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      Operando X-ray absorption spectroscopy of a Pd/γ-NiOOH 2 nm cubes hydrogen oxidation catalyst in an alkaline membrane fuel cell

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          Abstract

          The mechanism of Pd/γ-NiOOH 2 nm cubes hydrogen oxidation catalyst for alkaline fuel cell is investigated by operando X-ray absorption spectroscopy.

          Abstract

          A fundamental understanding of the hydrogen oxidation reaction (HOR) mechanism requires the synthesis of model catalysts with designed surfaces, and advanced characterization techniques of the active sites. Although HOR are fast under acidic conditions, HOR kinetics are sluggish under alkaline conditions, even on platinum group metals (PGMs). Herein, we propose the use of an effective high-surface-area carbon supported Pd/γ-NiOOH HOR electrocatalyst, made from organometallic precursors. The enhanced activity, provided by nickel oxy-hydroxide (γ-NiOOH) 2 nm nanocubes, was confirmed experimentally in an alkaline exchange membrane fuel cell. Contrary to previous reports, the phase and crystallographic orientation of the γ-NiOOH nanocubes (<2 nm in size) were fully ascribed through high-resolution transmission electron microscopy. Operando X-ray absorption spectroscopy revealed a redox behavior of Pd and Ni during the electrocatalysis. Each phase has an attributed role in the mechanism, i.e., hydrogen binding to the Pd metal and hydroxide binding to the γ-NiOOH, confirming the theory and experiments observed with bimetallic structures.

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          Trends in activity for the water electrolyser reactions on 3d M(Ni,Co,Fe,Mn) hydr(oxy)oxide catalysts.

          Design and synthesis of materials for efficient electrochemical transformation of water to molecular hydrogen and of hydroxyl ions to oxygen in alkaline environments is of paramount importance in reducing energy losses in water-alkali electrolysers. Here, using 3d-M hydr(oxy)oxides, with distinct stoichiometries and morphologies in the hydrogen evolution reaction (HER) and the oxygen evolution reaction (OER) regions, we establish the overall catalytic activities for these reaction as a function of a more fundamental property, a descriptor, OH-M(2+δ) bond strength (0 ≤ δ ≤ 1.5). This relationship exhibits trends in reactivity (Mn < Fe < Co < Ni), which is governed by the strength of the OH-M(2+δ) energetic (Ni < Co < Fe < Mn). These trends are found to be independent of the source of the OH, either the supporting electrolyte (for the OER) or the water dissociation product (for the HER). The successful identification of these electrocatalytic trends provides the foundation for rational design of 'active sites' for practical alkaline HER and OER electrocatalysts.
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            Enhancing hydrogen evolution activity in water splitting by tailoring Li⁺-Ni(OH)₂-Pt interfaces.

            Improving the sluggish kinetics for the electrochemical reduction of water to molecular hydrogen in alkaline environments is one key to reducing the high overpotentials and associated energy losses in water-alkali and chlor-alkali electrolyzers. We found that a controlled arrangement of nanometer-scale Ni(OH)(2) clusters on platinum electrode surfaces manifests a factor of 8 activity increase in catalyzing the hydrogen evolution reaction relative to state-of-the-art metal and metal-oxide catalysts. In a bifunctional effect, the edges of the Ni(OH)(2) clusters promoted the dissociation of water and the production of hydrogen intermediates that then adsorbed on the nearby Pt surfaces and recombined into molecular hydrogen. The generation of these hydrogen intermediates could be further enhanced via Li(+)-induced destabilization of the HO-H bond, resulting in a factor of 10 total increase in activity.
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              Anion-exchange membranes in electrochemical energy systems

              A detailed perspective on the use of anion-exchange membranes in fuel cells, electrolysers, flow batteries, reverse electrodialysis, and bioelectrochemical systems.
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                Author and article information

                Contributors
                Journal
                CSTAGD
                Catalysis Science & Technology
                Catal. Sci. Technol.
                Royal Society of Chemistry (RSC)
                2044-4753
                2044-4761
                March 2 2021
                2021
                : 11
                : 4
                : 1337-1344
                Affiliations
                [1 ]Department of Chemistry
                [2 ]Bar Ilan Institute of Technology and Advanced Materials (BINA)
                [3 ]Bar Ilan University
                [4 ]Ramat Gan
                [5 ]Israel
                [6 ]Institute of Materials and Environmental Chemistry
                [7 ]Hungarian Academy of Sciences
                [8 ]Budapest
                [9 ]Hungary
                [10 ]Department of Chemistry and Chemical Biology
                [11 ]Northeastern University
                [12 ]Boston
                [13 ]USA
                [14 ]PO-CellTech Ltd.
                [15 ]Caesarea
                [16 ]30889 Israel
                Article
                10.1039/D0CY01815E
                9367a5bf-bc75-443d-9f5d-9ff487271d74
                © 2021

                Free to read

                http://rsc.li/journals-terms-of-use#chorus

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