01969nas a2200265 4500008004100000022001400041245014300055210006900198260000900267300001600276490000700292520103800299653002001337653001801357653001901375653001301394653001901407100002101426700002801447700001701475700002101492700002901513700003001542856013101572 2020 eng d a1944-824400aCan half-a-monolayer of pt simulate activity like that of bulk pt? solar hydrogen activity demonstration with quasi-artificial leaf device0 aCan halfamonolayer of pt simulate activity like that of bulk pt  cJUL  a30420-304300 v123 a

Pt is the best cocatalyst for hydrogen production. It is also well-known that the surface atomic layer is critical for catalysis. To minimize the Pt content as cocatalyst, herein we report on half-a-monolayer of Pt (0.5 theta(Pt)) decorated on earth-abundant Ni-Cu cocatalyst, which is integrated with a quasiartificial leaf (QuAL) device (TiO2/ZnS/CdS) and demonstrated for efficient solar hydrogen production. For the QuAL, TiO2 is sensitized with ZnS and CdS quantum dots by the SILAR method. The 0.5 theta(Pt)-decorated Ni-Cu shows an onset potential of 0.05 V vs reversible hydrogen electrode for the hydrogen evolution reaction, which is almost similar to that of commercial Pt/C. Photoactivity of the present QuAL device with either bulk Pt or 0.5 theta(Pt)-coated Ni-Cu cocatalyst is, surprisingly, equal. Our findings underscore that a fraction of a monolayer of Pt can enhance the activity of the cocatalyst, and it is worth exploring further for the high activity associated with atomic Pt and other noble metals.

10aartificial leaf10anickel-copper10aPhotocatalysis10aplatinum10aSolar hydrogen1 aBajpai, Himanshu1 aPatra, Kshirodra, Kumar1 aRanjan, Ravi1 aNalajala, Naresh1 aReddy, Kasala, Prabhakar1 aGopinath, Chinnakonda, S. uhttps://library.ncl.res.in/content/can-half-monolayer-pt-simulate-activity-bulk-pt-solar-hydrogen-activity-demonstration-quasi02344nas a2200181 4500008004100000022001400041245017700055210006900232260000800301300001600309490000600325520161800331100001701949700001701966700003001983700001802013856013102031 2020 eng d a2050-748800aDirected holey and ordered g-C(3)N(4.5)nanosheets by a hard template nanocasting approach for sustainable visible-light hydrogen evolution with prominent quantum efficiency0 aDirected holey and ordered gC3N45nanosheets by a hard template n cJUL a13328-133390 v83 a

It is desirable yet challenging to synthesize a highly ordered holey carbon nitride material with excess nitrogen atoms for a sustainable solar H(2)evolution. Herein, we report the development of directed highly ordered nitrogen-rich honeycomb-like mesoporous carbon nitride nanosheets by using a novel synthetic approach for this purpose. The unique formation route, surface structure and charge carrier dynamics of the two dimensional holey nanosheets are comprehensively monitored and confirmed by SAXS, HRTEM, AFM, BET, XPS and TRPL analyses. Non-stoichiometric high nitrogen content mesoporous nanosheets with the final stoichiometry of g-C(3)N(4.5)acquiring a high specific surface area (382 m(2)g(-1)), remarkable pore size (7.2 nm) and sheet thickness similar to 5-6 nm are realized in this first report. This elegant material possesses unique low band-gap energy (2.42 eV). Remarkably, the as-synthesized g-C(3)N(4.5)NSs exhibit a record high photocatalytic H(2)evolution rate of 8180 mu mol g(-1)h(-1)under the present light irradiation (420 <=lambda <= 510 nm) condition. The apparent quantum efficiency is found to be as high as 27.14% at 420 nm and retains its photocatalytic activity for longer consecutive catalytic cycles. Bigger pore size and pore volume, and thin walls leading to shortening of the path length of exciton pairs, efficient charge separation and the prolonged average life time of the charge carriers, and lone electron pairs associated with the excess nitrogen content are found to be the reasons behind the excellent visible light driven water splitting reaction.

