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

Abstract

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 throughmore » 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.« less

Authors:
 [1];  [2];  [2];  [3];  [1];  [4];  [1];  [3]; ;  [1];  [3]
+ Show Author Affiliations
  1. Univ. of Roma, Rome (Italy)
  2. ETH Zurich, Zurich (Switzerland)
  3. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
  4. Univ. of Salerno, Salerno (Italy)
Publication Date:
Research Org.:
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Sciences (CNMS)
Sponsoring Org.:
USDOE Office of Science (SC)
OSTI Identifier:
1261530
Grant/Contract Number:  
AC05-00OR22725
Resource Type:
Accepted Manuscript
Journal Name:
ACS Applied Materials and Interfaces
Additional Journal Information:
Journal Volume: 8; Journal Issue: 23; Journal ID: ISSN 1944-8244
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; defect associations; doped ceria; electrochemical strain microscopy; epitaxial thin films; Raman

Citation Formats

Yang, Nan, Shi, Yanuo, Schweiger, Sebastian, Strelcov, Evgheni, Foglietti, Vittorio, Orgiani, Pasquale, Balestrino, Giuseppe, Kalinin, Sergei V., Jennifer L. M. Rupp, Aruta, Carmela, and Belianinov, Alex. Role of associated defects in oxygen ion conduction and surface exchange reaction for epitaxial samaria-doped ceria thin films as catalytic coatings. United States: N. p., 2016. Web. doi:10.1021/acsami.6b03909.
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Yang, Nan, Shi, Yanuo, Schweiger, Sebastian, Strelcov, Evgheni, Foglietti, Vittorio, Orgiani, Pasquale, Balestrino, Giuseppe, Kalinin, Sergei V., Jennifer L. M. Rupp, Aruta, Carmela, & Belianinov, Alex. Role of associated defects in oxygen ion conduction and surface exchange reaction for epitaxial samaria-doped ceria thin films as catalytic coatings. United States. https://doi.org/10.1021/acsami.6b03909
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Yang, Nan, Shi, Yanuo, Schweiger, Sebastian, Strelcov, Evgheni, Foglietti, Vittorio, Orgiani, Pasquale, Balestrino, Giuseppe, Kalinin, Sergei V., Jennifer L. M. Rupp, Aruta, Carmela, and Belianinov, Alex. Wed . "Role of associated defects in oxygen ion conduction and surface exchange reaction for epitaxial samaria-doped ceria thin films as catalytic coatings". United States. https://doi.org/10.1021/acsami.6b03909. https://www.osti.gov/servlets/purl/1261530.
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@article{osti_1261530,
title = {Role of associated defects in oxygen ion conduction and surface exchange reaction for epitaxial samaria-doped ceria thin films as catalytic coatings},
author = {Yang, Nan and Shi, Yanuo and Schweiger, Sebastian and Strelcov, Evgheni and Foglietti, Vittorio and Orgiani, Pasquale and Balestrino, Giuseppe and Kalinin, Sergei V. and Jennifer L. M. Rupp and Aruta, Carmela and Belianinov, Alex},
abstractNote = {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.},
doi = {10.1021/acsami.6b03909},
journal = {ACS Applied Materials and Interfaces},
number = 23,
volume = 8,
place = {United States},
year = {Wed May 18 00:00:00 EDT 2016},
month = {Wed May 18 00:00:00 EDT 2016}
}
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https://doi.org/10.1021/acsami.6b03909
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Works referenced in this record:

Catalytic Properties of Ceria and CeO 2 -Containing Materials
journal, November 1996

Use of CeO2-based oxides in the three-way catalysis
journal, April 1999

Structural characterization and oxygen nonstoichiometry of ceria-zirconia (Ce1−xZrxO2−δ) solid solutions
journal, June 2013

