Role of associated defects in oxygen ion conduction and surface exchange reaction for epitaxial samaria-doped ceria thin films as catalytic coatings

Yang, Nan; Shi, Yanuo; Schweiger, Sebastian; Strelcov, Evgheni; Foglietti, Vittorio; Orgiani, Pasquale; Balestrino, Giuseppe; Kalinin, Sergei V.; Aruta, Carmela; Belianinov, Alex

doi:10.1021/acsami.6b03909

Title: Role of associated defects in oxygen ion conduction and surface exchange reaction for epitaxial samaria-doped ceria thin films as catalytic coatings

Journal Article · Wed May 18 00:00:00 EDT 2016 · ACS Applied Materials and Interfaces

DOI:https://doi.org/10.1021/acsami.6b03909· OSTI ID:1261530

Yang, Nan ^[1]; Shi, Yanuo ^[2]; Schweiger, Sebastian ^[2]; Strelcov, Evgheni ^[3]; Foglietti, Vittorio ^[1]; Orgiani, Pasquale ^[4]; Balestrino, Giuseppe ^[1]; Kalinin, Sergei V. ^[3]; Aruta, Carmela ^[1]; Belianinov, Alex ^[3]

Univ. of Roma, Rome (Italy)
ETH Zurich, Zurich (Switzerland)
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Univ. of Salerno, Salerno (Italy)

Samaria-doped ceria (SDC) thin films are particularly important for energy and electronic applications such as micro-solid oxide fuel cells, electrolysers, sensors and memristors. In this paper we report a comparative study investigating ionic conductivity and surface reactions for well-grown epitaxial SDC films varying the samaria doping concentration. With increasing doping above 20 mol% of samaria, an enhancement in the defect association was observed by Raman spectroscopy. The role of such defect associates on the films` oxygen ion transport and exchange was investigated by electrochemical impedance spectroscopy and electrochemical strain microscopy (ESM). The measurements reveal that the ionic transport has a sharp maximum in ionic conductivity and drop in its activation energy down to 0.6 eV for 20 mol% doping. Increasing the doping concentration further up to 40 mol%, raises the activation energy substantially by a factor of two. We ascribe the sluggish transport kinetics to the "bulk" ionic-near ordering in case of the heavily doped epitaxial films. Analysis of the ESM first order reversal curve measurements indicate that these associated defects may have a beneficial role by lowering the activation of the oxygen exchange "surface" reaction for heavily doped 40 mol% of samaria. We reveal in a model experiment through a solid solution series of samaria doped ceria epitaxial films that the occurrence of associate defects in the bulk affects the surface charging state of the films to increase the exchange rates. Lastly, the implication of these findings are the design of coatings with tuned oxygen surface exchange by control of bulk associate clusters for future electro-catalytic applications.

View Accepted Manuscript (DOE)

Cite

Export

Save

Research Organization:: Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Sciences (CNMS)

Sponsoring Organization:: USDOE Office of Science (SC)

Grant/Contract Number:: AC05-00OR22725

OSTI ID:: 1261530

Journal Information:: ACS Applied Materials and Interfaces, Vol. 8, Issue 23; ISSN 1944-8244

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

Citation Metrics:

Cited by: 34 works

Citation information provided by
Web of Science

References (52)