1 aAntil, Bindu1 aRanjan, Ravi1 aGopinath, Chinnakonda, S.1 aDeka, Sasanka uhttps://library.ncl.res.in/content/directed-holey-and-ordered-g-c3n45nanosheets-hard-template-nanocasting-approach-sustainable02859nas a2200193 4500008004100000022001400041245014100055210006900196260000800265300001600273490000700289520211300296100002702409700002902436700002302465700001702488700003002505856013002535 2020 eng d a1463-907600aGas-solid interactions with reactive and inert gas molecules by NAPUPS: can work function be a better descriptor of chemical reactivity?0 aGassolid interactions with reactive and inert gas molecules by N cJUL a15528-155400 v223 a

The gas-phase vibrational spectra of reactive (H(2)and O-2) and inert gases (N(2)and Ar) have been studied by near-ambient pressure (NAP) ultraviolet photoelectron spectroscopy (NAPUPS) up to 0.3 mbar pressure. The results obtained are divided into two parts and discussed. In the first part, the photoelectron spectra of monoatomic Ar and some homonuclear diatomic molecules, such as H-2, O-2, and N-2, have been recorded by NAPUPS and the effect of pressure on their energy position has been studied. It has been demonstrated that NAPUPS could be an essential tool to determine the intermolecular or interatomic interactions. In the second part, we have evaluated the influence of different solid surfaces on the binding energy (BE) position, the pattern of the vibrational features of diatomic N(2)molecules, and the first atomic levels (3p(3/2)and 3p(1/2)) of monoatomic Ar. It has been observed that with a change in the (electronic/chemical) nature of the surface, the BE of the above features also changes and reflects the change in the work function (phi) of the material. It is to be noted that Ar is an inert/noble gas and N(2)is the most stable molecule, and the above changes observed underscore that they can be employed as probe atoms/molecules to explore even the minor changes that occur on a solid surface due to a variety of reasons. Further, if the solid surface undergoes any chemical/electronic changes due to gas-solid interaction, such as oxidation/reduction, the phi of the surface changes again; this highlights the precise identification of the changes that occur under the reaction/measurement conditions. Therefore, the change in the BE of the gas-phase features can be used to determine even the minor changes in the phi of solid surfaces during the reaction or due to the reaction. The present findings have implications in probing the surface changes that occur in any surface-dependent phenomena, such as heterogeneous catalysis, electrochemistry, and materials that are predominantly controlled by surface contribution, such as layered (2D) materials, nanomaterials.

