-circuit voltage (V-OC) by avoiding the charge recombination process. SQA7-10 dyes showed an absorption between lambda(max) 536-540 nm, with molar extinction coefficients of 1.62-2.13 x 10(5) M-1 cm(-1) in CH3CN. Further, ultraviolet-visible (UV-vis) studies on TiO2 indicated the formation of H-aggregated dyes (505-510 nm), which can be controlled by appending the alkyl groups. The energy levels of the highest occupied molecular orbital (HOMO) of these dyes are well aligned with the Nernst potentials of I-/I(3)(-)electrolyte and [Cu(tmby)(2)](+/2+) electrolytes with sufficient overpotentials required for the dye regeneration process. DSSC devices made with these dyes showed systematic enhancements of open-circuit voltage (V-OC) and device efficiency with respect to alkyl group incorporation for SQA7-10 with I-/I-3(-) electrolytes. All of the SQA dyes exhibited the device V-OC of more than 805 mV, where the introduction of alkyl groups systematically enhanced the V-OC in the order of SQA7 (805 mV) < SQA8 (829 mV) < SQA9 (843 mV) < SQA10 (862 mV) without any addition of CDCA. Within the SQA dye series, SQA10 dye has achieved the highest DSSC device efficiency of 7.52% (J(sc) of 11.16 mA/cm(2), V-oc of 862 mV, and ff of 78%) with I-/I-3(-) electrolyte, whereas use of [Cu(tmby)(2)](+/2+) redox shuttle with SQA10 showed enhanced V-oc (1080 mV) and device efficiency (8.35%). The IPCE profile for the device fabricated with SQA dyes showed good response at 480 and 560 nm, which indicates the photocurrent generation from the aggregated structures.

10aaggregation of dyes10acharge recombination10aDye-sensitized solar cells10aindoline and indolenine donors10avisible-light-activeunsymmetrical squaraine dye1 aJadhav, Avinash, P.1 aSingh, Ambarish, Kumar1 aShivankar, Bhavana, R.1 aSiby, Jesna1 aKrishnamurty, Sailaja1 aKrishnamoorthy, Kothandam1 aNithyanandhan, Jayaraj uhttps://library.ncl.res.in/content/effect-cyclization-and-alkyl-group-wrapping-visible-light-active-unsymmetrical-squaraine02126nas a2200169 4500008004100000022001400041245011900055210006900174260000800243300001400251490000800265520147900273100002501752700002701777700002601804856012601830 2025 eng d a1932-744700aEffect of doping on electrocatalytic dehydrogenation and hydrogenation of methyl decalin-methyl naphthalene system0 aEffect of doping on electrocatalytic dehydrogenation and hydroge cJAN a2367-23800 v1293 a

The hydrogen economy can benefit from the use of liquid organic hydrogen carriers (LOHCs) for cross-continent hydrogen transportation in the future. However, dehydrogenation and hydrogenation of hydrogen require catalytic systems. Current research emphasizes selective Pt/Rh doping of Fe, Co, and Ni surfaces as catalysts for the dehydrogenation and hydrogenation of the methyl naphthalene-methyl decalin LOHC system, which has more than 7% hydrogen weight capacity and meets the practical requirements established by the European Union and the United States Department of Energy. Density functional theory-based computational techniques demonstrate how the chemical modification of these surfaces with a Pt and Rh single-atom catalyst (SAC) can improve the efficiency of dehydrogenation and hydrogenation. With a sustainable method, electrochemical dehydrogenation and hydrogenation on these robust surfaces produce effective hydrogen storage for extended periods without losing hydrogen. Furthermore, optimal results for the hydrogenation of 2-methyl naphthalene on Fe-Rh SAC with path-determining step (PDS) = 0.98 eV and dehydrogenation of 1-methyl decalin on Fe-Pt SAC with PDS = 1.49 eV were obtained for the most effective active sites for the enhanced electrochemical process. This study offers new possibilities for the catalytic dehydrogenation and hydrogenation of LOHC systems by highlighting the impact of doping on transition-metal-based catalysts.

1 aVerma, Tushar, Singh1 aSelvaraj, Kaliaperumal1 aKrishnamurty, Sailaja uhttps://library.ncl.res.in/content/effect-doping-electrocatalytic-dehydrogenation-and-hydrogenation-methyl-decalin-methyl02268nas a2200169 4500008004100000022001400041245015900055210006900214260000900283300001400292490000700306520158300313100002001896700002601916700002601942856013001968 2025 eng d a1463-907600aEvaluating the preferential adsorption of N2 from a binary mixture of N2/O2 on extra-framework cations of zeolites: a computational and experimental study0 aEvaluating the preferential adsorption of N2 from a binary mixtu cAPR  a7846-78570 v273 a

Separation of N2 from a N2/O2 gas mixture is critical for various industrial/medical applications. Temperature/pressure swing adsorption is the top-notch industrial technology used for this separation, where zeolites are the materials used for adsorption. Zeolite X/Y with Li+ as an extra-framework cation is the best-known sorbent for N2 gas molecules. However, the present net zero emission scenario has made lithium a critical element, making it imperative to implement its alternative in various other technologies. In this context, the present work is a computational evaluation to identify a cation that can replace Li+ for preferential adsorption of N2 over O2. The DFT study, based on parameters such as selective adsorption energies of N2 over O2 and IR stretching frequencies of the adsorbed N2 and O2 molecules, identifies Mg2+, Ca2+, Sr2+, Co2+ and Zn2+ as potential cations. These cations have preferential adsorption for N2 over O2 by 10 kJ mol-1 or more. However, BOMD simulations reveal that only Mg2+, Ca2+, Co2+ and Zn2+ keep the N2 molecule bound at 300 K and the O2 molecule gets desorbed from these frameworks. The desorption temperature of N2 on Ca2+ and Zn2+ is 350 K and on Mg2+ is 400 K. These observations are corroborated by electronic charges on cations and molecular orbitals. Significantly, Ca2+ is identified to adsorb up to 2 N2 molecules, making it an ideal candidate for N2/O2 separation in place of Li+. To validate this, we have carried out an experimental study that showed a good N2 adsorption capacity of 2.1 mmol g-1 for Ca2+.

