DFT Study on Regulating the Electronic Structure and CO2 Reduction Reaction in BiOBr/Sulphur-Doped G-C3N4 S-Scheme Heterojunctions

Photocatalytic CO2 reduction is a promising method to mitigate the greenhouse effect and energy shortage problem. Development of effective photocatalysts is vital in achieving high photocatalytic activity. Herein, the S-scheme heterojunctions composed by BiOBr and g-C3N4 with or without S doping are thoroughly investigated for CO2 reduction by density functional theory (DFT) calculation. Work function and charge density difference demonstrate the existence of a built-in electric field in the system, which contributes to the separation of photogenerated electron-hole pairs. Enhanced strength of a built-in electric field is revealed by analysis of Bader charge and electric field intensity. The results indicate that S doping can tailor the electronic structures and thus improve the photocatalytic activity. According to the change in absorption coefficient, system doping can also endow the heterojunction with increased visible light absorption. The in-depth investigation indicates that the superior CO2 reduction activity is ascribed to low rate-determining energy. And both of the heterojunctions are inclined to generate CH3OH rather than CH4. Furthermore, S doping can further reduce the energy from 1.23 to 0.44 eV, indicating S doping is predicted to be an efficient photocatalyst for reducing CO2 into CH3OH. Therefore, this paper provides a theoretical basis for designing appropriate catalysts through element doping and heterojunction construction.

Automated summary

In this study, the effect of S doping on S-scheme heterojunctions composed of BiOBr and g-C3N4 for CO2 reduction was thoroughly investigated using DFT calculations. The results showed that S doping can improve photocatalytic activity and enhance visible light absorption, leading to the preferential production of CH3OH over CH4. The study suggests that S doping is predicted to be an efficient photocatalyst for reducing CO2 into CH3OH.