CO2 Reactivity on Cobalt-Based Perovskites

Hwang, Jonathan; Rao, Reshma R.; Katayama, Yu; Lee, Dongkyu; Wang, Xiao Renshaw; Crumlin, Ethan J.; Venkatesan, Thirumalai; Lee, Ho Nyung; Shao-Horn, Yang

doi:10.1021/acs.jpcc.8b06104

CO₂ Reactivity on Cobalt-Based Perovskites

Journal Article · Thu Aug 09 00:00:00 EDT 2018 · Journal of Physical Chemistry. C

DOI:https://doi.org/10.1021/acs.jpcc.8b06104· OSTI ID:1483179

^[1]; ^[1]; ^[2]; ^[3]; ^[4]; ^[5]; Venkatesan, Thirumalai ^[6]; ^[7]; ^[1]

Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States)
Yamaguchi Univ., Yamaguchi (Japan)
Univ. of South Carolina, Columbia, SC (United States); Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Nanyang Technological Univ. (Singapore)
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
NUSNNI-Nanocore (Singapore); National Univ. of Singapore (Singapore)
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)

Understanding the interaction of CO₂ with perovskite metal oxide surfaces is crucial for the design of various perovskite (electro)chemical functionalities, such as solid oxide fuel cells, catalytic oxidation reactions, and gas sensing. In this study, we experimentally investigated the reactivity of CO₂ with a series of cobalt-based perovskites (i.e., LaCoO₃, La_0.4Sr_0.6CoO₃, SrCoO_2.5, and Pr_0.5Ba_0.5CoO_3–δ) by a combined ambient-pressure XPS (AP-XPS) and diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) approach. Isobaric measurements by AP-XPS on epitaxial pulsed laser deposition-grown (100)-oriented thin films under 1 mTorr CO₂ showed the formation and uptake of adsorbed adventitious-like C–C/C–H, –CO species, monodentate carbonate, and bidentate (bi)carbonates. DRIFTS measurements on powder samples under CO₂ atmosphere revealed the presence of multiple configurations of carbonate in the asymmetric O–C–O stretching region with peak splittings of ~100 and ~300 cm^–1 correlated to the monodentate- and bidentate-bound carbonate adsorbates, respectively. The synergy between chemical state identification by AP-XPS and vibrational state detection by DRIFTS allows both the carbonaceous species type and the configuration to be identified. We further demonstrate that the surface chemistry of the A-site cation strongly influences CO₂ reactivity; the La, Sr, and Ba cations in the LaCoO₃, La_0.4Sr_0.6CoO₃, SrCoO_2.5, and Pr_0.5Ba_0.5CoO₃ thin films showed significant carbon adsorbate speciation. Additionally, we link the La_0.4Sr_0.6CoO₃ surface chemistry to its surface reactivity toward formation of bidentate (bi)carbonate species via exchange of lattice oxygen with carbonate oxygen. In conclusion, we show that the perovskite electronic structure ultimately dictates the driving force for formation of oxidized oxo-carbonaceous species (CO₃) versus reduced species (C–C/C–H). Furthermore, a higher O 2p-band center relative to the Fermi level was correlated with a higher degree of (bi)carbonate formation relative to the other carbonaceous species observed (C–C/C–H and –CO) due to a more facile charge transfer from oxygen states at the Fermi level to free CO₂ gas.

View Accepted Manuscript (DOE)

Research Organization:: Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

Grant/Contract Number:: AC05-00OR22725

OSTI ID:: 1483179

Journal Information:: Journal of Physical Chemistry. C, Journal Name: Journal of Physical Chemistry. C Journal Issue: 35 Vol. 122; ISSN 1932-7447

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

References (62)

