02781nas 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<p>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.</p>
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-surface03405nas 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<p>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.</p>
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<p>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.</p>
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<p>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.</p>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<p>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.</p>
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<p>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.</p>1 aJoshi, Krati1 aMaibam, Ashakiran1 aKrishnamurty, Sailaja  uhttps://library.ncl.res.in/content/finite-temperature-behavior-carbon-atom-doped-silicon-clusters-depressed-thermal-stabilities02742nas 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<p><span style="color: rgb(33, 33, 33); font-family: BlinkMacSystemFont, -apple-system, &quot;Segoe UI&quot;, Roboto, Oxygen, Ubuntu, Cantarell, &quot;Fira Sans&quot;, &quot;Droid Sans&quot;, &quot;Helvetica Neue&quot;, sans-serif; font-size: 16px; font-style: normal; font-variant-ligatures: normal; font-variant-caps: normal; font-weight: 400;">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 N</span><span style="box-sizing: inherit; font-size: 12px; line-height: 0; position: relative; bottom: -0.25em; color: rgb(33, 33, 33); font-family: BlinkMacSystemFont, -apple-system, &quot;Segoe UI&quot;, Roboto, Oxygen, Ubuntu, Cantarell, &quot;Fira Sans&quot;, &quot;Droid Sans&quot;, &quot;Helvetica Neue&quot;, sans-serif; font-style: normal; font-variant-ligatures: normal; font-variant-caps: normal; font-weight: 400;">2</span><span style="color: rgb(33, 33, 33); font-family: BlinkMacSystemFont, -apple-system, &quot;Segoe UI&quot;, Roboto, Oxygen, Ubuntu, Cantarell, &quot;Fira Sans&quot;, &quot;Droid Sans&quot;, &quot;Helvetica Neue&quot;, sans-serif; font-size: 16px; font-style: normal; font-variant-ligatures: normal; font-variant-caps: normal; font-weight: 400;">. 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.</span></p>1 aMaibam, Ashakiran1 aKrishnamurty, Sailaja  uhttps://library.ncl.res.in/content/nitrogen-activation-reduction-recyclable-v-sacbn-graphene-heterocatalyst-sifted-through-dual02002nas a2200241   4500008004100000022001400041245010600055210006900161260000800230300001100238490000800249520116900257653002101426653000801447653002101455653003201476653002201508653002901530100002201559700002501581700002901606856012501635       2022                        eng d  a0169-433200aDoped 2D VX2 (X = S, Se, Te) monolayers as electrocatalysts for ammonia production: a DFT based study0 aDoped 2D VX2 X S Se Te monolayers as electrocatalysts for ammoni  cNOV  a1544010 v6023 a<p>
	Electrocatalytic nitrogen fixation under ambient conditions on vanadium dichalcogenides (VX2) with non-metal dopants has been explored herein. Understanding the interface chemistry, inherent electronic and acute synergistic nature of non-metal dopants on two unique phases of VX2 has been meticulously explored through a scrutiny of several non-metal atoms as catalytic centers. The efficacity of N-2 chemisorption and N-N bond activation has been implemented as crucial parameters to realize boron and carbon doped VX2 monolayers to be electrocatalytically active for nitrogen reduction reaction (NRR). Detailed investigation on the NRR mechanism brings out the pivotal role of thermodynamic favourability for product formation obtained from Gibbs free energy differences. The charge transfer on N and pi-pi* orbital hybridization and electron ``donor-acceptor `` mechanism between the non-metal and N-2 has been found to modulate the electrocatalytic barrier for NRR on VX2 monolayers. This study proposes boron doped VS2 as an efficient chemically feasible, earth abundant sustainable electrocatalyst for NRR with an overpotential as low as 0.06 eV.</p>
