skip to main content
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: The role of defects and excess surface charges at finite temperature for optimizing oxide photoabsorbers

Abstract

Computational screening of materials for solar to fuel conversion technologies has mostly focused on bulk properties, thus neglecting the structure and chemistry of surfaces and interfaces with water. We report a finite temperature study of WO3, a promising anode for photoelectrochemical cells, carried out using first-principles molecular dynamics simulations coupled with many-body perturbation theory. We identified three major factors determining the chemical reactivity of the material interfaced with water: the presence of surface defects, the dynamics of excess charge at the surface, and finite temperature fluctuations of the surface electronic orbitals. These general descriptors are essential for the understanding and prediction of optimal oxide photoabsorbers for water oxidation.

Authors:
ORCiD logo [1];  [2];  [3];  [3]
  1. Univ. of Chicago, IL (United States)
  2. Univ. of California, Davis, CA (United States)
  3. Argonne National Lab. (ANL), Argonne, IL (United States); Univ. of Chicago, IL (United States)
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
National Science Foundation (NSF) - Centers for Chemical Innovation (CCI); USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1490163
Grant/Contract Number:  
AC02-06CH11357
Resource Type:
Accepted Manuscript
Journal Name:
Nature Materials
Additional Journal Information:
Journal Volume: 17; Journal Issue: 12; Journal ID: ISSN 1476-1122
Publisher:
Springer Nature - Nature Publishing Group
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE

Citation Formats

Gerosa, Matteo, Gygi, Francois, Govoni, Marco, and Galli, Giulia. The role of defects and excess surface charges at finite temperature for optimizing oxide photoabsorbers. United States: N. p., 2018. Web. doi:10.1038/s41563-018-0192-4.
Gerosa, Matteo, Gygi, Francois, Govoni, Marco, & Galli, Giulia. The role of defects and excess surface charges at finite temperature for optimizing oxide photoabsorbers. United States. doi:10.1038/s41563-018-0192-4.
Gerosa, Matteo, Gygi, Francois, Govoni, Marco, and Galli, Giulia. Mon . "The role of defects and excess surface charges at finite temperature for optimizing oxide photoabsorbers". United States. doi:10.1038/s41563-018-0192-4. https://www.osti.gov/servlets/purl/1490163.
@article{osti_1490163,
title = {The role of defects and excess surface charges at finite temperature for optimizing oxide photoabsorbers},
author = {Gerosa, Matteo and Gygi, Francois and Govoni, Marco and Galli, Giulia},
abstractNote = {Computational screening of materials for solar to fuel conversion technologies has mostly focused on bulk properties, thus neglecting the structure and chemistry of surfaces and interfaces with water. We report a finite temperature study of WO3, a promising anode for photoelectrochemical cells, carried out using first-principles molecular dynamics simulations coupled with many-body perturbation theory. We identified three major factors determining the chemical reactivity of the material interfaced with water: the presence of surface defects, the dynamics of excess charge at the surface, and finite temperature fluctuations of the surface electronic orbitals. These general descriptors are essential for the understanding and prediction of optimal oxide photoabsorbers for water oxidation.},
doi = {10.1038/s41563-018-0192-4},
journal = {Nature Materials},
number = 12,
volume = 17,
place = {United States},
year = {2018},
month = {10}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 9 works
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

Generalized Gradient Approximation Made Simple
journal, October 1996

  • Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias
  • Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868
  • DOI: 10.1103/PhysRevLett.77.3865

Band gap states in nanocrystalline WO 3 thin films studied by soft x-ray spectroscopy and optical spectrophotometry
journal, September 2016


Optical properties of tungsten trioxide from first-principles calculations
journal, April 2013


The W5+ polaron in crystalline low temperature WO3 ESR and optical absorption
journal, January 1980


Effect of a Cobalt-Based Oxygen Evolution Catalyst on the Stability and the Selectivity of Photo-Oxidation Reactions of a WO 3 Photoanode
journal, March 2011

  • Seabold, Jason A.; Choi, Kyoung-Shin
  • Chemistry of Materials, Vol. 23, Issue 5
  • DOI: 10.1021/cm1019469

Solvation effects on the band edge positions of photocatalysts from first principles
journal, January 2015

  • Ping, Yuan; Sundararaman, Ravishankar; Goddard III, William A.
  • Physical Chemistry Chemical Physics, Vol. 17, Issue 45
  • DOI: 10.1039/C5CP05740J

Architecture of Qbox: A scalable first-principles molecular dynamics code
journal, January 2008