Calculations of electron inelastic mean free paths. V. Data for 14 organic compounds over the 50-2000 eV range Tanuma, S.; Powell, C. J.; Penn, D. R. Surface and Interface Analysis, Vol. 21, Issue 3 https://doi.org/10.1002/sia.740210302	journal	March 1994
Promotion of CO and CO2 Hydrogenation over Rh by Metal Oxides: The Influence of Oxide Lewis Acidity and Reducibility Boffa, A.; Lin, C.; Bell, A. T. Journal of Catalysis, Vol. 149, Issue 1 https://doi.org/10.1006/jcat.1994.1280	journal	September 1994
Adsorption and Reaction of CO2 on Metal Surfaces. Detection of an Intrinsic Precursor to Dissociation Bartos, B.; Freund, H. -J.; Kuhlenbeck, H. Kinetics of Interface Reactions https://doi.org/10.1007/978-3-642-72675-0_13	book	January 1987
Oxidation of methanol at copper surfaces Carley, A. F.; Owens, A. W.; Rajumon, M. K. Catalysis Letters, Vol. 37, Issue 1-2 https://doi.org/10.1007/BF00813523	journal	January 1996
Physicochemical properties of rare earth perovskite oxides used as gas sensor material Arakawa, Tsuyoshi; Kurachi, Hiroshi; Shiokawa, Jiro Journal of Materials Science, Vol. 20, Issue 4 https://doi.org/10.1007/BF01026315	journal	April 1985
Near-Ambient Pressure XPS of High-Temperature Surface Chemistry in Sr2Co2O5 Thin Films Hong, Wesley T.; Stoerzinger, Kelsey A.; Crumlin, Ethan J. Topics in Catalysis, Vol. 59, Issue 5-7 https://doi.org/10.1007/s11244-015-0532-4	journal	February 2016
Electronegativity values from thermochemical data Allred, A. L. Journal of Inorganic and Nuclear Chemistry, Vol. 17, Issue 3-4 https://doi.org/10.1016/0022-1902(61)80142-5	journal	June 1961
On the formation and bonding of a surface carbonate on Ni(100) Behm, R. J.; Brundle, C. R. Surface Science, Vol. 255, Issue 3 https://doi.org/10.1016/0039-6028(91)90690-T	journal	September 1991
Infrared spectroscopic identification of species arising from reactive adsorption of carbon oxides on metal oxide surfaces Busca, G.; Lorenzelli, V. Materials Chemistry, Vol. 7, Issue 1 https://doi.org/10.1016/0390-6035(82)90059-1	journal	January 1982
Acid–base behavior of oxides and their electronic structure Portier, J.; Poizot, P.; Campet, G. Solid State Sciences, Vol. 5, Issue 5 https://doi.org/10.1016/S1293-2558(03)00031-1	journal	May 2003
Investigation of a Ba0.5Sr0.5Co0.8Fe0.2O3−δ based cathode SOFC Yan, Aiyu; Maragou, Vasiliki; Arico, Antonino Applied Catalysis B: Environmental, Vol. 76, Issue 3-4 https://doi.org/10.1016/j.apcatb.2007.06.010	journal	November 2007
Global challenges and strategies for control, conversion and utilization of CO2 for sustainable development involving energy, catalysis, adsorption and chemical processing Song, Chunshan Catalysis Today, Vol. 115, Issue 1-4 https://doi.org/10.1016/j.cattod.2006.02.029	journal	June 2006
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
Study of the origin of the deactivation of a Pt/CeO catalyst during reverse water gas shift (RWGS) reaction Goguet, A.; Meunier, F.; Breen, J. Journal of Catalysis, Vol. 226, Issue 2 https://doi.org/10.1016/j.jcat.2004.06.011	journal	September 2004
Ca-containing CO2-tolerant perovskite materials for oxygen separation Efimov, Konstantin; Klande, Tobias; Juditzki, Nadine Journal of Membrane Science, Vol. 389 https://doi.org/10.1016/j.memsci.2011.10.030	journal	February 2012
CO2 gas sensors based on La1−xSrxFeO3 nanocrystalline powders Fan, Kai; Qin, Hongwei; Wang, Lei Sensors and Actuators B: Chemical, Vol. 177 https://doi.org/10.1016/j.snb.2012.11.004	journal	February 2013
