Tuning Point Defects by Elastic Strain Modulates Nanoparticle Exsolution on Perovskite Oxides
Abstract
Exsolution generates stable and catalytically active metal nanoparticles via phase precipitation out of a host oxide. An ability to control the size and dispersion of the exsolution particles is desirable for design of nanostructured (electro)catalysts. In this work, we demonstrate that tuning point defects by lattice strain affects both the thermodynamics and the kinetics of iron (Fe0) exsolution on La0.6Sr0.4FeO3 (LSF) thin film model. By combining in situ surface characterization and ab initio defect modeling, we show oxygen vacancy and Schottky defects to be the primary point defects formed upon Fe0 exsolution. Lattice strain tunes the formation energy, and thus the abundance of these defects, and alters the amount and size of the resulting exsolution particles. In addition, we find that the density of exsolved nanoparticles matches the concentration of oxygen vacancy pairs, thus pointing to the surface oxygen vacancy pairs as preferential nucleation sites for exsolution. The tensile-strained LSF with a facile formation of these critical point defects results in a higher Fe0 metal concentration, a larger density of nanoparticles, and a reduced particle size at its surfaces. These results provide important mechanistic insights and highlight the role of point-defect engineering in designing nanostructured catalysts in energy and fuelmore »
- Authors:
-
[1];
[1];
[2];
[1];
[3];
[1];
[5];
[1]
- Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States)
- Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States); Technische Univ. Wien, Austria (Austria)
- Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States); Univ. of Amsterdam (Netherlands)
- Technische Univ. Wien, Austria (Austria)
- Brookhaven National Lab. (BNL), Upton, NY (United States)
- Sorbonne Univ., Paris (France); Synchrotron SOLEIL, Gif-sur-Yvette (France)
- Publication Date:
- Research Org.:
- Brookhaven National Lab. (BNL), Upton, NY (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1807942
- Report Number(s):
- BNL-221797-2021-JAAM
Journal ID: ISSN 0897-4756
- Grant/Contract Number:
- SC0012704
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Chemistry of Materials
- Additional Journal Information:
- Journal Volume: 33; Journal Issue: 13; Journal ID: ISSN 0897-4756
- Publisher:
- American Chemical Society (ACS)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 36 MATERIALS SCIENCE; nanoparticles; lattices; metal oxide nanoparticles; defects in solids; defects
Citation Formats
Wang, Jiayue, Yang, Jing, Opitz, Alexander K., Bowman, William, Bliem, Roland, Dimitrakopoulos, Georgios, Nenning, Andreas, Waluyo, Iradwikanari, Hunt, Adrian, Gallet, Jean-Jacques, and Yildiz, Bilge. Tuning Point Defects by Elastic Strain Modulates Nanoparticle Exsolution on Perovskite Oxides. United States: N. p., 2021.
Web. doi:10.1021/acs.chemmater.1c00821.
Wang, Jiayue, Yang, Jing, Opitz, Alexander K., Bowman, William, Bliem, Roland, Dimitrakopoulos, Georgios, Nenning, Andreas, Waluyo, Iradwikanari, Hunt, Adrian, Gallet, Jean-Jacques, & Yildiz, Bilge. Tuning Point Defects by Elastic Strain Modulates Nanoparticle Exsolution on Perovskite Oxides. United States. https://doi.org/10.1021/acs.chemmater.1c00821
Wang, Jiayue, Yang, Jing, Opitz, Alexander K., Bowman, William, Bliem, Roland, Dimitrakopoulos, Georgios, Nenning, Andreas, Waluyo, Iradwikanari, Hunt, Adrian, Gallet, Jean-Jacques, and Yildiz, Bilge. Tue .
"Tuning Point Defects by Elastic Strain Modulates Nanoparticle Exsolution on Perovskite Oxides". United States. https://doi.org/10.1021/acs.chemmater.1c00821. https://www.osti.gov/servlets/purl/1807942.
