Influence of LaFeO3 Surface Termination on Water Reactivity
Abstract
© 2017 American Chemical Society. The polarity of oxide surfaces can dramatically impact their surface reactivity, in particular, with polar molecules such as water. The surface species that result from this interaction change the oxide electronic structure and chemical reactivity in applications such as photoelectrochemistry but are challenging to probe experimentally. Here, we report a detailed study of the surface chemistry and electronic structure of the perovskite LaFeO 3 in humid conditions using ambient-pressure X-ray photoelectron spectroscopy. Comparing the two possible terminations of the polar (001)-oriented surface, we find that the LaO-terminated surface is more reactive toward water, forming hydroxyl species and adsorbing molecular water at lower relative humidity than its FeO 2 -terminated counterpart. However, the FeO 2 -terminated surface forms more hydroxyl species during water adsorption at higher humidity, suggesting that adsorbate-adsorbate interactions may impact reactivity. Our results demonstrate how the termination of a complex oxide can dramatically impact its reactivity, providing insight that can aid in the design of catalyst materials.
- Authors:
-
[1];
[2];
[1];
[4];
- Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Physical and Computational Sciences Directorate
- Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Physical and Computational Sciences Directorate; Auburn Univ., AL (United States). Dept. of Physics
- Pohang Accelerator Lab. (PAL) (Korea, Republic of)
- Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Advanced Light Source
- Publication Date:
- Research Org.:
- Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Biological and Environmental Research (BER); USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1343949
- Alternate Identifier(s):
- OSTI ID: 1379758
- Report Number(s):
- PNNL-SA-123478
Journal ID: ISSN 1948-7185
- Grant/Contract Number:
- AC0576RL01830; AC02-05CH11231
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Journal of Physical Chemistry Letters
- Additional Journal Information:
- Journal Volume: 8; Journal Issue: 5; Journal ID: ISSN 1948-7185
- Publisher:
- American Chemical Society
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Citation Formats
Stoerzinger, Kelsey A., Comes, Ryan, Spurgeon, Steven R., Thevuthasan, Suntharampillai, Ihm, Kyuwook, Crumlin, Ethan J., and Chambers, Scott A. Influence of LaFeO3 Surface Termination on Water Reactivity. United States: N. p., 2017.
Web. doi:10.1021/acs.jpclett.7b00195.
Stoerzinger, Kelsey A., Comes, Ryan, Spurgeon, Steven R., Thevuthasan, Suntharampillai, Ihm, Kyuwook, Crumlin, Ethan J., & Chambers, Scott A. Influence of LaFeO3 Surface Termination on Water Reactivity. United States. https://doi.org/10.1021/acs.jpclett.7b00195
Stoerzinger, Kelsey A., Comes, Ryan, Spurgeon, Steven R., Thevuthasan, Suntharampillai, Ihm, Kyuwook, Crumlin, Ethan J., and Chambers, Scott A. Thu .
"Influence of LaFeO3 Surface Termination on Water Reactivity". United States. https://doi.org/10.1021/acs.jpclett.7b00195. https://www.osti.gov/servlets/purl/1343949.
@article{osti_1343949,
title = {Influence of LaFeO3 Surface Termination on Water Reactivity},
author = {Stoerzinger, Kelsey A. and Comes, Ryan and Spurgeon, Steven R. and Thevuthasan, Suntharampillai and Ihm, Kyuwook and Crumlin, Ethan J. and Chambers, Scott A.},
abstractNote = {© 2017 American Chemical Society. The polarity of oxide surfaces can dramatically impact their surface reactivity, in particular, with polar molecules such as water. The surface species that result from this interaction change the oxide electronic structure and chemical reactivity in applications such as photoelectrochemistry but are challenging to probe experimentally. Here, we report a detailed study of the surface chemistry and electronic structure of the perovskite LaFeO 3 in humid conditions using ambient-pressure X-ray photoelectron spectroscopy. Comparing the two possible terminations of the polar (001)-oriented surface, we find that the LaO-terminated surface is more reactive toward water, forming hydroxyl species and adsorbing molecular water at lower relative humidity than its FeO 2 -terminated counterpart. However, the FeO 2 -terminated surface forms more hydroxyl species during water adsorption at higher humidity, suggesting that adsorbate-adsorbate interactions may impact reactivity. Our results demonstrate how the termination of a complex oxide can dramatically impact its reactivity, providing insight that can aid in the design of catalyst materials.},
doi = {10.1021/acs.jpclett.7b00195},
journal = {Journal of Physical Chemistry Letters},
number = 5,
volume = 8,
place = {United States},
year = {Thu Feb 16 00:00:00 EST 2017},
month = {Thu Feb 16 00:00:00 EST 2017}
}
Free Publicly Available Full Text
Publisher's Version of Record
Other availability
Search WorldCat to find libraries that may hold this journal
Cited by: 43 works
Citation information provided by
Web of Science
Web of Science
Save to My Library
You must Sign In or Create an Account in order to save documents to your library.