1 aDevasia, George1 aNandanwar, Sachin, U.1 aKrishnamurty, Sailaja uhttps://library.ncl.res.in/content/evaluating-preferential-adsorption-n2-binary-mixture-n2o2-extra-framework-cations-zeolites02341nas a2200265 4500008004100000022001400041245011900055210006900174260000900243300001100252490000800263520140100271653002401672653001601696653003001712653002801742653001801770100002801788700003101816700001701847700002601864700003001890700002701920856012801947 2025 eng d a1010-603000aFar-red active squaraine dye-sensitized photoanode for dye-sensitized solar cells with a copper (II/I) electrolyte0 aFarred active squaraine dyesensitized photoanode for dyesensitiz cFEB  a1160860 v4593 a

In dye-sensitized solar cells (DSSC), controlling the dye-aggregation on TiO2 and charge recombination between electrons present in TiO2 and electrolyte can be achieved by wrapping the long alkyl groups around the dye structure and further introducing bulky donor on the dye is a potential approach to enhance both the open-circuit potential and short-circuit current parameters. Additionally, bulky donor containing dye structures modulates the photophysical and electrochemical properties of the sensitizer which helps reducing the over potentials required for the dye regeneration process by utilizing a multidentate ligand containing [Cu(tme)]2+/+ and I- /I3redox electrolytes. Hagfeldt donor appended far-red NIR active unsymmetrical squaraine dye (SQ-HF) has been designed, synthesized, and characterized. SQ-HF dye showed an intense absorption at 676 nm (epsilon 1.7 x 105 M- 1cm- 1). Photophysical and electrochemical studies indicated that the LUMO and HOMO energy levels of the SQ-HF dye were suited for charge injection (from the LUMO of the dye to the conduction band of TiO2) and dyeregeneration processes, respectively. The DSSC device efficiency of 5.15 % (JSC of 10.83 mA/cm2 and VOC of 0.690 V) has been achieved for SQ-HF dye by utilizing a literature reported [Cu(tme)]2+/+ and 4.11 % (JSC of 8.74 mA/cm2 and VOC of 0.702 V) in I- /I3- redox shuttles, respectively.

10aaggregation of dyes10aBulky donor10adye-sensitized solar cell10aPhotocurrent generation10asquaraine dye1 aNawghare, Indrajeet, S.1 aDeshmukh, Shivdeep, Suresh1 aJoshi, Krati1 aKrishnamurty, Sailaja1 aKrishnamoorthy, Kothandam1 aNithyanandhan, Jayaraj uhttps://library.ncl.res.in/content/far-red-active-squaraine-dye-sensitized-photoanode-dye-sensitized-solar-cells-copper-iii02018nas a2200229 4500008004100000022001400041245013100055210006900186260000800255490000700263520115500270653002201425653002101447653002901468653003201497653002301529653002401552653003201576100002401608700002601632856013001658 2025 eng d a1439-423500aGraphitic carbon nitride supported boron quantum dots: a transition metal free alternative for di-nitrogen to ammonia reaction0 aGraphitic carbon nitride supported boron quantum dots a transiti cMAR0 v263 a

Presently, a sustainable electrochemical Nitrogen Reduction Reaction (NRR) has been essentially found to be viable on transition metal-based catalysts. However, being cost-effective and non-corrosive, metal-free catalysts present an ideal solution for a sustainable world. Herein, through a DFT-based study, we demonstrate metal-free NRR catalysts, boron quantum dots with 13 atoms as a case study and their chemically modified counterparts when anchored on graphitic carbon nitride (g-C3N4) surface. The best catalyst among the studied, a silicon-doped boron quantum dot with a cagelike structure, is found to favour the dinitrogen to ammonia reaction pathway with a low liming potential and potential rate-determining step (PDS) of -0.11 V and 0.27 eV, respectively. The present work demonstrates as to how boron quantum dots, which are reported to be experimentally synthesised, can be exploited for ammonia synthesis when supported on the surface. These catalysts effectively suppress the HER, thus establishing its suitability as an ideal catalyst. The work also represents a futuristic pathway towards a metal-free catalyst for NRR.

