Dual Microenvironment Modulation of Pd Nanoparticles in Covalent Organic Frameworks for Semihydrogenation of Alkynes |
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| Authors: | Mingchun Guo Dr Qiangqiang Meng Dr Wenyao Chen Prof?Dr Zheng Meng Dr Ming-Liang Gao Prof?Dr Qunxiang Li Prof?Dr Xuezhi Duan Prof?Dr Hai-Long Jiang |
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| Institution: | 1. Hefei National Research Center for Physical Sciences at the Microscale, Department of Chemistry, Collaborative Innovation Center of Chemistry for Energy Materials (iChEM), University of Science and Technology of China, Hefei, Anhui, 230026 P.?R. China;2. Department of Chemical Physics, University of Science and Technology of China, Hefei, Anhui, 230026 P.?R. China;3. State Key Laboratory of Chemical Engineering, East China University of Science and Technology, 130 Meilong Road, Shanghai, 200237 P.?R. China |
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| Abstract: | The chemical microenvironment modulation of metal nanoparticles (NPs) holds promise for tackling the long-lasting challenge of the trade-off effect between activity and selectivity in catalysis. Herein, ultrafine PdCu2 NPs incorporated into covalent organic frameworks (COFs) with diverse groups on their pore walls have been fabricated for the semihydrogenation of alkynes. The Cu species, as the primary microenvironment of Pd active sites, greatly improves the selectivity. The functional groups as the secondary microenvironment around PdCu2 NPs effectively regulate the activity, in which PdCu2 NPs encapsulated in the COF bearing ?CH3 groups exhibit the highest activity with >99 % conversion and 97 % selectivity. Both experimental and calculation results suggest that the functional group affects the electron-donating ability of the COFs, which successively impacts the charge transfer between COFs and Pd sites, giving rise to a modulated Pd electronic state and excellent catalytic performance. |
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| Keywords: | Covalent-Organic Frameworks Heterogeneous Catalysis Hydrogenation Metal Nanoparticles Microenvironment Modulation |
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