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

References (47)

Exploiting Noncovalent Interactions in an Imine-Based Covalent Organic Framework for Quercetin Delivery Vyas, Vijay S.; Vishwakarma, Medhavi; Moudrakovski, Igor Advanced Materials, Vol. 28, Issue 39 https://doi.org/10.1002/adma.201603006	journal	August 2016
Predesigned Covalent Organic Frameworks as Effective Platforms for Pd(II) Coordination Enabling Cross‐Coupling Reactions under Sustainable Conditions López‐Magano, Alberto; Mas‐Ballesté, Rubén; Alemán, José Advanced Sustainable Systems, Vol. 6, Issue 3 https://doi.org/10.1002/adsu.202100409	journal	December 2021
Hybrid Porous Crystalline Materials from Metal Organic Frameworks and Covalent Organic Frameworks Chen, Ziman; Li, Xinle; Yang, Chongqing Advanced Science, Vol. 8, Issue 20 https://doi.org/10.1002/advs.202101883	journal	August 2021
Beyond Solvothermal: Alternative Synthetic Methods for Covalent Organic Frameworks Hu, Jiyun; Huang, Zhiyuan; Liu, Yi Angewandte Chemie International Edition, Vol. 62, Issue 37 https://doi.org/10.1002/anie.202306999	journal	June 2023
Scalable Mechanochemical Synthesis of β ‐Ketoenamine‐linked Covalent Organic Frameworks for Methane Storage Asokan, Kiran; Patil, Manoj Krishnat; Mukherjee, Shatabdi Porel Chemistry – An Asian Journal, Vol. 17, Issue 24 https://doi.org/10.1002/asia.202201012	journal	November 2022
A Pd(II)‐Functionalized Covalent Organic Framework for Catalytic Conjugate Additions of Arylboronic Acids to β,β‐Disubstituted Enones Heintz, Patrick M.; Schumacher, Brian P.; Chen, Minda ChemCatChem, Vol. 11, Issue 17 https://doi.org/10.1002/cctc.201900894	journal	July 2019
One‐Pot Fabrication of Pd Nanoparticles@Covalent‐Organic‐Framework‐Derived Hollow Polyamine Spheres as a Synergistic Catalyst for Tandem Catalysis Yang, Xinyi; He, Yajun; Li, Liuyi Chemistry – A European Journal, Vol. 26, Issue 8 https://doi.org/10.1002/chem.201904731	journal	November 2019
Microwave‐Assisted Synthesis of Covalent Organic Frameworks: A Review Díaz de Greñu, Borja; Torres, Juan; García‐González, Javier ChemSusChem, Vol. 14, Issue 1 https://doi.org/10.1002/cssc.202001865	journal	September 2020
Anchoring Positively Charged Pd Single Atoms in Ordered Porous Ceria to Boost Catalytic Activity and Stability in Suzuki Coupling Reactions Tao, Xueqin; Long, Ran; Wu, Di Small, Vol. 16, Issue 43 https://doi.org/10.1002/smll.202001782	journal	October 2020
Palladium Immobilized on a Polyimide Covalent Organic Framework: An Efficient and Recyclable Heterogeneous Catalyst for the Suzuki–Miyaura Coupling Reaction and Nitroarene Reduction in Water Dong, Zhenhua; Pan, Hongguo; Gao, Pengwei Catalysis Letters, Vol. 152, Issue 1 https://doi.org/10.1007/s10562-021-03637-1	journal	April 2021
Transition metal nanoparticles as nanocatalysts for Suzuki, Heck and Sonogashira cross-coupling reactions Ashraf, Muhammad; Ahmad, Muhammad Sohail; Inomata, Yusuke Coordination Chemistry Reviews, Vol. 476 https://doi.org/10.1016/j.ccr.2022.214928	journal	February 2023
A sulfonate-functionalized covalent organic framework for record-high adsorption and effective separation of organic dyes Li, Rui; Tang, Xihao; Wu, Jialin Chemical Engineering Journal, Vol. 464 https://doi.org/10.1016/j.cej.2023.142706	journal	May 2023
Dynamic Covalent Synthesis of Crystalline Porous Graphitic Frameworks Li, Xinle; Wang, Hongxia; Chen, Hao Chem, Vol. 6, Issue 4 https://doi.org/10.1016/j.chempr.2020.01.011	journal	April 2020
Covalent-Organic-Framework-Based Composite Materials Liu, Yu; Zhou, Weiqiang; Teo, Wei Liang Chem, Vol. 6, Issue 12 https://doi.org/10.1016/j.chempr.2020.08.021	journal	December 2020
In situ monitoring of mechanochemical covalent organic framework formation reveals templating effect of liquid additive Emmerling, Sebastian T.; Germann, Luzia S.; Julien, Patrick A. Chem, Vol. 7, Issue 6 https://doi.org/10.1016/j.chempr.2021.04.012	journal	June 2021
Synthesis strategies of covalent organic frameworks: An overview from nonconventional heating methods and reaction media Xiao, Jing; Chen, Jia; Liu, Juewen Green Energy & Environment, Vol. 8, Issue 6 https://doi.org/10.1016/j.gee.2022.05.003	journal	December 2023
