Comparing Quasiparticle H2O Level Alignment on Anatase and Rutile TiO2

Sun, Huijuan; Mowbray, Duncan J.; Migani, Annapaola; Zhao, Jin; Petek, Hrvoje; Rubio, Angel

doi:10.1021/acscatal.5b00529

Title: Comparing Quasiparticle H₂O Level Alignment on Anatase and Rutile TiO₂

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Abstract

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) G₀W₀ calculations, we assess the relative photocatalytic activity of intact and dissociated H₂O on coordinately unsaturated (Ticus) sites of idealized stoichiometric A-TiO₂(101)/R-TiO₂(110) and bridging O vacancies (O_br^vac) of defective A-TiO_2-x(101)/R-TiO_2-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 RTiO₂(110) and (2) HO@Ti_cus is moremore »« less

Authors:: Sun, Huijuan; Mowbray, Duncan J.; Migani, Annapaola; Zhao, Jin; Petek, Hrvoje; Rubio, Angel

Publication Date:: Thu Jul 02 00:00:00 EDT 2015

Research Org.:: Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Environmental Molecular Sciences Lab. (EMSL)

Sponsoring Org.:: USDOE

OSTI Identifier:: 1214069

DOE Contract Number:: AC05-76RL01830

Resource Type:: Journal Article

Journal Name:: ACS Catalysis, 5(7):4242–4254

Additional Journal Information:: Journal Name: ACS Catalysis, 5(7):4242–4254

Country of Publication:: United States

Language:: English

Subject:: Environmental Molecular Sciences Laboratory

Citation Formats


                    Sun, Huijuan, Mowbray, Duncan J., Migani, Annapaola, Zhao, Jin, Petek, Hrvoje, and Rubio, Angel. Comparing Quasiparticle H2O Level Alignment on Anatase and Rutile TiO2.  United States: N. p., 2015. 
        Web.  doi:10.1021/acscatal.5b00529.

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                    Sun, Huijuan, Mowbray, Duncan J., Migani, Annapaola, Zhao, Jin, Petek, Hrvoje, & Rubio, Angel. Comparing Quasiparticle H2O Level Alignment on Anatase and Rutile TiO2.  United States.  https://doi.org/10.1021/acscatal.5b00529

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                    Sun, Huijuan, Mowbray, Duncan J., Migani, Annapaola, Zhao, Jin, Petek, Hrvoje, and Rubio, Angel. 2015.  
        "Comparing Quasiparticle H2O Level Alignment on Anatase and Rutile TiO2".  United States.  https://doi.org/10.1021/acscatal.5b00529.

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@article{osti_1214069,

  title        = {Comparing Quasiparticle H2O Level Alignment on Anatase and Rutile TiO2},

  author       = {Sun, Huijuan and Mowbray, Duncan J. and Migani, Annapaola and Zhao, Jin and Petek, Hrvoje and Rubio, Angel},

  abstractNote = {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) G0W0 calculations, we assess the relative photocatalytic activity of intact and dissociated H2O on coordinately unsaturated (Ticus) sites of idealized stoichiometric A-TiO2(101)/R-TiO2(110) and bridging O vacancies (Obrvac) 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 RTiO2(110) and (2) HO@Ticus is more photocatalytically active than intact H2O@Ticus.},

  doi          = {10.1021/acscatal.5b00529},

  url          = {https://www.osti.gov/biblio/1214069},
  journal      = {ACS Catalysis, 5(7):4242–4254},
number       = ,

  volume       = ,

  place        = {United States},

  year         = {Thu Jul 02 00:00:00 EDT 2015},

  month        = {Thu Jul 02 00:00:00 EDT 2015}

}

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Title: Comparing Quasiparticle H2O Level Alignment on Anatase and Rutile TiO2

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Citation Formats

Title: Comparing Quasiparticle H₂O Level Alignment on Anatase and Rutile TiO₂