@article{osti_1807942,
title = {Tuning Point Defects by Elastic Strain Modulates Nanoparticle Exsolution on Perovskite Oxides},
author = {Wang, Jiayue and Yang, Jing and Opitz, Alexander K. and Bowman, William and Bliem, Roland and Dimitrakopoulos, Georgios and Nenning, Andreas and Waluyo, Iradwikanari and Hunt, Adrian and Gallet, Jean-Jacques and Yildiz, Bilge},
abstractNote = {Exsolution generates stable and catalytically active metal nanoparticles via phase precipitation out of a host oxide. An ability to control the size and dispersion of the exsolution particles is desirable for design of nanostructured (electro)catalysts. In this work, we demonstrate that tuning point defects by lattice strain affects both the thermodynamics and the kinetics of iron (Fe0) exsolution on La0.6Sr0.4FeO3 (LSF) thin film model. By combining in situ surface characterization and ab initio defect modeling, we show oxygen vacancy and Schottky defects to be the primary point defects formed upon Fe0 exsolution. Lattice strain tunes the formation energy, and thus the abundance of these defects, and alters the amount and size of the resulting exsolution particles. In addition, we find that the density of exsolved nanoparticles matches the concentration of oxygen vacancy pairs, thus pointing to the surface oxygen vacancy pairs as preferential nucleation sites for exsolution. The tensile-strained LSF with a facile formation of these critical point defects results in a higher Fe0 metal concentration, a larger density of nanoparticles, and a reduced particle size at its surfaces. These results provide important mechanistic insights and highlight the role of point-defect engineering in designing nanostructured catalysts in energy and fuel conversion technologies.},
doi = {10.1021/acs.chemmater.1c00821},
journal = {Chemistry of Materials},
number = 13,
volume = 33,
place = {United States},
year = {Tue Jun 15 00:00:00 EDT 2021},
month = {Tue Jun 15 00:00:00 EDT 2021}
}
Free Publicly Available Full Text
Publisher's Version of Record
Other availability
Search WorldCat to find libraries that may hold this journal
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:
Oxygen ion diffusivity in strained yttria stabilized zirconia: where is the fastest strain?
journal, January 2010
- Kushima, Akihiro; Yildiz, Bilge
- Journal of Materials Chemistry, Vol. 20, Issue 23
Role of Defects in the Nucleation and Growth of Au Nanoclusters on SiO 2 Thin Films
journal, October 2004
- Min, B. K.; Wallace, W. T.; Santra, A. K.
- The Journal of Physical Chemistry B, Vol. 108, Issue 42
Surface strontium enrichment on highly active perovskites for oxygen electrocatalysis in solid oxide fuel cells
journal, January 2012
- Crumlin, Ethan J.; Mutoro, Eva; Liu, Zhi
- Energy & Environmental Science, Vol. 5, Issue 3
Nucleation and growth of supported clusters at defect sites: Pd/MgO(001)
journal, April 2000
- Haas, G.; Menck, A.; Brune, H.
- Physical Review B, Vol. 61, Issue 16
Point Defects in Oxides: Tailoring Materials Through Defect Engineering
journal, August 2011
- Tuller, Harry L.; Bishop, Sean R.
- Annual Review of Materials Research, Vol. 41, Issue 1
Atomic and subnanometer resolution in ambient conditions by atomic force microscopy
journal, March 2009
- Gan, Yang
- Surface Science Reports, Vol. 64, Issue 3
Demonstration of chemistry at a point through restructuring and catalytic activation at anchored nanoparticles
journal, November 2017
- Neagu, Dragos; Papaioannou, Evangelos I.; Ramli, Wan K. W.
- Nature Communications, Vol. 8, Issue 1
Lattice mismatch accommodation via oxygen vacancy ordering in epitaxial La 0.5 Sr 0.5 CoO 3-δ thin films
journal, July 2013
- Gazquez, J.; Bose, Shameek; Sharma, M.
- APL Materials, Vol. 1, Issue 1
New Opportunity for in Situ Exsolution of Metallic Nanoparticles on Perovskite Parent
journal, July 2016
- Sun, Yi-Fei; Zhang, Ya-Qian; Chen, Jian
- Nano Letters, Vol. 16, Issue 8
Nucleation and growth of transition metals on a thin alumina film
journal, May 2000
- Bäumer, M.; Frank, M.; Heemeier, M.