1 aGhosalya, Manoj, Kumar1 aReddy, Kasala, Prabhakar1 aMhamane, Nitin, B.1 aRanjan, Ravi1 aGopinath, Chinnakonda, S. uhttps://library.ncl.res.in/content/gas-solid-interactions-reactive-and-inert-gas-molecules-napups-can-work-function-be-better02045nas a2200337 4500008004100000022001400041245014400055210006900199260000900268300001100277490000800288520095100296653001401247653001401261653001901275653000901294653001601303100002101319700001801340700001701358700002301375700002601398700002401424700002101448700001701469700002001486700003001506700002301536700001701559856013101576 2021 eng d a0926-860X00aIn-situ experimental and computational approach to investigate the nature of active site in low-temperature CO-PROX over CuOx-CeO2 catalyst0 aInsitu experimental and computational approach to investigate th cAUG  a1183050 v6243 aPreferential oxidation (PROX) of carbon monoxide (CO) in presence of excess hydrogen is a necessity to prevent poisoning of the Pt-anode by CO in PEMFCs (Polymer Electrolyte Membrane Fuel Cell). A highly active catalyst, 5 wt% Cu-CeO2 showed 100 % CO conversion at 65 degrees C without any undesirable oxidation of H-2. The catalyst showed no deactivation even after 100 h on stream, making it viable for practical fuel cell application. Operando EPR in the PROX reaction condition revealed highly dispersed mixed valent cations with oxygen vacancies, responsible for the low-temperature PROX activity. At the active site, both Cu and Ce ions were shown to reversibly change their valence states to facilitate the abstraction of bridging lattice oxygen for CO oxidation to CO2. This surface oxygen mediated CO oxidation was found to be much faster than that of H-2 to H2O, which could explain the complete selectivity of oxygen for CO2 formation.10aCuOx-CeO210ainterface10aOxygen vacancy10aPROX10aSynergistic1 aAdak, Shubhadeep1 aRabeah, Jabor1 aRanjan, Ravi1 aKhan, Tuhin, Suvra1 aPoddar, Mukesh, Kumar1 aGupta, Rishi, Kumar1 aSasaki, Takehiko1 aKumar, Sagar1 aBordoloi, Ankur1 aGopinath, Chinnakonda, S.1 aBruckner, Angelika1 aBal, Rajaram uhttps://library.ncl.res.in/content/situ-experimental-and-computational-approach-investigate-nature-active-site-low-temperature02731nas a2200277 4500008004100000022001400041245015700055210006900212260000900281300001400290490000600304520175500310653001902065653003002084653003202114653001802146653001802164100001702182700001902199700001702218700002302235700002202258700003002280700001802310856012502328 2021 eng d a2574-096200aOne-dimensional multichannel g-C3N4.7 nanostructure realizing an efficient photocatalytic hydrogen evolution reaction and its theoretical investigations0 aOnedimensional multichannel gC3N47 nanostructure realizing an ef cAPR  a3118-31290 v43 a

The emerging metal-free carbon nitride (C3N4) offers prominent possibilities for realizing the highly effective hydrogen evolution reaction (HER). However, its poor surface conductivity and insufficient catalytic sites hinder the HER performance. Herein, a one-dimensional vermicular rope-like graphitic carbon nitride nanostructure is demonstrated that consists of multichannel tubular pores and high nitrogen content, which is fabricated through a cost-effective approach having the final stoichiometry g-C3N4.7 for HER application. The present g-C3N4.7 is unique owing to the presence of abundant channels for the diffusion process, modulated surface chemistry with rich- electroactive sites from N-electron lone pairs, greatly reduced recombination rate of photoexcited exciton pairs, and a high donor concentration (4.26 x 10(17) cm(3)). The catalyst offers a visible-light-driven photocatalytic H-2 evolution rate as high as 4910 mu mol h(-1)g(-1) with an apparent quantum yield of 14.07% at band gap absorption (2.59 eV, 479 nm) under 7.68 mW cm(-2) illumination. The number of hydrogen gas molecules produced is 1.307 x 10(15) s(-1) cm(-2), which remained constant for a minimum of 18 h of repeated cycling in the HER without any degradation of the catalyst. In density functional theory calculations, a significant change in the band offset is observed due to N doping into the system in favor of electron catalysis. The theoretical band gap of a monolayer of g-C3N4.7 was enormously reduced because of the presence of additional densities of states from the doped N atom inside the band gap. These impurity or donor bands are formed inside the band gap region, which ultimately enhance the hydrogen ion reduction reaction enormously.

10acarbon nitride10aDensity functional theory10ahydrogen evolution reaction10anitrogen-rich10aPhotocatalyst1 aAntil, Bindu1 aKumar, Lakshya1 aRanjan, Ravi1 aShenoy, Sulakshana1 aTarafder, Kartick1 aGopinath, Chinnakonda, S.1 aDeka, Sasanka uhttps://library.ncl.res.in/content/one-dimensional-multichannel-g-c3n47-nanostructure-realizing-efficient-photocatalytic02941nas a2200181 4500008004100000022001400041245012200055210006900177260000800246300001600254490000800270520225900278100001702537700002302554700002302577700003002600856012902630 2022 eng d a1932-744700aElectronic structure evolution from metallic vanadium to metallic VxOy: a nappes study for o2+v gas-solid interaction0 aElectronic structure evolution from metallic vanadium to metalli cNOV a19136-191460 v1263 a

