Real-time insight into the multistage mechanism of nanoparticle exsolution from a perovskite host surface

Calì, Eleonora; Thomas, Melonie P.; Vasudevan, Rama K.; Wu, Ji; Gavalda-Diaz, Oriol; Marquardt, Katharina; Saiz, Eduardo; Neagu, Dragos; Unocic, Raymond R.; Parker, Stephen C.; Guiton, Beth S.; Payne, David J.

doi:10.1038/s41467-023-37212-6

Real-time insight into the multistage mechanism of nanoparticle exsolution from a perovskite host surface

Journal Article · Wed Mar 29 00:00:00 EDT 2023 · Nature Communications

DOI:https://doi.org/10.1038/s41467-023-37212-6· OSTI ID:2000422

^[1]; Thomas, Melonie P. ^[2]; ^[3]; Wu, Ji ^[4]; Gavalda-Diaz, Oriol ^[5]; Marquardt, Katharina ^[6]; Saiz, Eduardo ^[6]; ^[7]; ^[3]; ^[8]; ^[9]; ^[10]

Imperial College, London (United Kingdom); Polytechnic University of Turin (Italy)
Univ. of Kentucky, Lexington, KY (United States); University of Peradeniya (Sri Lanka)
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Sciences (CNMS)
Univ. of Bath (United Kingdom); Queen Mary Univ. of London (United Kingdom)
Imperial College, London (United Kingdom); Univ. of Nottingham (United Kingdom)
Imperial College, London (United Kingdom)
Univ. of Strathclyde, Glasgow, Scotland (United Kingdom)
Univ. of Bath (United Kingdom)
Univ. of Kentucky, Lexington, KY (United States)
Imperial College, London (United Kingdom); Harwell Science and Innovation Campus, Didcot (United Kingdom)

In exsolution, nanoparticles form by emerging from oxide hosts by application of redox driving forces, leading to transformative advances in stability, activity, and efficiency over deposition techniques, and resulting in a wide range of new opportunities for catalytic, energy and net-zero-related technologies. However, the mechanism of exsolved nanoparticle nucleation and perovskite structural evolution, has, to date, remained unclear. Herein, we shed light on this elusive process by following in real time Ir nanoparticle emergence from a SrTiO₃ host oxide lattice, using in situ high-resolution electron microscopy in combination with computational simulations and machine learning analytics. We show that nucleation occurs via atom clustering, in tandem with host evolution, revealing the participation of surface defects and host lattice restructuring in trapping Ir atoms to initiate nanoparticle formation and growth. These insights provide a theoretical platform and practical recommendations to further the development of highly functional and broadly applicable exsolvable materials.

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). Scientific User Facilities (SUF)

Grant/Contract Number:: AC05-00OR22725

OSTI ID:: 2000422

Journal Information:: Nature Communications, Journal Name: Nature Communications Journal Issue: 1 Vol. 14; ISSN 2041-1723

Publisher:: Nature Publishing GroupCopyright Statement

Country of Publication:: United States

Language:: English

References (48)

