Ye Yuting, Tang Qing
School of Chemistry and Chemical Engineering, Chongqing Key Laboratory of Chemical Theory and Mechanism, Chongqing University, Chongqing 401331, China.
Nanoscale Horiz. 2025 Jul 21;10(8):1597-1614. doi: 10.1039/d5nh00153f.
Ultrasmall metal nanoclusters (NCs) with atomic precision possess a size range between individual atoms and plasmonic nanomaterials. These atomically precise materials represent an emerging class of nanocatalysts, offering unique opportunities to explore electrocatalytic properties and establish precise structure-property correlations at the atomic scale. Among the large number of metal NCs that are stabilized by various ligands, thiolate-protected metal NCs are a particularly prominent class for electrocatalytic investigations. Recent experimental and theoretical studies have demonstrated the significant potential of these materials in enhancing various electrocatalytic reactions, including hydrogen evolution, oxygen reduction and CO reduction reactions. However, comprehensive and in-depth discussions regarding their catalytic properties, particularly from a theoretical standpoint, are limited and require further explorations. In this review, we focus on the recent progress in thiolate-protected metal NCs in the field of electrocatalysis. The influences of structure, ligand, doping and interface control on their electrocatalytic activity/selectivity and the reaction mechanisms are discussed. Importantly, the perspectives we propose regarding future research endeavors are expected to offer valuable references for subsequent investigations in this area.
具有原子精度的超小金属纳米团簇（NCs）的尺寸范围介于单个原子和等离子体纳米材料之间。这些具有原子精度的材料代表了一类新兴的纳米催化剂，为探索电催化性能以及在原子尺度上建立精确的结构-性能关系提供了独特的机会。在众多由各种配体稳定的金属NCs中，硫醇盐保护的金属NCs是电催化研究中特别突出的一类。最近的实验和理论研究表明，这些材料在增强各种电催化反应方面具有巨大潜力，包括析氢反应、氧还原反应和CO还原反应。然而，关于它们的催化性能，特别是从理论角度进行的全面深入讨论有限，需要进一步探索。在这篇综述中，我们关注硫醇盐保护的金属NCs在电催化领域的最新进展。讨论了结构、配体、掺杂和界面控制对其电催化活性/选择性以及反应机理的影响。重要的是，我们对未来研究工作提出的观点有望为该领域的后续研究提供有价值的参考。