Nanocrystalline undoped ceria oxygen sensor
journal, October 2003

Oxygen gas sensors based on CeO2 thick and thin films
journal, June 1991

A Microdot Multilayer Oxide Device: Let Us Tune the Strain-Ionic Transport Interaction
journal, April 2014

  • Schweiger, Sebastian; Kubicek, Markus; Messerschmitt, Felix
  • ACS Nano, Vol. 8, Issue 5
  • DOI: 10.1021/nn501128y

High-Flux Solar-Driven Thermochemical Dissociation of CO2 and H2O Using Nonstoichiometric Ceria
journal, December 2010

Kinetics of CO 2 Reduction over Nonstoichiometric Ceria
journal, July 2015

  • Ackermann, Simon; Sauvin, Laurent; Castiglioni, Roberto
  • The Journal of Physical Chemistry C, Vol. 119, Issue 29
  • DOI: 10.1021/acs.jpcc.5b03464

Highly Efficient Oxygen-Storage Material with Intrinsic Coke Resistance for Chemical Looping Combustion-Based CO 2 Capture
journal, April 2015

  • Imtiaz, Qasim; Kurlov, Alexey; Rupp, Jennifer Lilia Marguerite
  • ChemSusChem, Vol. 8, Issue 12
  • DOI: 10.1002/cssc.201403426

The effect of mechanical twisting on oxygen ionic transport in solid-state energy conversion membranes
journal, June 2015

  • Shi, Yanuo; Bork, Alexander Hansen; Schweiger, Sebastian
  • Nature Materials, Vol. 14, Issue 7
  • DOI: 10.1038/nmat4278

Review on microfabricated micro-solid oxide fuel cell membranes
journal, October 2009

On the proton conductivity in pure and gadolinium doped nanocrystalline cerium oxide
journal, January 2011

  • Shirpour, Mona; Gregori, Giuliano; Merkle, Rotraut
  • Phys. Chem. Chem. Phys., Vol. 13, Issue 3
  • DOI: 10.1039/C0CP01702G

Water uptake of nanocrystalline ceria: weight and conductance effects
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
journal, January 2015

  • Feng, Zhuoluo A.; Machala, Michael L.; Chueh, William C.
  • Physical Chemistry Chemical Physics, Vol. 17, Issue 18
  • DOI: 10.1039/C5CP00114E

Fast vacancy-mediated oxygen ion incorporation across the ceria–gas electrochemical interface
journal, July 2014

  • Feng, Zhuoluo A.; El Gabaly, Farid; Ye, Xiaofei
  • Nature Communications, Vol. 5, Issue 1
  • DOI: 10.1038/ncomms5374

A thermochemical study of ceria: exploiting an old material for new modes of energy conversion and CO 2 mitigation
journal, July 2010

  • Chueh, William C.; Haile, Sossina M.
  • Philosophical Transactions of the Royal Society A: Mathematical, Physical and Engineering Sciences, Vol. 368, Issue 1923
  • DOI: 10.1098/rsta.2010.0114

Ionic conductivity of CeO 2 with trivalent dopants of different ionic radii
journal, October 1981

A combined DFT + U and Monte Carlo study on rare earth doped ceria
journal, January 2014

  • Grieshammer, Steffen; Grope, Benjamin O. H.; Koettgen, Julius
  • Physical Chemistry Chemical Physics, Vol. 16, Issue 21
  • DOI: 10.1039/c3cp54811b

Highly Enhanced Concentration and Stability of Reactive Ce 3+ on Doped CeO 2 Surface Revealed In Operando
journal, May 2012

  • Chueh, William C.; McDaniel, Anthony H.; Grass, Michael E.
  • Chemistry of Materials, Vol. 24, Issue 10
  • DOI: 10.1021/cm300574v

Electron Localization Determines Defect Formation on Ceria Substrates
journal, July 2005

Effect of temperature and dopant concentration on the conductivity of samaria-doped ceria electrolyte
journal, November 2001

