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Exsolution Synthesis of Nanocomposite Perovskites with Tunable Electrical and Magnetic Properties

Journal Article · · Advanced Functional Materials
 [1];  [2];  [3];  [4];  [4];  [5];  [6];  [1];  [2];  [1]
  1. Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States)
  2. Univ. of California, Irvine, CA (United States)
  3. Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States); Nankai Univ., Tianjin (China)
  4. Brookhaven National Lab. (BNL), Upton, NY (United States). National Synchrotron Light Source II (NSLS-II)
  5. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Advanced Light Source (ALS)
  6. Technische Univ. Wien (Austria)
Nanostructured functional oxides play an important role in enabling clean energy technologies and novel memory and processor devices. Using thin-film La0.6Sr0.4FeO3 (LSF) as a model system, the novel utility of exsolution in fabricating self-assembled metal oxide nanocomposites with tunable functionalities is shown. Exsolution triggers the formation of metallic iron (Fe0) nanoparticles, Ruddlesden–Popper domains, and nm-scale percolated Fe-deficient channels in LSF. Combining multimodal characterization with numerical modeling, the chemical, magnetic, and electrical properties of the exsolution-synthesized nanocomposite at different stages of Fe0 exsolution as well as during redox cycling are assessed. After exsolution, the electronic conductivity of the nanocomposite LSF increased by more than two orders of magnitude. Based on numerical analysis representing all the constituents, it is expected that this increase in conductivity originates mainly from the Fe-deficient percolating channels formed during exsolution. Moreover, the exsolved nanocomposite is redox-active even at moderate temperatures. Such redox capabilities can enable dynamic control of the nanocomposite functionality by tailoring the oxygen non-stoichiometry. This concept is demonstrated with a continuous modulation of magnetization between 0 and 110 emu cm-3. These findings point out that exsolution may serve as a platform for scalable fabrication of complex metal oxide nanocomposites for electrochemical and electronic applications.
Research Organization:
Brookhaven National Laboratory (BNL), Upton, NY (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
SC0012704
OSTI ID:
1844587
Alternate ID(s):
OSTI ID: 23123995
Report Number(s):
BNL--222714-2022-JAAM
Journal Information:
Advanced Functional Materials, Journal Name: Advanced Functional Materials Journal Issue: 9 Vol. 32; ISSN 1616-301X
Publisher:
WileyCopyright Statement
Country of Publication:
United States
Language:
English

References (95)

Understanding Chemical Expansion in Non-Stoichiometric Oxides: Ceria and Zirconia Case Studies journal February 2012
Tunable Oxygen Diffusion and Electronic Conduction in SrTiO 3 by Dislocation-Induced Space Charge Fields journal April 2017
Highly Uniform Resistive Switching in HfO 2 Films Embedded with Ordered Metal Nanoisland Arrays journal April 2019
Ionically Conducting Two-Dimensional Heterostructures journal June 2009
Highly Improved Uniformity in the Resistive Switching Parameters of TiO 2 Thin Films by Inserting Ru Nanodots journal February 2013
Metal Oxide Nanocomposites: A Perspective from Strain, Defect, and Interface journal October 2018
Engineering Transport in Manganites by Tuning Local Nonstoichiometry in Grain Boundaries journal December 2018
Cluster‐Assembled Nanocomposites: Functional Properties by Design journal December 2018
In Situ Investigation of Reversible Exsolution/Dissolution of CoFe Alloy Nanoparticles in a Co‐Doped Sr 2 Fe 1.5 Mo 0.5 O 6− δ Cathode for CO 2 Electrolysis journal December 2019
Shape‐Preserving Chemical Conversion of Architected Nanocomposites journal November 2020
Nanostructured Materials and Interfaces for Advanced Ionic Electronic Conducting Oxides journal May 2019
Electronic Activation of Cathode Superlattices at Elevated Temperatures - Source of Markedly Accelerated Oxygen Reduction Kinetics journal May 2013
Progress and Prospects in Symmetrical Solid Oxide Fuel Cells with Two Identical Electrodes journal May 2015
Mesoscopic Charge Carriers Chemistry in Nanocrystalline SrTiO3 journal November 2010
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
Endogenous Nanoparticles Strain Perovskite Host Lattice Providing Oxygen Capacity and Driving Oxygen Exchange and CH 4 Conversion to Syngas journal February 2020
Oxidation Kinetics and Magnetic Properties of Elemental Iron Nanoparticles journal June 2013
