On-Surface Bottom-Up Construction of COF Nanoshells towards Photocatalytic H2 Production

Yao Chen; Dong Yang; Yuchen Gao; Runlai Li; Ke An; Wenjing Wang; Zhanfeng Zhao; Xin Xin; Hanjie Ren; Zhongyi Jiang

doi:10.34133/2021/9798564

On-Surface Bottom-Up Construction of COF Nanoshells towards Photocatalytic H₂ Production

Research (Wash D C). 2021 Aug 2:2021:9798564. doi: 10.34133/2021/9798564. eCollection 2021.

Authors

Yao Chen^{1

2}, Dong Yang^{3

4}, Yuchen Gao^{1

2}, Runlai Li⁵, Ke An^{1

2}, Wenjing Wang^{1

3

4}, Zhanfeng Zhao^{1

2}, Xin Xin^{1

2

3}, Hanjie Ren^{1

2}, Zhongyi Jiang^{1

2

6}

Affiliations

¹ Key Laboratory for Green Chemical Technology, School of Chemical Engineering and Technology, Tianjin University, Tianjin 300072, China.
² Collaborative Innovation Center of Chemical Science and Engineering (Tianjin), Tianjin 300072, China.
³ Key Laboratory of Systems Bioengineering of Ministry of Education, School of Chemical Engineering and Technology, Tianjin University, Tianjin 300072, China.
⁴ School of Environmental Science and Engineering, Tianjin University, Tianjin 300072, China.
⁵ College of Polymer Science and Engineering, Sichuan University, Chengdu 610065, China.
⁶ Joint School of National University of Singapore and Tianjin University, International Campus of Tianjin University, Binhai New City, Fuzhou 350207, China.

Abstract

The rational design of an outer shell is of great significance to promote the photocatalytic efficiency of core-shell structured photocatalysts. Herein, a covalent organic framework (COF) nanoshell was designed and deposited on the cadmium sulfide (CdS) core surface. A typical COF material, TPPA, featuring exceptional stability, was synthesized through interfacial polymerization using 1, 3, 5-triformylphloroglucinol (TP) and p-phenylenediamine (PA) as monomers. The nanoshell endows the CdS@TPPA nanosphere with ordered channels for unimpeded light-harvesting and fast diffusion of reactants/products and well-defined modular building blocks for spatially charge separation. Moreover, the heterojunction formed between CdS and TPPA can further facilitate the effective charge separation at the interface via lower exciton binding energy compared with that of pristine TPPA. By modulating the thickness of TPPA nanoshell, the CdS@TPPA nanosphere photocatalyst with the nanoshell thickness of about 8 ± 1 nm exhibits the highest photocatalytic H₂ evolution of 194.1 μmol h^-1 (24.3 mmol g^-1 h^-1, 8 mg), which is superior to most of the reported COF-based photocatalysts. The framework nanoshell in this work may stimulate the thinking about how to design advanced shell architecture in the core-shell structured photocatalysts to achieve coordinated charge and molecule transport.