Correlation between reconstructive phase transitions and transport properties from SrCoO2.5 brownmillerite: A neutron diffraction study de la Calle, C.; Aguadero, A.; Alonso, J. A. Solid State Sciences, Vol. 10, Issue 12 https://doi.org/10.1016/j.solidstatesciences.2008.03.015	journal	December 2008
Ta-doped SrCo0.8Fe0.2O3-δ membranes: Phase stability and oxygen permeation in CO2 atmosphere Chen, Wei; Chen, Chu-sheng; Winnubst, Louis Solid State Ionics, Vol. 196, Issue 1 https://doi.org/10.1016/j.ssi.2011.06.011	journal	August 2011
Surface chemistry of carbon dioxide revisited Taifan, William; Boily, Jean-François; Baltrusaitis, Jonas Surface Science Reports, Vol. 71, Issue 4 https://doi.org/10.1016/j.surfrep.2016.09.001	journal	December 2016
LDA+U evaluation of the stability of low-index facets of LaCoO3 perovskite Chen, Zhengzheng; Kim, Chang H.; Thompson, Levi T. Surface Science, Vol. 619 https://doi.org/10.1016/j.susc.2013.09.012	journal	January 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
Catalytic Activity and Stability of Oxides: The Role of Near-Surface Atomic Structures and Compositions Feng, Zhenxing; Hong, Wesley T.; Fong, Dillon D. Accounts of Chemical Research, Vol. 49, Issue 5 https://doi.org/10.1021/acs.accounts.5b00555	journal	April 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
Ambient Pressure XPS Study of Mixed Conducting Perovskite-Type SOFC Cathode and Anode Materials under Well-Defined Electrochemical Polarization Nenning, Andreas; Opitz, Alexander K.; Rameshan, Christoph The Journal of Physical Chemistry C, Vol. 120, Issue 3 https://doi.org/10.1021/acs.jpcc.5b08596	journal	January 2016
Oxygen Scrambling of CO ₂ Adsorbed on CaO(001) Solis, Brian H.; Sauer, Joachim; Cui, Yi The Journal of Physical Chemistry C, Vol. 121, Issue 34 https://doi.org/10.1021/acs.jpcc.7b05293	journal	August 2017
Evaluation of the CO ₂ Poisoning Effect on a Highly Active Cathode SrSc _0.175 Nb _0.025 Co _0.8 O _3-δ in the Oxygen Reduction Reaction Zhang, Yuan; Yang, Guangming; Chen, Gao ACS Applied Materials & Interfaces, Vol. 8, Issue 5 https://doi.org/10.1021/acsami.5b09780	journal	January 2016
Behavior of Ba(Co, Fe, Nb)O _3-δ Perovskite in CO ₂ -Containing Atmospheres: Degradation Mechanism and Materials Design Yi, Jianxin; Schroeder, Michael; Weirich, Thomas Chemistry of Materials, Vol. 22, Issue 23 https://doi.org/10.1021/cm101665r	journal	December 2010
Perovskites as Substitutes of Noble Metals for Heterogeneous Catalysis: Dream or Reality Royer, Sébastien; Duprez, Daniel; Can, Fabien Chemical Reviews, Vol. 114, Issue 20 https://doi.org/10.1021/cr500032a	journal	September 2014
Vibrational Analysis of Bidentate Nitrate and Carbonate Complexes Hester, R. E.; Grossman, W. E. L. Inorganic Chemistry, Vol. 5, Issue 8 https://doi.org/10.1021/ic50042a002	journal	August 1966
Production of Carbon from Carbon Dioxide with Iron Oxides and High-Temperature Solar Energy Ehrensberger, K.; Palumbo, R.; Larson, C. Industrial & Engineering Chemistry Research, Vol. 36, Issue 3 https://doi.org/10.1021/ie950780y	journal	March 1997
Electron spectroscopy for chemical analysis of liquids and solutions Siegbahn, Hans The Journal of Physical Chemistry, Vol. 89, Issue 6 https://doi.org/10.1021/j100252a005	journal	March 1985
Surface Electronic Structure Transitions at High Temperature on Perovskite Oxides: The Case of Strained La _0.8 Sr _0.2 CoO ₃ Thin Films Cai, Zhuhua; Kuru, Yener; Han, Jeong Woo Journal of the American Chemical Society, Vol. 133, Issue 44 https://doi.org/10.1021/ja2059445	journal	November 2011
Qualitative Differences in the Adsorption Chemistry of Acidic (CO₂, SO_x) and Amphiphilic (NO_x) Species on the Alkaline Earth Oxides Schneider, W. F. The Journal of Physical Chemistry B, Vol. 108, Issue 1 https://doi.org/10.1021/jp036323+	journal	December 2003