  • Gygi, F.
  • IBM Journal of Research and Development, Vol. 52, Issue 1.2
  • DOI: 10.1147/rd.521.0137

Electrochemical deposition and photoelectrochemistry of CuWO4, a promising photoanode for water oxidation
journal, January 2011

  • Yourey, Joseph E.; Bartlett, Bart M.
  • Journal of Materials Chemistry, Vol. 21, Issue 21
  • DOI: 10.1039/c1jm11259g

DFT Study of Hydrogen Adsorption On the Monoclinic WO 3 (001) Surface
journal, May 2012

  • Wang, Fenggong; Di Valentin, Cristiana; Pacchioni, Gianfranco
  • The Journal of Physical Chemistry C, Vol. 116, Issue 19
  • DOI: 10.1021/jp302210y

QUANTUM ESPRESSO: a modular and open-source software project for quantum simulations of materials
journal, September 2009

  • Giannozzi, Paolo; Baroni, Stefano; Bonini, Nicola
  • Journal of Physics: Condensed Matter, Vol. 21, Issue 39, Article No. 395502
  • DOI: 10.1088/0953-8984/21/39/395502

Nanostructured hematite: synthesis, characterization, charge carrier dynamics, and photoelectrochemical properties
journal, January 2012

  • Wheeler, Damon A.; Wang, Gongming; Ling, Yichuan
  • Energy & Environmental Science, Vol. 5, Issue 5
  • DOI: 10.1039/c2ee00001f

A mechanism for the hole-mediated water photooxidation on TiO 2 (1 0 1) surfaces
journal, January 2016


Facet-dependent trapping and dynamics of excess electrons at anatase TiO2 surfaces and aqueous interfaces
journal, June 2016

  • Selcuk, Sencer; Selloni, Annabella
  • Nature Materials, Vol. 15, Issue 10
  • DOI: 10.1038/nmat4672

Platinized WO 3 as an Environmental Photocatalyst that Generates OH Radicals under Visible Light
journal, September 2010

  • Kim, Jungwon; Lee, Chul Wee; Choi, Wonyong
  • Environmental Science & Technology, Vol. 44, Issue 17
  • DOI: 10.1021/es101981r

Anisotropic Effects of Oxygen Vacancies on Electrochromic Properties and Conductivity of γ-Monoclinic WO 3
journal, May 2016

  • Gerosa, Matteo; Di Valentin, Cristiana; Onida, Giovanni
  • The Journal of Physical Chemistry C, Vol. 120, Issue 21
  • DOI: 10.1021/acs.jpcc.6b02707

Dissolution kinetics of WO3 in acidic solutions
journal, February 2006


Materials for solar fuels and chemicals
journal, December 2016

  • Montoya, Joseph H.; Seitz, Linsey C.; Chakthranont, Pongkarn
  • Nature Materials, Vol. 16, Issue 1
  • DOI: 10.1038/nmat4778

Ab initio study of oxygen point defects on tungsten trioxide surface
journal, January 2012


Optimized norm-conserving Vanderbilt pseudopotentials
journal, August 2013


Heterojunction BiVO4/WO3 electrodes for enhanced photoactivity of water oxidation
journal, January 2011

  • Hong, Suk Joon; Lee, Seungok; Jang, Jum Suk
  • Energy & Environmental Science, Vol. 4, Issue 5
  • DOI: 10.1039/c0ee00743a

Interfacial Effects on the Band Edges of Functionalized Si Surfaces in Liquid Water
journal, November 2014

  • Pham, Tuan Anh; Lee, Donghwa; Schwegler, Eric
  • Journal of the American Chemical Society, Vol. 136, Issue 49
  • DOI: 10.1021/ja5079865

Improving O2 production of WO3 photoanodes with IrO2 in acidic aqueous electrolyte
journal, January 2014

  • Spurgeon, Joshua M.; Velazquez, Jesus M.; McDowell, Matthew T.
  • Physical Chemistry Chemical Physics, Vol. 16, Issue 8
  • DOI: 10.1039/c3cp55527e

Ab initio DFT computation of SnO2 and WO3 slabs and gas–surface interactions
journal, September 2007


Alignment of Redox Levels at Semiconductor–Water Interfaces
journal, December 2017


First-Principles Approach to Calculating Energy Level Alignment at Aqueous Semiconductor Interfaces
journal, October 2014


Thermally Stable N 2 -Intercalated WO 3 Photoanodes for Water Oxidation
journal, October 2012

