First-principles study on the mechanism of photocatalytic reduction of nitrobenzene on the rutile TiO2(110) surface

Yongfei Ji; Ting Fan; Yi Luo

doi:10.1039/c9cp05010h

First-principles study on the mechanism of photocatalytic reduction of nitrobenzene on the rutile TiO₂(110) surface

Phys Chem Chem Phys. 2020 Jan 21;22(3):1187-1193. doi: 10.1039/c9cp05010h. Epub 2019 Dec 18.

Authors

Yongfei Ji¹, Ting Fan², Yi Luo³

Affiliations

¹ School of Chemistry and Chemical Engineering, Guangzhou University, Guangzhou 510006, Guangdong, P. R. China. [email protected].
² School of Chemistry and Chemical Engineering, South China University of Technology, Guangzhou 510641, Guangdong, P. R. China. [email protected].
³ Hefei National Laboratory for Physical Sciences at the Microscale, University of Science and Technology of China, Hefei, Anhui 230026, China and KTH, the Royal Institute of Technology, Department of Theoretical Chemistry and Biology, S-106 91 Stockholm, Sweden.

PMID: 31848529
DOI: 10.1039/c9cp05010h

Abstract

Photocatalytic synthesis of organic compounds has attracted more and more attention recently. In this work, we present a theoretical study on the molecular mechanism of the photocatalytic reduction of nitrobenzene to aniline on the rutile TiO₂(110) surface. We have studied the adsorption and conversion of nitrobenzene at both the surface Ti site and the oxygen vacancy (O_v) site. The full reaction pathways at these two sites were calculated. The rate-limiting step and possible intermediates were identified. The results suggest that O_v is more active in the adsorption and conversion of nitrobenzene. Interestingly, we found that the chemistry of nitrobenzene on the rutile TiO₂(110) surface, especially the breaking of the N-O bond, is closely related to the number of excess electrons available. Based on the calculation, we have proposed a full molecular mechanism which is compatible with the existing experiments. The results should be helpful for the design of more efficient photocatalysts for the conversion of nitrobenzene.