TiO2-based photocatalysts are eco-friendly,
cost-effective,
and stable but only exert catalytic performance in the ultraviolet
region, and the photocatalytic efficiency is very low. In this work,
we employ DFT calculations to deeply investigate the effect of nonmetallic
C-doped TiO2 (101) on the photocatalytic hydrogen evolution
performance. Specifically, the effects of C substitution or interstitial
doping at the surface, subsurface, and bulk on the electronic structure,
optical properties, and catalytic hydrogen evolution activity were
substantially investigated. We discovered that different C atom doping
strategies impinge different effects on the catalytic activity. Among
them, the CO-bulk4, CTi-surf2, and Cinter-surf systems showed superior catalytic activities with ΔG of −0.012, −0.055, and −0.024 eV,
respectively. The C atom replaces the Ti atom and alters the original
coordination environment, which leads to charge redistribution and
consequently to the activation of the O sites. Additionally, carbon-self-doped
TiO2 photocatalysts were fabricated using an experimental
hydrothermal synthesis, and the XPS analyses confirmed that O is replaced
by C. In addition, the photocatalytic hydrogen evolution rate is 0.3
mmol g–1 h–1, while there is no
hydrogen evolution for pure TiO2. Our findings suggest
that nonmetallic doped TiO2(101) photocatalysts can improve
light absorption, modulate charge distribution, and enhance hydrogen
evolution activity.