Catalytic Properties of Ceria and CeO ₂ -Containing Materials Trovarelli, Alessandro Catalysis Reviews, Vol. 38, Issue 4 https://doi.org/10.1080/01614949608006464	journal	November 1996
Use of CeO2-based oxides in the three-way catalysis Kašpar, J.; Fornasiero, P.; Graziani, M. Catalysis Today, Vol. 50, Issue 2 https://doi.org/10.1016/S0920-5861(98)00510-0	journal	April 1999
Structural characterization and oxygen nonstoichiometry of ceria-zirconia (Ce1−xZrxO2−δ) solid solutions Kuhn, M.; Bishop, S. R.; Rupp, J. L. M. Acta Materialia, Vol. 61, Issue 11 https://doi.org/10.1016/j.actamat.2013.04.001	journal	June 2013
Nanocrystalline undoped ceria oxygen sensor Jasinski, Piotr; Suzuki, Toshio; Anderson, Harlan U. Sensors and Actuators B: Chemical, Vol. 95, Issue 1-3 https://doi.org/10.1016/S0925-4005(03)00407-6	journal	October 2003
Oxygen gas sensors based on CeO2 thick and thin films Beie, H. -J.; Gnörich, A. Sensors and Actuators B: Chemical, Vol. 4, Issue 3-4 https://doi.org/10.1016/0925-4005(91)80141-6	journal	June 1991
A Microdot Multilayer Oxide Device: Let Us Tune the Strain-Ionic Transport Interaction Schweiger, Sebastian; Kubicek, Markus; Messerschmitt, Felix ACS Nano, Vol. 8, Issue 5 https://doi.org/10.1021/nn501128y	journal	April 2014
High-Flux Solar-Driven Thermochemical Dissociation of CO2 and H2O Using Nonstoichiometric Ceria Chueh, W. C.; Falter, C.; Abbott, M. Science, Vol. 330, Issue 6012 https://doi.org/10.1126/science.1197834	journal	December 2010
Kinetics of CO ₂ Reduction over Nonstoichiometric Ceria Ackermann, Simon; Sauvin, Laurent; Castiglioni, Roberto The Journal of Physical Chemistry C, Vol. 119, Issue 29 https://doi.org/10.1021/acs.jpcc.5b03464	journal	July 2015
Highly Efficient Oxygen-Storage Material with Intrinsic Coke Resistance for Chemical Looping Combustion-Based CO 2 Capture Imtiaz, Qasim; Kurlov, Alexey; Rupp, Jennifer Lilia Marguerite ChemSusChem, Vol. 8, Issue 12 https://doi.org/10.1002/cssc.201403426	journal	April 2015
The effect of mechanical twisting on oxygen ionic transport in solid-state energy conversion membranes Shi, Yanuo; Bork, Alexander Hansen; Schweiger, Sebastian Nature Materials, Vol. 14, Issue 7 https://doi.org/10.1038/nmat4278	journal	June 2015
Review on microfabricated micro-solid oxide fuel cell membranes Evans, Anna; Bieberle-Hütter, Anja; Rupp, Jennifer L. M. Journal of Power Sources, Vol. 194, Issue 1 https://doi.org/10.1016/j.jpowsour.2009.03.048	journal	October 2009
On the proton conductivity in pure and gadolinium doped nanocrystalline cerium oxide Shirpour, Mona; Gregori, Giuliano; Merkle, Rotraut Phys. Chem. Chem. Phys., Vol. 13, Issue 3 https://doi.org/10.1039/C0CP01702G	journal	January 2011
Water uptake of nanocrystalline ceria: weight and conductance effects Kim, S. Solid State Ionics, Vol. 161, Issue 1-2 https://doi.org/10.1016/S0167-2738(03)00262-5	journal	July 2003
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
Fast vacancy-mediated oxygen ion incorporation across the ceria–gas electrochemical interface Feng, Zhuoluo A.; El Gabaly, Farid; Ye, Xiaofei Nature Communications, Vol. 5, Issue 1 https://doi.org/10.1038/ncomms5374	journal	July 2014
A thermochemical study of ceria: exploiting an old material for new modes of energy conversion and CO ₂ mitigation Chueh, William C.; Haile, Sossina M. Philosophical Transactions of the Royal Society A: Mathematical, Physical and Engineering Sciences, Vol. 368, Issue 1923 https://doi.org/10.1098/rsta.2010.0114	journal	July 2010
Ionic conductivity of CeO 2 with trivalent dopants of different ionic radii Gerhardt-Anderson, R.; Nowick, A. S. Solid State Ionics, Vol. 5 https://doi.org/10.1016/0167-2738(81)90313-1	journal	October 1981
A combined DFT + U and Monte Carlo study on rare earth doped ceria Grieshammer, Steffen; Grope, Benjamin O. H.; Koettgen, Julius Physical Chemistry Chemical Physics, Vol. 16, Issue 21 https://doi.org/10.1039/c3cp54811b	journal	January 2014
