Excitonic Effects of the Excited-State Photocatalytic Reaction at the Molecule/Metal Oxide Interface

作者：Wang, Lei; Liu, Xiaofeng; Wan, Lingyun; Gao, Yunzhi; Wang, Xiaoning; Liu, Jie; Tan, Shijing; Guo, Qing; Zhao, Wenhui; Hu, Wei^*; Li, Qunxiang^*; Yang, Jinlong

来源：Journal of Physical Chemistry Letters, 2024, 15(7): 2096-2104.

DOI：10.1021/acs.jpclett.3c03075

• MOLECULAR-HYDROGEN FORMATION
• TOTAL-ENERGY CALCULATIONS
• ELASTIC BAND METHOD
• ELECTRON-TRANSFER
• MATLAB TOOLBOX
• WATER
• METHANOL
• SURFACE
• OXIDATION
• DYNAMICS

Excitonic effects caused by the Coulomb interaction between electrons and holes play a crucial role in photocatalysis at the molecule/metal oxide interface. As an ideal model for investigating the excitonic effect, coadsorption and photodissociation of water and methanol molecules on titanium dioxide involve complex ground-state thermalcatalytic and excited-state photocatalytic reaction processes. Herein, we systemically investigate the excited-state electronic structures of the coadsorption of H2O and CH3OH molecules on a rutile TiO2(110) surface by linear-response time-dependent density functional theory calculations and probe the reaction path for generating HCOOH or CO2, from ground-state and excited-state perspectives. The reaction barriers in excited-state calculations are significantly different from those in ground-state calculations during three processes, with the largest decrease being 0.94 eV for the Ti5c -O-CH2-O-Ti5c formation process.