Phosphine‐Based Covalent Organic Framework for the Controlled Synthesis of Broad‐Scope Ultrafine Nanoparticles

Abstract In this work, a phosphine‐based covalent organic framework (Phos‐COF‐1) is successfully synthesized and employed as a template for the confined growth of broad‐scope nanoparticles (NPs). Ascribed to the ordered distribution of phosphine coordination sites in the well‐defined pores, various stable and well‐dispersed ultrafine metal NPs including Pd, Pt, Au, and bimetallic PdAuNPs with narrow size distributions are successfully prepared as determined by transmission electron microscopy, X‐ray photoelectron spectroscopy, inductively coupled plasma, and powder X‐ray diffraction analyses. It is also demonstrated that the as‐prepared Phos‐COF‐1‐supported ultrafine NPs exhibit excellent catalytic activities and recyclability toward the Suzuki–Miyaura coupling reaction, reduction of nitro‐phenol and 1‐bromo‐4‐nitrobenzene, and even tandem coupling and reduction of p ‐nitroiodobenzene. This work will open many new possibilities for preparing COF‐supported ultrafine NPs with good dispersity and stability for a broad range of applications.