  • Jung, Guor-Bin; Huang, Ta-Jen; Chang, Chung-Liang
  • Journal of Solid State Electrochemistry, Vol. 6, Issue 4
  • DOI: 10.1007/s100080100238

Oxygen ion conductivity of the ceria-samarium oxide system with fluorite structure
journal, July 1988

  • Yahiro, Hidenori; Eguchi, Yukari; Eguchi, Koichi
  • Journal of Applied Electrochemistry, Vol. 18, Issue 4
  • DOI: 10.1007/BF01022246

Effect of Doping on Surface Reactivity and Conduction Mechanism in Samarium-Doped Ceria Thin Films
journal, November 2014

  • Yang, Nan; Belianinov, Alex; Strelcov, Evgheni
  • ACS Nano, Vol. 8, Issue 12
  • DOI: 10.1021/nn505345c

Computer simulations of large-scale defect clustering and nanodomain structure in gadolinia-doped ceria
journal, March 2011

Fast oxygen transport in acceptor doped oxides
journal, April 2000

Defect cluster formation in M2O3-doped CeO2
journal, January 1999

Oxygen Vacancy Clusters Promoting Reducibility and Activity of Ceria Nanorods
journal, March 2009

  • Liu, Xiangwen; Zhou, Kebin; Wang, Lei
  • Journal of the American Chemical Society, Vol. 131, Issue 9
  • DOI: 10.1021/ja808433d

Atomic Layer Deposition of Yttria-Stabilized Zirconia for Solid Oxide Fuel Cells
journal, July 2007

  • Shim, Joon Hyung; Chao, Cheng-Chieh; Huang, Hong
  • Chemistry of Materials, Vol. 19, Issue 15
  • DOI: 10.1021/cm070913t

Stability and Structural Evolution of Ce IV 1– x Ln III x O 2– x /2 Solid Solutions: A Coupled μ-Raman/XRD Approach
journal, August 2011

  • Horlait, D.; Claparède, L.; Clavier, N.
  • Inorganic Chemistry, Vol. 50, Issue 15
  • DOI: 10.1021/ic200751m

Fabrication and Electrochemical Properties of Epitaxial Samarium-Doped Ceria Films on SrTiO 3 -Buffered MgO Substrates
journal, June 2009

  • Sanna, Simone; Esposito, Vincenzo; Pergolesi, Daniele
  • Advanced Functional Materials, Vol. 19, Issue 11
  • DOI: 10.1002/adfm.200801768

Impact of uniaxial strain and doping on oxygen diffusion in CeO2
journal, August 2014

  • Rushton, M. J. D.; Chroneos, A.
  • Scientific Reports, Vol. 4, Issue 1
  • DOI: 10.1038/srep06068

Effect of Gd (Sm) doping on properties of ceria electrolyte for solid oxide fuel cells
journal, March 2003

Crystal Structure-Ionic Conductivity Relationships in Doped Ceria Systems
journal, November 2009

Identifying Defects in Ceria-Based Nanocrystals by UV Resonance Raman Spectroscopy
journal, October 2009

  • Taniguchi, Takaaki; Watanabe, Tomoaki; Sugiyama, Naota
  • The Journal of Physical Chemistry C, Vol. 113, Issue 46
  • DOI: 10.1021/jp9049457

Influence of Gd content on the room temperature mechanical properties of Gd-doped ceria
journal, February 2012

Engineering disorder in precipitation-based nano-scaled metal oxide thin films
journal, January 2010

  • Rupp, Jennifer L. M.; Scherrer, Barbara; Gauckler, Ludwig J.
  • Physical Chemistry Chemical Physics, Vol. 12, Issue 36
  • DOI: 10.1039/b920971a

Raman and x‐ray studies of Ce 1− x RE x O 2− y , where RE=La, Pr, Nd, Eu, Gd, and Tb
journal, August 1994

  • McBride, J. R.; Hass, K. C.; Poindexter, B. D.
  • Journal of Applied Physics, Vol. 76, Issue 4
  • DOI: 10.1063/1.357593

