Effective nitrogen doping of TiO2 polymorphs at mild temperatures for visible-light-responsive hydrogen evolution

Herein, a mild-temperature nitrogen doping route with the urea-derived gaseous species as the active doping agent is proposed to realize visible-light-responsive photocatalytic hydrogen evolution both for the anatase and rutile TiO2. DFT simulations reveal that the cyanic acid (HOCN), derived from the decomposition of urea, plays a curial role in the effective doping of nitrogen in TiO2 at mild temperatures. Photocatalytic performance demonstrates that both the anatase and rutile TiO2 doped at mild temperatures exhibit the highest hydrogen evolution rates, although the ones prepared at high temperatures possess higher absorbance in the visible range. Steady-state and transient surface photovoltage characterizations of these doped TiO2 polymorphs prepared at different temperatures reveal that harsh conditions (high temperature reaction) typically result in the formation of intrinsic defects that are detrimental to the transport of the low-energy visible-light-induced electrons, while the mild-temperature nitrogen-doping could flatten the pristine upward band bending without triggering the formation of Ti3+, thus achieving enhanced visible-light-responsive hydrogen evolution rates. We anticipate that our findings will provide inspiring information for shrinking the gap between the visible-light-absorbance and the visible-light-responsiveness in the band engineering of wide-bandgap metal-oxide photocatalysts.