Gas-solid interactions between molecular oxygen and metallic vanadium surfaces and the systematic evolution in the electronic structure of vanadium oxide (VOx) surfaces have been explored in the present work by near-ambient pressure photo-electron spectroscopy (NAPPES). The current article studies the evolution of various oxides of vanadium as a function of partial pressure of O2 (ultrahigh vacuum to 1 mbar), temperature (298- 875 K), and the exposure time to oxygen (up to 18 h). Valence -band (VB) and core-level spectral measurements recorded with UV (He-I = 21.2 eV) and Al K alpha (1486.6 eV) photons, respectively, show interesting changes. (1) Oxidation is limited to the top layers of vanadium at 298 K and up to a partial pressure of 1 mbar O2. About 50% of vanadium gets oxidized, and the remaining amount exists as metal within the top 10 nm. (2) Metallic vanadium disappears above 625 K, and it is predominantly oxidized to a mixture of V4+ and V5+ oxidation states at a 0.1 mbar partial pressure of O2. Points 1 and 2 suggest the predominantly thermodynamically controlled nature of vanadium oxidation through oxygen diffusion into the subsurface and bulk layers. (3) The Fermi-level (EF) feature observed first at >= 725 K at a 0.1 mbar O2 pressure demonstrates the formation of metallic VO2; however, its metallic nature is preserved even at ambient temperature due to interweaving nanodomains of VOx with VO2. (4) Only partial conversion of surface layers to V5+ (V2O5) along with VO2 and V2O3 (within the probing depth of 8-10 nm by near-ambient pressure X-ray photoelectron spectroscopy (NAP-XPS)) was observed even after prolonged heating (18 h) in 1 mbar O2 pressure. (5) The nature of the surface changes between metal and semiconducting/ insulator oxides is substantiated by the observation of changes in work function (phi) and EF features. Typical VB features and Fermi intensity of V-metal and vanadium oxides were observed, and the results were corroborated with core-level and VB spectra. The present results extend the capabilities of NAPPES to explore the electronic structure evolution as a function of reaction conditions and underscore its relevance to areas such as heterogeneous catalysis and sensing.

1 aRanjan, Ravi1 aMhamane, Nitin, B.1 aKolekar, Sadhu, K.1 aGopinath, Chinnakonda, S. uhttps://library.ncl.res.in/content/electronic-structure-evolution-metallic-vanadium-metallic-vxoy-nappes-study-o2v-gas-solid02754nas a2200253 4500008004100000022001400041245014800055210006900203260000800272300001400280490000700294520185500301653002802156653001902184653003102203653000902234653001802243100002302261700001702284700001702301700002602318700003002344856012602374 2022 eng d a2168-048500aSustainable CO2 reduction on in (2)O(3 )with exclusive CO selectivity: catalysis and in situ valence band photoelectron spectral investigations0 aSustainable CO2 reduction on in 2O3 with exclusive CO selectivit cMAR a3521-35310 v103 a

This study demonstrates a sustainable catalytic CO2 conversion to near 100% CO selectivity at ambient pressure on In2O3. Critically, high CO yield could be observed at the cost of undesired methanation, using a lower than stoichiometric amount of hydrogen in the feed; 1:1 and 1:0.67 CO2:H-2 ratios exhibit 98-99.6% CO selectivity with 25-38% CO2 conversion between 773 and 873 K. CO2 and H-2 conversion under steady-state conditions at 773-873 K suggests a 1:1 ratio of adsorbed reactants (with 1:0.67 CO2:H-2 feed) on the catalyst surface, underscoring the presence of an ideal reactant composition for the reverse water-gas shift reaction, while H-2-rich feed compositions show the H-2-dominated surface. Surface electronic structure changes, under near-operating conditions, were explored with near ambient pressure photoelectron spectroscopy (NAPPES), and the interesting findings are as follows: (a) A shift in the valence band to lower binding energy, up to 0.6 eV, was observed because of electron filling at high temperatures. (b) An observation of heterogeneous nature of the catalyst surface under NAPPES measurement conditions is attributed to the generation of active oxygen vacancy (O-v) sites, which in turn changes the work function of In2O3. (c) The above changes are found to be reversible, when the reaction was stopped. Vibrational features of the reactant molecules were observed to be broadened in the active temperature window of the catalyst supporting the heterogeneous character of the catalyst surface because of dynamic O-v generation. By optimizing gas hourly space velocity, CO2:H-2 ratio, and reaction temperature, exclusive CO selectivity is possible with a H-2:CO2 ratio of similar to 0.67, which will avoid the product separation stage altogether, while minimizing the expensive H-2 in the reactant feed.

