Prediction of Feasibility of Polaronic OER on (110) Surface of Rutile TiO2

Sarker, Hori Pada; Abild‐Pedersen, Frank; Bajdich, Michal

doi:10.1002/cphc.202400060

Title: Prediction of Feasibility of Polaronic OER on (110) Surface of Rutile TiO₂

Journal Article · 29 February 2024 · ChemPhysChem

DOI: https://doi.org/10.1002/cphc.202400060 · OSTI ID:2337510

Sarker, Hori Pada ^[1]; Abild‐Pedersen, Frank ^[2];

^[2]

California Institute of Technology (CalTech), Pasadena, CA (United States); Stanford Univ., CA (United States); SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States). SUNCAT Center for Interface Science and Catalysis; SLAC National Accelerator Laboratory
California Institute of Technology (CalTech), Pasadena, CA (United States); SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States). SUNCAT Center for Interface Science and Catalysis

The polaronic effects at the atomic level hold paramount significance for advancing the efficacy of transition metal oxides in applications pertinent to renewable energy. The lattice–distortion mediated localization of photoexcited carriers in the form of polarons plays a pivotal role in the photocatalysis. This investigation focuses on rutile TiO₂, an important material extensively explored for solar energy conversion in artificial photosynthesis, specifically targeting the generation of green H₂ through photoelectrochemical (PEC) H₂O splitting. By employing Hubbard-U corrected and hybrid density functional theory (DFT) methods, we systematically probe the polaronic effects in the catalysis of oxygen evolution reaction (OER) on the (110) surface of rutile TiO₂. Theoretical understanding of polarons within the surface, coupled with simulations of OER at distinct titanium (Ti) and oxygen (O) active sites, reveals diverse polaron formation energies within the lattice sites with strong preference for bulk and surface bridge (O_b) oxygen sites. Moreover, we provide the evidence for the facilitative role of polarons in OER. Here, we find that hole polarons situated at the equatorial oxygen sites near the Ti–active site, along with bridge site hole polarons distal from the O_b active site yield a small reduction in OER overpotential by ~0.06 eV and ~0.12 eV, respectively. However, subsurface, equatorial, and bridge site hole polarons significantly reduce the Ti-active site OER overpotential by ~0.4 eV through the peroxo–type oxygen pathway. We also observe that the presence of hole polarons stabilizes the *OH, *O, and *OOH intermediate species compared to the scenario without hole polarons. Overall, this study provides a detailed mechanistic insight into polaron–mediated OER, offering a promising avenue for improving the catalytic activity of transition metal oxide-based photocatalysts catering to renewable energy requisites.

View Accepted Manuscript (DOE)

Cite

Export

Save

Research Organization:: SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB); USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities (SUF)

Grant/Contract Number:: SC0021266; AC02-05CH11231

OSTI ID:: 2337510

Journal Information:: ChemPhysChem, Journal Name: ChemPhysChem Journal Issue: 11 Vol. 25; ISSN 1439-4235

Publisher:: ChemPubSoc EuropeCopyright Statement

Country of Publication:: United States

Language:: English

References (60)

