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Abstract Doping gold nanoparticles within covalent organic frameworks (AuNPs@COFs) has garnered enormous momentum due to their unique properties and broad applications. Nevertheless, prevailing multi‐step synthesis is plagued with low time efficiency, eco‐unfriendliness, and tedious protocols. Herein, we introduce a rapid, sustainable, scalable, one‐step mechanochemical strategy for synthesizing up to four AuNPs‐doped COFs via steel ball milling within an hour under ambient conditions. This approach overcomes the synthetic barriers of conventional multi‐step solution‐based methods, such as extended reaction times (5 days), milligram scale, the use of toxic solvents, elevated temperatures, and reliance on external reducing agents. One exemplary AuNPs@COF (AuNPs@DMTP‐TPB) exhibits high crystallinity, porosity, small AuNP size, and uniform dispersion (5.4±0.6 nm), surpassing its counterpart synthesized via multi‐step solution‐based methods (6.4±1.1 nm). Notably, the gram‐scale synthesis of AuNPs@DMTP‐TPB can be successfully achieved. Control experiments suggest that thein situformation of AuNPs is attributed to the galvanic reduction of gold precursor by stainless steel apparatus. As a proof‐of‐concept catalytic application, AuNPs@DMTP‐TPB demonstrates remarkable catalytic activity and recyclability for the aqueous reduction of 4‐nitrophenol under ambient conditions. This study provides an environmentally benign and fast pathway to synthesize AuNPs@COFs via mechanochemistry for the first time, opening tremendous possibilities for heterogeneous catalysis and beyond. 

Covalent organic framework (COF)-supported palladium catalysts have garnered enormous attention for cross-coupling reactions. However, the limited linkage types in COF hosts and their suboptimal catalytic performance have hindered their widespread implementation. Herein, we present the first study immobilizing palladium acetate onto a dioxin-linked COF (Pd/COF-318) through a facile solution impregnation approach. By virtue of its permanent porosity, accessible Pd sites arranged in periodic skeletons, and framework robustness, the resultant Pd/COF-318 exhibits exceptionally high activity and broad substrate scope for the Suzuki–Miyaura coupling reaction between aryl bromides and arylboronic acids at room temperature within an hour, rendering it among the most effective Pd/COF catalysts for Suzuki–Miyaura coupling reactions to date. Moreover, Pd/COF-318 demonstrates excellent recyclability, retaining high activity over five cycles without significant deactivation. The leaching test confirms the heterogeneity of the catalyst. This work uncovers the vast potential of dioxin-linked COFs as catalyst supports for highly active, selective, and durable organometallic catalysis. 

Delineated here is the first mechanochemical synthesis of covalent organic frameworks (COF) adsorbents that exhibited exceptional iodine adsorption capacities of 6.4–7.1 g g⁻¹, surpassing those of most existing COFs.