Influence of LaFeO 3 Surface Termination on Water Reactivity

Stoerzinger, Kelsey A.; Comes, Ryan; Spurgeon, Steven R.; Thevuthasan, Suntharampillai; Ihm, Kyuwook; Crumlin, Ethan J.; Chambers, Scott A.

doi:10.1021/acs.jpclett.7b00195

Title: Influence of LaFeO ₃ Surface Termination on Water Reactivity

Journal Article · Fri Feb 17 00:00:00 EST 2017 · Journal of Physical Chemistry Letters

DOI:https://doi.org/10.1021/acs.jpclett.7b00195· OSTI ID:1347856

;

; Thevuthasan, Suntharampillai; Ihm, Kyuwook;

; Chambers, Scott A.

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 with atomic-scale understanding. Here we report a detailed study of the surface chemistry and electronic structure of the perovskite LaFeO3 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 surface is more reactive toward water, forming hydroxyl species and adsorbing molecular water at lower relative humidity than its FeO2-terminated counterpart. Our results demonstrate how the termination of a complex oxide can dramatically impact its reactivity, providing insight into the design of catalyst materials.

Cite

Export

Save

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

Sponsoring Organization:: USDOE Office of Science (SC), Biological and Environmental Research (BER); USDOE Office of Science (SC), Basic Energy Sciences (BES)

DOE Contract Number:: AC05-76RL01830

OSTI ID:: 1347856

Report Number(s):: PNNL-SA-123478; 49306

Journal Information:: Journal of Physical Chemistry Letters, Vol. 8, Issue 5; ISSN 1948-7185

Publisher:: American Chemical Society

Country of Publication:: United States

Language:: English

References (44)