- Surface Science, Vol. 454-456
Mechanisms of Nucleation and Growth of Nanoparticles in Solution
journal, July 2014
- Thanh, Nguyen T. K.; Maclean, N.; Mahiddine, S.
- Chemical Reviews, Vol. 114, Issue 15
Facet-Dependent in Situ Growth of Nanoparticles in Epitaxial Thin Films: The Role of Interfacial Energy
journal, April 2019
- Kim, Kun Joong; Han, Hyeon; Defferriere, Thomas
- Journal of the American Chemical Society, Vol. 141, Issue 18
Control of transition metal–oxygen bond strength boosts the redox ex-solution in a perovskite oxide surface
journal, January 2020
- Kim, Kyeounghak; Koo, Bonjae; Jo, Yong-Ryun
- Energy & Environmental Science, Vol. 13, Issue 10
In situ catalyst exsolution on perovskite oxides for the production of CO and synthesis gas in ceramic membrane reactors
journal, January 2019
- Dimitrakopoulos, Georgios; Ghoniem, Ahmed F.; Yildiz, Bilge
- Sustainable Energy & Fuels, Vol. 3, Issue 9
Self-assembled single-crystal ferromagnetic iron nanowires formed by decomposition
journal, July 2004
- Mohaddes-Ardabili, L.; Zheng, H.; Ogale, S. B.
- Nature Materials, Vol. 3, Issue 8
Water Splitting on Model-Composite La0.6Sr0.4FeO3- (LSF) Electrodes in H2/H2O Atmosphere
journal, June 2015
- Opitz, A. K.; Nenning, A.; Kogler, S.
- ECS Transactions, Vol. 68, Issue 1
Threshold catalytic onset of carbon formation on CeO 2 during CO 2 electrolysis: mechanism and inhibition
journal, January 2019
- Wang, Jiayue; Bishop, Sean R.; Sun, Lixin
- Journal of Materials Chemistry A, Vol. 7, Issue 25
Mixed ionic-electronic conducting (MIEC) membranes for thermochemical reduction of CO2: A review
journal, September 2019
- Wu, Xiao-Yu; Ghoniem, Ahmed F.
- Progress in Energy and Combustion Science, Vol. 74
In Situ Observation of Rh-CaTiO 3 Catalysts during Reduction and Oxidation Treatments by Transmission Electron Microscopy
journal, January 2017
- Dai, Sheng; Zhang, Shuyi; Katz, Michael B.
- ACS Catalysis, Vol. 7, Issue 3
Tunable magnetic anisotropy of self-assembled Fe nanostructures within a La 0.5 Sr 0.5 FeO 3 matrix
journal, January 2018
- Zhang, Bruce; Fan, Meng; Li, Leigang
- Applied Physics Letters, Vol. 112, Issue 1
Oxygen vacancy formation characteristics in the bulk and across different surface terminations of La (1−x) Sr x Fe (1−y) Co y O (3−δ) perovskite oxides for CO 2 conversion
journal, January 2016
- Maiti, Debtanu; Daza, Yolanda A.; Yung, Matthew M.
- Journal of Materials Chemistry A, Vol. 4, Issue 14
Structural investigations of La 0.6 Sr 0.4 FeO 3−δ under reducing conditions: kinetic and thermodynamic limitations for phase transformations and iron exsolution phenomena
journal, January 2018
- Götsch, Thomas; Schlicker, Lukas; Bekheet, Maged F.
- RSC Advances, Vol. 8, Issue 6
Growth Kinetics of Individual Co Particles Ex-solved on SrTi 0.75 Co 0.25 O 3-δ Polycrystalline Perovskite Thin Films
journal, April 2019
- Jo, Yong-Ryun; Koo, Bonjae; Seo, Min-Ji
- Journal of the American Chemical Society, Vol. 141, Issue 16
Evolution of Exsolved Nanoparticles on a Perovskite Oxide Surface during a Redox Process
journal, March 2018
- Lai, Ke-Yu; Manthiram, Arumugam
- Chemistry of Materials, Vol. 30, Issue 8
Ni-Substituted Sr(Ti,Fe)O3 SOFC Anodes: Achieving High Performance via Metal Alloy Nanoparticle Exsolution
journal, March 2018
- Zhu, Tenglong; Troiani, Horacio E.; Mogni, Liliana V.