Chemisorption of CO ₂ on Nickel Surfaces Wang, Sheng-Guang; Cao, Dong-Bo; Li, Yong-Wang The Journal of Physical Chemistry B, Vol. 109, Issue 40 https://doi.org/10.1021/jp052355g	journal	October 2005
FTIR Spectroscopy Combined with Isotope Labeling and Quantum Chemical Calculations to Investigate Adsorbed Bicarbonate Formation Following Reaction of Carbon Dioxide with Surface Hydroxyl Groups on Fe ₂ O ₃ and Al ₂ O ₃ Baltrusaitis, Jonas; Jensen, Jan H.; Grassian, Vicki H. The Journal of Physical Chemistry B, Vol. 110, Issue 24 https://doi.org/10.1021/jp057437j	journal	June 2006
Estimation of Electronegativity Values of Elements in Different Valence States Li, Keyan; Xue, Dongfeng The Journal of Physical Chemistry A, Vol. 110, Issue 39 https://doi.org/10.1021/jp062886k	journal	October 2006
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
Probing LaMO ₃ Metal and Oxygen Partial Density of States Using X-ray Emission, Absorption, and Photoelectron Spectroscopy Hong, Wesley T.; Stoerzinger, Kelsey A.; Moritz, Brian The Journal of Physical Chemistry C, Vol. 119, Issue 4 https://doi.org/10.1021/jp511931y	journal	January 2015
Reversible Compositional Control of Oxide Surfaces by Electrochemical Potentials Mutoro, Eva; Crumlin, Ethan J.; Pöpke, Hendrik The Journal of Physical Chemistry Letters, Vol. 3, Issue 1 https://doi.org/10.1021/jz201523y	journal	December 2011
Dynamic Behavior of Carbonate Species on Metal Oxide Surface: Oxygen Scrambling between Adsorbed Carbon Dioxide and Oxide Surface Tsuji, Hideto; Okamura-Yoshida, Akie; Shishido, Tetsuya Langmuir, Vol. 19, Issue 21 https://doi.org/10.1021/la0342666	journal	October 2003
Fundamental Principles of Selective Heterogeneous Oxidation Catalysis Grasselli, Robert Karl Topics in Catalysis, Vol. 21, Issue 1/3, p. 79-88 https://doi.org/10.1023/A:1020556131984	journal	October 2002
Double perovskites as a family of highly active catalysts for oxygen evolution in alkaline solution Grimaud, Alexis; May, Kevin J.; Carlton, Christopher E. Nature Communications, Vol. 4, Issue 1 https://doi.org/10.1038/ncomms3439	journal	September 2013
Improved chemical and electrochemical stability of perovskite oxides with less reducible cations at the surface Tsvetkov, Nikolai; Lu, Qiyang; Sun, Lixin Nature Materials, Vol. 15, Issue 9 https://doi.org/10.1038/nmat4659	journal	June 2016
CO ₂ activation and carbonate intermediates: an operando AP-XPS study of CO ₂ electrolysis reactions on solid oxide electrochemical cells Yu, Yi; Mao, Baohua; Geller, Aaron Phys. Chem. Chem. Phys., Vol. 16, Issue 23 https://doi.org/10.1039/C4CP01054J	journal	January 2014
Surface termination and subsurface restructuring of perovskite-based solid oxide electrode materials Druce, J.; Téllez, H.; Burriel, M. Energy Environ. Sci., Vol. 7, Issue 11 https://doi.org/10.1039/C4EE01497A	journal	January 2014
Density functional theory calculations of atomic, electronic and thermodynamic properties of cubic LaCoO ₃ and La _1−x Sr _x CoO ₃ surfaces Zhang, Shuguang; Han, Ning; Tan, Xiaoyao RSC Advances, Vol. 5, Issue 1 https://doi.org/10.1039/C4RA12563K	journal	January 2015
Surface electrochemistry of CO ₂ reduction and CO oxidation on Sm-doped CeO _2−x : coupling between Ce ³⁺ and carbonate adsorbates Feng, Zhuoluo A.; Machala, Michael L.; Chueh, William C. Physical Chemistry Chemical Physics, Vol. 17, Issue 18 https://doi.org/10.1039/C5CP00114E	journal	January 2015
