Lawrence Berkeley National Laboratory

Photo-catalytic fixation of nitrogen by titania catalysts at ambient conditions has been reported for decades, yet the active site capable of adsorbing an inert N₂ molecule at ambient pressure and the mechanism of dissociating the strong dinitrogen triple bond at room temperature remain unknown. In this work in situ near-ambient-pressure X-ray photo-electron spectroscopy and density functional theory calculations are used to probe the active state of the rutile (110) surface. The experimental results indicate that photon-driven interaction of N₂ and TiO₂ is observed only if adventitious surface carbon is present, and computational results show a remarkably strong interaction between N₂ and carbon substitution (C*) sites that act as surface-bound carbon radicals. A carbon-assisted nitrogen reduction mechanism is proposed and shown to be thermodynamically feasible. The findings provide a molecular-scale explanation for the long-standing mystery of photo-catalytic nitrogen fixation on titania. The results suggest that controlling and characterizing carbon-based active sites may provide a route to engineering more efficient photo(electro)-catalysts and improving experimental reproducibility.