10aBoron quantum dot10aElectro-catalyst10aGraphitic carbon nitride10ahydrogen evolution reaction10aLimiting potential10ametal free catalyst10aNitrogen Reduction Reaction1 aSamudre, Nikhil, S.1 aKrishnamurty, Sailaja uhttps://library.ncl.res.in/content/graphitic-carbon-nitride-supported-boron-quantum-dots-transition-metal-free-alternative-di02589nas a2200325 4500008004100000022001400041245014000055210006900195260000800264490000700272520142200279653002001701653001901721653002801740653002801768653003001796653003901826653001601865653001801881653005001899100002201949700002401971700002701995700002402022700001802046700002602064700001802090700002402108856013102132 2025 eng d a1613-681000aHot injection assisted electronically modulated twin and grain boundary rich sub-2 nm pt3co alloy resistant to phosphate ion for PEMFCs0 aHot injection assisted electronically modulated twin and grain b cMAY0 v213 a

Modulation of the electronic d-band center, structural defects (line defects), and particle size of Pt3Co alloy electrocatalyst have huge significance in elevating its electrochemical oxygen reduction reaction activity. Deviating from traditional high-temperature strategies, the current work focuses on ripening these benefits by implying a simple economically viable hot-injection-assisted modified polyol process. A conclusive control over decrementing particle size starting from 2.7 to 1.3 nm, an increasing degree of strain (twin boundary), and shifting of the d-band center away from the Fermi level are obtained via varying the temperature to which the solution is injected. The catalyst prepared via the injection at 200 degrees C (Pt3Co(1.3 t,g-b)/fVC-200) has delivered an electrochemical surface area of 84 m(2) g(Pt)(-1) with the onset and half-wave potentials of 0.980 and 0.858 V, respectively, versus RHE and a limiting current of -6.0 mA cm(-2) with stability till 20k cycles. In the high-temperature proton exchange membrane fuel cell Pt3Co(1.3 t,g-b)/fVC-200-based cell has outperformed Pt/C rendering 600 mWcm(-2) under H-2-Air compared to 529 mWcm(-2) of Pt/C with 20% lower Pt loading and double the stability due to enhanced resistance toward phosphoric acid for accelerated voltage cycling. A similar enhancement is seen while employing the catalyst for low-temperature fuel cells.

10aelectrocatalyst10agrain boundary10ahot injection synthesis10amodified polyol process10aoxygen reduction reaction10aproton exchange membrane fuel cell10aPt3Co alloy10atwin boundary10avalance band X-ray photoelectron spectroscopy1 aSingh, Mayank, U.1 aJadhav, Swapnil, D.1 aShivankar, Bhavana, R.1 aPandikassala, Ajmal1 aKumar, Yogesh1 aKrishnamurty, Sailaja1 aVinod, C., P.1 aKurungot, Sreekumar uhttps://library.ncl.res.in/content/hot-injection-assisted-electronically-modulated-twin-and-grain-boundary-rich-sub-2-nm-pt3co02247nas a2200277 4500008004100000022001400041245012000055210006900175260000800244300001400252490000700266520131300273653002001586653002401606653002501630653001401655653001101669653001401680100002401694700002901718700002201747700002201769700002601791700002001817856013201837 2025 eng d a2155-543500aHybrid pincer (PNN)Ni(II) complex catalyzed selective C-H alkylation of pyridones using unactivated alkyl chlorides0 aHybrid pincer PNNNiII complex catalyzed selective CH alkylation  cFEB a2987-29990 v153 a

The use of readily accessible unactivated alkyl chlorides in the alkylation reaction to install valuable alkyl and methyl motifs into privileged heterocycles is an underdeveloped area. Herein, we report the regioselective C-H alkylation of diverse pyridones employing challenging unactivated alkyl chlorides as coupling partners, enabled by a strategically developed quinolinyl-based pincer (Ph2PNNQ)Ni(II) complex. The air-stable nickel catalyst is highly effective for the selective alkylation of functionalized 2-pyridones with both primary and secondary alkyl chlorides as well as for the unexpected C6 methylation, furnishing a wide range of 6-alkyl-2-pyridone scaffolds (78 examples). Remarkably, the alkyls bearing biologically and pharmacologically significant motifs, such as pterostilbene, nonyl phenol, sesamol, estrone, vitamin E, stigmasterol, cholesterol, and diosgenin, were compatible under this catalytic approach. The insights into the mechanism suggest that the alkylation reaction follows a Ni(II)/Ni(III)/Ni(IV) pathway involving the crucial two-step, one-electron oxidative addition of alkyl chloride. Several control studies, kinetics, and EPR analyses were performed to understand the detailed reaction pathway, further supported by density functional theory calculations.

10aalkyl chlorides10aC-H/C-Cl activation10ahybrid pincer ligand10aMechanism10aNickel10apyridones1 aVerma, Suryadev, K.1 aSamal, Pragnya, Paramita1 aPradhan, Chandini1 aPandey, Dilip, K.1 aKrishnamurty, Sailaja1 aPunji, Benudhar uhttps://library.ncl.res.in/content/hybrid-pincer-pnnniii-complex-catalyzed-selective-c-h-alkylation-pyridones-using-unactivated02891nas a2200313 4500008004100000022001400041245016200055210006900217260000800286300001400294490000700308520176200315653003302077653002402110653001402134653002502148653001302173653004502186653003402231100003002265700001802295700002002313700002502333700002002358700001802378700002602396700002402422856013102446 2025 eng d a1944-824400aHydrogel electrolyte-mediated in situ Zn-anode modification and the Ru-RuO2/NGr-coated cathode for high-performance solid-state rechargeable Zn-air batteries0 aHydrogel electrolytemediated in situ Znanode modification and th cJAN a3188-32040 v173 a