10a1T and 2H phases10aDFT10aelectrocatalysts10aNitrogen Reduction Reaction10aNon metal dopants10aVanadium dichalcogenides1 aMaibam, Ashakiran1 aBabaRao, Ravichandar1 aKrishnamurty, Sailaj, A.  uhttps://library.ncl.res.in/content/doped-2d-vx2-x-s-se-te-monolayers-electrocatalysts-ammonia-production-dft-based-study02535nas a2200277   4500008004100000245020600041210006900247260000800316300001200324490000600336520152200342653001501864653002501879653001901904653002101923653002301944653002001967100002901987700002202016700001902038700001802057700002502075700001902100700001902119856011902138       2022                        eng d00aHigh-alkaline water-splitting activity of mesoporous 3D heterostructures: an amorphous-shell@crystalline-core nano-assembly of Co-Ni-phosphate ultrathin-nanosheets and V- doped cobalt-nitride nanowires0 aHighalkaline watersplitting activity of mesoporous 3D heterostru  cAUG  a22013110 v93 a<p>
	Introducing amorphous and ultrathin nanosheets of transition bimetal phosphate arrays that are highly active in the oxygen evolution reaction (OER) as shells over an electronically modulated crystalline core with low hydrogen absorption energy for an excellent hydrogen evolution reaction (HER) can boost the sluggish kinetics of the OER and HER in alkaline electrolytes. Therefore, in this study, ultrathin and amorphous cobalt-nickel-phosphate (CoNiPOx) nanosheet arrays are deposited over vanadium (V)-doped cobalt-nitride (V-3%-Co4N) crystalline core nanowires to obtain amorphous-shell@crystalline-core mesoporous 3D-heterostructures (CoNiPOx@V-Co4N/NF) as bifunctional electrocatalysts. The optimized electrocatalyst shows extremely low HER and OER overpotentials of 53 and 270 mV at 10 mA cm(-2), respectively. The CoNiPOx@V-3%-Co4N/NF (+/-) electrolyzer utilizing the electrocatalyst as both anode and cathode demonstrates remarkable overall water-splitting activity, requiring a cell potential of only 1.52 V at 10 mA cm(-2), 30 mV lower than that of the RuO2/NF (+)/20%-Pt/C/NF (-) electrolyzer. Such impressive bifunctional activities can be attributed to abundant active sites, adjusted electronic structure, lower charge-transfer resistance, enhanced electrochemically active surface area (ECSA), and surface- and volume-confined electrocatalysis resulting from the synergistic effects of the crystalline V-3%-Co4N core and amorphous CoNiPOx shells boosting water splitting in alkaline media.</p>
10acore-shell10ahydrogen productions10ametal nitrides10ametal phosphates10asynergistic effect10awater-splitting1 aSingh, Thangjam, Ibomcha1 aMaibam, Ashakiran1 aCha, Dun, Chan1 aYoo, Sunghoon1 aBabaRao, Ravichandar1 aLee, Sang, Uck1 aLee, Seunghyun  uhttps://library.ncl.res.in/content/high-alkaline-water-splitting-activity-mesoporous-3d-heterostructures-amorphous01582nas 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<p>
	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.</p>
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-case02241nas 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-effective02388nas 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<p>
	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.</p>
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-and03709nas a2200229   4500008004100000245010900041210006900150260000800219300001400227490000600241520291400247100002103161700001903182700002903201700002203230700002203252700002003274700002103294700001803315700001903333856012703352       2023                        eng d00aCritical review on amorphous-crystalline heterostructured electrocatalysts for efficient water splitting0 aCritical review on amorphouscrystalline heterostructured electro  cDEC  a6254-62800 v73 a<p>