Solar-driven liquid multi-carbon fuel production using a standalone perovskite–BiVO4 artificial leaf Rahaman, Motiar; Andrei, Virgil; Wright, Demelza Nature Energy, Vol. 8, Issue 6 https://doi.org/10.1038/s41560-023-01262-3	journal	May 2023
Heterogeneous photocatalyst materials for water splitting Kudo, Akihiko; Miseki, Yugo Chem. Soc. Rev., Vol. 38, Issue 1 https://doi.org/10.1039/B800489G	journal	January 2009
Solar-driven chemistry: towards new catalytic solutions for a sustainable world Balzani, Vincenzo; Pacchioni, Gianfranco; Prato, Maurizio Rendiconti Lincei. Scienze Fisiche e Naturali, Vol. 30, Issue 3 https://doi.org/10.1007/s12210-019-00836-2	journal	August 2019
The atomic simulation environment—a Python library for working with atoms Hjorth Larsen, Ask; Jørgen Mortensen, Jens; Blomqvist, Jakob Journal of Physics: Condensed Matter, Vol. 29, Issue 27 https://doi.org/10.1088/1361-648X/aa680e	journal	June 2017
Universality in Oxygen Evolution Electrocatalysis on Oxide Surfaces Man, Isabela C.; Su, Hai‐Yan; Calle‐Vallejo, Federico ChemCatChem, Vol. 3, Issue 7 https://doi.org/10.1002/cctc.201000397	journal	March 2011
Enhanced transport in transistor by tuning transition-metal oxide electronic states interfaced with diamond Yin, Zongyou; Tordjman, Moshe; Lee, Youngtack Science Advances, Vol. 4, Issue 9 https://doi.org/10.1126/sciadv.aau0480	journal	September 2018
Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set Kresse, G.; Furthmüller, J. Computational Materials Science, Vol. 6, Issue 1, p. 15-50 https://doi.org/10.1016/0927-0256(96)00008-0	journal	July 1996
A DFT+U description of oxygen vacancies at the TiO2 rutile (110) surface Morgan, Benjamin J.; Watson, Graeme W. Surface Science, Vol. 601, Issue 21 https://doi.org/10.1016/j.susc.2007.08.025	journal	November 2007
Intrinsic Hole Migration Rates in TiO ₂ from Density Functional Theory Deskins, N. Aaron; Dupuis, Michel The Journal of Physical Chemistry C, Vol. 113, Issue 1 https://doi.org/10.1021/jp802903c	journal	December 2008
Projector augmented-wave method Blöchl, P. E. Physical Review B, Vol. 50, Issue 24, p. 17953-17979 https://doi.org/10.1103/PhysRevB.50.17953	journal	December 1994
Photoelectrolysis of water using semiconducting TiO2 crystals Nozik, A. J. Nature, Vol. 257, Issue 5525 https://doi.org/10.1038/257383a0	journal	October 1975
Photoelectrochemical cells Grätzel, Michael Nature, Vol. 414, Issue 6861 https://doi.org/10.1038/35104607	journal	November 2001
Electrolysis of water on oxide surfaces Rossmeisl, J.; Qu, Z. -W.; Zhu, H. Journal of Electroanalytical Chemistry, Vol. 607, Issue 1-2 https://doi.org/10.1016/j.jelechem.2006.11.008	journal	September 2007
Surface Science Studies of the Photoactivation of TiO ₂ New Photochemical Processes Thompson, Tracy L.; Yates, John T. Chemical Reviews, Vol. 106, Issue 10 https://doi.org/10.1021/cr050172k	journal	October 2006
The nature of photogenerated charge separation among different crystal facets of BiVO ₄ studied by density functional theory Liu, Taifeng; Zhou, Xin; Dupuis, Michel Physical Chemistry Chemical Physics, Vol. 17, Issue 36 https://doi.org/10.1039/C5CP04299B	journal	January 2015
Electronic defects in metal oxide photocatalysts Pastor, Ernest; Sachs, Michael; Selim, Shababa Nature Reviews Materials, Vol. 7, Issue 7 https://doi.org/10.1038/s41578-022-00433-0	journal	May 2022
Electron transport via polaron hopping in bulk Ti O 2 : A density functional theory characterization Deskins, N. Aaron; Dupuis, Michel Physical Review B, Vol. 75, Issue 19 https://doi.org/10.1103/PhysRevB.75.195212	journal	May 2007
CO Adsorbate Promotes Polaron Photoactivity on the Reduced Rutile TiO₂(110) Surface Cheng, Cheng; Zhu, Yonghao; Fang, Wei-Hai JACS Au, Vol. 2, Issue 1 https://doi.org/10.1021/jacsau.1c00508	journal	December 2021
Catalysis-Hub.org, an open electronic structure database for surface reactions Winther, Kirsten T.; Hoffmann, Max J.; Boes, Jacob R. Scientific Data, Vol. 6, Issue 1 https://doi.org/10.1038/s41597-019-0081-y	journal	May 2019
Electrocatalytic Conversion of Carbon Dioxide to Methane and Methanol on Transition Metal Surfaces Kuhl, Kendra P.; Hatsukade, Toru; Cave, Etosha R. Journal of the American Chemical Society, Vol. 136, Issue 40 https://doi.org/10.1021/ja505791r	journal	August 2014