This work aims to deal with the challenges associated with designing complementary bifunctional electrocatalysts and a separator/membrane that enables rechargeable zinc-air batteries (RZABs) with nearly solid-state operability. This solid-state RZAB was accomplished by integrating a bifunctional electrocatalyst based on Ru-RuO2 interface nanoparticles supported on nitrogen-doped (N-doped) graphene (Ru-RuO2/NGr) and a dual-doped poly(acrylic acid) hydrogel (d-PAA) electrolyte soaked in KOH with sodium stannate additive. The catalyst shows enhanced activity and stability toward the two oxygen reactions, i.e., oxygen reduction and evolution reactions (ORR and OER), with a very low potential difference (Delta E) of 0.64 V. The computational insights bring out the electronic factors contributing to the enhanced catalytic activity of Ru-RuO2/NGr based on the charge density difference (CDD) between the interfaces. The disadvantages of the existing solid-state RZABs, such as their limited lifespan brought on by passivation, dendritic growth, corrosion, and shape change, have also been taken into account. The introduction of the stannate additive to the electrolyte induced an in situ Zn-anode modification, which subsequently improved the interfacial stability of the ZABs and, hence, the battery life cycles. The experimental observations reveal that, during the charging process, the Sn nanoparticles enable the homogeneous Zn deposition on the surface of the anode. Thus, the in situ Zn-anode surface modification assisted in achieving a high-rate cycle capability, viz., the homemade catalyst-based system exhibited continuous charge-discharge cycles for 20 h at a current density of 2.0 mA cm-2, with each cycle lasting for 5 min.

10aBifunctional Electrocatalyst10aCore-ShellStructure10aDFT study10aelectrolyte additive10aHydrogel10asolid-state rechargeable zinc-airbattery10aX-ray absorption spectroscopy1 aKharabe, Geeta, Pandurang1 aVerma, Tushar1 aBarik, Sidharth1 aUrkude, Rajashri, R.1 aAyasha, Nadeema1 aGhosh, Biplab1 aKrishnamurty, Sailaja1 aKurungot, Sreekumar uhttps://library.ncl.res.in/content/hydrogel-electrolyte-mediated-situ-zn-anode-modification-and-ru-ruo2ngr-coated-cathode-high01914nas a2200229 4500008004100000022001400041245012900055210006900184260000900253300001100262490000800273520114500281653000901426653001901435653000801454653000801462653000801470100002701478700002501505700002601530856012801556 2025 eng d a0360-319900aIn silico designing of electrocatalysts for hydrogen evolution reaction: a focus on titanium metal-based diboride monolayers0 aIn silico designing of electrocatalysts for hydrogen evolution r cJUN  a91-1000 v1333 a

Enhancing the efficiency of Hydrogen Evolution Reaction (HER) using chemically modified electrocatalytic titanium diboride surfaces with transition metal-based Single Atom Catalysts (SACs) is illustrated using Density Functional Theory (DFT) based methods employing solvent effects. With higher surface concentrations of nonmetal boron rather than titanium metal, these highly conductive, extremely hard, chemically, and thermally stable electrocatalysts are more cost-effective and superior to their MBene analogs. A systematic analysis of these transition metal-based SACs from the 3d, 4d, and 5d groups embedded in TiB2 monolayer for its HER activity reveals the reduction in limiting potential. As the most effective SAC for improved HER, Zn@TiB2 SAC has a limiting potential of 0.08 eV in acidic and 0.21 eV in alkaline media. The higher exchange current density of Zn@TiB2 (5.74 x 10-5 A cm-2), which exceeds most previously reported electrocatalysts, indicates exceptional HER performance. This work shows that transition metal boride electrocatalysts are economically viable for HER and pave a path for experimentalists.

10aAIMD10aD -band center10aDFT10aHER10aSAC1 aShivankar, Bhavana, R.1 aVerma, Tushar, Singh1 aKrishnamurty, Sailaja uhttps://library.ncl.res.in/content/silico-designing-electrocatalysts-hydrogen-evolution-reaction-focus-titanium-metal-based02257nas a2200265 4500008004100000022001400041245008600055210006900141260000900210490000700219520138700226653001601613653001501629653003901644653002001683653001201703100001701715700002201732700002901754700002201783700002501805700002601830700002001856856011501876 2025 eng d a1864-563100aIntegrated flue gas CO2 capture and conversion to formate: a sustainable approach0 aIntegrated flue gas CO2 capture and conversion to formate a sust cDEC 0 v183 a

Industrial CO2 emissions, characterized by dilute streams and impurity complexity, demand energy-efficient mitigation strategies beyond conventional capture technologies. Here, an integrated CO2 capture and conversion (ICCC) system is reported employing a heterogenized iridium catalyst-hydroxyquinoline-ligated Cp*Ir-Cl immobilized on amine-functionalized silica-that directly converts CO2 from synthetic flue gas containing SOx, NOx, and O2 to formate with 100% selectivity. The catalyst delivers remarkable activity, achieving turnover numbers up to 10,286 within 16 h. Density functional theory reveals that its square pyramidal geometry, induced by the hydroxyquinoline ligand, enhances Ir-N(ring) bond strength and electronic delocalization, thereby improving hydration energy, structural robustness, and catalytic efficiency. Importantly, the catalyst system demonstrates excellent durability, maintaining full activity over five regeneration cycles. Hydrogenation in a 1 M DABCO medium, followed by thermal decomposition of the amine-formate adduct at 150 degrees C, enables efficient lean amine regeneration, allowing subsequent flue gas capture and formate production without performance loss. This closed-loop strategy delivers a sustainable, contaminant-tolerant, and recyclable CO2-to-formate platform with strong promise for scalable industrial deployment.

