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

Abstract

AbstractSynergistic sites (M1+Mn) integrating single atoms (M1) and clusters (Mn) 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 M1 and Mn 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 M1+Mn sites. This is systematically altered that the interface of Pd1+Pdn 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 Pd1+Pdn sites with varying interfaces and hydrogenation activities are observed, peaking for those supported on NC/HAP. The obtained Pd1+Pdn@NC/HAP exhibits superior activity for alkynol‐to‐enol conversion, achieving a formation rate up to 3707.7 mol molPd−1 h−1 while maintaining 97.2% selectivity. Comprehensive investigations propose d‐band center of Pd1+Pdn sites with different interfaces as a descriptor to elucidate the volcano‐type correlation for various selective hydrogenation reactions. Interfacial modification of Pd1+Pdn sites can optimize their electronic structure, adeptly managing substrates adsorption–desorption kinetic and interface H‐spillover between segregated metal sites, thereby breaking −the activity‐selectivity‐stability trade‐off.