	Introducing complementary active materials in tandem as heterostructures of various shapes and sizes can significantly improve the physicochemical properties of the developed materials. Recently, the use of amorphous materials in conjunction with crystalline moieties as highly efficient electrocatalysts for water-splitting electrolyzers has surged rapidly. Excellent bifunctional activity for hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) can be achieved from amorphous-crystalline-based materials owing to their remarkably conductive crystalline phase as well as their long-range disordered amorphous phase. In addition, the high specific surface area, disordered structure, and enhanced structural stability can accommodate various defects and strains that develop during in situ electrochemical reactions. Consequently, amorphous materials can be used as both surface-confined and volume-confined electrocatalysts. Although crystalline materials have better electronic properties as well as higher thermal and mechanical stability, they suffer from limited activity due to only surface-confined electrocatalysis. In this regard, the judicious integration of crystalline and amorphous active materials suitable for the OER and HER can tremendously enhance their bifunctional electrocatalytic activities owing to their synergistic effects. The variety in the choice of amorphous and crystalline counterparts presents ample opportunities for further exploration of the development of amorphous-crystalline heterostructured materials with unique properties. However, considering the recent massive developments in the understanding and protocols for fabricating such heterostructures, a critical review is vital for further advancement in this direction. Although some review papers have focused only on amorphous materials, including their synthesis methods, properties, and applications, no critical review that provides an overview emphasizing amorphous-crystalline heterostructures for electrocatalytic water-splitting applications has been published. In this regard, this review aims to present comprehensive details on the recent developments in the fabrication of different amorphous-crystalline heterostructures, the choice of the composition of each component, and the resulting physicochemical properties for the OER, HER, and overall water-splitting. It provides an in-depth understanding of amorphous-crystalline material synthesis protocols, their selection rationale, and their targeted physicochemical properties. This review also provides thought-provoking ideas and long-term perspectives for future research. This review presents comprehensive details on recent developments in the fabrication of different amorphous-crystalline heterostructures, their compositions, and the resulting physicochemical properties for OER, HER, and overall water splitting.</p>
1 aSingh, Manjinder1 aCha, Dun, Chan1 aSingh, Thangjam, Ibomcha1 aMaibam, Ashakiran1 aPaudel, Dasu, Ram1 aNam, Dong, Hwan1 aKim, Tae, Hyeong1 aYoo, Sunghoon1 aLee, Seunghyun  uhttps://library.ncl.res.in/content/critical-review-amorphous-crystalline-heterostructured-electrocatalysts-efficient-water02065nas 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<p>
	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.</p>
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<p>
	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.</p>
1 aMaibam, Ashakiran1 aKrishnamurty, Sailaja1 aBabaRao, Ravichandar  uhttps://library.ncl.res.in/content/electrocatalytic-nitrogen-reduction-defective-graphene-modulated-single-atom-catalyst02738nas 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<p>
	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.</p>
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-boron02595nas a2200277   4500008004100000022001400041245018300055210006900238260000800307490000700315520155700322653002401879653002501903653002101928653003301949653002901982653003102011100001902042700002902061700002202090700002102112700002002133700002502153700001902178856012002197       2023                        eng d  a1613-681000aMetal-organic framework-derived mesoporous B-doped CoO/Co@N-doped carbon hybrid 3D heterostructured interfaces with modulated cobalt oxidation states for alkaline water splitting0 aMetalorganic frameworkderived mesoporous Bdoped CoOCoNdoped carb  cAUG0 v193 a<p>