10aCO2 capture10aflue gases10aintegrated capture and conversions10anet zero future10aRecycle1 aKumar, Rohit1 aMajumder, Supriyo1 aSingh, Chadrodai, Pratap1 aSamanta, Chanchal1 aNewalkar, Bharat, L.1 aKrishnamurty, Sailaja1 aDas, Raj, Kumar uhttps://library.ncl.res.in/content/integrated-flue-gas-co2-capture-and-conversion-formate-sustainable-approach02974nas a2200253 4500008004100000022001400041245015100055210006900206260000800275300001400283490000600297520205900303653001902362653002502381653001302406653001902419653002102438100002402459700002902483700002002512700002602532700003002558856013202588 2025 eng d a2637-610500aLong cycling stability imparted to li-ion batteries by conjugated polymers with low dihedral angles and high electron density on functional groups0 aLong cycling stability imparted to liion batteries by conjugated cJUN a7719-77280 v73 a

In conjugated polymers, dihedral angles at bonds connecting their monomers impact the polymers' properties such as the packing of the polymer chains, bandgap, and conductivity. These properties are expected to impact the performance of rechargeable Li-ion batteries because the Li-ion transport and conductivity of the polymers are two important parameters. To understand this, we designed and synthesized two polymers with two different dihedral angles. The polymer, Poly(EDOT-DPP), comprising diketopyrrolopyrrole (DPP) and ethylenedioxythiophene (EDOT) as monomers, showed a low dihedral angle of 2 degrees. On the other hand, the polymer, Poly(EDOT-i-Ind), comprising EDOT and i-Indigo (i-Ind) showed a dihedral angle of 17 degrees. Density functional theory (DFT) studies showed that the electron density at the carbonyl moiety of EDOT-DPP is higher than that of EDOT-i-Ind. This resulted in a higher Li+ binding energy of -3.665 eV for EDOT-DPP and a lower Li+ binding energy of -3.464 eV for EDOT-i-Ind. Battery electrodes were fabricated using either Poly(EDOT-DPP) or Poly(EDOT-i-Ind) with multiwalled carbon nanotubes as conducting fillers in the absence of any binders. The Li+ ion diffusion coefficient ( D Li + ) measured for the as prepared batteries based on Poly(EDOT-DPP) was found to be 3.9 x 10-19 cm2/s, which is slightly higher than that found for Poly(EDOT-i-Ind). However, after 2000 cycles, the D Li + increased by about two orders of magnitude for both polymers. Due to the low dihedral angle in the case of Poly(EDOT-DPP), the D Li + was found to be 21% higher than that of Poly(EDOT-i-Ind). The higher binding of Li+ ions with Poly(EDOT-DPP) and Li+ ion diffusion improved the specific capacity and cycling performance of batteries fabricated with this polymer. At a current density of 0.2 A/g, Poly(EDOT-DPP) showed a 39% higher specific capacity than the Poly(EDOT-i-Ind) polymer after 2000 cycles. The batteries also showed stable performance over 2000 cycles with an insignificant decrease in specific capacity.

10adihedral angle10adiketopyrrolopyrrole10ai-indigo10aLi-ion battery10aLi-ion transport1 aKargude, Radhakisan1 aSrinivasalu, Hari, Haran1 aDevasia, George1 aKrishnamurty, Sailaja1 aKrishnamoorthy, Kothandam uhttps://library.ncl.res.in/content/long-cycling-stability-imparted-li-ion-batteries-conjugated-polymers-low-dihedral-angles-and01994nas a2200229 4500008004100000022001400041245010000055210006900155260000800224300001100232490000800243520116600251653001701417653003601434653003201470653004401502653002401546100002501570700001801595700002601613856012501639 2025 eng d a0016-236100aMimicking characteristics of cast iron for enhanced electrocatalytic dehydrogenation of methane0 aMimicking characteristics of cast iron for enhanced electrocatal cFEB a1336740 v3813 a

Enhancing the efficiency of methane dehydrogenation through chemical modification of electrocatalytic iron surfaces with impurities that resemble cast iron properties is demonstrated computationally using Density Functional Theory methodologies. Investigating methane dehydrogenation on thermally stable Fe surfaces with discrete planes and anchoring impurities such as Al, C, and Si minimized reduction barriers. Electrochemical treatment of methane on these robust surfaces yields clean hydrogen and carbon-based compounds, such as carbon nanomaterials and carbon black. As for the most efficient active sites for enhanced methane dehydrogenation, the active plane 100 with 5.5 % C impurities and 0.51 eV reduction barrier is determined to be the most dependable, followed by the active plane 110 with 5.5 % Si impurities and the lower 0.98 eV reduction barrier. Utilizing CI-NEB (Nudged Elastic Band), the dissociation barrier investigation established the electrolytic catalysts' performance. This work paves the way for experimentalists and demonstrates the economic viability of Fe-based catalysts for the Catalytic Dehydrogenation of Methane.