First-Principles Modeling of Polaron Formation in TiO ₂ Polymorphs Elmaslmane, A. R.; Watkins, M. B.; McKenna, K. P. Journal of Chemical Theory and Computation, Vol. 14, Issue 7 https://doi.org/10.1021/acs.jctc.8b00199	journal	May 2018
Electron-energy-loss spectra and the structural stability of nickel oxide: An LSDA+U study Dudarev, S. L.; Botton, G. A.; Savrasov, S. Y. Physical Review B, Vol. 57, Issue 3, p. 1505-1509 https://doi.org/10.1103/PhysRevB.57.1505	journal	January 1998
Role of Polarons in Water Splitting: The Case of BiVO 4 Wiktor, Julia; Ambrosio, Francesco; Pasquarello, Alfredo ACS Energy Letters, Vol. 3, Issue 7 https://doi.org/10.1021/acsenergylett.8b00938	journal	June 2018
Defect States at the TiO 2 ( 110 ) Surface Probed by Resonant Photoelectron Diffraction Krüger, P.; Bourgeois, S.; Domenichini, B. Physical Review Letters, Vol. 100, Issue 5 https://doi.org/10.1103/PhysRevLett.100.055501	journal	February 2008
Hybrid functionals based on a screened Coulomb potential Heyd, Jochen; Scuseria, Gustavo E.; Ernzerhof, Matthias The Journal of Chemical Physics, Vol. 118, Issue 18 https://doi.org/10.1063/1.1564060	journal	May 2003
Solar-powered synthesis of hydrocarbons from carbon dioxide and water Kunene, Thabiso; Xiong, Lu; Rosenthal, Joel Proceedings of the National Academy of Sciences https://doi.org/10.1073/pnas.1904856116	journal	May 2019
Imaging Water Dissociation on TiO ₂ (110): Evidence for Inequivalent Geminate OH Groups Zhang, Z.; Bondarchuk, O.; Kay, Bruce D. The Journal of Physical Chemistry B, Vol. 110, Issue 43 https://doi.org/10.1021/jp063619h	journal	November 2006
Charge carrier transport dynamics in W/Mo-doped BiVO ₄ : first principles-based mesoscale characterization Pasumarthi, Viswanath; Liu, Taifeng; Dupuis, Michel Journal of Materials Chemistry A, Vol. 7, Issue 7 https://doi.org/10.1039/C8TA09899A	journal	January 2019
The surface science of titanium dioxide Diebold, Ulrike Surface Science Reports, Vol. 48, Issue 5-8 https://doi.org/10.1016/S0167-5729(02)00100-0	journal	January 2003
Research opportunities to advance solar energy utilization Lewis, N. S. Science, Vol. 351, Issue 6271 https://doi.org/10.1126/science.aad1920	journal	January 2016
Femtosecond time-resolved X-ray absorption spectroscopy of anatase TiO2 nanoparticles using XFEL Obara, Yuki; Ito, Hironori; Ito, Terumasa Structural Dynamics, Vol. 4, Issue 4 https://doi.org/10.1063/1.4989862	journal	June 2017
Intrinsic small polarons in rutile TiO 2 Yang, Shan; Brant, A. T.; Giles, N. C. Physical Review B, Vol. 87, Issue 12 https://doi.org/10.1103/PhysRevB.87.125201	journal	March 2013
Effect of on-site Coulomb repulsion term U on the band-gap states of the reduced rutile (110) Ti O 2 surface Calzado, Carmen J.; Hernández, Norge Cruz; Sanz, Javier Fdez. Physical Review B, Vol. 77, Issue 4 https://doi.org/10.1103/PhysRevB.77.045118	journal	January 2008
Formation and dynamics of small polarons on the rutile TiO 2 (110) surface Reticcioli, Michele; Setvin, Martin; Schmid, Michael Physical Review B, Vol. 98, Issue 4 https://doi.org/10.1103/PhysRevB.98.045306	journal	July 2018
Limitation of Fermi level shifts by polaron defect states in hematite photoelectrodes Lohaus, Christian; Klein, Andreas; Jaegermann, Wolfram Nature Communications, Vol. 9, Issue 1 https://doi.org/10.1038/s41467-018-06838-2	journal	October 2018
Oxidation and Photo-Oxidation of Water on TiO ₂ Surface Valdés, Á.; Qu, Z. -W.; Kroes, G. -J. The Journal of Physical Chemistry C, Vol. 112, Issue 26 https://doi.org/10.1021/jp711929d	journal	June 2008
How copper catalyzes the electroreduction of carbon dioxide into hydrocarbon fuels Peterson, Andrew A.; Abild-Pedersen, Frank; Studt, Felix Energy & Environmental Science, Vol. 3, Issue 9 https://doi.org/10.1039/c0ee00071j	journal	January 2010
Polarons in materials Franchini, Cesare; Reticcioli, Michele; Setvin, Martin Nature Reviews Materials, Vol. 6, Issue 7 https://doi.org/10.1038/s41578-021-00289-w	journal	March 2021
Semiconducting transition metal oxides Lany, Stephan Journal of Physics: Condensed Matter, Vol. 27, Issue 28 https://doi.org/10.1088/0953-8984/27/28/283203	journal	June 2015
Localized Electronic States from Surface Hydroxyls and Polarons in TiO ₂ (110) Deskins, N. Aaron; Rousseau, Roger; Dupuis, Michel The Journal of Physical Chemistry C, Vol. 113, Issue 33 https://doi.org/10.1021/jp9037655	journal	July 2009
Electrochemical Photolysis of Water at a Semiconductor Electrode Fujishima, Akira; Honda, Kenichi Nature, Vol. 238, Issue 5358, p. 37-38 https://doi.org/10.1038/238037a0	journal	July 1972
