Integrating electrolytic hydrogen production from water with thermodynamically more favorable aqueous organic oxidation reactions is highly desired, because it can enhance the energy conversion efficiency in relation to traditional water electrolysis, and produce value-added chemicals instead of oxygen at the anode. In this Minireview, we introduce some key considerations for anodic auxiliary electrosynthesis and outline three types of electrocatalytic organic reactions including biomass derivative, alcohol and amine oxidation reactions, which can boost cathodic hydrogen generation. Furthermore, frequently used noble-metal-free electrocatalysts are classified into nickel-based, cobalt-based, other transition-metal-based and bimetallic electrocatalysts. The preparation methods of these catalysts and their performance towards electrochemical oxidation reactions are also discussed in detail. We specifically highlight the importance of redox active sites on the surface of the electrocatalysts, which act as electron mediators to promote oxidation reactions. Finally, the current challenges and future developments in this emerging field are also discussed.

中文翻译：

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在非贵金属电催化剂上通过阳极电合成水中的增值化学品加速氢气的释放

非常需要将水电解制氢与热力学上更有利的水性有机氧化反应相结合，因为它可以提高与传统水电解相比的能量转换效率，并在阳极产生增值化学品而不是氧气。在这篇 Minireview 中，我们介绍了阳极辅助电合成的一些关键考虑因素，并概述了三种类型的电催化有机反应，包括生物质衍生物、醇和胺氧化反应，它们可以促进阴极氢气的产生。此外，常用的不含贵金属的电催化剂分为镍基、钴基、其他过渡金属基和双金属电催化剂。还详细讨论了这些催化剂的制备方法及其对电化学氧化反应的性能。我们特别强调了电催化剂表面氧化还原活性位点的重要性，它们作为电子介体促进氧化反应。最后，还讨论了这一新兴领域的当前挑战和未来发展。