A Perovskite Oxide Optimized for Oxygen Evolution Catalysis from Molecular Orbital Principles Suntivich, J.; May, K. J.; Gasteiger, H. A. Science, Vol. 334, Issue 6061 https://doi.org/10.1126/science.1212858	journal	October 2011
Design principles for oxygen-reduction activity on perovskite oxide catalysts for fuel cells and metal–air batteries Suntivich, Jin; Gasteiger, Hubert A.; Yabuuchi, Naoaki Nature Chemistry, Vol. 3, Issue 7, p. 546-550 https://doi.org/10.1038/nchem.1069	journal	June 2011
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
Materials for Solid Oxide Fuel Cells ^† Jacobson, Allan J. Chemistry of Materials, Vol. 22, Issue 3 https://doi.org/10.1021/cm902640j	journal	February 2010
Thickness-Dependent Photoelectrochemical Water Splitting on Ultrathin LaFeO ₃ Films Grown on Nb:SrTiO ₃ May, Kevin J.; Fenning, David P.; Ming, Tian The Journal of Physical Chemistry Letters, Vol. 6, Issue 6 https://doi.org/10.1021/acs.jpclett.5b00169	journal	March 2015
Surface modification of LaFeO ₃ by Co-Pi electrochemical deposition as an efficient photoanode under visible light Peng, Q.; Wang, J.; Wen, Y. W. RSC Advances, Vol. 6, Issue 31 https://doi.org/10.1039/C6RA01810F	journal	January 2016
Fabrication of nanocrystalline LaFeO3: An efficient sol–gel auto-combustion assisted visible light responsive photocatalyst for water decomposition Parida, K. M.; Reddy, K. H.; Martha, S. International Journal of Hydrogen Energy, Vol. 35, Issue 22 https://doi.org/10.1016/j.ijhydene.2010.08.029	journal	November 2010
Perovskite oxides for semiconductor-based gas sensors Fergus, Jeffrey W. Sensors and Actuators B: Chemical, Vol. 123, Issue 2 https://doi.org/10.1016/j.snb.2006.10.051	journal	May 2007
Highly sensitive humidity sensor based on high surface area mesoporous LaFeO3 prepared by a nanocasting route Zhao, Jing; Liu, Yinping; Li, Xiaowei Sensors and Actuators B: Chemical, Vol. 181 https://doi.org/10.1016/j.snb.2013.02.077	journal	May 2013
Water-Induced Decoupling of Tracer and Electrochemical Oxygen Exchange Kinetics on Mixed Conducting Electrodes Nenning, Andreas; Navickas, Edvinas; Hutter, Herbert The Journal of Physical Chemistry Letters, Vol. 7, Issue 14 https://doi.org/10.1021/acs.jpclett.6b00778	journal	June 2016
Reactivity of Perovskites with Water: Role of Hydroxylation in Wetting and Implications for Oxygen Electrocatalysis Stoerzinger, Kelsey A.; Hong, Wesley T.; Azimi, Gisele The Journal of Physical Chemistry C, Vol. 119, Issue 32 https://doi.org/10.1021/acs.jpcc.5b06621	journal	July 2015
Reactions on Atmospheric Dust Particles: Surface Photochemistry and Size-Dependent Nanoscale Redox Chemistry Rubasinghege, Gayan; Elzey, Sherrie; Baltrusaitis, Jonas The Journal of Physical Chemistry Letters, Vol. 1, Issue 11 https://doi.org/10.1021/jz100371d	journal	May 2010
The interaction of water with solid surfaces: fundamental aspects revisited Henderson, M. Surface Science Reports, Vol. 46, Issue 1-8 https://doi.org/10.1016/S0167-5729(01)00020-6	journal	May 2002
Metal Oxide Surfaces and Their Interactions with Aqueous Solutions and Microbial Organisms Brown, Gordon E.; Henrich, Victor E.; Casey, William H. Chemical Reviews, Vol. 99, Issue 1 https://doi.org/10.1021/cr980011z	journal	January 1999
Fast Interconversion of Hydrogen Bonding at the Hematite (001)–Liquid Water Interface von Rudorff, Guido Falk; Jakobsen, Rasmus; Rosso, Kevin M. The Journal of Physical Chemistry Letters, Vol. 7, Issue 7 https://doi.org/10.1021/acs.jpclett.6b00165	journal	March 2016
Water Reactivity on the LaCoO ₃ (001) Surface: An Ambient Pressure X-ray Photoelectron Spectroscopy Study Stoerzinger, Kelsey A.; Hong, Wesley T.; Crumlin, Ethan J. The Journal of Physical Chemistry C, Vol. 118, Issue 34 https://doi.org/10.1021/jp502970r	journal	August 2014
Insights into Electrochemical Reactions from Ambient Pressure Photoelectron Spectroscopy Stoerzinger, Kelsey A.; Hong, Wesley T.; Crumlin, Ethan J. Accounts of Chemical Research, Vol. 48, Issue 11 https://doi.org/10.1021/acs.accounts.5b00275	journal	August 2015
Interface Structure, Band Alignment, and Built-In Potentials at ${LaFeO}_{3} / n − {SrTiO}_{3}$ Heterojunctions Comes, Ryan; Chambers, Scott Physical Review Letters, Vol. 117, Issue 22 https://doi.org/10.1103/PhysRevLett.117.226802	journal	November 2016
Impact of built-in potential across LaFeO3/SrTiO3 heterojunctions on photocatalytic activity Nakamura, Kentarou; Mashiko, Hisanori; Yoshimatsu, Kohei Applied Physics Letters, Vol. 108, Issue 21 https://doi.org/10.1063/1.4952736	journal	May 2016
Spontaneous Polarization and Bulk Photovoltaic Effect Driven by Polar Discontinuity in ${LaFeO}_{3} / {SrTiO}_{3}$ Heterojunctions Nakamura, M.; Kagawa, F.; Tanigaki, T. Physical Review Letters, Vol. 116, Issue 15 https://doi.org/10.1103/PhysRevLett.116.156801	journal	April 2016
Reversible Formation of 2D Electron Gas at the LaFeO ₃ /SrTiO ₃ Interface via Control of Oxygen Vacancies Xu, Pengfa; Han, Wei; Rice, Philip M. Advanced Materials, Vol. 29, Issue 10 https://doi.org/10.1002/adma.201604447	journal	January 2017
Understanding and Controlling the Work Function of Perovskite Oxides Using Density Functional Theory Jacobs, Ryan; Booske, John; Morgan, Dane Advanced Functional Materials, Vol. 26, Issue 30 https://doi.org/10.1002/adfm.201600243	journal	May 2016
