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A MoO3–MoO2@NiMo heterostructure catalyst shows superior activity for the hydrogen evolution reaction in the universal pH range.

C 2+ through a single process via the CO 2 reduction reaction. Thus, this review focuses on C 2+ products generated through CO 2 ECRR, PCRR, and PECRR.

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The development of electrocatalysts for energy conversion systems is essential for alleviating environmental problems and producing useful energy sources as alternatives to fossil fuels. Improving the catalytic performance and stability of electrocatalysts is a major challenge in the development of energy conversion systems. Moreover, understanding their electrode structure is important for enhancing the energy efficiency. Recently, binder-free self-supported electrodes have been investigated because the seamless contact between the electrocatalyst and substrate minimizes the contact resistance as well as facilitates fast charge transfer at the catalyst/substrate interface and high catalyst utilization. Electrodeposition is an effective and facile method for fabricating self-supported electrodes in aqueous solutions under mild conditions. Facile fabrication without a polymer binder and controlability of the compositional and morphological properties of the electrocatalyst make electrodeposition methods suitable for enhancing the performance of energy conversion systems. Herein, we summarize recent research on self-supported electrodes fabricated by electrodeposition for energy conversion reactions, particularly focusing on cathodic reactions of electrolyzer system such as hydrogen evolution, electrochemical CO 2 reduction, and electrochemical N 2 reduction reactions. The deposition conditions, morphological and compositional properties, and catalytic performance of the electrocatalyst are reviewed. Finally, the prospective directions of electrocatalyst development for energy conversion systems are discussed.

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Summary The production of CO via electrochemical CO2 reduction has been recognised as a promising technology that overcomes the environmental issues caused by global warming. It also facilitates the conversion of CO2 into energy sources. Earth‐abundant Zn is a well‐known alternative to noble metal catalysts such as Au and Ag for the electrochemical CO2 reduction to CO. In particular, Zn‐based materials in the form of nanowires are potentially applicable as electrocatalysts in the electrochemical CO2 reduction. However, the conventional methods for manufacturing the nanowire structure are difficult as they require harsh conditions such as high temperatures and excess energy. In this study, Zn‐based nanowire catalysts are prepared by the facile electrodeposition of Zn nanostructures on a substrate followed by their energy‐free solution‐phase reconstitution. Further, their electrochemical performance in the CO2 reduction is investigated in a CO2‐purged 0.5 M KHCO3 electrolyte. By optimising the deposition conditions, hexagonal Zn (h‐Zn) plates with dominant Zn(101) facets, the favoured crystal structure for CO2 reduction, are fabricated on carbon paper. Furthermore, it is found that, during the solution‐phase reconstruction over 16 hours, the h‐Zn plate transforms to a nanowire owing to the differences between the oxidation rates of different crystal facets and the formation of a hydroxide complex. The activity of the reconstructed Zn‐based nanowire catalyst is enhanced further by forming an oxide layer via thermal treatment in a H2 atmosphere. This treatment boosted the reaction kinetics, thereby enhancing the catalyst performance in the CO2 reduction.