Interface Modification of Single Atom‐Nanocluster Synergistic Sites to Break the Activity‐Selectivity‐Stability Trade‐Off in Selective Hydrogenations

作者：Zemin Chen, Chufei Wang, Boning Zhang, Jianing Li, Dechen Wang, Guangyue Xu, Junjie Zhang, Mi Peng, Ding Ma, Ying Zhang · 发表于：Advanced Materials · 年份：2025 · DOI：10.1002/adma.202503841 · 被引用次数：26 · 研究领域：Nanomaterials for catalytic reactions、Nanocluster Synthesis and Applications、Advanced Photocatalysis Techniques

Abstract Synergistic sites (M 1 +M n ) integrating single atoms (M 1 ) and clusters (M n ) exhibit tremendous promise for overcoming linear scaling relationships. However, metal entities spatial segregation within synergistic sites impedes the overall optimization and structure‐property analysis, and the support interface of the M 1 and M n sites critical for intermediate adsorption‐transfer kinetics has yet unexplored. Here, for the first time, interfacial modification strategy is proposed to modulate the interface and electronic structure of M 1 +M n sites. This is systematically altered that the interface of Pd 1 +Pd n sites from hydroxyapatite (HAP) to nitrogen‐doped carbon‐modified HAP (NC/HAP) and pure NC, with all sites maintaining the comparable size and content. In the semi‐hydrogenation of alkynes, volcano‐type correlations between Pd 1 +Pd n sites with varying interfaces and hydrogenation activities are observed, peaking for those supported on NC/HAP. The obtained Pd 1 +Pd n @NC/HAP exhibits superior activity for alkynol‐to‐enol conversion, achieving a formation rate up to 3707.7 mol mol Pd −1 h −1 while maintaining 97.2% selectivity. Comprehensive investigations propose d‐band center of Pd 1 +Pd n sites with different interfaces as a descriptor to elucidate the volcano‐type correlation for various selective hydrogenation reactions. Interfacial modification of Pd 1 +Pd n sites can optimize their electronic structure, adeptly managing substrates adsorption–desorptio...