Surface chemistry of La _0.6 Sr _0.4 CoO _3−δ thin films and its impact on the oxygen surface exchange resistance Rupp, Ghislain M.; Téllez, Helena; Druce, John Journal of Materials Chemistry A, Vol. 3, Issue 45 https://doi.org/10.1039/C5TA05279C	journal	January 2015
Charge-transfer-energy-dependent oxygen evolution reaction mechanisms for perovskite oxides Hong, Wesley T.; Stoerzinger, Kelsey A.; Lee, Yueh-Lin Energy & Environmental Science, Vol. 10, Issue 10 https://doi.org/10.1039/C7EE02052J	journal	January 2017
Prediction of solid oxide fuel cell cathode activity with first-principles descriptors Lee, Yueh-Lin; Kleis, Jesper; Rossmeisl, Jan Energy & Environmental Science, Vol. 4, Issue 10 https://doi.org/10.1039/c1ee02032c	journal	January 2011
Surface strontium enrichment on highly active perovskites for oxygen electrocatalysis in solid oxide fuel cells Crumlin, Ethan J.; Mutoro, Eva; Liu, Zhi Energy & Environmental Science, Vol. 5, Issue 3 https://doi.org/10.1039/c2ee03397f	journal	January 2012
Revealing the atomic structure and strontium distribution in nanometer-thick La0.8Sr0.2CoO3−δ grown on (001)-oriented SrTiO3 Feng, Zhenxing; Yacoby, Yizhak; Hong, Wesley T. Energy & Environmental Science, Vol. 7, Issue 3 https://doi.org/10.1039/c3ee43164a	journal	January 2014
Adsorption of CO2 on the perovskite-type oxide LaCoO3 Tascón, Juan M. D.; Tejuca, Luis G. Journal of the Chemical Society, Faraday Transactions 1: Physical Chemistry in Condensed Phases, Vol. 77, Issue 3 https://doi.org/10.1039/f19817700591	journal	January 1981
Infrared spectroscopic study of the adsorption of pyridine, carbon monoxide and carbon dioxide on the perovskite-type oxides LaMO3 Tejuca, Luis González; Rochester, Colin H.; Fierro, José Luis Garciá Journal of the Chemical Society, Faraday Transactions 1: Physical Chemistry in Condensed Phases, Vol. 80, Issue 5 https://doi.org/10.1039/f19848001089	journal	January 1984
Chemisorption and catalysis on LaMO3 oxides Kremenić, Gojko; Nieto, José M. L.; Tascón, Juan M. D. Journal of the Chemical Society, Faraday Transactions 1: Physical Chemistry in Condensed Phases, Vol. 81, Issue 4 https://doi.org/10.1039/f19858100939	journal	January 1985
Oxygen diffusion pathways in brownmillerite SrCoO _2.5 : Influence of structure and chemical potential Mitra, Chandrima; Meyer, Tricia; Lee, Ho Nyung The Journal of Chemical Physics, Vol. 141, Issue 8 https://doi.org/10.1063/1.4893950	journal	August 2014
Photoemission and quantum chemical study of SrTiO 3 ( 001 ) surfaces and their interaction with CO 2 Baniecki, J. D.; Ishii, M.; Kurihara, K. Physical Review B, Vol. 78, Issue 19 https://doi.org/10.1103/PhysRevB.78.195415	journal	November 2008
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
Perovskite Oxides: Materials Science in Catalysis Voorhoeve, R. J. H.; Johnson, D. W.; Remeika, J. P. Science, Vol. 195, Issue 4281 https://doi.org/10.1126/science.195.4281.827	journal	March 1977
Perovskites in catalysis and electrocatalysis Hwang, Jonathan; Rao, Reshma R.; Giordano, Livia Science, Vol. 358, Issue 6364 https://doi.org/10.1126/science.aam7092	journal	November 2017
Oxygen Permeation from Oxygen Ion-Conducting Membranes Coated with Porous Metals or Mixed Ionic and Electronic Conducting Oxides Imashuku, Susumu; Wang, Lei; Mezghani, Khaled Journal of The Electrochemical Society, Vol. 160, Issue 11 https://doi.org/10.1149/2.068311jes	journal	January 2013
Plasma Enhanced Complete Oxidation of Ultrathin Epitaxial Praseodymia Films on Si(111) Kuschel, Olga; Dieck, Florian; Wilkens, Henrik Materials, Vol. 8, Issue 9 https://doi.org/10.3390/ma8095312	journal	September 2015

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