Liquid-Jet X-ray Photoelectron Spectra of TiO ₂ Nanoparticles in an Aqueous Electrolyte Solution Makowski, Michael J.; Galhenage, Randima P.; Langford, Joel The Journal of Physical Chemistry Letters, Vol. 7, Issue 9 https://doi.org/10.1021/acs.jpclett.6b00445	journal	April 2016
Investigation of solid/vapor interfaces using ambient pressure X-ray photoelectron spectroscopy Starr, D. E.; Liu, Z.; Hävecker, M. Chemical Society Reviews, Vol. 42, Issue 13 https://doi.org/10.1039/c3cs60057b	journal	January 2013
In situ investigation of electrochemical devices using ambient pressure photoelectron spectroscopy Crumlin, Ethan J.; Bluhm, Hendrik; Liu, Zhi Journal of Electron Spectroscopy and Related Phenomena, Vol. 190 https://doi.org/10.1016/j.elspec.2013.03.002	journal	October 2013
Direct observation of the energetics at a semiconductor/liquid junction by operando X-ray photoelectron spectroscopy Lichterman, Michael F.; Hu, Shu; Richter, Matthias H. Energy & Environmental Science, Vol. 8, Issue 8 https://doi.org/10.1039/C5EE01014D	journal	January 2015
Direct Work Function Measurement by Gas Phase Photoelectron Spectroscopy and Its Application on PbS Nanoparticles Axnanda, Stephanus; Scheele, Marcus; Crumlin, Ethan Nano Letters, Vol. 13, Issue 12 https://doi.org/10.1021/nl403524a	journal	November 2013
XPS study of the surface carbonation/hydroxylation state of metal oxides Gonzalez-Elipe, A. R.; Espinos, J. P.; Fernandez, A. Applied Surface Science, Vol. 45, Issue 2 https://doi.org/10.1016/0169-4332(90)90060-D	journal	September 1990
La1−xCaxCoO3 perovskite-type oxides: Identification of the surface oxygen species by XPS Merino, Nora A.; Barbero, Bibiana P.; Eloy, Pierre Applied Surface Science, Vol. 253, Issue 3 https://doi.org/10.1016/j.apsusc.2006.02.035	journal	November 2006
Growth and surface modification of LaFeO3 thin films induced by reductive annealing Flynn, Brendan T.; Zhang, Kelvin H. L.; Shutthanandan, Vaithiyalingam Applied Surface Science, Vol. 330 https://doi.org/10.1016/j.apsusc.2015.01.028	journal	March 2015
Water adsorption on SrTiO3(001): II. Water, water, everywhere Becerra-Toledo, A. E.; Enterkin, J. A.; Kienzle, D. M. Surface Science, Vol. 606, Issue 9-10 https://doi.org/10.1016/j.susc.2012.01.010	journal	May 2012
Anion charge storage through oxygen intercalation in LaMnO3 perovskite pseudocapacitor electrodes Mefford, J. Tyler; Hardin, William G.; Dai, Sheng Nature Materials, Vol. 13, Issue 7 https://doi.org/10.1038/nmat4000	journal	June 2014
Adsorption and diffusion of Mg, O, and O2 on the MgO(001) flat surface Geneste, Grégory; Morillo, Joseph; Finocchi, Fabio The Journal of Chemical Physics, Vol. 122, Issue 17 https://doi.org/10.1063/1.1886734	journal	May 2005
The effect of preparation: Pechini and Schiff base methods, on adsorbed oxygen of LaCoO3 perovskite oxidation catalysts Worayingyong, Attera; Kangvansura, Praewpilin; Ausadasuk, Siritha Colloids and Surfaces A: Physicochemical and Engineering Aspects, Vol. 315, Issue 1-3 https://doi.org/10.1016/j.colsurfa.2007.08.002	journal	February 2008
Perovskite-type oxides synthesized by reactive grinding Kaliaguine, S.; Van Neste, A.; Szabo, V. Applied Catalysis A: General, Vol. 209, Issue 1-2 https://doi.org/10.1016/S0926-860X(00)00779-1	journal	February 2001
Formation of hydroxyl and water layers on MgO films studied with ambient pressure XPS Newberg, John T.; Starr, David E.; Yamamoto, Susumu Surface Science, Vol. 605, Issue 1-2 https://doi.org/10.1016/j.susc.2010.10.004	journal	January 2011
Surface reactivity of reduced LaFeO3 as studied by TPD and IR spectroscopies of CO, CO2 and H2 Corber�n, V. Cort�s; Tejuca, Luis G.; Bell, Alexis T. Journal of Materials Science, Vol. 24, Issue 12 https://doi.org/10.1007/BF00544527	journal	December 1989
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 Kendelewicz, T.; Kaya, S.; Newberg, J. T. The Journal of Physical Chemistry C, Vol. 117, Issue 6 https://doi.org/10.1021/jp3078024	journal	February 2013
Water Adsorption on α-Fe ₂ O ₃ (0001) at near Ambient Conditions Yamamoto, Susumu; Kendelewicz, Tom; Newberg, John T. The Journal of Physical Chemistry C, Vol. 114, Issue 5 https://doi.org/10.1021/jp909876t	journal	January 2010
Origin of Overpotential-Dependent Surface Dipole at CeO _{2– x} /Gas Interface During Electrochemical Oxygen Insertion Reactions Feng, Zhuoluo A.; Balaji Gopal, Chirranjeevi; Ye, Xiaofei Chemistry of Materials, Vol. 28, Issue 17 https://doi.org/10.1021/acs.chemmater.6b02427	journal	August 2016
XPS characterisation of in situ treated lanthanum oxide and hydroxide using tailored charge referencing and peak fitting procedures Sunding, M. F.; Hadidi, K.; Diplas, S. Journal of Electron Spectroscopy and Related Phenomena, Vol. 184, Issue 7 https://doi.org/10.1016/j.elspec.2011.04.002	journal	July 2011
Band alignment of epitaxial SrTiO3 thin films with (LaAlO3)0.3-(Sr2AlTaO6)0.7 (001) Comes, Ryan B.; Xu, Peng; Jalan, Bharat Applied Physics Letters, Vol. 107, Issue 13 https://doi.org/10.1063/1.4932063	journal	September 2015
Unintentional F doping of SrTiO3(001) etched in HF acid-structure and electronic properties Chambers, S. A.; Droubay, T. C.; Capan, C. Surface Science, Vol. 606, Issue 3-4 https://doi.org/10.1016/j.susc.2011.11.029	journal	February 2012
New ambient pressure photoemission endstation at Advanced Light Source beamline 9.3.2 Grass, Michael E.; Karlsson, Patrik G.; Aksoy, Funda Review of Scientific Instruments, Vol. 81, Issue 5 https://doi.org/10.1063/1.3427218	journal	May 2010

