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    28 October 2022, Volume 28 Issue 10
    Special Issue on Water Electrolysis for Hydrogen Production
    Table of Contents
    2022, 28(10):  0-0. 
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    2022, 28(10):  2214111. 
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    Alkaline Seawater Electrolysis at Industrial Level:Recent Progress and Perspective
    Tao Zhang, Yi-Pu Liu, Qi-Tong Ye, Hong-Jin Fan
    2022, 28(10):  2214006.  doi:10.13208/j.electrochem.2214006
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    Industrial hydrogen generation through water splitting, powered by renewable energy such as solar, wind and marine, paves a potential way for energy and environment sustainability. However, state-of-the-art electrolysis using high purity water as hydrogen source at an industrial level would bring about crisis of freshwater resource. Seawater splitting provides a practical path to solve potable water shortage, but still faces great challenges for large-scale industrial operation. Here we summarize recent developments in seawater splitting, covering general mechanisms, design criteria for electrodes, and industrial electrolyzer for direct seawater splitting. Multi-objective optimization methods to address the key challenges of active sites, reaction selectivity, corrosion resistance, and mass transfer ability will be discussed. The recent development in seawater electrolyzer and acquaint efficient strategies to design direct devices for long-time operation are also highlighted. Finally, we provide our own perspective to future opportunities and challenges towards direct seawater electrolysis.

    Electrochemical Syntheses of Nanomaterials and Small Molecules for Electrolytic Hydrogen Production
    Jia-Qi Wei, Xiao-Dong Chen, Shu-Zhou Li
    2022, 28(10):  2214012.  doi:10.13208/j.electrochem.2214012
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    Hydrogen is a clean, efficient, renewable energy resource and the most promising alternative to fossil fuels for future carbon-neutral energy supply. Therefore, sustainable hydrogen production is highly attractive and urgently demanded, especially via water electrolysis that has clean, abundant precursors and zero emission. However, current water electrolysis is hindered by the sluggish kinetics and low cost/energy efficiency of both hydrogen evolution reaction (HER) and oxygen evolution reaction (OER). In this regard, electrochemical synthesis offers prospects to raise the efficiency and benefit of water electrolysis by fabricating advanced electrocatalysts and providing more efficient/value-adding co-electrolysis alternatives. It is an eco-friendly and facile fabrication method for materials ranging from molecular to nano scales via electrolysis or other electrochemical operations. In this review, we firstly introduce the basic concepts, design protocols, and typical methods of electrochemical synthesis. Then, we summarize the applications and advances of electrochemical synthesis in the field of electrocatalytic water splitting. We focus on the synthesis of nanostructured electrocatalysts towards more efficient HER, as well as electrochemical oxidation of small molecules to replace OER for more efficient and/or value-adding co-electrolysis with HER. We systematically discuss the relationship between electrochemical synthetic conditions and the product morphology, selectivity to enlighten future explorations. Finally, challenges and perspectives for electrochemical synthesis towards advanced water electrolysis, as well as other energy conversion and storage applications are featured.

    Alkaline Water Electrolysis for Efficient Hydrogen Production
    Wen-Fu Xie, Ming-Fei Shao
    2022, 28(10):  22014008.  doi:10.13208/j.electrochem.2214008
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    Hydrogen production from water electrolysis is a sustainable and environmentally benign strategy in comparison with fossil fuel-based hydrogen. However, this promising technique suffers from the high energy consumption and unsatisfactory cost due to the sluggish kinetics of both half reaction and inferior stability of electrocatalysts. To address this challenge, herein, we present a timely and comprehensive review on advances in alkaline water electrolysis that is already commercialized for large scale hydrogen production. The design principles and strategies with aiming to promote the performance of hydrogen generation are discussed from the view of electrocatalyst, electrode, reaction and system. The challenges and related prospects are presented at last, hopefully to provide essential ideas and to promote the wide application of hydrogen production.

    A Self-Supported Ru-Cu3P Catalyst toward Alkaline Hydrogen Evolution
    Zi-Xuan Wan, Chao-Hui Wang, Xiong-Wu Kang
    2022, 28(10):  2214005.  doi:10.13208/j.electrochem.2214005
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    Transition metal phosphide (TMP) is a kind of effective catalysts toward hydrogen evolution reaction (HER) in alkaline electrolytes. However, the performance of TMP catalysts is strongly limited by water splitting. In this work, we developed a method to prepare a copper foam (CF) supported Ru-doped Cu3P catalyst (Ru-Cu3P/CF) by a consecutive growth of Cu(OH)2 nanoarrays, soaking in RuCl3 solution and phosphorization. A large surface area was obtained by the self-supported catalysts with the appropriative Ru doping. As an excellent HER catalyst, it exhibited a low overpotential of 95.6 mV at a current density of 10 mA·cm-2, which is 149.4 mV lower than that of Cu3P/CF without Ru-doping. The Tafel slope was reduced from 136.6 to 73.6 mA·dec-1 and the rate determining step was changed from Volmer step to Heyrovsky step. The improvement of HER performance might be attributed to the facilitated water splitting step by Ru-doping, which provides more active sites for water splitting. The nanoparticles morphology of Ru-Cu3P derived from the Cu(OH)2 arrays ensured large electrochemical surface areas of the supported electrodes, which could promote the mass and electron transfers, and promote gas production and bubble release. This work highlights the importance of the tuning of the water splitting step and surface engineering by the transition metal with emptier d orbitals, which may pave the road for design of high-performance HER electrocatalyst.

    Catalytic Effect of Disordered Ru-O Configurations for Electrochemical Hydrogen Evolution
    Xue Sun, Ya-Jie Song, Ren-Long Li, Jia-Jun Wang
    2022, 28(10):  2214011.  doi:10.13208/j.electrochem.2214011
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    Phase engineering is considered as an effective method for modulating the electronic structure and catalytic activity of catalysts. The disordered conformation of amorphous materials allows flexible reforming of the surface electronic structure, showing their attractiveness as catalysts for hydrogen evolution reaction (HER). Herein, we designed and developed an amorphous ruthenium dioxide (a-RuO2) catalyst with a disordered Ru-O configuration. The conformational relationship between Ru-O ordering and HER performance is established by combining advanced electron microscopic techniques with detailed electrochemical tests. Specifically, the disordered Ru-O coordination significantly enhanced the HER catalytic activity in both acidic and alkaline media, ultimately leading to HER performance of a-RuO2 approaching that of commercial Pt/C with higher economics. In addition, a-RuO2 exhibited excellent stability after 10 h current-time (i-t) testing at 10 mA·cm-2. Further theoretical simulations showed that the lowered d-band center and optimized electron transport of a-RuO2 modulated the adsorption strength of the active site to the intermediate reactants, promoting HER kinetics. This work provides a new perspective for exploring highly active HER catalysts through phase engineering.