10acarbon black10aDensity Functional Theory (DFT)10aDry methane reforming (DMR)10aElectrochemical methane dehydrogenation10aFe surface catalyst1 aVerma, Tushar, Singh1 aDevi, Nandini1 aKrishnamurty, Sailaja uhttps://library.ncl.res.in/content/mimicking-characteristics-cast-iron-enhanced-electrocatalytic-dehydrogenation-methane02238nas a2200193 4500008004100000022001400041245013300055210006900188260000800257300001400265490000700279520150900286100002201795700002001817700002901837700002601866700002001892856013201912 2025 eng d a2044-475300asyn-Selective hydrosilylation and hydroboration of alkynes at room temperature catalyzed by a phosphine-free (NNN)Fe(ii) complex0 asynSelective hydrosilylation and hydroboration of alkynes at roo cNOV a6716-67250 v153 a

Catalytic hydrofunctionalization of alkynes is the ideal and atom-economical route to synthesize vinylsilanes and vinylboronates, which are valuable organic building blocks. However, the process suffers from using expensive phosphine-ligated catalysts, sensitive organometallic activators, and elevated reaction temperatures. To overcome these challenges, herein, we developed a series of phosphine-free (NNN)-ligated iron complexes and demonstrated their potential as efficient catalysts for the hydrosilylation and hydroboration of both internal and terminal alkynes using NaOtBu as an activator. The reactions proceeded smoothly using 1.5 mol% catalyst loading at room temperature and provided syn-selective vinylsilanes and vinylboronates. This hydrofunctionalization exclusively delivered mono-silylated and mono-borylated vinyls with tolerance of sensitive functionalities. At the same time, terminal alkynes provided excellent anti-Markovnikov selectivity with thermodynamically feasible beta-(E)-vinylsilanes and beta-(E)-vinylboronates. The presence of an N-H moiety in the ligand backbone is crucial in generating an Fe(ii) active catalyst and facilitating the catalytic process. Mechanistic investigations, including controlled reactions and external additive experiments, were performed to propose a redox-neutral reaction mechanism with iron maintaining its +2 oxidation state throughout the cycle. The DFT energy calculations unanimously support the proposed reaction mechanism.

1 aPradhan, Chandini1 aDubey, Shivansh1 aSamal, Pragnya, Paramita1 aKrishnamurty, Sailaja1 aPunji, Benudhar uhttps://library.ncl.res.in/content/syn-selective-hydrosilylation-and-hydroboration-alkynes-room-temperature-catalyzed-phosphine02418nas a2200277 4500008004100000022001400041245015000055210006900205260000800274300001400282490000700296520143000303653002501733653001401758653002101772653002701793653002601820653001401846100002201860700001801882700002201900700003501922700002601957700002501983856013202008 2025 eng d a1944-824400aUnlocking enhanced redox dynamics: the power of a bifunctional catalytic zinc phosphide interface in full cell and pouch lithium-sulfur batteries0 aUnlocking enhanced redox dynamics the power of a bifunctional ca cJAN a7657-76690 v173 a

Lithium-sulfur (Li-S) batteries face significant challenges, such as polysulfide dissolution, sluggish reaction kinetics, and lithium anode corrosion, hindering their practical application. Herein, we report a highly effective approach using a zinc phosphide (ZnP2) bifunctional catalyst to address these issues. The ZnP2 catalyst effectively anchors lithium polysulfides (LiPSs), catalytically reactivates them, and enhances lithium-ion diffusion. Utilizing a ZnP2-modified separator in a Li-S half-cell achieves an impressive initial capacity of 1145.4 mAh g-1, retaining 954 mAh g-1 and 99.8% Coulombic efficiency after 100 cycles, compared to the pristine separator. The underlying reaction mechanisms are thoroughly investigated through post-mortem analyses and density functional theory (DFT) calculations. Moreover, a Li-S full cell with an E/S ratio of 10 mu L mg-1 demonstrates stable cycling performance, achieving an initial capacity of 797.5 and 534 mAh g-1 after 100 cycles at 0.1C, with a negative-to-positive mass ratio of 3:1. Additionally, the real-world feasibility of lightweight and flexible Li-S pouch batteries with ZnP2-modified separators is explored, showing a stable performance over 100 cycles at 0.1C with 80% capacity retention. This engineered separator can be integrated with advanced sulfur cathodes to create high-energy-density, stable Li-S batteries for commercial applications.

10acatalytic interlayer10afull cell10alithium dendrite10alithium sulfur battery10apolysulfide shuttling10apouchcell1 aDas, Anoushka, K.1 aYadav, Poonam1 aVerma, Tushar, S.1 aMarulasiddappa, Thripuranthaka1 aKrishnamurty, Sailaja1 aShelke, Manjusha, V. uhttps://library.ncl.res.in/content/unlocking-enhanced-redox-dynamics-power-bifunctional-catalytic-zinc-phosphide-interface-full01955nas a2200181 4500008004100000022001400041245008700055210006900142260000800211300001400219490000700233520132300240100002901563700001901592700002601611700001901637856011701656 2026 eng d a1463-907600aCO2, N2 and H2 adsorption in Zn2+-containing zeolites and metal-organic frameworks0 aCO2 N2 and H2 adsorption in Zn2containing zeolites and metalorga cFEB a5161-51740 v283 a

We employ a chemically accurate (+/- 4 kJ mol-1) embedding approach to calculate enthalpies for CO2, N2, and H2 adsorption in the Zn2+-containing zeolites FAU and CHA, and for CO2 and H2 in the metal-organic frameworks (MOFs) Zn-MOF-74 and CALF-20. Using MP2 as the high-level method and PBE+D4 as the periodic low-level method (MP2:PBE+D4), we obtain CO2 adsorption enthalpies of -46, -34, and -36 kJ mol-1 for Zn-CHA, Zn-MOF-74, and CALF-20, respectively, all within chemical accuracy limits of the experimental values of -42, -30, and -39 kJ mol-1. For CO2 in Zn-FAU, where no experimental data exist, we provide an MP2:PBE+D4 prediction of -49 kJ mol-1. For N2, we predict MP2:PBE+D4 adsorption enthalpies of -41 and -39 kJ mol-1 in Zn-CHA and Zn-FAU, respectively. CO2 adsorption is stronger in the zeolites than in the studied MOFs. Across all systems, CO2 adsorption tends to be stronger than N2 adsorption and both are largely favoured over H2. We observe inconsistent accuracy of PBE+D4 for the two MOFs, despite their similar characteristics, underscoring the need for high-level approaches in predictive screening. Additionally, we conclude that Zn2+ cations with open coordination sites act as the primary binding sites and that these cations preferentially occupy 6-membered rings in zeolites.