10aheterogeneous catalysis10aOxygen vacancy10aphotoelectron spectroscopy10aRWGS10aWork function1 aMhamane, Nitin, B.1 aChetry, Sibo1 aRanjan, Ravi1 aRaja, Thirumalaiswamy1 aGopinath, Chinnakonda, S. uhttps://library.ncl.res.in/content/sustainable-co2-reduction-2o3-exclusive-co-selectivity-catalysis-and-situ-valence-band02553nas a2200265 4500008004100000022001400041245009700055210006900152260000800221300001100229490000800240520168600248653002701934653002801961653000901989653000801998653002002006100001702026700002102043700001602064700002302080700002602103700003002129856012802159 2023 eng d a1385-894700aCo3O4 for sustainable CO2 reduction and possible fine-tuning towards selective CO production0 aCo3O4 for sustainable CO2 reduction and possible finetuning towa cSEP a1444590 v4713 a

Two main challenges involved in heterogeneous catalytic CO2 reduction are: (a) decreasing the consumption of H2 to the minimum required level with possibly the maximum CO2 conversion, and (b) concurrently enhancing the selectivity of the desired CO, at the cost of methane. Towards meeting these two challenges, Co3O4 spinel has been identified as a potential catalyst and it exhibits predominant CO selectivity > 673 K at atmospheric pressure. CO2 conversion begins > 523 K, with 100% CO selectivity observed > 673 K with CO2:H2 = 3:2. Current work shows a sustainable catalytic CO2 conversion to 100% CO selectivity with Co3O4-Nanocube (NC). Critically, CO selectivity and yield is observed to increase at the cost of methane with smaller amount of H2. 1:1 and 3:2 CO2:H2 ratio exhibits 88-100% CO selectivity with 24-32.5% CO2 conversion between 623 and 823 K. Irrespective of the input CO2:H2, ratio of CO2:H2 uptake changes from around 1:3 at 523 K to 1:1-1.5 at 823 K with concurrent production of significant methane to predominant CO, respectively. Surface electronic state changes was explored by near ambient pressure photoelectron spectroscopy, and the results suggests that Co3O4 is the active phase that promotes CO2 reduction selectively to CO. Broadening observed with the vibrational feature of the CO2 molecules at high temperature underscores the heterogeneous character of the catalyst surface, under operating conditions, due to changing electron density. By optimizing the gas hourly space velocity (GHSV), H2-lean CO2:H2 ratio, and the reaction temperature/pressure, 100% CO selectivity could be broadened to a range of operating conditions.

10aCarbon neutral economy10aheterogeneous catalysis10aRWGS10aSDG10aSurface Science1 aRanjan, Ravi1 aTekawadia, Jyoti1 aJain, Ruchi1 aMhamane, Nitin, B.1 aRaja, Thirumalaiswamy1 aGopinath, Chinnakonda, S. uhttps://library.ncl.res.in/content/co3o4-sustainable-co2-reduction-and-possible-fine-tuning-towards-selective-co-production02861nas a2200241 4500008004100000022001400041245018000055210006900235260000900304300001600313490000700329520193900336100002602275700002002301700002602321700001702347700003002364700002602394700002102420700001902441700003302460856012602493 2023 eng d a1463-907600aPossible handle for broadening the catalysis regime towards low temperatures: proof of concept and mechanistic studies with CO oxidation on surface modified Pd-TiO20 aPossible handle for broadening the catalysis regime towards low  cAUG  a22040-220540 v253 a