Flexible all-organic nanocomposite films interlayered with in situ synthesized covalent organic frameworks for electrostatic energy storage Li, He; Xie, Zongliang; Yang, Chongqing Nano Energy, Vol. 113 https://doi.org/10.1016/j.nanoen.2023.108544	journal	August 2023
A two-dimensional amide-linked covalent organic framework anchored Pd catalyst for Suzuki-Miyaura coupling reaction in the aqueous phase at room temperature Wu, Shang; Ding, Ning; Jiang, Pengwei Tetrahedron Letters, Vol. 61, Issue 51 https://doi.org/10.1016/j.tetlet.2020.152656	journal	December 2020
Pd Metal Catalysts for Cross-Couplings and Related Reactions in the 21st Century: A Critical Review Biffis, Andrea; Centomo, Paolo; Del Zotto, Alessandro Chemical Reviews, Vol. 118, Issue 4 https://doi.org/10.1021/acs.chemrev.7b00443	journal	February 2018
Covalent Organic Frameworks: Design, Synthesis, and Functions Geng, Keyu; He, Ting; Liu, Ruoyang Chemical Reviews https://doi.org/10.1021/acs.chemrev.9b00550	journal	January 2020
Metal Nanoparticles Covered with a Metal–Organic Framework: From One-Pot Synthetic Methods to Synergistic Energy Storage and Conversion Functions Kobayashi, Hirokazu; Mitsuka, Yuko; Kitagawa, Hiroshi Inorganic Chemistry, Vol. 55, Issue 15 https://doi.org/10.1021/acs.inorgchem.6b00911	journal	June 2016
Ultralow-Content Palladium Dispersed in Covalent Organic Framework for Highly Efficient and Selective Semihydrogenation of Alkynes Li, Jian Hong; Yu, Zhi Wu; Gao, Zhi Inorganic Chemistry, Vol. 58, Issue 16 https://doi.org/10.1021/acs.inorgchem.9b01117	journal	August 2019
Mechanochemical Construction 2D/2D Covalent Organic Nanosheets Heterojunctions Based on Substoichiometric Covalent Organic Frameworks Yang, Yongliang; Zhao, Weijia; Niu, Hongyun ACS Applied Materials & Interfaces, Vol. 13, Issue 35 https://doi.org/10.1021/acsami.1c11775	journal	August 2021
Facile and Site-Selective Synthesis of an Amine-Functionalized Covalent Organic Framework Zhang, Shu-Yuan; Tang, Xi-Hao; Yan, Yi-Lun ACS Macro Letters, Vol. 10, Issue 12 https://doi.org/10.1021/acsmacrolett.1c00607	journal	November 2021
Carbon−Carbon Coupling Reactions Catalyzed by Heterogeneous Palladium Catalysts No authors listed Chemical Reviews, Vol. 107, Issue 1 https://doi.org/10.1021/cr0505674	journal	January 2007
Tandem Catalysis by Palladium Nanoclusters Encapsulated in Metal–Organic Frameworks Li, Xinle; Guo, Zhiyong; Xiao, Chaoxian ACS Catalysis, Vol. 4, Issue 10 https://doi.org/10.1021/cs5006635	journal	September 2014
Construction of Covalent Organic Framework for Catalysis: Pd/COF-LZU1 in Suzuki–Miyaura Coupling Reaction Ding, San-Yuan; Gao, Jia; Wang, Qiong Journal of the American Chemical Society, Vol. 133, Issue 49 https://doi.org/10.1021/ja206846p	journal	December 2011
Electron Beam Irradiation as a General Approach for the Rapid Synthesis of Covalent Organic Frameworks under Ambient Conditions Zhang, Mingxing; Chen, Junchang; Zhang, Shitong Journal of the American Chemical Society, Vol. 142, Issue 20 https://doi.org/10.1021/jacs.0c03941	journal	May 2020
Constructing Ultraporous Covalent Organic Frameworks in Seconds via an Organic Terracotta Process Karak, Suvendu; Kandambeth, Sharath; Biswal, Bishnu P. Journal of the American Chemical Society, Vol. 139, Issue 5 https://doi.org/10.1021/jacs.6b08815	journal	January 2017
Facile Microwave-Assisted Synthesis of 2D Imine-Linked Covalent Organic Frameworks for Exceptional Iodine Capture Alsudairy, Ziad; Brown, Normanda; Yang, Chongqing Precision Chemistry https://doi.org/10.1021/prechem.3c00006	journal	March 2023
Stable, crystalline, porous, covalent organic frameworks as a platform for chiral organocatalysts Xu, Hong; Gao, Jia; Jiang, Donglin Nature Chemistry, Vol. 7, Issue 11 https://doi.org/10.1038/nchem.2352	journal	September 2015
Facile transformation of imine covalent organic frameworks into ultrastable crystalline porous aromatic frameworks Li, Xinle; Zhang, Changlin; Cai, Songliang Nature Communications, Vol. 9, Issue 1 https://doi.org/10.1038/s41467-018-05462-4	journal	July 2018