1 aSamal, Pragnya, Paramita1 aBerger, Fabian1 aKrishnamurty, Sailaja1 aSauer, Joachim uhttps://library.ncl.res.in/content/co2-n2-and-h2-adsorption-zn2-containing-zeolites-and-metal-organic-frameworks02744nas a2200205 4500008004100000022001400041245016100055210006900216260000900285300001400294490000700308520194100315100002702256700002102283700003002304700002602334700002602360700002102386856013102407 2026 eng d a1477-922600aDual-functional phosphomolybdic acid-polypyrrole-ionic liquid nanocomposites for energy storage and hydrogen evolution: experimental and theoretical studies0 aDualfunctional phosphomolybdic acidpolypyrroleionic liquid nanoc cJAN  a1455-14720 v553 a

Recent advancements in pseudocapacitive materials for energy storage and catalytic activities highlight the benefits of incorporating nanostructured active materials. This study investigates the modification of polypyrrole (PPy) surfaces using polyoxometalate H4[PVMo11O40].xH2O (PVMo11) combined with ionic liquids hexadecyltrimethylammonium chloride (CTAC) and 1-benzyl-3-methylimidazolium chloride (BMI). Among various synthesized nanocomposites, PVMo11-BMI-PPy demonstrated superior electrochemical properties in a 0.25 M H2SO4 aqueous electrolyte, achieving a remarkable specific capacitance of 400 F g-1, an energy density of 49.5 W h kg-1 and a power density of 906 W kg-1 at a current density of 1 A g-1. It achieves a capacitive contribution of 94.5% at 10 mV s-1 with an impressive cyclic retention rate of 91.1% and a coulombic efficiency of 98.9% after 10 000 GCD cycles. Additionally, PVMo11-BMI-PPy exhibited outstanding electrocatalytic activity for hydrogen evolution reaction (HER), achieving the highest catalytic activity of 19 mV at a current density of 10 mA cm-2, outperforming the benchmark Pt catalyst. Its superior performance is underscored by a high TOF of 6.91 x 10-7 s-1 and excellent long-term stability in 0.5 M H2SO4 over 24 hours. It is a promising candidate for bifunctional activities such as energy storage and catalytic applications. Additionally, density functional theory (DFT) studies were conducted to gain insights into the enhanced performance of PVMo11-BMI-PPy. The thermodynamic and electronic characteristics indicate that the V site of PVMo11-BMI-PPy offers the most efficient and balanced catalytic environment for hydrogen evolution reaction (HER) compared with all other sites examined. These theoretical findings align well with experimental observations, demonstrating superior HER activity of the PVMo11-BMI-PPy catalyst, thereby confirming the computational predictions.

1 aAnees, Muhammed, P. K.1 aIniyan, Selvaraj1 aSingh, Chandrodai, Pratap1 aKathiresan, Murugavel1 aKrishnamurty, Sailaja1 aMal, Sib, Sankar uhttps://library.ncl.res.in/content/dual-functional-phosphomolybdic-acid-polypyrrole-ionic-liquid-nanocomposites-energy-storage02195nas a2200265 4500008004100000022001400041245011700055210006900172260000800241490000700249520126700256653001201523653000801535653002401543653001801567653001401585100002901599700003401628700002901662700002001691700002601711700003001737700003001767856013201797 2026 eng d a1613-681000aOrthogonally Engineered Redox-Active Polyimide-Carbon Nanotube Hybrids for Long-Life Lithium-Ion Battery Cathode0 aOrthogonally Engineered RedoxActive PolyimideCarbon Nanotube Hyb cJAN0 v223 a

The diverse structural tunability and engineered electronic properties of organic polymers have sparked significant interest in their use as cathode materials for lithium-ion storage. Recent advances suggest that organic cathodes can serve as promising alternatives to conventional metal oxide counterparts due to their elemental abundance, safety, and high theoretical capacity. However, developing cathode materials that simultaneously exhibit high specific capacity, long cycle life, and excellent rate performance remains a critical challenge. In this study, the synthesis and application of a redox-active polyimide based on orthogonally positioned, active site-rich mellitic trianhydride (MTA) and naphthalene diimide (NDI), integrated with multi-walled carbon nanotubes (MWCNTs), referred to as MTA-NDI@CNT are reported. The pristine MTA-NDI polymer demonstrates a specific capacity of 60 mAh g-1 at a current density of 200 mA g-1 and exhibits remarkable cycling stability over 20 000 cycles. Upon hybridisation with CNT (10 wt.%), the composite (MTA-NDI@CNT) delivers a nearly threefold enhancement in specific capacity, reaching 170 mAh g-1 at 500 mA g-1, along with stable cycling performance over 1300 cycles and 60.5% capacity retention.