The present work demonstrates the effect of temperature-dependent surface modification (SM) treatment and its influence in broadening the catalysis regime with Pd-TiO2 catalysts prepared by various methods. Due to SM induced changes, a shift in the onset of CO oxidation activity as well as broadening of the oxidation catalysis regime by 30 to 65 K to lower temperatures is observed compared to the temperature required for virgin counterparts. SM carried out at 523 K for Pd-Photo-TiO2 exhibits the lowest onset (10% CO2 production - T-10) and T-100 for CO oxidation at 360 and 392 K, respectively, while its virgin counterpart shows T-10 and T-100 at 393 and 433 K, respectively. The SMd Pd-TiO2 catalysts were investigated using X-ray photoelectron spectroscopy (XPS), ultra-violet photoelectron spectroscopy (UPS) and atomic force microscopy (AFM). It is observed that diffusion of atomic oxygen into Pd-subsurfaces leads to SM and changes the nature of the surface significantly. These changes are demonstrated by work function (& phi;), surface potential, catalytic activity, and correlation among them. UPS results demonstrate the maximum increase in & phi; by 0.5 eV for Pd-Photo-TiO2 after SM, compared to all other catalysts. XPS study shows a moderate to severe change in the oxidation states of Pd due to atomic oxygen diffusion into the subsurface layers of Pd. Kelvin probe force microscopy (KPFM) study also reveals corroborating evidence that the surface potential increases linearly with increasing temperature deployed for SM up to 523 K, followed by a marginal decrease at 573 K. The & phi; measured by KPFM and UPS shows a similar trend and correlates well with the changes in catalysis observed. Our results indicate that there is a strong correlation between surface physical and chemical properties, and & phi; changes could be considered as a global marker for chemical reactivity.

1 aMhamane, Nitin, B. B.1 aPanchal, Suresh1 aKolekar, Sadhu, K. K.1 aRanjan, Ravi1 aSalgaonkar, Kranti, N. N.1 aBurange, Anand, S. S.1 aNalajala, Naresh1 aDatar, Suwarna1 aGopinath, Chinnakonda, S. S. uhttps://library.ncl.res.in/content/possible-handle-broadening-catalysis-regime-towards-low-temperatures-proof-concept-and02817nas a2200229 4500008004100000022001400041245015400055210006900209260000900278300001400287490000600301520197100307100001802278700002902296700001702325700002302342700002802365700002102393700001802414700003002432856012502462 2024 eng d a2398-490200aDesign of Bi-functional mixed oxide electrodes for selective oxidative C-C cleavage of glycerol to formate and synchronized green hydrogen production0 aDesign of Bifunctional mixed oxide electrodes for selective oxid cJUN  a2954-29680 v83 a

Alkaline water electrolysis is a mature method to produce green hydrogen; however, it suffers from significantly high cost as high overpotentials are required for the oxygen evolution reaction (OER). However, the OER could be avoided altogether by replacing it with kinetically favorable oxidation of abundantly available feedstock molecules at a significantly low potential to value-added product(s) together with green hydrogen generation. This is a potential method to address the high cost of green hydrogen production while converting waste to wealth. Herein, we report green, template-free hydrothermal synthesis of an electrochemically active NiCoMn mixed oxide (NCMO) electrocatalyst with multiple sites, porous structure, large surface area, and nanoneedle (NN) morphology deposited directly over Ni foam (NF). Sustainable electrocatalytic performance was demonstrated for 120 h in 0.2 M alkaline glycerol using chronoamperometry and chronopotentiometry. Highly selective formate production demonstrated an exclusive C-C cleavage with the present catalyst system. Oxides of individual metal-ions (Ni, Co, and Mn) and their bimetallic combination (NiCo, NiMn, and CoMn) exhibited lower activity and product selectivity than the trimetallic NCMO electrocatalyst. The membrane-free two-electrode electrolyzer setup with NCMO/NF at both the anode and cathode (NCMO/NF & Vert;NCMO/NF) requires 1.63 V to accomplish 100 mA cm-2 with 0.2 M glycerol, which is 296 mV less than that of 1 M KOH solution. High faradaic efficiency was observed for hydrogen (98%) with highly selective formate (90%) production. Electrocatalytic formate generation from an alkaline glycerol solution with NCMO is an energy-efficient and promising approach that also supplies carbon-negative green H2. NiCoMn oxide nanoneedles with a cactus-like morphology are shown as bifunctional electrocatalysts that selectively oxidize glycerol to HCOOH and concurrently produce H2.