Highly Enhanced Concentration and Stability of Reactive Ce ³⁺ on Doped CeO ₂ Surface Revealed In Operando Chueh, William C.; McDaniel, Anthony H.; Grass, Michael E. Chemistry of Materials, Vol. 24, Issue 10 https://doi.org/10.1021/cm300574v	journal	May 2012
Electron Localization Determines Defect Formation on Ceria Substrates Esch, F. Science, Vol. 309, Issue 5735 https://doi.org/10.1126/science.1111568	journal	July 2005
Effect of temperature and dopant concentration on the conductivity of samaria-doped ceria electrolyte Jung, Guor-Bin; Huang, Ta-Jen; Chang, Chung-Liang Journal of Solid State Electrochemistry, Vol. 6, Issue 4 https://doi.org/10.1007/s100080100238	journal	November 2001
Oxygen ion conductivity of the ceria-samarium oxide system with fluorite structure Yahiro, Hidenori; Eguchi, Yukari; Eguchi, Koichi Journal of Applied Electrochemistry, Vol. 18, Issue 4 https://doi.org/10.1007/BF01022246	journal	July 1988
Effect of Doping on Surface Reactivity and Conduction Mechanism in Samarium-Doped Ceria Thin Films Yang, Nan; Belianinov, Alex; Strelcov, Evgheni ACS Nano, Vol. 8, Issue 12 https://doi.org/10.1021/nn505345c	journal	November 2014
Computer simulations of large-scale defect clustering and nanodomain structure in gadolinia-doped ceria Wang, Bu; Lewis, Raymond J.; Cormack, Alastair N. Acta Materialia, Vol. 59, Issue 5 https://doi.org/10.1016/j.actamat.2010.12.003	journal	March 2011
Fast oxygen transport in acceptor doped oxides Kilner, J. Solid State Ionics, Vol. 129, Issue 1-4 https://doi.org/10.1016/S0167-2738(99)00313-6	journal	April 2000
Defect cluster formation in M2O3-doped CeO2 Minervini, L. Solid State Ionics, Vol. 116, Issue 3-4 https://doi.org/10.1016/S0167-2738(98)00359-2	journal	January 1999
Oxygen Vacancy Clusters Promoting Reducibility and Activity of Ceria Nanorods Liu, Xiangwen; Zhou, Kebin; Wang, Lei Journal of the American Chemical Society, Vol. 131, Issue 9 https://doi.org/10.1021/ja808433d	journal	March 2009
Atomic Layer Deposition of Yttria-Stabilized Zirconia for Solid Oxide Fuel Cells Shim, Joon Hyung; Chao, Cheng-Chieh; Huang, Hong Chemistry of Materials, Vol. 19, Issue 15 https://doi.org/10.1021/cm070913t	journal	July 2007
Stability and Structural Evolution of Ce ^IV _{1– x} Ln ^III _x O _{2– x /2} Solid Solutions: A Coupled μ-Raman/XRD Approach Horlait, D.; Claparède, L.; Clavier, N. Inorganic Chemistry, Vol. 50, Issue 15 https://doi.org/10.1021/ic200751m	journal	August 2011
Fabrication and Electrochemical Properties of Epitaxial Samarium-Doped Ceria Films on SrTiO ₃ -Buffered MgO Substrates Sanna, Simone; Esposito, Vincenzo; Pergolesi, Daniele Advanced Functional Materials, Vol. 19, Issue 11 https://doi.org/10.1002/adfm.200801768	journal	June 2009
Impact of uniaxial strain and doping on oxygen diffusion in CeO2 Rushton, M. J. D.; Chroneos, A. Scientific Reports, Vol. 4, Issue 1 https://doi.org/10.1038/srep06068	journal	August 2014
Effect of Gd (Sm) doping on properties of ceria electrolyte for solid oxide fuel cells Zha, Shaowu; Xia, Changrong; Meng, Guangyao Journal of Power Sources, Vol. 115, Issue 1 https://doi.org/10.1016/S0378-7753(02)00625-0	journal	March 2003
Crystal Structure-Ionic Conductivity Relationships in Doped Ceria Systems Omar, Shobit; Wachsman, Eric D.; Jones, Jacob L. Journal of the American Ceramic Society, Vol. 92, Issue 11 https://doi.org/10.1111/j.1551-2916.2009.03273.x	journal	November 2009
Identifying Defects in Ceria-Based Nanocrystals by UV Resonance Raman Spectroscopy Taniguchi, Takaaki; Watanabe, Tomoaki; Sugiyama, Naota The Journal of Physical Chemistry C, Vol. 113, Issue 46 https://doi.org/10.1021/jp9049457	journal	October 2009
Influence of Gd content on the room temperature mechanical properties of Gd-doped ceria Korobko, Roman; Chen, Chien-Ting; Kim, Sangtae Scripta Materialia, Vol. 66, Issue 3-4 https://doi.org/10.1016/j.scriptamat.2011.10.027	journal	February 2012
Engineering disorder in precipitation-based nano-scaled metal oxide thin films Rupp, Jennifer L. M.; Scherrer, Barbara; Gauckler, Ludwig J. Physical Chemistry Chemical Physics, Vol. 12, Issue 36 https://doi.org/10.1039/b920971a	journal	January 2010
