Double-hole codoped huge-gap semiconductor ZrO 2 for visible-light photocatalysis

Double-hole doping is an effective approach to engineer the band structures of semiconductors for enhancing the photoelectrochemical performance. Here, we explore the anionic monodoping ( i.e. N, C, and P) and codoping ( i.e. N + N, C + S, and N + P pairs) effects on the electronic structures and photocatalytic activities of ZrO 2 by performing extensive density functional theory calculations. Upon anionic monodoping, several unoccupied impurity states appear within the band gap, which may trap the photogenerated carriers and then reduce the photocatalytic efficiency. Remarkably, double-hole doping via introducing three anionic (N + N), (C + S), and (N + P) codoping pairs in ZrO 2 can not only effectively narrow the band gap, but can also create several fully filled delocalized intermediate bands for preventing the recombination of the photogenerated electron–hole pairs. Moreover, the band edge positions matching well with the redox potentials of water and the improved visible light absorption ability indicate that the three examined codoped ZrO 2 systems are promising photocatalysts for visible light water splitting. In short, double-hole doping via anionic pairs provides an effective path to tune the huge-gap semiconductor band structures and to develop high efficient catalysts for solar-driven water splitting.