Probing Photocatalytic Nitrogen Reduction to Ammonia with Water on the Rutile 
TiO2 (110) Surface by First-Principles Calculations

Xie, Xiao-Ying; Xiao, Pin; Fang, Wei-Hai; Cui, Ganglong; Thiel, Walter

doi:10.1021/acscatal.9b01551

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Probing Photocatalytic Nitrogen Reduction to Ammonia with Water on the Rutile TiO₂ (110) Surface by First-Principles Calculations

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Thiel, Walter
Research Department Thiel, Max-Planck-Institut für Kohlenforschung, Max Planck Society;

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Citation

Xie, X.-Y., Xiao, P., Fang, W.-H., Cui, G., & Thiel, W. (2019). Probing Photocatalytic Nitrogen Reduction to Ammonia with Water on the Rutile TiO₂ (110) Surface by First-Principles Calculations. ACS Catalysis, 9(10), 9178-9187. doi:10.1021/acscatal.9b01551.

Cite as: https://hdl.handle.net/21.11116/0000-0004-E688-F

Abstract

Photocatalytic ammonia production from air and water under ambient conditions is ideally suited for artificial nitrogen fixation. It has been the subject of several recent experimental studies with titanium dioxide and titania-based semiconductors as catalysts. The TiO₂-mediated photocatalytic NH₃ production from H₂O and N₂ is a very complex process that is not yet well understood mechanistically, which hampers further advances. In the present work, we address the detailed mechanism of N₂ reduction to NH₃ driven by the photolysis of water adsorbed on the rutile TiO₂ (110) surface containing oxygen vacancies, by means of reliable density functional calculations (HSE06+D3//PBE+U+D3). We show that each major step of the reaction is driven by H₂O photolysis and can proceed under ambient conditions. The initial N₂ adsorption, the activation of the inert N≡N bond, and the N–N cleavage are all efficiently promoted by TiO₂ surface hydroxylation and photogenerated electrons, as well as their synergistic effects, while proton-coupled electron transfers play a decisive role in the N₂ reduction to NH₃. These mechanistic insights can probably guide further experimental studies of TiO₂ photocatalytic nitrogen fixation and NH₃ photosynthesis.