	Heteroatom-doped transition metal-oxides of high oxygen evolution reaction (OER) activities interfaced with metals of low hydrogen adsorption energy barrier for efficient hydrogen evolution reaction (HER) when uniformly embedded in a conductive nitrogen-doped carbon (NC) matrix, can mitigate the low-conductivity and high-agglomeration of metal-nanoparticles in carbon matrix and enhances their bifunctional activities. Thus, a 3D mesoporous heterostructure of boron (B)-doped cobalt-oxide/cobalt-metal nanohybrids embedded in NC and grown on a Ni foam substrate (B-CoO/Co@NC/NF) is developed as a binder-free bifunctional electrocatalyst for alkaline water-splitting via a post-synthetic modification of the metal-organic framework and subsequent annealing in different Ar/H-2 gas ratios. B-CoO/Co@NC/NF prepared using 10% H-2 gas (B-CoO/Co@NC/NF [10% H-2]) shows the lowest HER overpotential (196 mV) and B-CoO/Co@NC/NF (Ar), developed in Ar, shows an OER overpotential of 307 mV at 10 mA cm(-2) with excellent long-term durability for 100 h. The best anode and cathode electrocatalyst-based electrolyzer (B-CoO/Co@NC/NF (Ar)(+)//B-CoO/Co@NC/NF (10% H-2)(-)) generates a current density of 10 mA cm(-2) with only 1.62 V with long-term stability. Further, density functional theory investigations demonstrate the effect of B-doping on electronic structure and reaction mechanism of the electrocatalysts for optimal interaction with reaction intermediates for efficient alkaline water-splitting which corroborates the experimental results.</p>
10a3D heterostructures10aB-doped metal-oxides10aelectrocatalysts10ahydrogen evolution reactions10ametal-organic frameworks10aoxygen evolution reactions1 aCha, Dun, Chan1 aSingh, Thangjam, Ibomcha1 aMaibam, Ashakiran1 aKim, Tae, Hyeong1 aNam, Dong, Hwan1 aBabaRao, Ravichandar1 aLee, Seunghyun  uhttps://library.ncl.res.in/content/metal-organic-framework-derived-mesoporous-b-doped-coocon-doped-carbon-hybrid-3d02862nas 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<p>
	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.</p>
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-properties02043nas a2200229   4500008004100000022001400041245010200055210006900157260000900226300001600235490000700251520124200258100002301500700003001523700002201553700002101575700001901596700002801615700002501643700001701668856012801685       2023                        eng d  a0020-166900aRobust zeolitic tetrazole framework for electrocatalytic dopamine detection with high selectivity0 aRobust zeolitic tetrazole framework for electrocatalytic dopamin  cNOV   a20236-202410 v623 a<p>
	A novel zeolitic tetrazolate framework (ZTF-8) has been synthesized by solvent-free heat-assisted (70 C-degrees) mechanochemical grinding of zinc acetate and 5-methyl tetrazole in the presence of NaOH powder. The structure of ZTF-8 adopts the zeolitic sodalite (SOD) topology with uncoordinated N-heteroatom sites and resembles the structure of the well-known zeolitic imidazole framework ZIF-8. ZTF-8 is exceptionally stable in 0.1 M aqueous acid and base solutions for 60 days at 25 C-degrees. The unique structure with uncoordinated N-heteroatom active sites and exceptional stability of ZTF-8 facilitated the electrocatalytic oxidation of dopamine to dopamine quinone at neutral pH. Without any postsynthetic modification, ZTF-8 is directly used for the facile electrochemical detection of dopamine over a wide range of concentrations (5-550 mu M) with a high sensitivity (2410.8 mu A mM-1 cm-2). It also demonstrated promising selectivity over other interferents of similar oxidation potential, such as ascorbic acid and uric acid. The DFT study revealed that the ZTF-8 framework has a higher binding energy (-145.07 kJ/mol) and stronger interaction with dopamine than its isostructural ZIF-8 structure (-130.42 kJ/mol).</p>
1 aSarfudeen, Shafeeq1 aSruthi, Vadakke, Purakkal1 aMaibam, Ashakiran1 aPanda, Premchand1 aJhariat, Pampa1 aSenthilkumar, Sellappan1 aBabaRao, Ravichandar1 aPanda, Tamas  uhttps://library.ncl.res.in/content/robust-zeolitic-tetrazole-framework-electrocatalytic-dopamine-detection-high-selectivity03453nas 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<p>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.</p>