10acathode10aCNT10alithium-ion battery10aorthogonality10aPolyimide1 aThanasekar, Chandragopal1 aJavaregowda, Bharathkumar, H.1 aVeer, Sairam, Dnyaneshwa1 aDevasia, George1 aKrishnamurty, Sailaja1 aKrishnamoorthy, Kothandam1 aBabu, Sukumaran, Santhosh uhttps://library.ncl.res.in/content/orthogonally-engineered-redox-active-polyimide-carbon-nanotube-hybrids-long-life-lithium-ion02691nas a2200289 4500008004100000022001400041245019800055210006900253260000800322490000700330520153400337653002401871653004501895653003601940653004601976100004002022700002602062700002402088700003302112700001702145700002902162700001702191700002302208700002602231700002402257856012002281 2026 eng d a1614-683200aSelf-healing hydrogel electrolyte enabled by dynamic polar covalent and noncovalent interactions for high-performance rechargeable zinc-metal batteries: a leap toward sustainable energy storage0 aSelfhealing hydrogel electrolyte enabled by dynamic polar covale cJAN0 v163 a

Hydrogel polymer electrolytes with superior multifunctional properties are promising alternatives to aqueous electrolytes for resolving interfacial issues in rechargeable zinc-metal batteries. In this study, an intrinsic self-healing hydrogel polymer electrolyte (PHBC-4) is synthesized, engineered through an integrated approach involving the polar covalent (B & horbar;O bond), hydrogen-bond (polyvinyl alcohol-hydroxypropyl methylcellulose interface), and coordination-type (Zn & horbar;O) interactions to enable self-healing functionality. The PHBC-4 has demonstrated high ionic conductivity (4.6 x 10-2 S cm-1), good oxidative stability (2.3 V vs Zn|Zn2+), a high cation transference number (0.89), superior tensile strength (0.32 MPa), and an impressive healing efficiency of 93% achieved just within 5 min, confirming its robust self-healing capability. In Zn||Zn symmetric cells, it effectively suppresses dendrite growth, ensuring stable cycling for over 1032 h with an areal capacity of 1.0 mAh cm-2 at a current density of 1.0 mA cm-2. When paired with a Zn-doped MnO cathode in the rechargeable homemade pouch cell, the system delivers a high specific capacity of 160 mAh g-1 at 0.10 A g-1 and cycling stability up to 493 charge-discharge cycles at 2.0 A g-1. The self-healing ability of PHBC-4 HGPE is confirmed in a homemade pouch cell via OCV and charge-discharge tests, demonstrating stable performance. The DFT studies confirm molecular-level interactions within the hydrogel heterostructure.

10adendrite inhibition10aflexible rechargeable zinc metal battery10ahigh cation transference number10aself-healing hydrogel polymer electrolyte1 aPuthiyaveetil, Priyanka, Pandinhare1 aKurian, Rachna, Maria1 aSamudre, Nikhil, S.1 aBalasubramanian, Rajalakshmi1 aTorris, Arun1 aPockil, Fayis, Kanheeram1 aBhat, Suresh1 aAjithkumar, T., G.1 aKrishnamurty, Sailaja1 aKurungot, Sreekumar uhttps://library.ncl.res.in/content/self-healing-hydrogel-electrolyte-enabled-dynamic-polar-covalent-and-noncovalent02223nas a2200241 4500008004100000022001400041245009300055210006900148260000800217300001400225490000700239520137500246653001501621653001601636653002101652653003201673653004501705653003101750100002401781700002901805700002601834856012101860 2026 eng d a2168-048500aSilico imine-based ligand engineering of CALF-20 for electrocatalytic ammonia production0 aSilico iminebased ligand engineering of CALF20 for electrocataly cAPR a7217-72280 v143 a

Electrocatalytic ammonia synthesis is emerging as a globally compelling, sustainable alternative to the Haber-Bosch process under ambient conditions. As a result, active-site engineering has taken center stage in the development of stable and effective electrocatalysts. In this work, we report how the introduction of an imine group in the ligand backbone of CALF-20, a Zn-based, moisture-stable MOF with high surface area, results in the formation of an N-4 macrocycle for transition-metal anchoring. PBE + D3 calculations, supported by spectroscopic, ab initio molecular dynamics, and electronic analyses, identify Fe-bound modified CALF-20 as the most stable configuration among the Mn-, Fe-, Co-, Ni-, Cu-, Ru-, Rh-, Ag-, and Au-anchored within the modified CALF-20 framework. Upon modification, the d-band center shifts from -5.08 to -4.44 eV in M-Fe-CALF-20. Adsorption studies confirm activation of both N-2 and NO2, reflected by bond elongation and red-shifted IR peaks. Mechanistic studies show that M-Fe-CALF-20 selectively facilitates NH3 formation, exhibiting PDS values of 0.69 and 0.62 eV for the NRR and NO2RR, respectively, while a competitive adsorption shows a clear preference over HER. Our study illustrates how functionalization tunes CALF-20 for dual application as an adsorbent and as an electrocatalyst for NH3 synthesis and storage.

10aAdsorption10aCALF-20 MOF10aelectrocatalysis10ahydrogen evolution reaction10anitrogen oxide reductionreaction (NO2RR)10anitrogen reductionreaction1 aSamudre, Nikhil, S.1 aSamal, Pragnya, Paramita1 aKrishnamurty, Sailaja uhttps://library.ncl.res.in/content/silico-imine-based-ligand-engineering-calf-20-electrocatalytic-ammonia-production