The Keto-Switched Photocatalysis of Reconstructed Covalent Organic Frameworks for Efficient Hydrogen Evolution

被引：50

作者：

Wu, Shuhong ^{[1
]}

Li, Chao ^{[1
]}

Wang, Ying ^{[1
]}

Zhuang, Yan ^{[1
]}

Pan, Yi ^{[1
]}

Wen, Na ^{[1
,2
]}

Wang, Shuo ^{[1
]}

Zhang, Zizhong ^{[1
]}

Ding, Zhenxin ^{[1
]}

Yuan, Rusheng ^{[1
]}

Dai, Wenxin ^{[1
]}

Fu, Xianzhi ^{[1
]}

Long, Jinlin ^{[1
]}

机构：

[1] Fuzhou Univ, Coll Chem, State Key Lab Photocatalysis Energy & Environm, Fuzhou 350108, Peoples R China

[2] Fuzhou Univ, Coll Mat Sci & Engn, Fuzhou 350108, Peoples R China

来源：

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION | 2023年 / 62卷 / 36期

关键词：

Electric Field; Enol-Keto Tautomerism; H-2; Production; MIS Heterostructure; Photocatalysis; WATER OXIDATION; PLATFORM;

D O I：

10.1002/anie.202309026

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

The keto-switched photocatalysis of covalent organic frameworks (COFs) for efficient H-2 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 & pi;-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 H-2 evolution rate as high as 0.96 mmol g(-1) h(-1). Also, the photocatalytic H-2 evolution rates of the reconstructed BT-COFs-2 and -3 with two and three keto-injectors were significantly enhanced by alkaline post-treatment.

引用

页数：9