Works referenced in this record:
A Perovskite Oxide Optimized for Oxygen Evolution Catalysis from Molecular Orbital Principles
journal, October 2011
- Suntivich, J.; May, K. J.; Gasteiger, H. A.
- Science, Vol. 334, Issue 6061
Design principles for oxygen-reduction activity on perovskite oxide catalysts for fuel cells and metal–air batteries
journal, June 2011
- Suntivich, Jin; Gasteiger, Hubert A.; Yabuuchi, Naoaki
- Nature Chemistry, Vol. 3, Issue 7, p. 546-550
Universality in Oxygen Evolution Electrocatalysis on Oxide Surfaces
journal, March 2011
- Man, Isabela C.; Su, Hai‐Yan; Calle‐Vallejo, Federico
- ChemCatChem, Vol. 3, Issue 7
Materials for Solid Oxide Fuel Cells †
journal, February 2010
- Jacobson, Allan J.
- Chemistry of Materials, Vol. 22, Issue 3
Thickness-Dependent Photoelectrochemical Water Splitting on Ultrathin LaFeO 3 Films Grown on Nb:SrTiO 3
journal, March 2015
- May, Kevin J.; Fenning, David P.; Ming, Tian
- The Journal of Physical Chemistry Letters, Vol. 6, Issue 6
Surface modification of LaFeO 3 by Co-Pi electrochemical deposition as an efficient photoanode under visible light
journal, January 2016
- Peng, Q.; Wang, J.; Wen, Y. W.
- RSC Advances, Vol. 6, Issue 31
Fabrication of nanocrystalline LaFeO3: An efficient sol–gel auto-combustion assisted visible light responsive photocatalyst for water decomposition
journal, November 2010
- Parida, K. M.; Reddy, K. H.; Martha, S.
- International Journal of Hydrogen Energy, Vol. 35, Issue 22
Perovskite oxides for semiconductor-based gas sensors
journal, May 2007
- Fergus, Jeffrey W.
- Sensors and Actuators B: Chemical, Vol. 123, Issue 2
Gas sensing with semiconducting perovskite oxide LaFeO3
journal, April 2003
- Toan, N. N.; Saukko, S.; Lantto, V.
- Physica B: Condensed Matter, Vol. 327, Issue 2-4
Highly sensitive humidity sensor based on high surface area mesoporous LaFeO3 prepared by a nanocasting route
journal, May 2013
- Zhao, Jing; Liu, Yinping; Li, Xiaowei
- Sensors and Actuators B: Chemical, Vol. 181
Water-Induced Decoupling of Tracer and Electrochemical Oxygen Exchange Kinetics on Mixed Conducting Electrodes
journal, June 2016
- Nenning, Andreas; Navickas, Edvinas; Hutter, Herbert
- The Journal of Physical Chemistry Letters, Vol. 7, Issue 14
Reactivity of Perovskites with Water: Role of Hydroxylation in Wetting and Implications for Oxygen Electrocatalysis
journal, July 2015
- Stoerzinger, Kelsey A.; Hong, Wesley T.; Azimi, Gisele
- The Journal of Physical Chemistry C, Vol. 119, Issue 32
Reactions on Atmospheric Dust Particles: Surface Photochemistry and Size-Dependent Nanoscale Redox Chemistry
journal, May 2010
- Rubasinghege, Gayan; Elzey, Sherrie; Baltrusaitis, Jonas
- The Journal of Physical Chemistry Letters, Vol. 1, Issue 11
The interaction of water with solid surfaces: fundamental aspects revisited
journal, May 2002
- Henderson, M.
- Surface Science Reports, Vol. 46, Issue 1-8
Metal Oxide Surfaces and Their Interactions with Aqueous Solutions and Microbial Organisms
journal, January 1999
- Brown, Gordon E.; Henrich, Victor E.; Casey, William H.
- Chemical Reviews, Vol. 99, Issue 1
Fast Interconversion of Hydrogen Bonding at the Hematite (001)–Liquid Water Interface
journal, March 2016
- von Rudorff, Guido Falk; Jakobsen, Rasmus; Rosso, Kevin M.
- The Journal of Physical Chemistry Letters, Vol. 7, Issue 7
Water Reactivity on the LaCoO 3 (001) Surface: An Ambient Pressure X-ray Photoelectron Spectroscopy Study
journal, August 2014
- Stoerzinger, Kelsey A.; Hong, Wesley T.; Crumlin, Ethan J.
