In recent years, single-atom site catalysts (SACs) have achieved great advancements in heterogeneous and electrochemical catalysis due to the merits of maximal atom utilization, unique electronic and geometric structures, low costs, and high catalytic performances. The electronic structures of the isolated metal centers can greatly influence the adsorption energies of reactants and intermediates, thus determining the catalytic activities of SACs. Especially, the electronic structure regulation of the metal sites has been advanced to the atomic level and proven a powerful strategy to enhance their electrocatalytic performances, which provides great opportunities for the further development of SACs. Based on the reported synthesis and structural modulation methods, in this review, the experimental and computational advances in the electronic structure regulation strategies for SACs, including coordination adjustment, electronic metal-support interaction, oxidation state modulation, and strain engineering, will be summarized. Then, the effects of electronic structures on the adsorption behaviors and, thus, the electrocatalytic activities of water splitting and O₂/CO₂ reduction reactions will be emphatically exemplified and discussed. In the end, a brief conclusion of this paper and the existing challenges and future opportunities in this research direction will be proposed. This review aims to highlight the understanding of electronic structure in association to the electrocatalytic activity for SACs and provide guidance for their further development in electrochemical applications.

中文翻译：

---

单原子位点催化剂的电子结构规律及其对电催化性能的影响

近年来，单原子位点催化剂（SACs）由于最大的原子利用率、独特的电子和几何结构、低成本和高催化性能等优点，在多相催化和电化学催化方面取得了长足进步。孤立的金属中心的电子结构可以极大地影响反应物和中间体的吸附能，从而决定 SAC 的催化活性。特别是，金属位点的电子结构调控已被推进到原子水平，并被证明是提高其电催化性能的有力策略，这为 SAC 的进一步发展提供了巨大的机遇。基于报道的合成和结构调制方法，在这篇综述中，将总结 SAC 电子结构调节策略的实验和计算进展，包括配位调节、电子金属-载体相互作用、氧化态调节和应变工程。然后，电子结构对吸附行为的影响，从而对水分解和 O 的电催化活性的影响₂ /CO ₂还原反应将被重点举例说明和讨论。最后，对本文进行简要总结，并提出该研究方向存在的挑战和未来的机遇。本综述旨在强调对与 SAC 电催化活性相关的电子结构的理解，并为其在电化学应用中的进一步发展提供指导。