02515nas a2200301 4500008004100000022001400041245012200055210006900177260000800246300001200254490000700266520151500273653002101788653002401809653001901833653002301852100001801875700001901893700002201912700001601934700001501950700002701965700003301992700001802025700002302043700002502066856012202091 2022 eng d a0935-964800aMorphology-tuned Pt3Ge accelerates water dissociation to industrial-standard hydrogen production over a wide pH range0 aMorphologytuned Pt3Ge accelerates water dissociation to industri cJUL a22022940 v343 a

The discovery of novel materials for industrial-standard hydrogen production is the present need considering the global energy infrastructure. A novel electrocatalyst, Pt3Ge, which is engineered with a desired crystallographic facet (202), accelerates hydrogen production by water electrolysis, and records industrially desired operational stability compared to the commercial catalyst platinum is introduced. Pt3Ge-(202) exhibits low overpotential of 21.7 mV (24.6 mV for Pt/C) and 92 mV for 10 and 200 mA cm(-2) current density, respectively in 0.5 m H2SO4. It also exhibits remarkable stability of 15 000 accelerated degradation tests cycles (5000 for Pt/C) and exceptional durability of 500 h (@10 mA cm(-2)) in acidic media. Pt3Ge-(202) also displays low overpotential of 96 mV for 10 mA cm(-2) current density in the alkaline medium, rationalizing its hydrogen production ability over a wide pH range required commercial operations. Long-term durability (>75 h in alkaline media) with the industrial level current density (>500 mA cm(-2)) has been demonstrated by utilizing the electrochemical flow reactor. The driving force behind this stupendous performance of Pt3Ge-(202) has been envisaged by mapping the reaction mechanism, active sites, and charge-transfer kinetics via controlled electrochemical experiments, ex situ X-ray photoelectron spectroscopy, in situ infrared spectroscopy, and in situ X-ray absorption spectroscopy further corroborated by first principles calculations.

10aElectrochemistry10ahydrogen production10aintermetallics10awater electrolysis1 aMondal, Soumi1 aSarkar, Shreya1 aBagchi, Debabrata1 aDas, Tisita1 aDas, Risov1 aSingh, Ashutosh, Kumar1 aPrasanna, Ponnappa, Kechanda1 aVinod, C., P.1 aChakraborty, Sudip1 aPeter, Sebastian, C. uhttps://library.ncl.res.in/content/morphology-tuned-pt3ge-accelerates-water-dissociation-industrial-standard-hydrogen02437nas a2200253 4500008004100000022001400041245012400055210006900179260000800248300001400256490000700270520155500277653001801832653002101850653003001871653002201901653001701923100002201940700001901962700002701981700002802008700002502036856012202061 2022 eng d a1936-085100aPotential- and time-dependent dynamic nature of an oxide-derived pdin nanocatalyst during electrochemical CO2 reduction0 aPotential and timedependent dynamic nature of an oxidederived pd cAPR a6185-61960 v163 a

Electrochemical reduction of CO2 into valuable fuels and chemicals is a promising route of replacing fossil fuels by reducing CO2 emissions and minimizing its adverse effects on the climate. Tremendous efforts have been carried out for designing efficient catalyst materials to selectively produce the desired product in high yield from CO2 by the electrochemical process. In this work, a strategy is reported to enhance the electrochemical CO2 reduction reaction (ECO2RR) by constructing an interface between a metal-based alloy (PdIn) nanoparticle and an oxide (In2O3), which was synthesized by a facile solution method. The oxide-derived PdIn surface has shown excellent eCO(2)RR activity and enhanced CO selectivity with a Faradaic efficiency (FE) of 92.13% at -0.9 V (vs RHE). On the other hand, surface PdO formation due to charge transfer on the bare PdIn alloy reduces the CO2RR activity. With the support of in situ (EXAFS and IR) and ex situ (XPS, Raman) spectroscopic techniques, the optimum presence of the Pd-In-O interface has been identified as a crucial parameter for enhancing eCO(2)RR toward CO in a reducing atmosphere. The influence of eCO(2)RR duration is reported to affect the overall performance by switching the product selectivity from H-2 (from water reduction) to CO (from eCO(2)RR) on the oxide-derived alloy surface. This work also succeeded in the multifold enhancement of the current density by employing the gas diffusion electrode (GDE) and optimizing its process parameters in a flow cell configuration.

10aCO2 reduction10aElectrochemistry10aheterostructure interface10ain situ mechanism10ananocatalyst1 aBagchi, Debabrata1 aSarkar, Shreya1 aSingh, Ashutosh, Kumar1 aVinod, Chathakudath, P.1 aPeter, Sebastian, C. uhttps://library.ncl.res.in/content/potential-and-time-dependent-dynamic-nature-oxide-derived-pdin-nanocatalyst-during02244nas a2200277 4500008004100000022001400041245013000055210006900185260000800254300001200262490000700274520132700281653001801608653000701626653002101633653001301654100002201667700001501689700002701704700002201731700002101753700002101774700001801795700002501813856012801838 2022 eng d a0935-964800aStructure-tailored surface oxide on Cu-Ga intermetallics enhances CO2 reduction selectivity to methanol at ultralow potential0 aStructuretailored surface oxide on CuGa intermetallics enhances  cMAY a21094260 v343 a

Electrochemical CO2 reduction reaction (eCO(2)RR) is performed on two intermetallic compounds formed by copper and gallium metals (CuGa2 and Cu9Ga4). Among them, CuGa2 selectively converts CO2 to methanol with remarkable Faradaic efficiency of 77.26% at an extremely low potential of -0.3 V vs RHE. The high performance of CuGa2 compared to Cu9Ga4 is driven by its unique 2D structure, which retains surface and subsurface oxide species (Ga2O3) even in the reduction atmosphere. The Ga2O3 species is mapped by X-ray photoelectron spectroscopy (XPS) and X-ray absorption fine structure (XAFS) techniques and electrochemical measurements. The eCO(2)RR selectivity to methanol are decreased at higher potential due to the lattice expansion caused by the reduction of the Ga2O3, which is probed by in situ XAFS, quasi in situ powder X-ray diffraction, and ex situ XPS measurements. The mechanism of the formation of methanol is visualized by in situ infrared (IR) spectroscopy and the source of the carbon of methanol at the molecular level is confirmed from the isotope-labeling experiments in presence of (CO2)-C-13. Finally, to minimize the mass transport limitations and improve the overall eCO(2)RR performance, a poly(tetrafluoroethylene)-based gas diffusion electrode is used in the flow cell configuration.

10a(2) reduction10aCO10aElectrochemistry10aMethanol1 aBagchi, Debabrata1 aRaj, Jithu1 aSingh, Ashutosh, Kumar1 aCherevotan, Arjun1 aRoy, Soumyabrata1 aManoj, Kaja, Sai1 aVinod, C., P.1 aPeter, Sebastian, C. uhttps://library.ncl.res.in/content/structure-tailored-surface-oxide-cu-ga-intermetallics-enhances-co2-reduction-selectivity