Advances in the study of HOR reaction mechanisms under alkaline conditions

Yuru Liao , Shengchen Wang , Yifan Zhang , Yue Zhang , Yun Gao , Xueqin Mu , Suli Liu , Dingsheng Wang , Zhihui Dai
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Abstract

Hydrogen energy is an important energy carrier, which is an ideal choice to meet energy demand and reduce harmful gas emissions. The green recycling of hydrogen energy depends on water electrolysis and hydrogen fuel cells, which involves hydrogen oxidation reaction (HOR) and hydrogen evolution reaction (HER). The activity of HER/HOR in alkaline electrolyte, however, exhibits a significantly lower magnitude (2–3 orders) compared to that observed in an acidic medium, which hinders the development of alkaline water electrolysis and alkaline membrane fuel cells. Therefore, comprehending the characteristics of HOR/HER activity in alkaline electrolytes and elucidating its underlying mechanism is a prerequisite for the design of advanced electrocatalysts. Based on this background, this review will briefly summarize the explanations and controversies about the basic HOR mechanism, including bifunctional mechanism and hydrogen binding energy theory. Moreover, the crucial affecting factors of the HOR kinetics, such as d-band center theory, interfacial water recombination, alkali metal cations and electronic effects, are discussed. Thus, based on the above theories, the design principle, catalytic performance, and latest progress of HOR electrocatalysts are summarized. An outlook and future research perspectives of advanced catalysts for hydrogen energy recycling are addressed. This review is helpful to understand the latest development of HOR mechanism and design cost-effective and high-performance HOR electrocatalysts towards the production of clean renewable energies.

碱性条件下 HOR 反应机制的研究进展
氢能是一种重要的能源载体,是满足能源需求和减少有害气体排放的理想选择。氢能的绿色循环利用依赖于水电解和氢燃料电池,其中涉及氢氧化反应(HOR)和氢进化反应(HER)。然而,与在酸性介质中观察到的氢氧化反应/氢进化反应相比,碱性电解质中的氢氧化反应/氢进化反应的活性明显较低(2-3 个数量级),这阻碍了碱性水电解和碱性膜燃料电池的发展。因此,了解碱性电解质中 HOR/HER 活性的特点并阐明其潜在机制是设计先进电催化剂的先决条件。基于这一背景,本综述将简要总结有关 HOR 基本机理的解释和争议,包括双功能机理和氢结合能理论。此外,还讨论了影响 HOR 动力学的关键因素,如 d 带中心理论、界面水重组、碱金属阳离子和电子效应。因此,基于上述理论,总结了 HOR 电催化剂的设计原理、催化性能和最新进展。并对先进的氢能回收催化剂进行了展望和未来的研究前景。本综述有助于了解 HOR 机理的最新发展,并设计出经济高效的高性能 HOR 电催化剂,从而生产出清洁的可再生能源。
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