Density-functional theory and strong interactions: Orbital ordering in Mott-Hubbard insulators Liechtenstein, A. I.; Anisimov, V. I.; Zaanen, J. Physical Review B, Vol. 52, Issue 8 https://doi.org/10.1103/PhysRevB.52.R5467	journal	August 1995
Surface Polarons Reducing Overpotentials in the Oxygen Evolution Reaction Gono, Patrick; Wiktor, Julia; Ambrosio, Francesco ACS Catalysis, Vol. 8, Issue 7 https://doi.org/10.1021/acscatal.8b01120	journal	May 2018
Anisotropic small-polaron hopping in W:BiVO4 single crystals Rettie, Alexander J. E.; Chemelewski, William D.; Lindemuth, Jeffrey Applied Physics Letters, Vol. 106, Issue 2 https://doi.org/10.1063/1.4905786	journal	January 2015
Band theory and Mott insulators: Hubbard U instead of Stoner I Anisimov, Vladimir I.; Zaanen, Jan; Andersen, Ole K. Physical Review B, Vol. 44, Issue 3, p. 943-954 https://doi.org/10.1103/PhysRevB.44.943	journal	July 1991
Excitation-wavelength-dependent small polaron trapping of photoexcited carriers in α-Fe2O3 Carneiro, Lucas M.; Cushing, Scott K.; Liu, Chong Nature Materials, Vol. 16, Issue 8 https://doi.org/10.1038/nmat4936	journal	July 2017
Electron traps and their effect on the surface chemistry of TiO2(110) Papageorgiou, A. C.; Beglitis, N. S.; Pang, C. L. Proceedings of the National Academy of Sciences, Vol. 107, Issue 6 https://doi.org/10.1073/pnas.0911349107	journal	January 2010
Design and exploration of semiconductors from first principles: A review of recent advances Oba, Fumiyasu; Kumagai, Yu Applied Physics Express, Vol. 11, Issue 6 https://doi.org/10.7567/APEX.11.060101	journal	May 2018
Visualization of dynamic polaronic strain fields in hybrid lead halide perovskites Guzelturk, Burak; Winkler, Thomas; Van de Goor, Tim W. J. Nature Materials, Vol. 20, Issue 5 https://doi.org/10.1038/s41563-020-00865-5	journal	January 2021
Tunable Polaronic Conduction in Anatase TiO 2 Moser, S.; Moreschini, L.; Jaćimović, J. Physical Review Letters, Vol. 110, Issue 19 https://doi.org/10.1103/PhysRevLett.110.196403	journal	May 2013
Niobium doped TiO2: Intrinsic transparent metallic anatase versus highly resistive rutile phase Zhang, S. X.; Kundaliya, D. C.; Yu, W. Journal of Applied Physics, Vol. 102, Issue 1 https://doi.org/10.1063/1.2750407	journal	July 2007
Facet-dependent trapping and dynamics of excess electrons at anatase TiO2 surfaces and aqueous interfaces Selcuk, Sencer; Selloni, Annabella Nature Materials, Vol. 15, Issue 10 https://doi.org/10.1038/nmat4672	journal	June 2016
Accurate and simple analytic representation of the electron-gas correlation energy Perdew, John P.; Wang, Yue Physical Review B, Vol. 45, Issue 23, p. 13244-13249 https://doi.org/10.1103/PhysRevB.45.13244	journal	June 1992
Polaron in TiO ₂ from First‐Principles: A Review De Lile, Jeffrey Roshan; Bahadoran, Ashkan; Zhou, Su Advanced Theory and Simulations, Vol. 5, Issue 2 https://doi.org/10.1002/adts.202100244	journal	November 2021
Electroreduction of carbon monoxide to liquid fuel on oxide-derived nanocrystalline copper Li, Christina W.; Ciston, Jim; Kanan, Matthew W. Nature, Vol. 508, Issue 7497 https://doi.org/10.1038/nature13249	journal	April 2014
Electronic Structure of Partially Reduced Rutile TiO ₂ (110) Surface: Where Are the Unpaired Electrons Located? Chrétien, Steeve; Metiu, Horia The Journal of Physical Chemistry C, Vol. 115, Issue 11 https://doi.org/10.1021/jp111209a	journal	February 2011
Role of dopant Ga in tuning the band gap of rutile TiO2 from first principles Fang, Yu-zhen; Kong, Xiang-jin; Wang, Dong-ting Chinese Journal of Physics, Vol. 56, Issue 4 https://doi.org/10.1016/j.cjph.2018.04.011	journal	August 2018
Ternary cobalt spinel oxides for solar driven hydrogen production: Theory and experiment Walsh, Aron; Ahn, Kwang-Soon; Shet, Sudhakar Energy & Environmental Science, Vol. 2, Issue 7 https://doi.org/10.1039/b822903a	journal	January 2009
Probing electrons in TiO2 polaronic trap states by IR-absorption: Evidence for the existence of hydrogenic states Sezen, Hikmet; Buchholz, Maria; Nefedov, Alexei Scientific Reports, Vol. 4, Issue 1 https://doi.org/10.1038/srep03808	journal	January 2014
Direct View at Excess Electrons in TiO 2 Rutile and Anatase Setvin, Martin; Franchini, Cesare; Hao, Xianfeng Physical Review Letters, Vol. 113, Issue 8 https://doi.org/10.1103/PhysRevLett.113.086402	journal	August 2014