Exsolution of Nickel Nanoparticles from Mixed‐Valence Metal Oxides: A Quantitative Evaluation by Magnetic Measurements journal January 2020
Toward Controlling Filament Size and Location for Resistive Switches via Nanoparticle Exsolution at Oxide Interfaces journal September 2020
Emergence and Future of Exsolved Materials journal March 2021
The Effect of Oxygen Stoichiometry on Phase Relations and Structure in the System La1-xSrxFeO3-δ (0 ≤ x ≤ 1, 0 ≤ δ ≤ 0.5) journal March 1994
High-Pressure crystal chemistry of spinel (MgAl2O4) and magnetite (Fe3O4): Comparisons with silicate spinels journal July 1986
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
A variational approach to the theory of the elastic behaviour of multiphase materials journal March 1963
Electron/hole and ion transport in La1−xSrxFeO3−δ journal April 2003
Percolation concepts in solid state ionics journal April 1999
A novel high performance composite anode with in situ growth of Fe-Ni alloy nanoparticles for intermediate solid oxide fuel cells journal May 2017
A novel anode for solid oxide fuel cells prepared from phase conversion of La0.3Sr0.7Fe0.7Cr0.3O3-δ perovskite under humid hydrogen journal September 2018
Evaluation of LaxSr2−xFeO4 layered perovskite as potential electrode materials for symmetrical solid oxide fuel cells journal October 2015
Magnetic and optical absorption properties of the Fe:LaSrFeO4 composite film prepared by pulsed laser decomposition journal April 2016
Nanometric nickel exsolution in the hexagonal perovskite Ba8Ta6NiO24: Survey of the structural, magnetic and catalytic features journal October 2018
Reversible precipitation/dissolution of precious-metal clusters in perovskite-based catalyst materials: Bulk versus surface re-dispersion journal September 2012
Topotactic phase transformations by concerted dual-ion migration of B-site cation and oxygen in multivalent cobaltite La–Sr–Co–Ox films journal December 2020
Oxygen nonstoichiometry, thermo-chemical stability and lattice expansion of La0.6Sr0.4FeO3−δ journal July 2011
Electrochemical XPS investigation of metal exsolution on SOFC electrodes: Controlling the electrode oxygen partial pressure in ultra-high-vacuum journal February 2019
The effect of vacancies on the annular dark field image contrast of grain boundaries: A SrTiO3 case study journal November 2011
Organic Photochemistry-Assisted Nanoparticle Segregation on Perovskites journal November 2020
Modeling Exsolution of Pt from ATiO 3 Perovskites (A = Ca/Sr/Ba) Using First-Principles Methods journal November 2020
Tuning Point Defects by Elastic Strain Modulates Nanoparticle Exsolution on Perovskite Oxides journal June 2021
Evolution of Exsolved Nanoparticles on a Perovskite Oxide Surface during a Redox Process journal March 2018
Nonstoichiometric Oxides as Low-Cost and Highly-Efficient Oxygen Reduction/Evolution Catalysts for Low-Temperature Electrochemical Devices journal August 2015
Oxygen K-edge X-ray Absorption Spectra journal April 2020
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
Ambient Pressure XPS Study of Mixed Conducting Perovskite-Type SOFC Cathode and Anode Materials under Well-Defined Electrochemical Polarization journal January 2016
Metal Nanoparticle Exsolution on a Perovskite Stannate Support with High Electrical Conductivity journal April 2020
In Situ Observation of Rh-CaTiO 3 Catalysts during Reduction and Oxidation Treatments by Transmission Electron Microscopy journal January 2017
Voltage Control of Magnetism above Room Temperature in Epitaxial SrCo 1– x Fe x O 3−δ journal June 2020
Exsolution of Embedded Nanoparticles in Defect Engineered Perovskite Layers journal February 2021
Recent Developments in the Synthesis of Supported Catalysts journal June 2015
In Situ Ambient Pressure X-ray Photoelectron Spectroscopy of Cobalt Perovskite Surfaces under Cathodic Polarization at High Temperatures journal July 2013
Designing New Lithium-Excess Cathode Materials from Percolation Theory: Nanohighways in Li x Ni 2–4 x /3 Sb x /3 O 2 journal December 2014
Mesoscopic fast ion conduction in nanometre-scale planar heterostructures journal December 2000
Self-regeneration of a Pd-perovskite catalyst for automotive emissions control journal July 2002
A high-mobility electron gas at the LaAlO3/SrTiO3 heterointerface journal January 2004
Stretchable nanoparticle conductors with self-organized conductive pathways journal July 2013
Switching on electrocatalytic activity in solid oxide cells journal August 2016
In situ growth of nanoparticles through control of non-stoichiometry journal October 2013
Exsolution trends and co-segregation aspects of self-grown catalyst nanoparticles in perovskites journal June 2017