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-cells03156nas 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<p>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 &amp; 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%.</p>
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<p>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</p>
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-sensitized01025nas a2200301   4500008004100000022001400041245010800055210006900163260000800232300001100240490000800251653002400259653002800283653003000311100002700341700001800368700002000386700002600406700002200432700002600454700001800480700001800498700001800516700002500534700001500559700001900574856013000593       2024                        eng d  a0927-796X00aBreaking the inactivity of MXenes to drive Ampere-level selective oxygen evolution reaction in seawater0 aBreaking the inactivity of MXenes to drive Amperelevel selective  cSEP  a1008350 v16010a2D heterostructures10aMetal-organic framework10aOxygen Evolution Reaction1 aGbadamasi, Sharafadeen1 aLoomba, Suraj1 aHaris, Muhammad1 aKhan, Muhammad, Waqas1 aMaibam, Ashakiran1 aMousavi, Seyed, Mahdi1 aMahmud, Sofiu1 aThomsen, Lars1 aTadich, Anton1 aBabaRao, Ravichandar1 aXian, Jian1 aMahmood, Nasir  uhttps://library.ncl.res.in/content/breaking-inactivity-mxenes-drive-ampere-level-selective-oxygen-evolution-reaction-seawater02325nas a2200277   4500008004100000022001400041245009700055210006900152260000800221300001500229490000700244520139000251653003301641653003701674653002101711653002001732653002601752100001901778700002201797700002201819700002501841700001801866700001801884700001701902856012801919       2024                        eng d  a1864-563100aHeterogeneous acid-base organocatalyst for cascade deacetalisation-knoevenagel condensations0 aHeterogeneous acidbase organocatalyst for cascade deacetalisatio  cDEC  ae2024008660 v173 a<p>
	Multifunctional heterogeneous catalysts are an effective strategy to drive chemical cascades, with attendant time, resource and cost efficiencies by eliminating unit operations arising in normal multistep processes. Despite advances in the design of such catalysts, the fabrication of proximate, chemically antagonistic active sites remains a challenge for inorganic materials science. Hydrogen-bonded organocatalysts offer new opportunities for the molecular level design of multifunctional structures capable of stabilising antagonistic active sites. We report the catalytic application of a charge-assisted, hydrogen-bonded crystalline material, bis(melaminium)adipate (BMA), synthesised from melamine and adipic acid, which possesses proximate acid-base sites. BMA exhibits high activity for the cascade deacetalisation-Knoevenagel condensation of dimethyl acetals to form benzylidenemalononitriles under mild conditions in water; BMA is amenable to large-scale manufacture and recycling with minimal deactivation. Computational modelling of the melaminium cation in protonated BMA explains the observed catalytic reactivity, and identifies the first demethoxylation step as rate-limiting, which is in good agreement with time-dependent 1H NMR and kinetic experiments. A broad substrate scope for the cascade transformation of aromatic dimethyl acetals is demonstrated.</p>
10aAntagonistic acid-base sites10aCharge-assisted hydrogen bonding10aChemical cascade10aorganocatalysis10aSustainable catalysis1 aChhetri, Ashis1 aMaibam, Ashakiran1 aManiam, Subashani1 aBabaRao, Ravichandar1 aWilson, Karen1 aLee, Adam, F.1 aMitra, Joyee  uhttps://library.ncl.res.in/content/heterogeneous-acid-base-organocatalyst-cascade-deacetalisation-knoevenagel-condensations01050nas a2200337   4500008004100000022001400041245010800055210006900163260000800232300001600240490000700256653001200263653001900275653001500294653001100309653001300320653001200333100001600345700002200361700002200383700001800405700002100423700001800444700002300462700002100485700001800506700001900524700002500543700001700568856012700585       2024                        eng d  a1944-824400aPurification of waste-generated biogas mixtures using covalent organic framework's high CO2 Selectivity0 aPurification of wastegenerated biogas mixtures using covalent or  cAPR  a22066-220780 v1610aCAPTURE10aCARBON-DIOXIDE10aEfficiency10aEnergy10aHydrogen10aSTORAGE1 aPaul, Ratul1 aMaibam, Ashakiran1 aChatterjee, Rupak1 aWang, Wenjing1 aMukherjee, Triya1 aDas, Nitumani1 aYellappa, Masapogu1 aBanerjee, Tanmay1 aBhaumik, Asim1 aMohan, Venkata1 aBabaRao, Ravichandar1 aMondal, John  uhttps://library.ncl.res.in/content/purification-waste-generated-biogas-mixtures-using-covalent-organic-frameworks-high-co202159nas 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<p>
