Integrated interfacial design of covalent organic framework photocatalysts to promote hydrogen evolution from water

Ting He; Wenlong Zhen; Yongzhi Chen; Yuanyuan Guo; Zhuoer Li; Ning Huang; Zhongping Li; Ruoyang Liu; Yuan Liu; Xu Lian; Can Xue; Tze Chien Sum; Wei Chen; Donglin Jiang

doi:10.1038/s41467-023-35999-y

Integrated interfacial design of covalent organic framework photocatalysts to promote hydrogen evolution from water

Nat Commun. 2023 Jan 19;14(1):329. doi: 10.1038/s41467-023-35999-y.

Authors

Ting He¹, Wenlong Zhen², Yongzhi Chen¹, Yuanyuan Guo³, Zhuoer Li^{1

4}, Ning Huang⁵, Zhongping Li¹, Ruoyang Liu¹, Yuan Liu¹, Xu Lian¹, Can Xue², Tze Chien Sum³, Wei Chen¹, Donglin Jiang^{6

7}

Affiliations

¹ Department of Chemistry, Faulty of Science, National University of Singapore, 3 Science Drive 3, Singapore, 117543, Singapore.
² School of Materials Science and Engineering, Nanyang Technological University, 50 Nanyang Avenue, Singapore, 639798, Singapore.
³ Division of Physics and Applied Physics, School of Physical and Mathematical Sciences, Nanyang Technological University, 21 Nanyang Link, Singapore, 637371, Singapore.
⁴ Joint School of National University of Singapore and Tianjin University, International Campus of Tianjin University, Binhai New City, Fuzhou, 350207, China.
⁵ MOE Key Laboratory of Macromolecular Synthesis and Functionalisation, Department of Polymer Science and Engineering, Zhejiang University, Hangzhou, 310027, China.
⁶ Department of Chemistry, Faulty of Science, National University of Singapore, 3 Science Drive 3, Singapore, 117543, Singapore. chmjd@nus.edu.sg.
⁷ Joint School of National University of Singapore and Tianjin University, International Campus of Tianjin University, Binhai New City, Fuzhou, 350207, China. chmjd@nus.edu.sg.

Abstract

Attempts to develop photocatalysts for hydrogen production from water usually result in low efficiency. Here we report the finding of photocatalysts by integrated interfacial design of stable covalent organic frameworks. We predesigned and constructed different molecular interfaces by fabricating ordered or amorphous π skeletons, installing ligating or non-ligating walls and engineering hydrophobic or hydrophilic pores. This systematic interfacial control over electron transfer, active site immobilisation and water transport enables to identify their distinct roles in the photocatalytic process. The frameworks, combined ordered π skeletons, ligating walls and hydrophilic channels, work under 300-1000 nm with non-noble metal co-catalyst and achieve a hydrogen evolution rate over 11 mmol g^-1 h^-1, a quantum yield of 3.6% at 600 nm and a three-order-of-magnitude-increased turnover frequency of 18.8 h^-1 compared to those obtained with hydrophobic networks. This integrated interfacial design approach is a step towards designing solar-to-chemical energy conversion systems.