1 aSaha, Arindam1 aMurugiah, Vasantharadevi1 aRanjan, Ravi1 aChauhan, Inderjeet1 aPatra, Kshirodra, Kumar1 aBajpai, Himanshu1 aSaha, Avisekh1 aGopinath, Chinnakonda, S. uhttps://library.ncl.res.in/content/design-bi-functional-mixed-oxide-electrodes-selective-oxidative-c-c-cleavage-glycerol07169nas a2200181 4500008004100000245014400041210006900185260000800254300001200262490000600274520645000280100002306730700002906753700001706782700002806799700003006827856013006857 2024 eng d00aElectrocatalytic and selective oxidation of glycerol to formate on 2D 3d-metal phosphate nanosheets and carbon-negative hydrogen generation0 aElectrocatalytic and selective oxidation of glycerol to formate  cJUN a500-5110 v43 a

In the landscape of green hydrogen production, alkaline water electrolysis is a well-established, yet not-so-cost-effective, technique due to the high overpotential requirement for the oxygen evolution reaction (OER). A low-voltage approach is proposed to overcome not only the OER challenge by favorably oxidizing abundant feedstock molecules with an earth-abundant catalyst but also to reduce the energy input required for hydrogen production. This alternative process not only generates carbon-negative green H2 but also yields concurrent value-added products (VAPs), thereby maximizing economic advantages and transforming waste into valuable resources. The essence of this study lies in a novel electrocatalyst material. In the present study, unique and two-dimensional (2D) ultrathin nanosheet phosphates featuring first-row transition metals are synthesized by a one-step solvothermal method, and evaluated for the electrocatalytic glycerol oxidation reaction (GLYOR) in an alkaline medium and simultaneous H2 production. Co3(PO4)2 (CoP), Cu3(PO4)2 (CuP), and Ni3(PO4)2 (NiP) exhibit 2D sheet morphologies, while FePO4 (FeP) displays an entirely different snowflake-like morphology. The 2D nanosheet morphology provides a large surface area and a high density of active sites. As a GLYOR catalyst, CoP ultrathin (∼5 nm) nanosheets exhibit remarkably low onset potential at 1.12 V (vs RHE), outperforming that of NiP, FeP, and CuP around 1.25 V (vs RHE). CoP displays 82% selective formate production, indicating a superior capacity for C–C cleavage and concurrent oxidation; this property could be utilized to valorize larger molecules. CoP also exhibits highly sustainable electrochemical stability for a continuous 200 h GLYOR operation, yielding 6.5 L of H2 production with a 4 cm2 electrode and 98 ± 0.5% Faradaic efficiency. The present study advances our understanding of efficient GLYOR catalysts and underscores the potential of sustainable and economically viable green hydrogen production methodologies.

1 aChauhan, Inderjeet1 aVijay, Pothoppurathu, M.1 aRanjan, Ravi1 aPatra, Kshirodra, Kumar1 aGopinath, Chinnakonda, S. uhttps://library.ncl.res.in/content/electrocatalytic-and-selective-oxidation-glycerol-formate-2d-3d-metal-phosphate-nanosheets