Redox activity of surface oxygen anions in oxygen-deficient perovskite oxides during electrochemical reactions journal January 2015
Nano-socketed nickel particles with enhanced coking resistance grown in situ by redox exsolution journal September 2015
Evolution of the electrochemical interface in high-temperature fuel cells and electrolysers journal January 2016
Self-assembled single-crystal ferromagnetic iron nanowires formed by decomposition journal July 2004
Multiferroics progress and prospects in thin films journal January 2007
Magneto-ionic control of interfacial magnetism journal November 2014
Demonstration of chemistry at a point through restructuring and catalytic activation at anchored nanoparticles journal November 2017
Lattice strain-enhanced exsolution of nanoparticles in thin films journal April 2019
Tuning proton-coupled electron transfer by crystal orientation for efficient water oxidization on double perovskite oxides journal August 2020
Understanding electrochemical switchability of perovskite-type exsolution catalysts journal September 2020
A high-entropy manganite in an ordered nanocomposite for long-term application in solid oxide cells journal May 2021
Magneto-ionic control of magnetism using a solid-state proton pump journal November 2018
Nanoscale percolation in doped BaZrO3 for high proton mobility journal December 2019
Modelling electrical conduction in nanostructure assemblies through complex networks journal April 2020
Correlation between particle size/domain structure and magnetic properties of highly crystalline Fe3O4 nanoparticles journal August 2017
Step-change in high temperature steam electrolysis performance of perovskite oxide cathodes with exsolution of B-site dopants journal January 2013
Chrysanthemum-like 3D hierarchical magnetic γ-Fe 2 O 3 and Fe 3 O 4 superstructures: facile synthesis and application in adsorption of organic pollutants from water journal January 2015
Reducibility of Co at the La 0.8 Sr 0.2 CoO 3 /(La 0.5 Sr 0.5 ) 2 CoO 4 hetero-interface at elevated temperatures journal January 2014
Vertically aligned nanocomposite La 0.8 Sr 0.2 CoO 3 /(La 0.5 Sr 0.5 ) 2 CoO 4 cathodes – electronic structure, surface chemistry and oxygen reduction kinetics journal January 2015
The determining factor for interstitial oxygen formation in Ruddlesden–Popper type La 2 NiO 4 -based oxides journal January 2016
Iron oxides with a reverse spinel structure: impact of active sites on molecule adsorption journal January 2019
In situ catalyst exsolution on perovskite oxides for the production of CO and synthesis gas in ceramic membrane reactors journal January 2019
Effect of oxygen vacancies on electrical conductivity of La 0.5 Sr 0.5 FeO 3−δ from first-principles calculations journal January 2020
Low temperature methane conversion with perovskite-supported exo / endo -particles journal January 2020
Unraveling bulk and grain boundary electrical properties in La 0.8 Sr 0.2 Mn 1−y O 3±δ thin films journal January 2019
Confined polaronic transport in (LaFeO 3 ) n /(SrFeO 3 ) 1 superlattices journal July 2019
Theory of the Role of Covalence in the Perovskite-Type Manganites [ La ,   M ( II ) ] Mn O 3 journal October 1955
Controlled-valence properties of La 1 − x Sr x FeO 3 and La 1 − x Sr x MnO 3 studied by soft-x-ray absorption spectroscopy journal August 1992
Magnetic structure and magnon dispersion in LaSrFeO 4 journal February 2013
Reversible Control of Co Magnetism by Voltage-Induced Oxidation journal December 2014
Electronic states in La 2 − x Sr x CuO 4 + δ probed by soft-x-ray absorption journal January 1991
Decomposition of L a 2 − x S r x Cu O 4 into several L a 2 O 3 phases at elevated temperatures in ultrahigh vacuum inside a transmission electron microscope journal May 2018
Effects of cation stoichiometry on electronic and structural properties of LaNiO 3
  • Smith, Cole R.; Lang, Andrew C.; Shutthanandan, Vaithiyalingam
  • Journal of Vacuum Science & Technology A: Vacuum, Surfaces, and Films, Vol. 33, Issue 4 https://doi.org/10.1116/1.4922346
journal July 2015
Water Splitting on Model-Composite La0.6Sr0.4FeO3-  (LSF) Electrodes in H2/H2O Atmosphere journal June 2015
Treading in the Limited Stability Regime of Lanthanum Strontium Ferrite — Reduction, Phase Change and Exsolution journal July 2019
High-Performance Metal-Supported Solid Oxide Fuel Cells by Advanced Cathode Processing journal January 2017
Comparison of Electrochemical Properties of La 0.6 Sr 0.4 FeO 3-δ Thin Film Electrodes: Oxidizing vs. Reducing Conditions journal December 2014

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