  • Mi, Qixi; Ping, Yuan; Li, Yan
  • Journal of the American Chemical Society, Vol. 134, Issue 44
  • DOI: 10.1021/ja3067622

Sputtered WO3 films for water splitting applications
journal, February 2016

  • Valerini, D.; Hernández, S.; Di Benedetto, F.
  • Materials Science in Semiconductor Processing, Vol. 42
  • DOI: 10.1016/j.mssp.2015.09.013

Dipole correction for surface supercell calculations
journal, May 1999


First principles scheme to evaluate band edge positions in potential transition metal oxide photocatalysts and photoelectrodes
journal, January 2011

  • Toroker, Maytal Caspary; Kanan, Dalal K.; Alidoust, Nima
  • Physical Chemistry Chemical Physics, Vol. 13, Issue 37, p. 16644-16654
  • DOI: 10.1039/c1cp22128k

Quantitative characterization of hydroxyl radicals produced by various photocatalysts
journal, May 2011

  • Xiang, Quanjun; Yu, Jiaguo; Wong, Po Keung
  • Journal of Colloid and Interface Science, Vol. 357, Issue 1
  • DOI: 10.1016/j.jcis.2011.01.093

Electronic and optical properties of nanocrystalline WO 3 thin films studied by optical spectroscopy and density functional calculations
journal, April 2013

  • Johansson, Malin B.; Baldissera, Gustavo; Valyukh, Iryna
  • Journal of Physics: Condensed Matter, Vol. 25, Issue 20
  • DOI: 10.1088/0953-8984/25/20/205502

Water Oxidation on Pure and Doped Hematite (0001) Surfaces: Prediction of Co and Ni as Effective Dopants for Electrocatalysis
journal, August 2012

  • Liao, Peilin; Keith, John A.; Carter, Emily A.
  • Journal of the American Chemical Society, Vol. 134, Issue 32
  • DOI: 10.1021/ja301567f

X-ray photon correlation spectroscopy
journal, August 2014


Self-consistent hybrid functional for condensed systems
journal, May 2014


Canonical sampling through velocity rescaling
journal, January 2007

  • Bussi, Giovanni; Donadio, Davide; Parrinello, Michele
  • The Journal of Chemical Physics, Vol. 126, Issue 1
  • DOI: 10.1063/1.2408420

Charge generation layers comprising transition metal-oxide/organic interfaces: Electronic structure and charge generation mechanism
journal, May 2010

  • Meyer, J.; Kröger, M.; Hamwi, S.
  • Applied Physics Letters, Vol. 96, Issue 19
  • DOI: 10.1063/1.3427430

Modelling heterogeneous interfaces for solar water splitting
journal, January 2017

  • Pham, Tuan Anh; Ping, Yuan; Galli, Giulia
  • Nature Materials, Vol. 16, Issue 4
  • DOI: 10.1038/nmat4803

Role of oxygen vacancies in crystalline WO 3
journal, January 2016

  • Wang, Wennie; Janotti, Anderson; Van de Walle, Chris G.
  • Journal of Materials Chemistry C, Vol. 4, Issue 27
  • DOI: 10.1039/C6TC01643J

Will Solar-Driven Water-Splitting Devices See the Light of Day?
journal, September 2013

  • McKone, James R.; Lewis, Nathan S.; Gray, Harry B.
  • Chemistry of Materials, Vol. 26, Issue 1
  • DOI: 10.1021/cm4021518

Structural and electronic properties of tungsten trioxides: from cluster to solid surface
journal, July 2011


Semiconducting materials for photoelectrochemical energy conversion
journal, January 2016


Energetics and Solvation Effects at the Photoanode/Catalyst Interface: Ohmic Contact versus Schottky Barrier
journal, April 2015

  • Ping, Yuan; Goddard, William A.; Galli, Giulia A.
  • Journal of the American Chemical Society, Vol. 137, Issue 16
  • DOI: 10.1021/jacs.5b00798

Oxidation and Photo-Oxidation of Water on TiO 2 Surface
journal, June 2008

  • Valdés, Á.; Qu, Z. -W.; Kroes, G. -J.
  • The Journal of Physical Chemistry C, Vol. 112, Issue 26
  • DOI: 10.1021/jp711929d

Role of the deep-lying electronic states of MoO3 in the enhancement of hole-injection in organic thin films
journal, September 2009

  • Kröger, M.; Hamwi, S.; Meyer, J.
  • Applied Physics Letters, Vol. 95, Issue 12
  • DOI: 10.1063/1.3231928