	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.</p>
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-conjugated00993nas a2200289   4500008004100000022001400041245012000055210006900175260001100244300001600255490000700271653001400278653001300292653000700305653001700312653002800329100002500357700002800382700002000410700002600430700002700456700002200483700002500505700002200530700002100552856013000573       2024                        eng d  a2050-748800aSynthesis of Hofmann-based metal-organic frameworks incorporating a bis-pyrazole linker for various gas separations0 aSynthesis of Hofmannbased metalorganic frameworks incorporating   cJUN 25  a15106-151140 v1210aacetylene10aC2H2/CH410aNi10aPurification10aSPIN-CROSSOVER BEHAVIOR1 aMatthews, Brooke, L.1 aHarvey-Reid, Nathan, C.1 aJangodaz, Elnaz1 aScott, Victoria-Jayne1 aPolson, Matthew, I. J.1 aMaibam, Ashakiran1 aBabaRao, Ravichandar1 aTelfer, Shane, G.1 aKruger, Paul, E.  uhttps://library.ncl.res.in/content/synthesis-hofmann-based-metal-organic-frameworks-incorporating-bis-pyrazole-linker-various01317nas 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<p>
	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.</p>
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<p>
	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</p>
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-thiol02243nas a2200313   4500008004100000022001400041245015900055210006900214260000800283300001100291490000800302520113800310653002401448653001901472653002301491653002001514653002001534653003501554653002301589100002801612700002601640700002201666700002901688700001801717700002301735700002201758700001801780856013101798       2025                        eng d  a1385-894700aUnravelling the Cu-Co nanoparticle synergy over Ceria-Zirconia support toward efficient reverse water gas shift (RWGS) conversion under H2 lean conditions0 aUnravelling the CuCo nanoparticle synergy over CeriaZirconia sup  cMAR  a1607050 v5083 a<p>
	CO2 emissions leading to global warming and environmental and socio-economic issues have propelled the research community to develop technologies capable of capturing and converting CO2 into valuable products. Controlling the selectivity toward platform molecules like CO, methanol, or methane is a fundamental challenge in CO2 hydrogenation. Supported cobalt nanoparticles are known for hydrocarbon production through FischerTropsch (FT) reaction, and Cu-based catalysts are known for reverse water gas shift (RWGS) reaction. Here, we show that d-band centre can be carefully modulated by making bimetallic combinations of Cu and Co for a highly active RWGS catalyst. An oxygen vacancy-rich nanostructured ceria-zirconia (CZ) support with Cu nanoparticles (2 wt%) modified with as low as 0.05 wt% Co shows excellent conversion for CO2 hydrogenation and selectivity for CO below 500 degrees C. The optimized catalyst shows CO2 conversion even under hydrogen lean conditions (H2/ CO2 ratio 0.5:1), with a breakthrough rate of 206023 mmol/gmetal/h for CO at 600 degrees C, having H2 utilization of 80% for the RWGS process.</p>
10aBimetallic catalyst10aCeria-zirconia10aCO 2 hydrogenation10aCobalt catalyst10aCopper catalyst10aReverse water gas shift (RWGS)10asynergistic effect1 aJagtap, Anuradha, Vijay1 aBamnia, Mahesh, Kumar1 aMaibam, Ashakiran1 aBajpai, Jyotsna, Paliwal1 aGupta, Sharad1 aThomas, Sharon, K.1 aDabke, Niteen, B.1 aVinod, C., P.  uhttps://library.ncl.res.in/content/unravelling-cu-co-nanoparticle-synergy-over-ceria-zirconia-support-toward-efficient-reverse