Designing of covalent organic framework/2D g-C3N4 heterostructure using a simple method for enhanced photocatalytic hydrogen production

Ahmed E Hassan; Ahmed M Elewa; Mai S A Hussien; Ahmed F M El-Mahdy; Islam M A Mekhemer; Ibrahim S Yahia; Tarek A Mohamed; Ho-Hsiu Chou; Zhenhai Wen

doi:10.1016/j.jcis.2023.10.010

Designing of covalent organic framework/2D g-C₃N₄ heterostructure using a simple method for enhanced photocatalytic hydrogen production

J Colloid Interface Sci. 2024 Jan;653(Pt B):1650-1661. doi: 10.1016/j.jcis.2023.10.010. Epub 2023 Oct 4.

Authors

Ahmed E Hassan¹, Ahmed M Elewa², Mai S A Hussien³, Ahmed F M El-Mahdy⁴, Islam M A Mekhemer⁵, Ibrahim S Yahia⁶, Tarek A Mohamed⁷, Ho-Hsiu Chou⁸, Zhenhai Wen⁹

Affiliations

¹ CAS Key Laboratory of Design and Assembly of Functional Nanostructures, and Fujian Provincial Key Laboratory of Nanomaterials, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, Fujian 350002, China; University of Chinese Academy of Sciences, Beijing 100049, China; Department of Chemistry, Faculty of Science, Al-Azhar University, Nasr City 11884, Cairo, Egypt.
² Department of Chemical Engineering, National Tsing Hua University, Hsinchu 300044, Taiwan; Nuclear Chemistry Department, Hot Laboratories Center, Atomic Energy Authority, Cairo 13759, Egypt.
³ Nanoscience Laboratory for Environmental and Biomedical Applications (NLEBA), Semiconductor Lab, Department of Physics, Faculty of Education, Ain Shams University, Roxy, Cairo 11757, Egypt; Department of Chemistry, Faculty of Education, Ain Shams University, Roxy, Cairo 11757, Egypt.
⁴ Department of Materials and Optoelectronic Science, National Sun Yat-Sen University, Kaohsiung, 80424, Taiwan.
⁵ Department of Chemical Engineering, National Tsing Hua University, Hsinchu 300044, Taiwan.
⁶ Laboratory of Nano-Smart Materials for Science and Technology (LNSMST), Department of Physics, Faculty of Science, King Khalid University, P.O. Box 9004, Abha, Saudi Arabia; Research Center for Advanced Materials Science (RCAMS), King Khalid University, Abha 61413, P.O. Box 9004, Saudi Arabia; Center of Medical and Bio-Allied Health Sciences Research (CMBHSR), Ajman University, Ajman P.O. Box 346, United Arab Emirates.
⁷ Department of Chemistry, Faculty of Science, Al-Azhar University, Nasr City 11884, Cairo, Egypt. Electronic address: tarek_ama@azhar.edu.eg.
⁸ Department of Chemical Engineering, National Tsing Hua University, Hsinchu 300044, Taiwan. Electronic address: hhchou@mx.nthu.edu.tw.
⁹ CAS Key Laboratory of Design and Assembly of Functional Nanostructures, and Fujian Provincial Key Laboratory of Nanomaterials, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, Fujian 350002, China. Electronic address: wen@fjirsm.ac.cn.

PMID: 37812841
DOI: 10.1016/j.jcis.2023.10.010

Abstract

Designing heterostructure photocatalysts is a promising approach for developing highly efficient photocatalysts for hydrogen energy production. In this work, we synthesized a series of a covalent organic framework (COF)/g-C₃N₄ (CN) heterojunction photocatalysts, denoted as x % COF/CN (in which x indicates the weight % of COF and x = 5, 10, 20, 30, 40, 50, 90, 95, 100), for hydrogen production. The COF, which is a key component of the photocatalyst, was prepared by assembling benzothiadiazole (BT) and pyrene (Py) derivatives as building blocks. Integrating COF rods into the two-dimensional (2D) layered g-C₃N₄ structure significantly improved photocatalytic H₂ production. The hybrid system (30 % COF/CN) displayed an outstanding hydrogen evolution rate (HER) of 27540 ± 805 μmol g^-1h^-1, outperforming most known COFs and g-C₃N₄-based photocatalysts, besides exhibiting stable photocatalytic performance. Moreover, the apparent quantum yield (AQY) was 15.5 ± 0.8 % at 420 nm. Experimental techniques and density functional theory (DFT) calculations demonstrated that the 30 % COF/CN heterostructure has broad visible-light absorption, adequate band energy levels, and the best chemical reactivity descriptors compared to the individual components, resulting in effective carrier separation and excellent performance. Our findings offer a valuable strategy for developing highly efficient and stable heterojunction photocatalysts for visible-light-driven H₂ evolution.

Keywords: Covalent organic framework; DFT; Heterostructure; Photocatalytic H(2) generation; g-C(3)N(4).