02343nas 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-molecules02052nas 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-nitrogen02525nas 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-dye02126nas 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-methyl02760nas a2200241 4500008004100000022001400041245016600055210006900221260000900290300001600299490000700315520185600322653005402178653002002232653003502252653000802287653001902295653000802314100001602322700002502338700002702363856012802390 2025 eng d a2155-543500aHarnessing AEM electrolyzer-level performance through strategically designing the electronic structure of electrocatalysts, enabling dynamic functional switching0 aHarnessing AEM electrolyzerlevel performance through strategical cDEC  a19968-199830 v153 a

The anion exchange membrane water electrolyzer (AEMWE) is a promising technology for cost-effective hydrogen production. To promote its development and adoption, targeted efforts are focused on finding non-platinum group metal (non-PGM) electrocatalysts that efficiently facilitate the hydrogen evolution reaction (HER) and the oxygen evolution reaction (OER). Nickel sulfides (NiS) are effective OER catalysts; however, they suffer due to leaching-related instability at electrolyzer stack operational conditions. We introduce a rational non-PGM design that enhances stability during the OER while excelling at the HER, showcasing molecular-level insights for a scalable AEMWE zero-gap stack device. NiS coating is applied to the Al-metal-organic framework supported by 3D porous nickel foam (NSMA), leading to charge localization at the interface, which helps in OER by requiring only 322 millivolts at 100 mA cm-2. The main innovation in the NSMA design is a controlled electroreduction process that converts the Millerite phase into Ni3S2, a catalyst (rNSMA). This transformation leads to charge delocalization at the surface and a low overpotential of -80 mV at -100 mA cm-2 for the HER. In a full cell, this catalyst duo requires an overpotential of 1.49 V, outperforming the commercial Pt/Ru catalyst pair at 1.58 V. In a scaled-up 12.96 cm2 AEM electrolyzer single-cell stack, current density rose from 398 to 1062 mA/cm2, maintained for over 100 h at high temperatures, achieving 99% Faradaic efficiency and 100% hydrogen purity. The AEM electrolyzer cell shows a good energy efficiency of 45.50 kWh/kg and a cell efficiency of 86.59%. Detailed studies, including DFT analyses, revealed that electronic structure modification enhances charge delocalization, driving its impressive performance on an industrially significant scale.

10aanion exchangemembrane water electrolyzer (AEMWE)10acharge transfer10adensity functional theory(DFT)10aHER10anickel sulfide10aOER1 aKumar, Sonu1 aVerma, Tushar, Singh1 aSelvaraj, Kaliaperumal uhttps://library.ncl.res.in/content/harnessing-aem-electrolyzer-level-performance-through-strategically-designing-electronic01914nas 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-based01994nas 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-methane02397nas a2200253 4500008004100000022001400041245011900055210006900174260000900243490000700252520151700259653001901776653001101795653003001806653002901836653001301865653001401878100002901892700002201921700002501943700001701968700002701985856013102012 2025 eng d a1864-563100aRational design of hydrophobic Cu/CuO electrodes for electrochemical oxygenation of tetralin: a strategic approach0 aRational design of hydrophobic CuCuO electrodes for electrochemi cAUG 0 v183 a

Electro-organic synthesis presents a sustainable and practical alternative to traditional organic synthesis methods, which typically utilize harsh reagents and require energy-intensive conditions. Nevertheless, the challenge of achieving satisfactory conversion and selectivity rates in electrocatalytic oxidation using a non-platinum group metal (PGM) catalyst pair still needs to be addressed. This study demonstrates the application of a non-PGM-based catalyst pair for the electrocatalytic oxidation of tetralin to 1-tetralone, a highly demanded raw material in the pharma industry. Copper electrodeposited on teflonated carbon paper combined with copper foam as the electrocatalyst pair has demonstrated impressive conversion and selectivity ratios to electro-synthesize 1-tetralone at room temperature and atmospheric pressure. The optimal choice of a non-PGM catalyst, ideal mass loading, and a unique electrode configuration resulted in an ultimate conversion of about 99% of tetralin and 1-tetralone selectivity -93.7%, yield -92.6%. The reaction pathway associated with the electrochemical phenomena is supported by first principles-based density functional theory calculations and X-ray photoelectron spectroscopy of the electrocatalyst. This process has exceptional performance that can be adapted for a wide range of substrates and is straightforward, ambient, reagent-free, scalable, and therefore beneficial for industrial use. Therefore, initiatives have been taken in this direction.

10aC-H activation10aCopper10aelectrochemical oxidation10anon-PGM electrocatalysts10atetralin10aTetralone1 aCherukuthota, Sri, Vidya1 aMathew, Elizabeth1 aVerma, Tushar, Singh1 aJoshi, Krati1 aSelvaraj, Kaliaperumal uhttps://library.ncl.res.in/content/rational-design-hydrophobic-cucuo-electrodes-electrochemical-oxygenation-tetralin-strategic