First-Principles Evaluation of Volatile Organic Compounds Degradation in Z-Scheme Photocatalytic Systems: MXene and Graphitic-CN Heterostructures

It is a formidable challenge to use the traditional trial-and-error method to identify suitable catalysts for the photocatalytic degradation of volatile organic compounds (VOCs). In this work, by performing density functional theory calculations, we designed three Z-scheme g-CN/M2CO2 (M = Hf, Zr, and Sc) heterostructures, which not only exhibit favorable structure stability but also show promising ability for photocatalytic degradation of VOCs. The enhancement of the photocatalytic activity of these three Z-scheme systems can be ascribed to the low recombination rate of electron–hole pairs because photoelectrons migrated from the g-CN layer to the M2CO2 layer as well as the internal electric fields in the Z-scheme heterojunction. Among the three heterostructures, only g-CN/Zr2CO2 presents favorable spectra utilization under photoirradiation as well as the direct band gap. As a result, in the Z-scheme g-CN/Zr2CO2 heterostructure, the electrons in the conduction band of g-CN migrate to the holes in the valence band of the Zr2CO2 layer, which improves extraction and utilization of photogenerated electrons in the g-CN sheet. Moreover, the Z-scheme g-CN/Zr2CO2 system shows superior performance for photocatalytic VOC degradation in comparison with individual g-CN and Zr2CO2, which can be attributed to the enhanced VOC adsorption capacity as well as excellent ability to photoactivate O2 and H2O into •O2– and •OH radicals. Our findings pave a new promising way to facilitate the application of MXene-based materials for VOC photocatalytic degradation.