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Single Site Coordination Enabled Construction of Metal-Diketimine-Linked Covalent Organic Frameworks for Boosted Electrooxidation of Biomass Derivative |
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| Authors: | Chaoyang Zheng Shun Zhang Zhixi Li Liyun Xiao Meina Song Jing Du Jun Guo Xiaoqing Gao Yongwu Peng Zhiyong Tang Meiting Zhao |
| Affiliation: | 1. Department of Chemistry, Institute of Molecular Aggregation Science, Tianjin Key Laboratory of Molecular Optoelectronic Sciences, Tianjin University, Tianjin, 30007 China;2. Department of Chemistry, Institute of Molecular Aggregation Science, Tianjin Key Laboratory of Molecular Optoelectronic Sciences, Tianjin University, Tianjin, 30007 China Wenzhou Institute, University of Chinese Academy of Sciences, Wenzhou, 325000 China;3. State Key Laboratory of Separation Membranes and Membrane Processes, School of Chemistry, Tiangong University, Tianjin, 300387 China;4. Wenzhou Institute, University of Chinese Academy of Sciences, Wenzhou, 325000 China;5. College of Materials Science and Engineering, Zhejiang University of Technology, Hangzhou, Zhejiang, 310014 China;6. CAS Key Laboratory of Nanosystem and Hierarchical Fabrication, CAS Center for Excellence in Nanoscience, National Center for Nanoscience and Technology, Beijing, 100190 China University of Chinese Academy of Sciences, Beijing, 100049 China |
| Abstract: | Aromatic aldehydes are widely used for the construction of covalent organic frameworks (COFs). However, due to the high flexibility, high steric hindrance, and low reactivity, it remains challenging to synthesize COFs using ketones as building units, especially the highly flexible aliphatic ones. Here, the single nickel site coordination strategy is reported to lock the configurations of the highly flexible diketimine to transform discrete oligomers or amorphous polymers into highly crystalline nickel-diketimine-linked COFs (named as Ni-DKI-COFs). The strategy has been successfully extended to the synthesis of a series of Ni-DKI-COFs by the condensation of three flexible diketones with two tridentate amines. Thanks to the ABC stacking model with high amount and easily accessible single nickel (II) sites on their 1D channels, Ni-DKI-COFs are exploited as well-defined electrocatalyst platforms for efficiently electro-upgrading biomass-derived 5-Hydroxymethylfurfural (HMF) into value-added 2,5-furandicarboxylic acid (FDCA) with a 99.9% yield and a 99.5% faradaic efficiency as well as a high turnover frequency of 0.31 s−1. |
| Keywords: | ABC stacking biomass electrocatalysis covalent organic frameworks nickel-diketimine single sites |