Advancing mechanochemical synthesis by combining milling with different energy sources Martinez, Valentina; Stolar, Tomislav; Karadeniz, Bahar Nature Reviews Chemistry, Vol. 7, Issue 1 https://doi.org/10.1038/s41570-022-00442-1	journal	November 2022
Using sound to synthesize covalent organic frameworks in water Zhao, Wei; Yan, Peiyao; Yang, Haofan Nature Synthesis, Vol. 1, Issue 1 https://doi.org/10.1038/s44160-021-00005-0	journal	January 2022
One-pot synthesis of Pd@MOF composites without the addition of stabilizing agents Chen, Liyu; Chen, Huirong; Li, Yingwei Chem. Commun., Vol. 50, Issue 94 https://doi.org/10.1039/C4CC06568A	journal	January 2014
A triazine-based covalent organic framework/palladium hybrid for one-pot silicon-based cross-coupling of silanes and aryl iodides Lin, Sha; Hou, Yuxia; Deng, Xiao RSC Advances, Vol. 5, Issue 51 https://doi.org/10.1039/C5RA04433B	journal	January 2015
One-step encapsulation of Pd nanoparticles in MOFs via a temperature control program Chen, Liyu; Chen, Xiaodong; Liu, Hongli Journal of Materials Chemistry A, Vol. 3, Issue 29 https://doi.org/10.1039/C5TA02860D	journal	January 2015
A mechanochemically synthesized covalent organic framework as a proton-conducting solid electrolyte Shinde, Digambar Balaji; Aiyappa, Harshitha Barike; Bhadra, Mohitosh Journal of Materials Chemistry A, Vol. 4, Issue 7 https://doi.org/10.1039/C5TA10521H	journal	January 2016
Main group mechanochemistry: from curiosity to established protocols Tan, Davin; García, Felipe Chemical Society Reviews, Vol. 48, Issue 8 https://doi.org/10.1039/C7CS00813A	journal	January 2019
Pd@COF-QA: a phase transfer composite catalyst for aqueous Suzuki–Miyaura coupling reaction Wang, Jian-Cheng; Liu, Cong-Xue; Kan, Xuan Green Chemistry, Vol. 22, Issue 4 https://doi.org/10.1039/C9GC03718G	journal	January 2020
Green mechanochemical synthesis of imine-linked covalent organic frameworks for high iodine capture Brown, Normanda; Alsudairy, Ziad; Behera, Ranjan Green Chemistry, Vol. 25, Issue 16 https://doi.org/10.1039/D3GC01927F	journal	January 2023
Covalent organic frameworks in heterogeneous catalysis: recent advances and future perspective Alsudairy, Ziad; Brown, Normanda; Campbell, Allea Materials Chemistry Frontiers https://doi.org/10.1039/D3QM00188A	journal	January 2023
The historical development of mechanochemistry Takacs, Laszlo Chemical Society Reviews, Vol. 42, Issue 18 https://doi.org/10.1039/c2cs35442j	journal	January 2013
Engineering metal–organic frameworks immobilize gold catalysts for highly efficient one-pot synthesis of propargylamines Lili, Liu; Xin, Zhang; Jinsen, Gao Green Chemistry, Vol. 14, Issue 6 https://doi.org/10.1039/c2gc35284b	journal	January 2012
Covalent organic framework supported palladium catalysts Salemi, Hadi; Debruyne, Maarten; Van Speybroeck, Veronique Journal of Materials Chemistry A, Vol. 10, Issue 39 https://doi.org/10.1039/d2ta05234b	journal	January 2022
The atom, the molecule, and the covalent organic framework Diercks, Christian S.; Yaghi, Omar M. Science, Vol. 355, Issue 6328 https://doi.org/10.1126/science.aal1585	journal	March 2017
Dioxin-Linked Covalent Organic Framework-Supported Palladium Complex for Rapid Room-Temperature Suzuki–Miyaura Coupling Reaction Campbell, Allea; Alsudairy, Ziad; Dun, Chaochao Crystals, Vol. 13, Issue 8 https://doi.org/10.3390/cryst13081268	journal	August 2023

Similar Records

A Rapid, Sustainable, One‐step Mechanochemical Strategy for Synthesizing Gold Nanoparticle‐Doped Covalent Organic Frameworks

Journal Article · Mon Apr 14 20:00:00 EDT 2025 · Chemistry - A European Journal · OSTI ID:2572887

Dioxin-Linked Covalent Organic Framework-Supported Palladium Complex for Rapid Room-Temperature Suzuki–Miyaura Coupling Reaction

Journal Article · Wed Aug 16 20:00:00 EDT 2023 · Crystals · OSTI ID:2337856

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
covalent organic frameworks
heterogeneous catalysis
in situ metal encapsulation
mechanochemistry
palladium

Mechanochemical in Situ Encapsulation of Palladium in Covalent Organic Frameworks

Citation Formats

References (47)

Similar Records

Related Subjects