Mechanochemical in Situ Encapsulation of Palladium in Covalent Organic Frameworks

作者：Normanda Brown, Qingsong Zhang, Ziad Alsudairy, Chaochao Dun, Yogendra Nailwal, Allea Campbell, Chelsea Harrod, Linfeng Chen, Spirit Williams, Jeffrey J. Urban, Yi Liu, Xinle Li · 发表于：ACS Sustainable Chemistry & Engineering · 年份：2024 · DOI：10.1021/acssuschemeng.4c04003 · 被引用次数：20 · 研究领域：Covalent Organic Framework Applications、Metal-Organic Frameworks: Synthesis and Applications、Luminescence and Fluorescent Materials

Palladium-encapsulated covalent organic frameworks (Pd/COFs) have garnered enormous attention in heterogeneous catalysis. However, the dominant ex situ encapsulation synthesis is tedious (multistep), time-consuming (typically 4 days or more), and involves the use of noxious solvents. Here we develop a mechanochemical in situ encapsulation strategy that enables the one-step, time-efficient, and environmentally benign synthesis of Pd/COFs. By ball milling COF precursors along with palladium acetate (Pd(OAc) 2 ) in one pot under air at room temperature, Pd/COF hybrids were readily synthesized within an hour, exhibiting high crystallinity, uniform Pd dispersion, and superb scalability up to gram scale. Moreover, this versatile strategy can be extended to the synthesis of three Pd/COFs. Remarkably, the resulting Pd/DMTP-TPB showcases extraordinary activity (96–99% yield in 1 h at room temperature) and broad substrate scope (>10 functionalized biaryls) for the Suzuki–Miyaura coupling reaction of aryl bromides and arylboronic acids. Furthermore, the heterogeneity of Pd/DMTP-TPB is verified by recycling and leaching tests. The mechanochemical in situ encapsulation strategy disclosed herein paves a facile, rapid, scalable, and environmentally benign avenue to access metal/COF catalysts for efficient heterogeneous catalysis.