- The Journal of Physical Chemistry C, Vol. 118, Issue 34
Insights into Electrochemical Reactions from Ambient Pressure Photoelectron Spectroscopy
journal, August 2015
- Stoerzinger, Kelsey A.; Hong, Wesley T.; Crumlin, Ethan J.
- Accounts of Chemical Research, Vol. 48, Issue 11
Interface Structure, Band Alignment, and Built-In Potentials at Heterojunctions
journal, November 2016
- Comes, Ryan; Chambers, Scott
- Physical Review Letters, Vol. 117, Issue 22
Impact of built-in potential across LaFeO3/SrTiO3 heterojunctions on photocatalytic activity
journal, May 2016
- Nakamura, Kentarou; Mashiko, Hisanori; Yoshimatsu, Kohei
- Applied Physics Letters, Vol. 108, Issue 21
Spontaneous Polarization and Bulk Photovoltaic Effect Driven by Polar Discontinuity in Heterojunctions
journal, April 2016
- Nakamura, M.; Kagawa, F.; Tanigaki, T.
- Physical Review Letters, Vol. 116, Issue 15
Reversible Formation of 2D Electron Gas at the LaFeO 3 /SrTiO 3 Interface via Control of Oxygen Vacancies
journal, January 2017
- Xu, Pengfa; Han, Wei; Rice, Philip M.
- Advanced Materials, Vol. 29, Issue 10
Understanding and Controlling the Work Function of Perovskite Oxides Using Density Functional Theory
journal, May 2016
- Jacobs, Ryan; Booske, John; Morgan, Dane
- Advanced Functional Materials, Vol. 26, Issue 30
Liquid-Jet X-ray Photoelectron Spectra of TiO 2 Nanoparticles in an Aqueous Electrolyte Solution
journal, April 2016
- Makowski, Michael J.; Galhenage, Randima P.; Langford, Joel
- The Journal of Physical Chemistry Letters, Vol. 7, Issue 9
Investigation of solid/vapor interfaces using ambient pressure X-ray photoelectron spectroscopy
journal, January 2013
- Starr, D. E.; Liu, Z.; Hävecker, M.
- Chemical Society Reviews, Vol. 42, Issue 13
In situ investigation of electrochemical devices using ambient pressure photoelectron spectroscopy
journal, October 2013
- Crumlin, Ethan J.; Bluhm, Hendrik; Liu, Zhi
- Journal of Electron Spectroscopy and Related Phenomena, Vol. 190
Direct observation of the energetics at a semiconductor/liquid junction by operando X-ray photoelectron spectroscopy
journal, January 2015
- Lichterman, Michael F.; Hu, Shu; Richter, Matthias H.
- Energy & Environmental Science, Vol. 8, Issue 8
Direct Work Function Measurement by Gas Phase Photoelectron Spectroscopy and Its Application on PbS Nanoparticles
journal, November 2013
- Axnanda, Stephanus; Scheele, Marcus; Crumlin, Ethan
- Nano Letters, Vol. 13, Issue 12
XPS study of the surface carbonation/hydroxylation state of metal oxides
journal, September 1990
- Gonzalez-Elipe, A. R.; Espinos, J. P.; Fernandez, A.
- Applied Surface Science, Vol. 45, Issue 2
La1−xCaxCoO3 perovskite-type oxides: Identification of the surface oxygen species by XPS
journal, November 2006
- Merino, Nora A.; Barbero, Bibiana P.; Eloy, Pierre
- Applied Surface Science, Vol. 253, Issue 3
Growth and surface modification of LaFeO3 thin films induced by reductive annealing
journal, March 2015
- Flynn, Brendan T.; Zhang, Kelvin H. L.; Shutthanandan, Vaithiyalingam
- Applied Surface Science, Vol. 330
Water adsorption on SrTiO3(001): II. Water, water, everywhere
journal, May 2012
- Becerra-Toledo, A. E.; Enterkin, J. A.; Kienzle, D. M.
- Surface Science, Vol. 606, Issue 9-10
Anion charge storage through oxygen intercalation in LaMnO3 perovskite pseudocapacitor electrodes
journal, June 2014
- Mefford, J. Tyler; Hardin, William G.; Dai, Sheng
- Nature Materials, Vol. 13, Issue 7
Adsorption and diffusion of Mg, O, and O2 on the MgO(001) flat surface
journal, May 2005
- Geneste, Grégory; Morillo, Joseph; Finocchi, Fabio
- The Journal of Chemical Physics, Vol. 122, Issue 17
The effect of preparation: Pechini and Schiff base methods, on adsorbed oxygen of LaCoO3 perovskite oxidation catalysts
journal, February 2008
- Worayingyong, Attera; Kangvansura, Praewpilin; Ausadasuk, Siritha
- Colloids and Surfaces A: Physicochemical and Engineering Aspects, Vol. 315, Issue 1-3
Perovskite-type oxides synthesized by reactive grinding
journal, February 2001
- Kaliaguine, S.; Van Neste, A.; Szabo, V.
