【摘要】 借助催化剂与电解液界面处的电催化过程如产氢（HER）、产氧（OER）、二氧化碳还原（CO₂RR）、固氮（NRR）等，能够实现非持续性风电、潮汐或太阳能到化学能的转换达到碳中和目的.其中高效电催化剂的构建是实现上述能源转换的关键因素之一.为提高能源转换效率，理想的电催化剂应具备但不限于活性位数量丰富、活性位本征活性优良、电传输性能高效且在相应pH电解液中能够长时间稳定工作.本文以电化学水解（HER/OER）为例，着眼于优良电催化剂构效关系中活性位的构建及其本征活性与局域电子结构中不饱和配位的正相关性展开研究.从酸性和碱性环境中HER和OER反应常用的机制出发，着重以过渡金属氧化物、氢氧化物、磷化物、硫化物等为例，综述了外因诱导产生的局域非均匀场分布处活性位，以及不饱和配位位点与水解中间体的相互作用、电荷转移和质量转移品质对电催化剂水解性能的影响.最后，讨论了过渡金属基电催化剂未来发展需解决的关键问题和挑战.更多还原

【Abstract】 With the help of electrocatalytic processes at the interface between electrocatalyst and electrolyte, non-sustainable wind power, tide or solar energy can be transformed into chemical energy, such as hydrogen evolution reaction（HER）,oxygen evolution reaction（OER）,CO₂ reduction reaction（CO₂RR）,nitrogen reduction reaction（NRR）,and so forth, which resulting the development goal of carbon neutrality.Among them, the construction of efficient electrocatalysts is one of the key factors to achieve the above energy conversion.In order to improve the energy conversion efficiency, the ideal electrocatalyst should have, but not limited to, abundant active sites, excellent intrinsic activity of active sites, high carrier transport performance, and can work stably for a long time in electrolyte with different pH.In this paper, the issue of how to construct efficient active sites in electrocatalysts was focused, and the positive correlation between the intrinsic activity and the unsaturated coordination in the local electronic structure of electrocatalysts was found taking electrochemical hydrolysis（HER/OER） as the example.Based on the mechanisms commonly used in HER and OER reactions for acidic or basic environments, several examples were listed, such as transition metal oxides, hydroxides, phosphides and sulphides, to insight the active sites located at the interfaces that induced by external, the interaction of unsaturated coordination sites to hydrolysis intermediates, and also the charge transfer and mass transfer mechanics during electrocatalyst overall water splitting by theoretical investigation.Finally, the key issues and the challenges to be addressed were discussed for the future development of transition metal-based electrocatalysts.更多还原