Similar Records

The electron-transfer intermediates of the oxygen evolution reaction (OER) as polarons by in situ spectroscopy

Journal Article · 2021 · Physical Chemistry Chemical Physics. PCCP · OSTI ID:1831510

Lyle, Hanna; Singh, Suryansh; Paolino, Michael; +2 more

Multiple Reaction Pathways for the Oxygen Evolution Reaction May Contribute to IrO₂ (110)’s High Activity

Journal Article · 2021 · Journal of the Electrochemical Society · OSTI ID:1772998

Ha, Mai-Anh; Larsen, Ross E.

Comparing Quasiparticle H₂O Level Alignment on Anatase and Rutile TiO₂

Journal Article · 2015 · ACS Catalysis, 5(7):4242–4254 · OSTI ID:1214069

Sun, Huijuan; Mowbray, Duncan J.; Migani, Annapaola; +3 more

Related Subjects

30 DIRECT ENERGY CONVERSION
14 SOLAR ENERGY
Photocatalysis
Water Splitting
Titanium Dioxide
Solar fuel
Hydrogen
Rutile TiO2
Polaron
Density Functional Theory (DFT)

Title: Prediction of Feasibility of Polaronic OER on (110) Surface of Rutile TiO2

Citation Formats

References (60)

Similar Records

Related Subjects

Title: Prediction of Feasibility of Polaronic OER on (110) Surface of Rutile TiO₂