- Applied Catalysis A: General, Vol. 209, Issue 1-2
Formation of hydroxyl and water layers on MgO films studied with ambient pressure XPS
journal, January 2011
- Newberg, John T.; Starr, David E.; Yamamoto, Susumu
- Surface Science, Vol. 605, Issue 1-2
Surface reactivity of reduced LaFeO3 as studied by TPD and IR spectroscopies of CO, CO2 and H2
journal, December 1989
- Corber�n, V. Cort�s; Tejuca, Luis G.; Bell, Alexis T.
- Journal of Materials Science, Vol. 24, Issue 12
X-ray Photoemission and Density Functional Theory Study of the Interaction of Water Vapor with the Fe 3 O 4 (001) Surface at Near-Ambient Conditions
journal, February 2013
- Kendelewicz, T.; Kaya, S.; Newberg, J. T.
- The Journal of Physical Chemistry C, Vol. 117, Issue 6
Water Adsorption on α-Fe 2 O 3 (0001) at near Ambient Conditions
journal, January 2010
- Yamamoto, Susumu; Kendelewicz, Tom; Newberg, John T.
- The Journal of Physical Chemistry C, Vol. 114, Issue 5
Origin of Overpotential-Dependent Surface Dipole at CeO 2– x /Gas Interface During Electrochemical Oxygen Insertion Reactions
journal, August 2016
- Feng, Zhuoluo A.; Balaji Gopal, Chirranjeevi; Ye, Xiaofei
- Chemistry of Materials, Vol. 28, Issue 17
XPS characterisation of in situ treated lanthanum oxide and hydroxide using tailored charge referencing and peak fitting procedures
journal, July 2011
- Sunding, M. F.; Hadidi, K.; Diplas, S.
- Journal of Electron Spectroscopy and Related Phenomena, Vol. 184, Issue 7
Band alignment of epitaxial SrTiO3 thin films with (LaAlO3)0.3-(Sr2AlTaO6)0.7 (001)
journal, September 2015
- Comes, Ryan B.; Xu, Peng; Jalan, Bharat
- Applied Physics Letters, Vol. 107, Issue 13
Unintentional F doping of SrTiO3(001) etched in HF acid-structure and electronic properties
journal, February 2012
- Chambers, S. A.; Droubay, T. C.; Capan, C.
- Surface Science, Vol. 606, Issue 3-4
New ambient pressure photoemission endstation at Advanced Light Source beamline 9.3.2
journal, May 2010
- Grass, Michael E.; Karlsson, Patrik G.; Aksoy, Funda
- Review of Scientific Instruments, Vol. 81, Issue 5
Works referencing / citing this record:
Surface termination effects on the oxygen reduction reaction rate at fuel cell cathodes
journal, January 2018
- Mastrikov, Yuri A.; Merkle, Rotraut; Kotomin, Eugene A.
- Journal of Materials Chemistry A, Vol. 6, Issue 25
Chemical and electronic structure analysis of a SrTiO3 (001)/p-Ge (001) hydrogen evolution photocathode
journal, March 2018
- Stoerzinger, Kelsey A.; Du, Yingge; Spurgeon, Steven R.
- MRS Communications, Vol. 8, Issue 02
Impact of Sr-Incorporation on Cr Oxidation and Water Dissociation in La (1- x ) Sr x CrO 3
journal, January 2018
- Stoerzinger, Kelsey A.; Du, Yingge; Ihm, Kyuwook
- Advanced Materials Interfaces, Vol. 5, Issue 6
Speciation and Electronic Structure of La1−xSrxCoO3−δ During Oxygen Electrolysis
journal, October 2018
- Stoerzinger, Kelsey A.; Renshaw Wang, Xiao; Hwang, Jonathan
- Topics in Catalysis, Vol. 61, Issue 20
Effect of Bi-doping on the electrocatalytic properties of LaFeO3 powders prepared by sol–gel method
journal, February 2019
- Li, Wanjun; Yang, Fujun; Xiong, Peng
- Journal of Materials Science, Vol. 54, Issue 10
The effects of the oxygen content on the photoelectrochemical properties of LaFeO3 perovskite thin films obtained by pulsed laser deposition
journal, November 2019
- Andrei, F.; Boerasu, I.; Birjega, R.
- Applied Physics A, Vol. 125, Issue 11
Surface phase diagrams of La-based perovskites towards the O-rich limit from first principles
journal, January 2019
- Li, Yang; Yang, Jie; Zhu, Yi-An
- Physical Chemistry Chemical Physics, Vol. 21, Issue 24