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Abstract Nitrate is an important raw material for chemical fertilizers, but it is industrially manufactured in multiple steps at high temperature and pressure, urgently motivating the design of a green and sustainable strategy for nitrate production. We report the photosynthesis of nitrate from N 2 and O 2 on commercial TiO 2 in a flow reactor under ambient conditions. The TiO 2 photocatalyst offered a high nitrate yield of 1.85 μmol h −1 as well as a solar‐to‐nitrate energy conversion efficiency up to 0.13 %. We combined reactivity and in situ Fourier transform infrared spectroscopy to elucidate the mechanism of nitrate formation and unveil the special role of O 2 in N≡N bond dissociation. The mechanistic insight into charge‐involved N 2 oxidation was further demonstrated by in situ transient absorption spectroscopy and electron paramagnetic resonance. This work exhibits the mechanistic origin of N 2 photooxidation and initiates a potential method for triggering inert catalytic reactions.
Zhang et al. (Thu,) studied this question.