Raman and x‐ray studies of Ce _{1− x} RE _x O _{2− y} , where RE=La, Pr, Nd, Eu, Gd, and Tb McBride, J. R.; Hass, K. C.; Poindexter, B. D. Journal of Applied Physics, Vol. 76, Issue 4 https://doi.org/10.1063/1.357593	journal	August 1994
Scalable Oxygen-Ion Transport Kinetics in Metal-Oxide Films: Impact of Thermally Induced Lattice Compaction in Acceptor Doped Ceria Films Rupp, Jennifer L. M.; Fabbri, Emiliana; Marrocchelli, Dario Advanced Functional Materials, Vol. 24, Issue 11 https://doi.org/10.1002/adfm.201302117	journal	January 2014
Defect-induced Raman spectra in doped ${CeO}_{2}$ Nakajima, A.; Yoshihara, A.; Ishigame, M. Physical Review B, Vol. 50, Issue 18 https://doi.org/10.1103/PhysRevB.50.13297	journal	November 1994
CeO2 based materials doped with lanthanides for applications in intermediate temperature electrochemical devices Pikalova, E. Yu.; Murashkina, A. A.; Maragou, V. I. International Journal of Hydrogen Energy, Vol. 36, Issue 10 https://doi.org/10.1016/j.ijhydene.2011.01.132	journal	May 2011
Scandia stabilized zirconia-ceria solid electrolyte (xSc1CeSZ, 5 Kumar, Ashutosh; Jaiswal, Abhishek; Sanbui, Mohit Scripta Materialia, Vol. 121 https://doi.org/10.1016/j.scriptamat.2016.04.023	journal	August 2016
Dopant-concentration dependence of grain-boundary conductivity in ceria: A space-charge analysis Avila-Paredes, Hugo J.; Choi, Kwanghoon; Chen, Chien-Ting Journal of Materials Chemistry, Vol. 19, Issue 27 https://doi.org/10.1039/b904583j	journal	January 2009
Structure and Oxide Ion Conductivity: Local Order, Defect Interactions and Grain Boundary Effects in Acceptor-Doped Ceria Giannici, Francesco; Gregori, Giuliano; Aliotta, Chiara Chemistry of Materials, Vol. 26, Issue 20 https://doi.org/10.1021/cm502810e	journal	October 2014
Fabrication and structural characterization of self-supporting electrolyte membranes for a micro solid-oxide fuel cell Baertsch, Chelsey D.; Jensen, Klavs F.; Hertz, Joshua L. Journal of Materials Research, Vol. 19, Issue 9 https://doi.org/10.1557/JMR.2004.0350	journal	September 2004
Measuring oxygen reduction/evolution reactions on the nanoscale Kumar, Amit; Ciucci, Francesco; Morozovska, Anna N. Nature Chemistry, Vol. 3, Issue 9 https://doi.org/10.1038/nchem.1112	journal	August 2011
Variable temperature electrochemical strain microscopy of Sm-doped ceria Kumar, Amit; Jesse, Stephen; Morozovska, Anna N. Nanotechnology, Vol. 24, Issue 14 https://doi.org/10.1088/0957-4484/24/14/145401	journal	March 2013
Strongly enhanced oxygen ion transport through samarium-doped CeO2 nanopillars in nanocomposite films Yang, Sang Mo; Lee, Shinbuhm; Jian, Jie Nature Communications, Vol. 6, Issue 1 https://doi.org/10.1038/ncomms9588	journal	October 2015
Nanoscale mapping of oxygen vacancy kinetics in nanocrystalline Samarium doped ceria thin films Doria, Sandra; Yang, Nan; Kumar, Amit Applied Physics Letters, Vol. 103, Issue 17 https://doi.org/10.1063/1.4826685	journal	October 2013
Real-space mapping of dynamic phenomena during hysteresis loop measurements: Dynamic switching spectroscopy piezoresponse force microscopy Kumar, A.; Ovchinnikov, O. S.; Funakubo, H. Applied Physics Letters, Vol. 98, Issue 20 https://doi.org/10.1063/1.3590919	journal	May 2011
Decoupling Electrochemical Reaction and Diffusion Processes in Ionically-Conductive Solids on the Nanometer Scale Balke, Nina; Jesse, Stephen; Kim, Yoongu ACS Nano, Vol. 4, Issue 12 https://doi.org/10.1021/nn101502x	journal	November 2010
Evidence of Filamentary Switching in Oxide-based Memory Devices via Weak Programming and Retention Failure Analysis Younis, Adnan; Chu, Dewei; Li, Sean Scientific Reports, Vol. 5, Issue 1 https://doi.org/10.1038/srep13599	journal	September 2015
Uncovering Two Competing Switching Mechanisms for Epitaxial and Ultrathin Strontium Titanate-Based Resistive Switching Bits Kubicek, Markus; Schmitt, Rafael; Messerschmitt, Felix ACS Nano, Vol. 9, Issue 11 https://doi.org/10.1021/acsnano.5b02752	journal	October 2015

