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      Self‐Supported Earth‐Abundant Carbon‐Based Substrates in Electrocatalysis Landscape: Unleashing the Potentials Toward Paving the Way for Water Splitting and Alcohol Oxidation

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          Abstract

          In the vast realm of scientific inquiry, the pursuit of hydrogen fuel production through electrochemical water splitting offers a promising gateway to green energy generation, alleviating the challenges posed by resource scarcity. However, conventional water splitting encounters hurdles like low efficiency and the sluggish oxygen evolution reaction (OER), which prompt searchers to seek for alternative oxidation process. Significant strides are made in conventional electrocatalytic research employing polymeric binders, resulting in commendable catalytic activity and minimal electron migration resistance. Yet, a pivotal breakthrough in this rapidly evolving field lies in the innovative conception of carbon‐based self‐supported electrocatalysts, heralding a promising trajectory ahead. This review delves into the essential electro‐activity parameters to establish the property‐activity nexus, emphasizing the benefits of self‐supported carbon‐based electrodes. Noteworthy advancements are demonstrated in electrochemical hydrogen evolution reaction (HER), OER, overall water splitting (OWS), and bifunctional HER and alcohol oxidation reaction (AOR), driven by a diverse range of self‐supported electrocatalysts. These include structure‐dependent materials such as metal oxides, hydroxides/oxyhydroxides, phosphides, sulfides, selenides, nitrides, and carbides, each meticulously tailored with nuanced modifications that shape their distinctive attributes. This field also acknowledges its challenges and opportunities, providing guidance for potential research directions and inspiring interdisciplinary collaboration among scientists.

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          Electrocatalysis for the oxygen evolution reaction: recent development and future perspectives

          We review the fundamental aspects of metal oxides, metal chalcogenides and metal pnictides as effective electrocatalysts for the oxygen evolution reaction. There is still an ongoing effort to search for sustainable, clean and highly efficient energy generation to satisfy the energy needs of modern society. Among various advanced technologies, electrocatalysis for the oxygen evolution reaction (OER) plays a key role and numerous new electrocatalysts have been developed to improve the efficiency of gas evolution. Along the way, enormous effort has been devoted to finding high-performance electrocatalysts, which has also stimulated the invention of new techniques to investigate the properties of materials or the fundamental mechanism of the OER. This accumulated knowledge not only establishes the foundation of the mechanism of the OER, but also points out the important criteria for a good electrocatalyst based on a variety of studies. Even though it may be difficult to include all cases, the aim of this review is to inspect the current progress and offer a comprehensive insight toward the OER. This review begins with examining the theoretical principles of electrode kinetics and some measurement criteria for achieving a fair evaluation among the catalysts. The second part of this review acquaints some materials for performing OER activity, in which the metal oxide materials build the basis of OER mechanism while non-oxide materials exhibit greatly promising performance toward overall water-splitting. Attention of this review is also paid to in situ approaches to electrocatalytic behavior during OER, and this information is crucial and can provide efficient strategies to design perfect electrocatalysts for OER. Finally, the OER mechanism from the perspective of both recent experimental and theoretical investigations is discussed, as well as probable strategies for improving OER performance with regards to future developments.
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            Design of electrocatalysts for oxygen- and hydrogen-involving energy conversion reactions.

            A fundamental change has been achieved in understanding surface electrochemistry due to the profound knowledge of the nature of electrocatalytic processes accumulated over the past several decades and to the recent technological advances in spectroscopy and high resolution imaging. Nowadays one can preferably design electrocatalysts based on the deep theoretical knowledge of electronic structures, via computer-guided engineering of the surface and (electro)chemical properties of materials, followed by the synthesis of practical materials with high performance for specific reactions. This review provides insights into both theoretical and experimental electrochemistry toward a better understanding of a series of key clean energy conversion reactions including oxygen reduction reaction (ORR), oxygen evolution reaction (OER), and hydrogen evolution reaction (HER). The emphasis of this review is on the origin of the electrocatalytic activity of nanostructured catalysts toward the aforementioned reactions by correlating the apparent electrode performance with their intrinsic electrochemical properties. Also, a rational design of electrocatalysts is proposed starting from the most fundamental aspects of the electronic structure engineering to a more practical level of nanotechnological fabrication.
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              Noble metal-free hydrogen evolution catalysts for water splitting.

              Sustainable hydrogen production is an essential prerequisite of a future hydrogen economy. Water electrolysis driven by renewable resource-derived electricity and direct solar-to-hydrogen conversion based on photochemical and photoelectrochemical water splitting are promising pathways for sustainable hydrogen production. All these techniques require, among many things, highly active noble metal-free hydrogen evolution catalysts to make the water splitting process more energy-efficient and economical. In this review, we highlight the recent research efforts toward the synthesis of noble metal-free electrocatalysts, especially at the nanoscale, and their catalytic properties for the hydrogen evolution reaction (HER). We review several important kinds of heterogeneous non-precious metal electrocatalysts, including metal sulfides, metal selenides, metal carbides, metal nitrides, metal phosphides, and heteroatom-doped nanocarbons. In the discussion, emphasis is given to the synthetic methods of these HER electrocatalysts, the strategies of performance improvement, and the structure/composition-catalytic activity relationship. We also summarize some important examples showing that non-Pt HER electrocatalysts could serve as efficient cocatalysts for promoting direct solar-to-hydrogen conversion in both photochemical and photoelectrochemical water splitting systems, when combined with suitable semiconductor photocatalysts.
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                Author and article information

                Contributors
                (View ORCID Profile)
                Journal
                Advanced Energy Materials
                Advanced Energy Materials
                Wiley
                1614-6832
                1614-6840
                April 2024
                December 31 2023
                April 2024
                : 14
                : 16
                Affiliations
                [1 ] School of Energy and Chemical Engineering Xiamen University Malaysia Selangor Darul Ehsan 43900 Malaysia
                [2 ] Center of Excellence for Nano Energy and Catalysis Technology (CONNECT) Xiamen University Malaysia Selangor Darul Ehsan 43900 Malaysia
                [3 ] State Key Laboratory of Physical Chemistry of Solid Surfaces College of Chemistry and Chemical Engineering Xiamen University Xiamen 361005 China
                [4 ] Gulei Innovation Institute Xiamen University Zhangzhou 363200 China
                [5 ] Shenzhen Research Institute of Xiamen University Shenzhen 518057 China
                Article
                10.1002/aenm.202303614
                b05ee229-1d0e-4845-b657-561fb4e60d1d
                © 2024

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