Cited By (8)

Surface termination effects on the oxygen reduction reaction rate at fuel cell cathodes Mastrikov, Yuri A.; Merkle, Rotraut; Kotomin, Eugene A. Journal of Materials Chemistry A, Vol. 6, Issue 25 https://doi.org/10.1039/c8ta02058b	journal	January 2018
Chemical and electronic structure analysis of a SrTiO3 (001)/p-Ge (001) hydrogen evolution photocathode Stoerzinger, Kelsey A.; Du, Yingge; Spurgeon, Steven R. MRS Communications, Vol. 8, Issue 02 https://doi.org/10.1557/mrc.2018.38	journal	March 2018
Impact of Sr-Incorporation on Cr Oxidation and Water Dissociation in La _(1- _x ₎ Sr _x CrO ₃ Stoerzinger, Kelsey A.; Du, Yingge; Ihm, Kyuwook Advanced Materials Interfaces, Vol. 5, Issue 6 https://doi.org/10.1002/admi.201701363	journal	January 2018
Speciation and Electronic Structure of La1−xSrxCoO3−δ During Oxygen Electrolysis Stoerzinger, Kelsey A.; Renshaw Wang, Xiao; Hwang, Jonathan Topics in Catalysis, Vol. 61, Issue 20 https://doi.org/10.1007/s11244-018-1070-7	journal	October 2018
Effect of Bi-doping on the electrocatalytic properties of LaFeO3 powders prepared by sol–gel method Li, Wanjun; Yang, Fujun; Xiong, Peng Journal of Materials Science, Vol. 54, Issue 10 https://doi.org/10.1007/s10853-019-03443-6	journal	February 2019
The effects of the oxygen content on the photoelectrochemical properties of LaFeO3 perovskite thin films obtained by pulsed laser deposition Andrei, F.; Boerasu, I.; Birjega, R. Applied Physics A, Vol. 125, Issue 11 https://doi.org/10.1007/s00339-019-3089-4	journal	November 2019
Water adsorption, dissociation and oxidation on SrTiO ₃ and ferroelectric surfaces revealed by ambient pressure X-ray photoelectron spectroscopy Domingo, Neus; Pach, Elzbieta; Cordero-Edwards, Kumara Physical Chemistry Chemical Physics, Vol. 21, Issue 9 https://doi.org/10.1039/c8cp07632d	journal	January 2019
Surface phase diagrams of La-based perovskites towards the O-rich limit from first principles Li, Yang; Yang, Jie; Zhu, Yi-An Physical Chemistry Chemical Physics, Vol. 21, Issue 24 https://doi.org/10.1039/c9cp02288k	journal	January 2019

Similar Records

Influence of LaFeO₃ Surface Termination on Water Reactivity

Journal Article · Thu Feb 16 00:00:00 EST 2017 · Journal of Physical Chemistry Letters · OSTI ID:1347856

Stoerzinger, Kelsey A.; Comes, Ryan; Spurgeon, Steven R.; +4 more

Decreasing the Hydroxylation Affinity of La _1–x Sr _x MnO ₃ Perovskites To Promote Oxygen Reduction Electrocatalysis

Journal Article · Fri Nov 17 00:00:00 EST 2017 · Chemistry of Materials · OSTI ID:1347856

Stoerzinger, Kelsey A.; Hong, Wesley T.; Wang, Xiao Renshaw; +9 more

Stabilization mechanisms of LaFeO3 (010) surfaces determined with first principles calculations

Journal Article · Sat Jan 01 00:00:00 EST 2011 · Journal of the American Ceramic Society · OSTI ID:1347856

Lee, Chan-Woo; Behera, Rakesh K; Okamoto, Satoshi; +4 more

Related Subjects

Environmental Molecular Sciences Laboratory

Title: Influence of LaFeO 3 Surface Termination on Water Reactivity

Citation Formats

References (44)

Cited By (8)

Similar Records

Related Subjects

Title: Influence of LaFeO ₃ Surface Termination on Water Reactivity