Surface Reconstruction-Induced Photocatalytic Methanol Reduction Reaction on a Rutile TiO<sub>2</sub>(001) Surface
Photochemistry of methanol on TiO<sub>2</sub> surfaces is of great importance both fundamentally and industrially. Methanol was previously reported only to occur photogenerated hole-participating oxidation reactions on TiO<sub>2</sub> surfaces. Herein, we report that, upon UV light illumination, the methoxy species formed by methanol dissociation at the 5-fold coordinated Ti<sup>4+</sup> sites (CH<sub>3</sub>O(a)<sub>Ti5c</sub>) of a reconstructed rutile TiO<sub>2</sub>(001)-(1 × 1) surface also undergoes the C-O bond cleavage into methyl fragments mediated by photogenerated electrons, in addition to the well-established photogenerated hole-participating oxidation reactions. Upon subsequent heating, the resulting methyl species undergoes hydrogenation and coupling reactions into methane and ethane, respectively. Accompanying theoretical calculations showed that the lowest unoccupied molecular orbital (LUMO) of CH<sub>3</sub>O(a)<sub>Ti5c</sub> is localized almost at the conduction band minimum of the CH<sub>3</sub>O-adsorbed reconstructed rutile TiO<sub>2</sub>(001)-(1 × 1) surface, indicating the likely TiO<sub>2</sub> → CH<sub>3</sub>O(a)<sub>Ti5c</sub> interfacial photoexcited-electron transfer. These results greatly broaden the photochemistry of methanol on TiO<sub>2</sub> surfaces and demonstrate a photocatalytic methanol-to-hydrocarbon reaction route.
Authors
- Zongfang Wu (ORCID: https://orcid.org/0000-0001-6826-6532)
- Xue‐Qing Gong (ORCID: https://orcid.org/0000-0002-9566-7427)
- Zhen Zhang (ORCID: https://orcid.org/0000-0001-6736-1677)
- Weixin Huang (ORCID: https://orcid.org/0000-0002-5025-3124)
- Zheng‐Ming Wang (ORCID: https://orcid.org/0000-0001-5908-8076)
- Fei Li (ORCID: https://orcid.org/0000-0003-0490-7411)
- Longxia Wu
Institutions
- University of Science and Technology of China (CN)
- Shanghai Jiao Tong University (CN)
- Wuhan University (CN)
- Hefei National Center for Physical Sciences at Nanoscale (CN)
- Collaborative Innovation Center of Chemistry for Energy Materials (CN)
- Shaanxi University of Science and Technology (CN)
Publication Details
- Journal
- The Journal of Physical Chemistry Letters
- Published
- 2024-08-12
- DOI
- https://doi.org/10.1021/acs.jpclett.4c02137
- Citations
- 5
- Primary Topic
- Advanced Photocatalysis Techniques
- Type
- article
- Field-Weighted Citation Impact
- 0.51
Funders
- National Natural Science Foundation of China
- Chinese Academy of Sciences
- Changjiang Scholar Program of Chinese Ministry of Education
- National Key Research and Development Program of China
- Fundamental Research Funds for the Central Universities