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The structure of water on rutile TiO2(110) for applications in solar hydrogen production: towards a predictive model using hybrid-exchange density functional theory

  • M. Patel (a1), G. Mallia (a1) and N. M. Harrison (a1) (a2)

Abstract

Periodic hybrid-exchange density functional theory (DFT) simulations are used to develop a predictive model of the structure of water on the rutile TiO2(110) surface (Θ ≤ 1 ML). A description of the adsorbed species is given: dissociated water molecules and either mixed or dissociative dimers. The behaviour of the adsorbates is rationalised by considering both direct intermolecular and surface-mediated interactions. Some of these results are then compared with those from water adsorption on the rutile SnO2(110) sur- face, isostructural to TiO2(110). Lastly, the electronic structure of the surface in contact with monolayer water (Θ = 1 ML) reveals the contributions of adsorbate states involved in the photocatalytic reaction that controls the water oxidation process.

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[22] Reciprocal space sampling for the bulk structure was performed on a Pack-Monkhorst net with a shrinking factor IS=8 along each periodic direction. The predicted structural parameters for bulk TiO2 are:abulk=bbulk= 4.639Å, cbulk = 2.979Å and u = 0.306. For bulk SnO2, abulk=bbulk= 4.822Å, cbulk = 3.254Å and u = 0.307. These structures agree well with experiment [18] and are consistent with that predicted in previous calculations [19].
[23] The corresponding TiO2 and SnO2 lattice parameters are as follows. TiO2: aslab = 2.979Å, bslab = 6.561Å; SnO2: aslab = 3.254Å, bslab = 6.820Å.
[24] The counter-poise correction to the BE was applied to take into account the basis set superposition error (BSSE) [20].
[25] The respective shrinking factors [8,8], [4,8], [4,8], [2,8], [8,4], and [4,4] were adopted in order to ensure consistent k-space sampling.
[26] The calculated band gap of the clean TiO2(110) surface is 2.90 eV, which is in good agreement with the experimental gap of 3.03 eV (polarised optical transmission measurements) [21].
[27] The calculated band gap of the clean SnO2(110) surface is 2.80 eV.
[28] This work made use of the high performance computing facilities of Imperial College London and - via membership of the UK’s HPC Materials Chemistry Consortium funded by EPSRC (EP/F067496) - of HECToR, the UK’s national high-performance computing service, which is provided by UoE HPCx Ltd at the University of Edinburgh, Cray Inc and NAG Ltd, and funded by the Office of Science and Technology through EPSRC’s High End Computing Programme.

Keywords

The structure of water on rutile TiO2(110) for applications in solar hydrogen production: towards a predictive model using hybrid-exchange density functional theory

  • M. Patel (a1), G. Mallia (a1) and N. M. Harrison (a1) (a2)

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