Cited By (4)

Tuning of ionic mobility to improve the resistive switching behavior of Zn-doped CeO2 Rehman, Shania; Kim, Honggyun; Farooq Khan, Muhammad Scientific Reports, Vol. 9, Issue 1 https://doi.org/10.1038/s41598-019-55716-4	journal	December 2019
Threshold catalytic onset of carbon formation on CeO ₂ during CO ₂ electrolysis: mechanism and inhibition Wang, Jiayue; Bishop, Sean R.; Sun, Lixin Journal of Materials Chemistry A, Vol. 7, Issue 25 https://doi.org/10.1039/c9ta03265g	journal	January 2019
A review of defect structure and chemistry in ceria and its solid solutions Schmitt, Rafael; Nenning, Andreas; Kraynis, Olga ETH Zurich https://doi.org/10.3929/ethz-b-000396556	text	January 2020
Preparative History vs Driving Force in Water Oxidation Catalysis: Parameter Space Studies of Cobalt Spinels Reith, Lukas; Lienau, Karla; Triana, C. A. ACS Omega, Vol. 4, Issue 13 https://doi.org/10.1021/acsomega.9b01677	journal	September 2019

Similar Records

Integrated experimental and modeling study of the ionic conductivity of samaria-doped ceria thin films

Journal Article · Mon Dec 12 00:00:00 EST 2011 · Solid State Ionics · OSTI ID:1261530

Sanghavi, Rahul P; Devanathan, Ramaswami; Nandasiri, Manjula I; +3 more

Influence of samaria doping on the resistance of ceria thin films and its implications to the planar oxygen sensing devices

Journal Article · Wed May 27 00:00:00 EDT 2009 · Sensors and Actuators. B, Chemical, 139(2):380-386 · OSTI ID:1261530

Gupta, Shilpi; Engelhard, Mark H; Shutthanandan, V; +5 more

Electrochemical characteristics of samaria-doped ceria infiltrated strontium-doped LaMnO3 cathodes with varied thickness for yttria-stabilized zirconia electrolytes

Journal Article · Tue Nov 09 00:00:00 EST 2010 · Journal of Power Sources · OSTI ID:1261530

Ding, Dong; Gonga, Mingyang; Xu, Chunchuan; +5 more

Related Subjects

36 MATERIALS SCIENCE
defect associations
doped ceria
electrochemical strain microscopy
epitaxial thin films
Raman

Title: Role of associated defects in oxygen ion conduction and surface exchange reaction for epitaxial samaria-doped ceria thin films as catalytic coatings

Citation Formats

References (52)

Cited By (4)

Similar Records

Related Subjects