The Keto-Switched Photocatalysis of Reconstructed Covalent Organic Frameworks for Efficient Hydrogen Evolution |
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Authors: | Dr Shuhong Wu Chao Li Prof Ying Wang Dr Yan Zhuang Yi Pan Prof Na Wen Dr Shuo Wang Prof Zizhong Zhang Zhenxin Ding Prof Rusheng Yuan Prof Wenxin Dai Prof Xianzhi Fu Prof Jinlin Long |
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Institution: | 1. State Key Laboratory of Photocatalysis on Energy and Environment, College of Chemistry, Fuzhou University, Fuzhou, 350108 P. R. China;2. State Key Laboratory of Photocatalysis on Energy and Environment, College of Chemistry, Fuzhou University, Fuzhou, 350108 P. R. China
College of Materials Science and Engineering, Fuzhou University, Fuzhou, 350108 P. R. China |
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Abstract: | The keto-switched photocatalysis of covalent organic frameworks (COFs) for efficient H2 evolution was reported for the first time by engineering, at a molecular level, the local structure and component of the skeletal building blocks. A series of imine-linked BT-COFs were synthesized by the Schiff-base reaction of 1, 3, 5-benzenetrialdehyde with diamines to demonstrate the structural reconstruction of enol to keto configurations by alkaline catalysis. The keto groups of the skeletal building blocks served as active injectors, where hot π-electrons were provided to Pt nanoparticles (NPs) across a polyvinylpyrrolidone (PVP) insulting layer. The characterization results, together with density functional theory calculations, indicated clearly that the formation of keto-injectors not only made the conduction band level more negative, but also led to an inhomogeneous charge distribution in the donor-acceptor molecular building blocks to form a strong intramolecular built-in electric field. As a result, visible-light photocatalysis of TP-COFs-1 with one keto group in the skeletal building blocks was successfully enabled and achieved an impressive H2 evolution rate as high as 0.96 mmol g?1 h?1. Also, the photocatalytic H2 evolution rates of the reconstructed BT-COFs-2 and -3 with two and three keto-injectors were significantly enhanced by alkaline post-treatment. |
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Keywords: | Electric Field Enol-Keto Tautomerism H2 Production MIS Heterostructure Photocatalysis |
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