期刊
出版社
WALTER DE GRUYTER GMBH
DOI: 10.1515/zpch-2019-1425
关键词
anatase; DFT; excited states; periodic slab calculation; titanium dioxide; water splitting
资金
- DFG through its Major Research Instrumentation Programme [INST 184/157-1 FUGG]
- Ministry of Science and Culture (MWK) of the Lower Saxony State
- DFG through the Research Training Group QuantumMechanical Materials Modelling (QM3) and its Priority Program Fuels Produced Regeneratively Through Light-Driven Water Splitting: Clarification of the Elemental Processes Involved and Prospects for Implemen [GRK 2247, SPP 1613]
A combined theoretical approach towards the accurate description of water on anatase-TiO2(101) was pursued in this study. Firstly, periodic slab calculations on the basis of density hybrid functionals (PBE0, HSE06) were performed in order to gain insight into the adsorption sites and geometric structure of the surface. For submonolayer coverage of H2O, the molecular adsorption of water is found to be the most stable one with quite similar energetics in PBE0 and HSE06. Moreover, the transition states towards the less preferred dissociative adsorption forms are predicted to be greater than 0.7 eV. Thus, water will not spontaneously dissociate and based on the Computational Hydrogen Electrode model an overpotential of about 1.71 V is needed to drive the overall oxidation. In addition, to validate our results for molecular adsorption of H2O, an embedded cluster model is carefully evaluated for the a-TiO2(101) surface based on the periodic slab calculations. Subsequent high-level DLPNO-CCSD(T) results are in close agreement with our periodic slab calculations since the interaction is found to mainly consist of electrostatic contributions which are captured by hybrid functionals. Finally, first results on optimized geometries in the excited state based on the photogenerated charge-transfer state are presented.
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