Modulating NH2 Lewis Basicity in CTF-NH2 through Donor-Acceptor Groups for Optimizing Photocatalytic Water Splitting

IF 10.8 2区化学 Q1 CHEMISTRY, PHYSICAL 物理化学学报 Pub Date : 2024-12-01 DOI:10.3866/PKU.WHXB202405005

Zhao Lu , Hu Lv , Qinzhuang Liu , Zhongliao Wang

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Abstract

Photocatalytic water splitting (PWS) provides an optimal approach for the sustainable production of green hydrogen. NH₂-modified covalent triazine frameworks (CTFs-NH₂) hold potential in PWS due to robust light uptake, optimal charge separation, and considerable redox potential. However, the high surface reaction barriers hinder the efficiency of PWS owing to the conversion difficulty of intermediate products. Modulating the Lewis basicity of NH₂ on CTFs offers a feasible route for addressing this challenge. In this work, electron-donating ethyl (C₂H₅) and electron-withdrawing 5-fluoroethyl groups (C₂F₅) are introduced at the para position of amine groups, producing C₂H₅-CTF-NH₂ and C₂F₅-CTF-NH₂, to adjust the Lewis basicity of CTF-NH₂. Through DFT calculations, the optical properties, excited states, electronic structures, dipole moments, and surface reaction processes of the CTF-NH₂, C₂H₅-CTF-NH₂ and C₂F₅-CTF-NH₂ are simulated. The results indicate that the electron-withdrawing C₂F₅ group can decrease the electron density and Lewis basicity on NH₂, thereby lowering the energy barriers for hydrogen and oxygen evolution reactions, effectively ameliorating the PWS efficiency of CTF-NH₂. This work unveils an innovative approach for donor-acceptor-regulated CTFs for the application of PWS.

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