Scalable Oxygen-Ion Transport Kinetics in Metal-Oxide Films: Impact of Thermally Induced Lattice Compaction in Acceptor Doped Ceria Films
journal, January 2014

  • Rupp, Jennifer L. M.; Fabbri, Emiliana; Marrocchelli, Dario
  • Advanced Functional Materials, Vol. 24, Issue 11
  • DOI: 10.1002/adfm.201302117

Defect-induced Raman spectra in doped CeO 2
journal, November 1994

CeO2 based materials doped with lanthanides for applications in intermediate temperature electrochemical devices
journal, May 2011

Scandia stabilized zirconia-ceria solid electrolyte (xSc1CeSZ, 5
journal, August 2016

Dopant-concentration dependence of grain-boundary conductivity in ceria: A space-charge analysis
journal, January 2009

  • Avila-Paredes, Hugo J.; Choi, Kwanghoon; Chen, Chien-Ting
  • Journal of Materials Chemistry, Vol. 19, Issue 27
  • DOI: 10.1039/b904583j

Structure and Oxide Ion Conductivity: Local Order, Defect Interactions and Grain Boundary Effects in Acceptor-Doped Ceria
journal, October 2014

  • Giannici, Francesco; Gregori, Giuliano; Aliotta, Chiara
  • Chemistry of Materials, Vol. 26, Issue 20
  • DOI: 10.1021/cm502810e

Fabrication and structural characterization of self-supporting electrolyte membranes for a micro solid-oxide fuel cell
journal, September 2004

  • Baertsch, Chelsey D.; Jensen, Klavs F.; Hertz, Joshua L.
  • Journal of Materials Research, Vol. 19, Issue 9
  • DOI: 10.1557/JMR.2004.0350

Measuring oxygen reduction/evolution reactions on the nanoscale
journal, August 2011

  • Kumar, Amit; Ciucci, Francesco; Morozovska, Anna N.
  • Nature Chemistry, Vol. 3, Issue 9
  • DOI: 10.1038/nchem.1112

Variable temperature electrochemical strain microscopy of Sm-doped ceria
journal, March 2013

Strongly enhanced oxygen ion transport through samarium-doped CeO2 nanopillars in nanocomposite films
journal, October 2015

  • Yang, Sang Mo; Lee, Shinbuhm; Jian, Jie
  • Nature Communications, Vol. 6, Issue 1
  • DOI: 10.1038/ncomms9588

Nanoscale mapping of oxygen vacancy kinetics in nanocrystalline Samarium doped ceria thin films
journal, October 2013

  • Doria, Sandra; Yang, Nan; Kumar, Amit
  • Applied Physics Letters, Vol. 103, Issue 17
  • DOI: 10.1063/1.4826685

Real-space mapping of dynamic phenomena during hysteresis loop measurements: Dynamic switching spectroscopy piezoresponse force microscopy
journal, May 2011

  • Kumar, A.; Ovchinnikov, O. S.; Funakubo, H.
  • Applied Physics Letters, Vol. 98, Issue 20
  • DOI: 10.1063/1.3590919

Decoupling Electrochemical Reaction and Diffusion Processes in Ionically-Conductive Solids on the Nanometer Scale
journal, November 2010

  • Balke, Nina; Jesse, Stephen; Kim, Yoongu
  • ACS Nano, Vol. 4, Issue 12
  • DOI: 10.1021/nn101502x

Evidence of Filamentary Switching in Oxide-based Memory Devices via Weak Programming and Retention Failure Analysis
journal, September 2015

  • Younis, Adnan; Chu, Dewei; Li, Sean
  • Scientific Reports, Vol. 5, Issue 1
  • DOI: 10.1038/srep13599

Uncovering Two Competing Switching Mechanisms for Epitaxial and Ultrathin Strontium Titanate-Based Resistive Switching Bits
journal, October 2015

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