New insight into the enhanced photocatalytic activity of N-, C- and S-doped ZnO photocatalysts

Abstract In general, N-, C- and S-doped ZnO exhibit much higher phototcatalytic activity than the pure ZnO. However, the essential factors and underlying mechanism regarding the enhancement of photocatalytic activity are still unclear. In this work, the electronic structures, optical properties and effective masses of charge carriers are investigated by first-principle density functional theory calculation. Due to the nature of p-type doping, N and C doping can generate vacant states above the Fermi level and shift the conduction band into lower energy region, resulting in narrowing of band gap. Thus, N- and C-doped ZnO demonstrate much stronger light absorption in both visible and ultraviolet region. In contrast, because of the absence of vacant states, only limited enhancement of light absorption is observed for S-doped ZnO whose improved photocatalytic performance can only be attributed to the direct reduction of band gap. The calculation of the effective masses show that ZnO typically possess light electrons and heavy holes, confirming its intrinsic character of n-type semiconductor, while N, C and S doping can generally render electrons lighter and holes heavier, resulting in slower recombination rate of photogenerated electron–hole pairs. Noticeably, C doping can discourage such recombination to the greatest extent and separate electron–hole pairs most efficiently compared with N and S doping, serving as a potentially promising pathway to increase the quantum efficiency of ZnO-based photocatalysts. This work will provide some new insights into the understanding of doping effect over the enhancement of photocatalytic activity of N-, C- and S-doped ZnO.