- Joule, Vol. 2, Issue 3
Energetics of Nanoparticle Exsolution from Perovskite Oxides
journal, June 2018
- Gao, Yang; Lu, Ziheng; You, Tsam Lung
- The Journal of Physical Chemistry Letters, Vol. 9, Issue 13
Exsolution of Fe and SrO Nanorods and Nanoparticles from Lanthanum Strontium Ferrite La 0.6 Sr 0.4 FeO 3−δ Materials by Hydrogen Reduction
journal, September 2015
- Thalinger, Ramona; Gocyla, Martin; Heggen, Marc
- The Journal of Physical Chemistry C, Vol. 119, Issue 38
Effect of epitaxial strain on cation and anion vacancy formation in MnO
journal, August 2015
- Aschauer, Ulrich; Vonrüti, Nathalie; Spaldin, Nicola A.
- Physical Review B, Vol. 92, Issue 5
Self-Regenerating Rh- and Pt-Based Perovskite Catalysts for Automotive-Emissions Control
journal, September 2006
- Tanaka, Hirohisa; Taniguchi, Masashi; Uenishi, Mari
- Angewandte Chemie International Edition, Vol. 45, Issue 36
Nano-socketed nickel particles with enhanced coking resistance grown in situ by redox exsolution
journal, September 2015
- Neagu, Dragos; Oh, Tae-Sik; Miller, David N.
- Nature Communications, Vol. 6, Issue 1
Electrochemical XPS investigation of metal exsolution on SOFC electrodes: Controlling the electrode oxygen partial pressure in ultra-high-vacuum
journal, February 2019
- Nenning, Andreas; Fleig, Jürgen
- Surface Science, Vol. 680
Control of metal-support interactions in heterogeneous catalysts to enhance activity and selectivity
journal, November 2019
- van Deelen, Tom W.; Hernández Mejía, Carlos; de Jong, Krijn P.
- Nature Catalysis, Vol. 2, Issue 11
Anchoring Sites for Initial Au Nucleation on CeO 2 {111}: O Vacancy versus Ce Vacancy
journal, March 2009
- Zhang, Changjun; Michaelides, Angelos; King, David A.
- The Journal of Physical Chemistry C, Vol. 113, Issue 16
Nickel- and Ruthenium-Doped Lanthanum Chromite Anodes: Effects of Nanoscale Metal Precipitation on Solid Oxide Fuel Cell Performance
journal, January 2010
- Kobsiriphat, W.; Madsen, B. D.; Wang, Y.
- Journal of The Electrochemical Society, Vol. 157, Issue 2
Local structural analysis for oxide ion transport in La0.6Sr0.4FeO3−δ cathodes
journal, January 2011
- Orikasa, Yuki; Nakao, Takayuki; Oishi, Masatsugu
- Journal of Materials Chemistry, Vol. 21, Issue 36
In situ growth of nanoparticles through control of non-stoichiometry
journal, October 2013
- Neagu, Dragos; Tsekouras, George; Miller, David N.
- Nature Chemistry, Vol. 5, Issue 11
Atomically Dispersed Supported Metal Catalysts
journal, July 2012
- Flytzani-Stephanopoulos, Maria; Gates, Bruce C.
- Annual Review of Chemical and Biomolecular Engineering, Vol. 3, Issue 1
Exsolution trends and co-segregation aspects of self-grown catalyst nanoparticles in perovskites
journal, June 2017
- Kwon, Ohhun; Sengodan, Sivaprakash; Kim, Kyeounghak
- Nature Communications, Vol. 8, Issue 1
Endogenous Nanoparticles Strain Perovskite Host Lattice Providing Oxygen Capacity and Driving Oxygen Exchange and CH 4 Conversion to Syngas
journal, February 2020
- Kousi, Kalliopi; Neagu, Dragos; Bekris, Leonidas
- Angewandte Chemie International Edition, Vol. 59, Issue 6
Recent Developments in the Synthesis of Supported Catalysts
journal, June 2015
- Munnik, Peter; de Jongh, Petra E.; de Jong, Krijn P.
