Interface Modification of Single Atom-Nanocluster Synergistic Sites to Break the Activity-Selectivity-Stability Trade-Off in Selective Hydrogenations.
basic_science · Level V
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- Record sourced from PubMed, PMID 40437891.
- Also identified by DOI 10.1002/adma.202503841.
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Abstract
Synergistic sites (M<sub>1</sub>+M<sub>n</sub>) integrating single atoms (M<sub>1</sub>) and clusters (M<sub>n</sub>) 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<sub>1</sub> and M<sub>n</sub> 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<sub>1</sub>+M<sub>n</sub> sites. This is systematically altered that the interface of Pd<sub>1</sub>+Pd<sub>n</sub> 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<sub>1</sub>+Pd<sub>n</sub> sites with varying interfaces and hydrogenation activities are observed, peaking for those supported on NC/HAP. The obtained Pd<sub>1</sub>+Pd<sub>n</sub>@NC/HAP exhibits superior activity for alkynol-to-enol conversion, achieving a formation rate up to 3707.7 mol mol<sub>Pd</sub> <sup>-1</sup> h<sup>-1</sup> while maintaining 97.2% selectivity. Comprehensive investigations propose d-band center of Pd<sub>1</sub>+Pd<sub>n</sub> sites with different interfaces as a descriptor to elucidate the volcano-type correlation for various selective hydrogenation reactions. Interfacial modification of Pd<sub>1</sub>+Pd<sub>n</sub> sites can optimize their electronic structure, adeptly managing substrates adsorption-desorption kinetic and interface H-spillover between segregated metal sites, thereby breaking <sup>-</sup>the activity-selectivity-stability trade-off.