Tailoring Catalysis of Encapsulated Pt Nanoparticles by Pore Wall Engineering of Covalent Organic Frameworks

Abstract While supported metal nanoparticles (NPs) have shown significant promise in heterogeneous catalysis, precise control over their interaction with the support, which profoundly impacts their catalytic performance, remains a significant challenge. In this study, Pt NPs are incorporated into thioether‐functionalized covalent organic frameworks (denoted COF‐S x ), enabling precise control over the size and electronic state of Pt NPs by adjusting the thioether density dangling on the COF pore walls. Notably, the resulting Pt@COF‐S x demonstrate exceptional selectivity (> 99 %) in catalytic hydrogenation of p ‐chloronitrobenzene to p ‐chloroaniline, in sharp contrast to the poor selectivity of Pt NPs embedded in thioether‐free COFs. Furthermore, the conversion over Pt@COF‐S x exhibits a volcano‐type curve as the thioether density increases, due to the corresponding change of accessible Pt sites. This work provides an effective approach to regulating the catalysis of metal NPs via their microenvironment modulation, with the aid of rational design and precise tailoring of support structure.