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      2D Metal–Organic Frameworks as Competent Electrocatalysts for Water Splitting

      1 , 1 , 1 , 1 , 2 , 1 , 2
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          Abstract

          Hydrogen, a clean and flexible energy carrier, can be efficiently produced by electrocatalytic water splitting. To accelerate the sluggish hydrogen evolution reaction and oxygen evolution reaction kinetics in the splitting process, highly active electrocatalysts are essential for lowering the energy barriers, thereby improving the efficiency of overall water splitting. Combining the distinctive advantages of metal–organic frameworks (MOFs) with the physicochemical properties of 2D materials such as large surface area, tunable structure, accessible active sites, and enhanced conductivity, 2D MOFs have attracted intensive attention in the field of electrocatalysis. Different strategies, such as improving the conductivities of MOFs, reducing the thicknesses of MOF nanosheets, and integrating MOFs with conductive particles or substrates, are developed to promote the catalytic performances of pristine MOFs. This review summarizes the recent advances of pristine 2D MOF‐based electrocatalysts for water electrolysis. In particular, their intrinsic electrocatalytic properties are detailly analyzed to reveal important roles of inherent MOF active centers, or other in situ generated active phases from MOFs responsible for the catalytic reactions. Finally, the challenges and development prospects of pristine 2D MOFs for the future applications in overall water splitting are discussed.

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          Combining theory and experiment in electrocatalysis: Insights into materials design

          Electrocatalysis plays a central role in clean energy conversion, enabling a number of sustainable processes for future technologies. This review discusses design strategies for state-of-the-art heterogeneous electrocatalysts and associated materials for several different electrochemical transformations involving water, hydrogen, and oxygen, using theory as a means to rationalize catalyst performance. By examining the common principles that govern catalysis for different electrochemical reactions, we describe a systematic framework that clarifies trends in catalyzing these reactions, serving as a guide to new catalyst development while highlighting key gaps that need to be addressed. We conclude by extending this framework to emerging clean energy reactions such as hydrogen peroxide production, carbon dioxide reduction, and nitrogen reduction, where the development of improved catalysts could allow for the sustainable production of a broad range of fuels and chemicals.
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            Universality in Oxygen Evolution Electrocatalysis on Oxide Surfaces

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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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                Author and article information

                Contributors
                Journal
                Small
                Small
                Wiley
                1613-6810
                1613-6829
                April 2023
                January 05 2023
                April 2023
                : 19
                : 15
                Affiliations
                [1 ] School of Materials Science and Engineering National Institute for Advanced Materials Nankai University Tianjin 300350 P. R. China
                [2 ] Smart Sensing Interdisciplinary Science Center Tianjin Key Laboratory of Metal and Molecule‐Based Material Chemistry Nankai University Tianjin 300350 P. R. China
                Article
                10.1002/smll.202207342
                22b5f5db-b7cc-4a5a-afbb-9a1da376b7ef
                © 2023

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