联产混合电解水策略实现节能电化学制氢的最新进展

Energy-saving electrochemical hydrogen production via co-generative strategies in hybrid water electrolysis:Recent advances and perspectives

随着全球能源需求增长和环境污染加剧,发展可持续能源减少对化石燃料(如石油、天然气和煤炭等)的消耗成为实现人类社会可持续发展的关键.氢能因其能量密度高、燃烧无污染、应用形式多样被认为是最理想的替代能源.电解水制氢包括阴极析氢反应(HER)和阳极析氧反应(OER),具有绿色环保、生产灵活和纯度高等特点,是理想的绿色生产技术之一.然而,阳极电解水产氧反应动力学缓慢,导致阴极的产氢效率低.此外,在电解水过程中,会产生高氧化性的过氧化氢(H_(2)O_(2)),降低电解水膜的寿命,阻碍电解水技术的实际应用.因此,亟待开发新型高效、稳定且具有高附加值的电解水催化剂.目前,电化学整体水分解(OWS)制氢技术存在安全风险、投资回报低、阳极OER动力学慢和电能消耗大等问题,将阳极氧化反应与混合电解水(HWE)装置中的HER相结合,借助热力学较好的电氧化反应取代缓慢的传统OER反应协同产氢,可以有效克服传统电解水的产率不足,解决污染排放和生物质回收问题.本文综述了协同电催化用于联产氢气和低能耗、高法拉第效率高价值产品的催化剂结构设计,揭示不同协同电催化系统的催化途径和意义,以实现更高效、零碳排放的目标.首先,介绍了HWE系统的发展现状,重点关注各种富氢物质的协同电解,例如酒精、生物质衍生物、葡萄糖和在阳极形成的高附加值化学品.与传统阳极OER工艺相比,有机/生物质底物小分子的OER表现出较低的热力学需求,降低产氢能耗.随后,详细介绍了基于阴极HER和阳极OER协同电解反应、协同催化HWE高效电极/电催化剂的合理设计,以实现高催化活性、高选择性和良好的电化学稳定性.重点讨论了新型电极/电催化剂设计、活性改进以及结构-催化活性关系提升的合成策略.再后,讨论了基于有机/生物质小分子协同HWE系统电催化的代表性研究进展和突破,强调了其在促进可持续低压制氢方面的重要作用,并回顾了近年来HWE的研究突破,同时,对一些可行性分析和机理探索进行比较,为制氢提供了新的研究方向.最后,提出了协同电催化制氢面临的挑战并展望未来的研究方向.综上,大多数电催化剂存在催化活性低、稳定性差等问题,要实现可持续、经济高效和清洁的产氢技术,仍有很多方面需要进一步的深入研究.本文综述了高效多功能HWE系统发展现状和催化剂结构设计,为电解水制氢和高附加值产品的节能联产提供一定的参考.

Traditional overall water splitting has been regarded as a potential pathway for H_(2)production,but the intrinsic slow kinetics of the anodic oxygen evolution reaction severely hampers the efficiency of H_(2)production.Given the challenges in traditional water electrolysis,coupling the kinetically favorable anodic electrooxidation reactions of easily oxidizable substances with the hydrogen evolution reaction in a hybrid water electrolysis(HWE)configuration not only solves the pollutant emission and biomass recycling problems but also maximizes the return on energy profiteering.Various advanced compounds have been engineered through compositional regulation,structural optimization,surface nano-building,and electronic structure modification,yet some issues like tedious preparation and unsatisfactory durability still exist.Considering the gap between research and practical deployment,this review amply addresses the state-of-the-art achievements of synergistic electrocatalysis systems for the co-production of high-purity H_(2)and valuable products with a low energy consumption and high Faradaic efficiency.An overview of HWE system is presented first accompanied by a discussion on the design and engineering of high reactive/selective/stable electrodes/electrocatalysts for anodic oxidation of organic/biomass substrates.Importantly,the in-depth understanding of possible reaction mechanisms from both experimental and theoretical perspectives is elucidated to promote the efficiency of synergistic electrocatalysis.Subsequently,the recent research breakthroughs in the field of HWE technology are emphatically reviewed,providing a new room for low-voltage H_(2)generation from waste products and renewable feedstock.Some mechanism explorations,feasibility analyses,and correlation comparisons are highlighted.Finally,we propose the prospects on existing challenges with some opportunities for future research directions to push forward the progress in synergistic electrocatalysis configurations.