Mechanochemical in Situ Encapsulation of Palladium in Covalent Organic Frameworks

Brown, Normanda; Zhang, Qingsong; Alsudairy, Ziad; Dun, Chaochao; Nailwal, Yogendra; Campbell, Allea; Harrod, Chelsea; Chen, Linfeng; Williams, Spirit; Urban, Jeffrey J.; Liu, Yi; Li, Xinle

doi:10.1021/acssuschemeng.4c04003

Mechanochemical in Situ Encapsulation of Palladium in Covalent Organic Frameworks

Journal Article · Tue Aug 27 00:00:00 EDT 2024 · ACS Sustainable Chemistry & Engineering

DOI:https://doi.org/10.1021/acssuschemeng.4c04003· OSTI ID:2439964

Brown, Normanda ^[1]; Zhang, Qingsong ^[2]; Alsudairy, Ziad ^[1]; ^[2]; Nailwal, Yogendra ^[1]; Campbell, Allea ^[1]; Harrod, Chelsea ^[1]; ^[2]; Williams, Spirit ^[1]; ^[2]; ^[2]; ^[1]

Clark Atlanta Univ., Atlanta, GA (United States)
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). Molecular Foundry

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. Finally, 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.

View Accepted Manuscript (DOE)

Research Organization:: Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities (SUF)

Grant/Contract Number:: AC02-05CH11231; SC0022000

OSTI ID:: 2439964

Journal Information:: ACS Sustainable Chemistry & Engineering, Journal Name: ACS Sustainable Chemistry & Engineering Journal Issue: 36 Vol. 12; ISSN 2168-0485

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
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heterogeneous catalysis
in situ metal encapsulation
mechanochemistry
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Mechanochemical in Situ Encapsulation of Palladium in Covalent Organic Frameworks

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