- Chemical Reviews, Vol. 115, Issue 14
A perspective on low-temperature solid oxide fuel cells
journal, January 2016
- Gao, Zhan; Mogni, Liliana V.; Miller, Elizabeth C.
- Energy & Environmental Science, Vol. 9, Issue 5
Nucleation of Pd Dimers at Defect Sites of the MgO(100) Surface
journal, March 2004
- Giordano, Livia; Di Valentin, Cristiana; Goniakowski, Jacek
- Physical Review Letters, Vol. 92, Issue 9
The Chemical Evolution of the La0.6Sr0.4CoO3−δ Surface Under SOFC Operating Conditions and Its Implications for Electrochemical Oxygen Exchange Activity
journal, October 2018
- Opitz, Alexander K.; Rameshan, Christoph; Kubicek, Markus
- Topics in Catalysis, Vol. 61, Issue 20
Toward a rational photocatalyst design: a new formation strategy of co-catalyst/semiconductor heterostructures via in situ exsolution
journal, January 2018
- Sun, Yi-Fei; Yang, Yan-Ling; Chen, Jian
- Chemical Communications, Vol. 54, Issue 12
Oxygen nonstoichiometry, thermo-chemical stability and lattice expansion of La0.6Sr0.4FeO3−δ
journal, July 2011
- Kuhn, M.; Hashimoto, S.; Sato, K.
- Solid State Ionics, Vol. 195, Issue 1
Competing strain effects in reactivity of with oxygen
journal, September 2010
- Kushima, Akihiro; Yip, Sidney; Yildiz, Bilge
- Physical Review B, Vol. 82, Issue 11
A Density Functional Theory Study of Self-Regenerating Catalysts LaFe 1– x M x O 3– y (M = Pd, Rh, Pt)
journal, November 2011
- Hamada, Ikutaro; Uozumi, Akifumi; Morikawa, Yoshitada
- Journal of the American Chemical Society, Vol. 133, Issue 46
Strain-controlled oxygen vacancy formation and ordering in CaMnO
journal, August 2013
- Aschauer, Ulrich; Pfenninger, Reto; Selbach, Sverre M.
- Physical Review B, Vol. 88, Issue 5
Switching on electrocatalytic activity in solid oxide cells
journal, August 2016
- Myung, Jae-ha; Neagu, Dragos; Miller, David N.
- Nature, Vol. 537, Issue 7621
Understanding electrochemical switchability of perovskite-type exsolution catalysts
journal, September 2020
- Opitz, Alexander K.; Nenning, Andreas; Vonk, Vedran
- Nature Communications, Vol. 11, Issue 1
Redox activity of surface oxygen anions in oxygen-deficient perovskite oxides during electrochemical reactions
journal, January 2015
- Mueller, David N.; Machala, Michael L.; Bluhm, Hendrik
- Nature Communications, Vol. 6, Issue 1
In Situ Observation of Nanoparticle Exsolution from Perovskite Oxides: From Atomic Scale Mechanistic Insight to Nanostructure Tailoring
journal, October 2019
- Neagu, Dragos; Kyriakou, Vasileios; Roiban, Ioan-Lucian
- ACS Nano, Vol. 13, Issue 11
Treading in the Limited Stability Regime of Lanthanum Strontium Ferrite — Reduction, Phase Change and Exsolution
journal, July 2019
- Götsch, Thomas; Köpfle, Norbert; Schlicker, Lukas
- ECS Transactions, Vol. 91, Issue 1
Bonding of Gold Nanoclusters to Oxygen Vacancies on Rutile
journal, January 2003
- Wahlström, E.; Lopez, N.; Schaub, R.