Recent Progress in Photoelectrochemical Water Splitting Activity of WO3 Photoanodes
journal, April 2018


Efficient Computation of Hartree–Fock Exchange Using Recursive Subspace Bisection
journal, December 2012

  • Gygi, François; Duchemin, Ivan
  • Journal of Chemical Theory and Computation, Vol. 9, Issue 1
  • DOI: 10.1021/ct3007088

Two-Dimensional Polaronic Behavior in the Binary Oxides m HfO 2 and m ZrO 2
journal, March 2012


Optimizing the Band Edges of Tungsten Trioxide for Water Oxidation: A First-Principles Study
journal, March 2014

  • Ping, Yuan; Galli, Giulia
  • The Journal of Physical Chemistry C, Vol. 118, Issue 12
  • DOI: 10.1021/jp410497f

H 2 O Adsorption on WO 3 and WO 3– x (001) Surfaces
journal, June 2017

  • Albanese, Elisa; Di Valentin, Cristiana; Pacchioni, Gianfranco
  • ACS Applied Materials & Interfaces, Vol. 9, Issue 27
  • DOI: 10.1021/acsami.7b06139

Assessing capability of semiconductors to split water using ionization potentials and electron affinities only
journal, January 2014

  • Stevanović, Vladan; Lany, Stephan; Ginley, David S.
  • Physical Chemistry Chemical Physics, Vol. 16, Issue 8
  • DOI: 10.1039/c3cp54589j

Optimization algorithm for the generation of ONCV pseudopotentials
journal, November 2015


Electronic Structure of Defect States in Hydroxylated and Reduced Rutile TiO 2 ( 110 ) Surfaces
journal, October 2006

  • Di Valentin, Cristiana; Pacchioni, Gianfranco; Selloni, Annabella
  • Physical Review Letters, Vol. 97, Issue 16
  • DOI: 10.1103/PhysRevLett.97.166803

Efficient iterative method for calculations of dielectric matrices
journal, September 2008


Alignment of electronic energy levels at electrochemical interfaces
journal, January 2012

  • Cheng, Jun; Sprik, Michiel
  • Physical Chemistry Chemical Physics, Vol. 14, Issue 32
  • DOI: 10.1039/c2cp41652b

Large Scale GW Calculations
journal, May 2015

  • Govoni, Marco; Galli, Giulia
  • Journal of Chemical Theory and Computation, Vol. 11, Issue 6
  • DOI: 10.1021/ct500958p

An STM study of surface structures on WO3(001)
journal, July 1996


Observation of a two-dimensional liquid of Fröhlich polarons at the bare SrTiO3 surface
journal, October 2015

  • Chen, Chaoyu; Avila, José; Frantzeskakis, Emmanouil
  • Nature Communications, Vol. 6, Issue 1
  • DOI: 10.1038/ncomms9585

    Works referencing / citing this record:

    Dielectric-dependent hybrid functionals for heterogeneous materials
    journal, July 2019


    The GW Compendium: A Practical Guide to Theoretical Photoemission Spectroscopy
    journal, July 2019


    Dielectric-dependent hybrid functionals for heterogeneous materials
    journal, July 2019


    The GW Compendium: A Practical Guide to Theoretical Photoemission Spectroscopy
    journal, July 2019


    Surface depletion field in 2D perovskite microplates: Structural phase transition, quantum confinement and Stark effect
    journal, October 2019


    The dual-defective SnS 2 monolayers: promising 2D photocatalysts for overall water splitting
    journal, January 2019

    • Sainbileg, Batjargal; Lai, Ying-Ren; Chen, Li-Chyong
    • Physical Chemistry Chemical Physics, Vol. 21, Issue 48
    • DOI: 10.1039/c9cp04649f

    Nanostructured tungsten oxide thin film devices: from optoelectronics and ionics to iontronics
    journal, January 2019

    • Hai, Zhenyin; Wei, Zihan; Xue, Chenyang
    • Journal of Materials Chemistry C, Vol. 7, Issue 42
    • DOI: 10.1039/c9tc04489b

    Quasi-degenerate states and their dynamics in oxygen deficient reducible metal oxides
    journal, February 2020

    • Daelman, Nathan; Hegner, Franziska Simone; Rellán-Piñeiro, Marcos
    • The Journal of Chemical Physics, Vol. 152, Issue 5
    • DOI: 10.1063/1.5138484

    Optical absorption induced by small polaron formation in transition metal oxides: The case of Co 3 O 4
    journal, October 2019