期刊
ACS CATALYSIS
卷 5, 期 7, 页码 4242-4254出版社
AMER CHEMICAL SOC
DOI: 10.1021/acscatal.5b00529
关键词
water splitting G(0)W(0); calculations; photocatalysis; photooxidation; hole trapping; titania
资金
- China Scholarship Council (CSC)
- European Project DYNamo [ERC-2010-AdG-267374]
- European Project CRONOS [280879-2 CRONOS CP-FP7]
- European Project Cost Action [CM1204, MP1306]
- Generalitat de Catalunya [2014SGR301, XRQTC]
- Grupos Consolidados UPV/EHU del Gobierno Vasco [IT-578-13]
- NSFC [21003113, 21121003]
- MOST [2011CB921404]
- Chinese Academy of Sciences
- NSF [CHE-1213189]
- [FIS2012-37549-C05-02]
- [FIS2013-46159-C3-1-P]
- [PIB2010US-00652]
- [RYC-2011-09582]
- [JCI-2010-08156]
- Direct For Mathematical & Physical Scien
- Division Of Chemistry [1213189] Funding Source: National Science Foundation
Knowledge of the alignment of molecular frontier levels in the ground state can be used to predict the photocatalytic activity of an interface. The position of the adsorbate's highest occupied molecular orbital (HOMO) levels relative to the substrate's valence band maximum (VBM) in the interface describes the favorability of photogenerated hole transfer from the VBM to the adsorbed molecule. This is a key quantity for assessing and comparing H2O photooxidation activities on two prototypical photocatalytic TiO2 surfaces: anatase (A)-TiO2(101) and rutile (R)-TiO2(110). Using the projected density of states (DOS) from state-of-the-art quasiparticle (QP) G(0)W(0) calculations, we assess the relative photocatalytic activity of intact and dissociated H2O on coordinately unsaturated (Ti-cus) sites of idealized stoichiometric A-TiO2(101)/R-TiO2(110) and bridging O vacancies (O-br(vac)) of defective A-TiO2-x(101)/R-TiO2-x(110) surfaces (x = 1/4, 1/8) for various coverages. Such a many-body treatment is necessary to correctly describe the anisotropic screening of electron electron interactions at a photocatalytic interface and, hence, obtain accurate interfacial level alignments. The more favorable ground state HOMO level alignment for A-TiO2(101) may explain why the anatase polymorph shows higher photocatalytic activities than the rutile polymorph. Our results indicate that (1) hole trapping is more favored on A-TiO2(101) than R-TiO2(110) and (2) HO@Ti-cus is more photocatalytically active than intact H2O@Ti-cus.
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