01948nas a2200265 4500008004100000022001400041245010200055210006900157260000900226300001200235490000600247520110500253100002201358700001501380700001901395700002101414700001901435700001501454700002801469700001601497700001701513700000501530700002501535856012201560 2021 eng d a2380-819500aOperando generated ordered heterogeneous catalyst for the selective conversion of CO2 to methanol0 aOperando generated ordered heterogeneous catalyst for the select cFEB  a509-5160 v63 a

The discovery of new materials for efficient transformation of carbon dioxide (CO2) into desired fuel can revolutionize large-scale renewable energy storage and mitigate environmental damage due to carbon emissions. In this work, we discovered an operando generated stable Ni-In kinetic phase that selectively converts CO2 to methanol (CTM) at low pressure compared to the state-of-the-art materials. The catalytic nature of a well-known methanation catalyst, nickel, has been tuned with the introduction of inactive indium, which enhances the CTM process. The remarkable change in the mechanistic pathways toward methanol production has been mapped by operando diffuse reflectance infrared Fourier transform spectroscopy analysis, corroborated by first-principles calculations. The ordered arrangement and pronounced electronegativity difference between metals are attributed to the complete shift in mechanism. The approach and findings of this work provide a unique advance toward the next-generation catalyst discovery for going beyond the state-of-the-art in CO2 reduction technologies.

1 aCherevotan, Arjun1 aRaj, Jithu1 aDheer, Lakshay1 aRoy, Soumyabrata1 aSarkar, Shreya1 aDas, Risov1 aVinod, Chathakudath, P.1 aXu, Shaojun1 aWells, Peter1 a1 aPeter, Sebastian, C. uhttp://library.ncl.res.in/content/operando-generated-ordered-heterogeneous-catalyst-selective-conversion-co2-methanol02243nas a2200277 4500008004100000022001400041245013000055210006900185260000800254300001200262490000700274520132700281653001801608653000701626653002101633653001301654100002201667700001501689700002701704700002201731700002101753700002101774700001801795700002501813856012701838 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. uhttp://library.ncl.res.in/content/structure-tailored-surface-oxide-cu-ga-intermetallics-enhances-co2-reduction-selectivity01803nas a2200205 4500008004100000022001400041245009700055210006900152260000800221300001400229490000700243520108500250100002701335700002501362700002201387700002101409700001801430700002501448856012401473 2023 eng d a0897-475600aMetal deficiency tailored by the 18-electron rule stabilizes metal-based inorganic compounds0 aMetal deficiency tailored by the 18electron rule stabilizes meta cJUL a6050-60580 v353 a

The 18-electron (18-e(-)) rule is typicallyrestrictedto predicting the stability of transition-metal-based complexes. Herein,we report the use of the 18-e(-) to predict the stabilityin a family of intermetallics MNiSn (M = V, Cr, Fe, and Co) crystallizingin the Co1.75Ge structure type. Site deficiencies at theM site obtained from single-crystal X-ray diffraction are understoodas attaining a stable noble gas electronic configuration. The densityfunctional theory -based structure calculation confirms that the deficientstructure is more stable than the ideal occupation available at thecrystal lattice. MnNiSn, which crystallizes in the half-Heusler crystalstructure, depicts the role of covalent radii of the constituent elementsin determining the crystal structure. Using X-ray absorption spectroscopyand X-ray photoelectron spectroscopy, the local structure of the above-mentionedcompounds was also elucidated, supporting the role of deficiency tunedvalence fluctuation to attain a 18-e(-) configurationthat eventually leads to the formation of stable compounds.

1 aSingh, Ashutosh, Kumar1 aMumbaraddi, Dundappa1 aMishra, Vidyanshu1 aRoy, Soumyabrata1 aVinod, C., P.1 aPeter, Sebastian, C. uhttp://library.ncl.res.in/content/metal-deficiency-tailored-18-electron-rule-stabilizes-metal-based-inorganic-compounds