- Physical Review Letters, Vol. 90, Issue 2
Self-Regeneration of Pd–LaFeO 3 Catalysts: New Insight from Atomic-Resolution Electron Microscopy
journal, November 2011
- Katz, Michael B.; Graham, George W.; Duan, Yingwen
- Journal of the American Chemical Society, Vol. 133, Issue 45
Reversible precipitation/dissolution of precious-metal clusters in perovskite-based catalyst materials: Bulk versus surface re-dispersion
journal, September 2012
- Katz, Michael B.; Zhang, Shuyi; Duan, Yingwen
- Journal of Catalysis, Vol. 293
AFM tip-sample convolution effects for cylinder protrusions
journal, November 2017
- Shen, Jian; Zhang, Dan; Zhang, Fei-Hu
- Applied Surface Science, Vol. 422
Understanding Chemical Expansion in Non-Stoichiometric Oxides: Ceria and Zirconia Case Studies
journal, February 2012
- Marrocchelli, Dario; Bishop, Sean R.; Tuller, Harry L.
- Advanced Functional Materials, Vol. 22, Issue 9
Search for a Self-Regenerating Perovskite Catalyst Using ab Initio Thermodynamics Calculations
journal, January 2013
- Yanagisawa, Susumu; Uozumi, Akifumi; Hamada, Ikutaro
- The Journal of Physical Chemistry C, Vol. 117, Issue 3
Metal Catalysts for Heterogeneous Catalysis: From Single Atoms to Nanoclusters and Nanoparticles
journal, April 2018
- Liu, Lichen; Corma, Avelino
- Chemical Reviews, Vol. 118, Issue 10
The kinetics of grain boundary nucleated reactions
journal, September 1956
- Cahn, John W.
- Acta Metallurgica, Vol. 4, Issue 5
Exsolved Fe–Ni nano-particles from Sr 2 Fe 1.3 Ni 0.2 Mo 0.5 O 6 perovskite oxide as a cathode for solid oxide steam electrolysis cells
journal, January 2016
- Wang, Y.; Liu, T.; Li, M.
- Journal of Materials Chemistry A, Vol. 4, Issue 37
Lattice strain-enhanced exsolution of nanoparticles in thin films
journal, April 2019
- Han, Hyeon; Park, Jucheol; Nam, Sang Yeol
- Nature Communications, Vol. 10, Issue 1
First-principles investigation on the segregation of Pd at LaFe1-xPdxO3-y surfaces
journal, January 2013
- Tian, Zhi-xue; Uozumi, Akifumi; Hamada, Ikutaro
- Nanoscale Research Letters, Vol. 8, Issue 1
Enhancing Electrochemical Water-Splitting Kinetics by Polarization-Driven Formation of Near-Surface Iron(0): An In Situ XPS Study on Perovskite-Type Electrodes
journal, December 2014
- Opitz, Alexander K.; Nenning, Andreas; Rameshan, Christoph
- Angewandte Chemie, Vol. 127, Issue 9
In situ synthesis of supported metal nanocatalysts through heterogeneous doping
journal, November 2018
- Kwak, No Woo; Jeong, Seung Jin; Seo, Han Gil
- Nature Communications, Vol. 9, Issue 1
Modeling Exsolution of Pt from ATiO 3 Perovskites (A = Ca/Sr/Ba) Using First-Principles Methods
journal, November 2020
- Raman, Abhinav S.; Vojvodic, Aleksandra
- Chemistry of Materials, Vol. 32, Issue 22
Origin and Tunability of Unusually Large Surface Capacitance in Doped Cerium Oxide Studied by Ambient-Pressure X-Ray Photoelectron Spectroscopy
journal, March 2016
- Gopal, Chirranjeevi Balaji; Gabaly, Farid El; McDaniel, Anthony H.
- Advanced Materials, Vol. 28, Issue 23
Self-regeneration of a Pd-perovskite catalyst for automotive emissions control
journal, July 2002
- Nishihata, Y.; Mizuki, J.; Akao, T.
- Nature, Vol. 418, Issue 6894