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 Lv, Houfu; Lin, Le; Zhang, Xiaomin Advanced Materials, Vol. 32, Issue 6 https://doi.org/10.1002/adma.201906193	journal	December 2019
New Insight into the Doped Strontium Titanate Cathode with In Situ Exsolved Nickel Nanoparticles for Electrolysis of Carbon Dioxide Bai, Lu; Li, Haibin; Yan, Zhen Advanced Materials Interfaces, Vol. 8, Issue 3 https://doi.org/10.1002/admi.202001598	journal	December 2020
Trends and Prospects of Bimetallic Exsolution Tang, Chenyang; Kousi, Kalliopi; Neagu, Dragos Chemistry – A European Journal, Vol. 27, Issue 22 https://doi.org/10.1002/chem.202004950	journal	February 2021
Plasma Driven Exsolution for Nanoscale Functionalization of Perovskite Oxides Kyriakou, Vasileios; Sharma, Rakesh Kumar; Neagu, Dragos Small Methods, Vol. 5, Issue 12 https://doi.org/10.1002/smtd.202100868	journal	October 2021
Quantum-mechanical condensed matter simulations with CRYSTAL Dovesi, Roberto; Erba, Alessandro; Orlando, Roberto Wiley Interdisciplinary Reviews: Computational Molecular Science, Vol. 8, Issue 4 https://doi.org/10.1002/wcms.1360	journal	March 2018
Defects on Strontium Titanate Marshall, Matthew S. J.; Becerra-Toledo, Andres E.; Marks, Laurence D. Defects at Oxide Surfaces https://doi.org/10.1007/978-3-319-14367-5_11	book	January 2015
Kinetic Model of the Initial Stage of the Nanowire Growth Filimonov, S. N.; Hervieu, Yu. Yu. Russian Physics Journal, Vol. 60, Issue 11 https://doi.org/10.1007/s11182-018-1322-9	journal	March 2018
Structure and quality controlled growth of InAs nanowires through catalyst engineering Zhang, Zhi; Lu, Zhenyu; Xu, Hongyi Nano Research, Vol. 7, Issue 11 https://doi.org/10.1007/s12274-014-0524-x	journal	August 2014
Reflection high-energy electron diffraction study on the SrTiO3 surface structure Naito, Michio; Sato, Hisashi Physica C: Superconductivity, Vol. 229, Issue 1-2 https://doi.org/10.1016/0921-4534(94)90805-2	journal	August 1994
Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set Kresse, G.; Furthmüller, J. Computational Materials Science, Vol. 6, Issue 1, p. 15-50 https://doi.org/10.1016/0927-0256(96)00008-0	journal	July 1996
Investigation of hetero-phases grown via in-situ exsolution on a Ni-doped (La,Sr)FeO3 cathode and the resultant activity enhancement in CO2 reduction Deka, Dhruba J.; Kim, Jaesung; Gunduz, Seval Applied Catalysis B: Environmental, Vol. 286 https://doi.org/10.1016/j.apcatb.2021.119917	journal	June 2021
Ni-Substituted Sr(Ti,Fe)O3 SOFC Anodes: Achieving High Performance via Metal Alloy Nanoparticle Exsolution Zhu, Tenglong; Troiani, Horacio E.; Mogni, Liliana V. Joule, Vol. 2, Issue 3 https://doi.org/10.1016/j.joule.2018.02.006	journal	March 2018
An atomistic modelling investigation of the defect chemistry of SrTiO3 and its Ruddlesden-Popper phases, Srn+1TinO3n+1 (n = 1–3) Wood, Nathan D.; Teter, David M.; Tse, Joshua S. Journal of Solid State Chemistry, Vol. 303 https://doi.org/10.1016/j.jssc.2021.122523	journal	November 2021
From material design to mechanism study: Nanoscale Ni exsolution on a highly active A-site deficient anode material for solid oxide fuel cells Gao, Yang; Chen, Dengjie; Saccoccio, Mattia Nano Energy, Vol. 27 https://doi.org/10.1016/j.nanoen.2016.07.013	journal	September 2016
In Situ Exsolved Metal Nanoparticles: A Smart Approach for Optimization of Catalysts Zhang, Jiawei; Gao, Min-Rui; Luo, Jing-Li Chemistry of Materials, Vol. 32, Issue 13 https://doi.org/10.1021/acs.chemmater.0c00721	journal	June 2020
Tuning Point Defects by Elastic Strain Modulates Nanoparticle Exsolution on Perovskite Oxides Wang, Jiayue; Yang, Jing; Opitz, Alexander K. Chemistry of Materials, Vol. 33, Issue 13 https://doi.org/10.1021/acs.chemmater.1c00821	journal	June 2021
Evolution of Exsolved Nanoparticles on a Perovskite Oxide Surface during a Redox Process Lai, Ke-Yu; Manthiram, Arumugam Chemistry of Materials, Vol. 30, Issue 8 https://doi.org/10.1021/acs.chemmater.8b01029	journal	March 2018
New Atomic-Scale Insight into Self-Regeneration of Pt-CaTiO ₃ Catalysts: Incipient Redox-Induced Structures Revealed by a Small-Angle Tilting STEM Technique Zhang, Shuyi; Katz, Michael B.; Dai, Sheng The Journal of Physical Chemistry C, Vol. 121, Issue 32 https://doi.org/10.1021/acs.jpcc.7b05200	journal	August 2017
Evidence and Model for Strain-Driven Release of Metal Nanocatalysts from Perovskites during Exsolution Oh, Tae-Sik; Rahani, Ehsan K.; Neagu, Dragos The Journal of Physical Chemistry Letters, Vol. 6, Issue 24 https://doi.org/10.1021/acs.jpclett.5b02292	journal	December 2015
Energetics of Nanoparticle Exsolution from Perovskite Oxides Gao, Yang; Lu, Ziheng; You, Tsam Lung The Journal of Physical Chemistry Letters, Vol. 9, Issue 13 https://doi.org/10.1021/acs.jpclett.8b01380	journal	June 2018
Phases and Interfaces from Real Space Atomically Resolved Data: Physics-Based Deep Data Image Analysis Vasudevan, Rama K.; Ziatdinov, Maxim; Jesse, Stephen Nano Letters, Vol. 16, Issue 9 https://doi.org/10.1021/acs.nanolett.6b02130	journal	August 2016
New Opportunity for in Situ Exsolution of Metallic Nanoparticles on Perovskite Parent Sun, Yi-Fei; Zhang, Ya-Qian; Chen, Jian Nano Letters, Vol. 16, Issue 8 https://doi.org/10.1021/acs.nanolett.6b02757	journal	July 2016
Exsolution of Catalytically Active Iridium Nanoparticles from Strontium Titanate Calì, Eleonora; Kerherve, Gwilherm; Naufal, Faris ACS Applied Materials & Interfaces, Vol. 12, Issue 33 https://doi.org/10.1021/acsami.0c08928	journal	July 2020
In Situ Observation of Rh-CaTiO ₃ Catalysts during Reduction and Oxidation Treatments by Transmission Electron Microscopy Dai, Sheng; Zhang, Shuyi; Katz, Michael B. ACS Catalysis, Vol. 7, Issue 3 https://doi.org/10.1021/acscatal.6b03604	journal	January 2017
High Electron Mobility of Nb-Doped SrTiO ₃ Films Stemming from Rod-Type Sr Vacancy Clusters Kobayashi, Shunsuke; Mizumukai, Yuki; Ohnishi, Tsuyoshi ACS Nano, Vol. 9, Issue 11 https://doi.org/10.1021/acsnano.5b05720	journal	October 2015
In Situ Observation of Nanoparticle Exsolution from Perovskite Oxides: From Atomic Scale Mechanistic Insight to Nanostructure Tailoring Neagu, Dragos; Kyriakou, Vasileios; Roiban, Ioan-Lucian ACS Nano, Vol. 13, Issue 11 https://doi.org/10.1021/acsnano.9b05652	journal	October 2019
Growth Kinetics of Individual Co Particles Ex-solved on SrTi _0.75 Co _0.25 O _3-δ Polycrystalline Perovskite Thin Films Jo, Yong-Ryun; Koo, Bonjae; Seo, Min-Ji Journal of the American Chemical Society, Vol. 141, Issue 16 https://doi.org/10.1021/jacs.9b01882	journal	April 2019
Surface Diffusion and Substrate−Nanowire Adatom Exchange in InAs Nanowire Growth Dayeh, Shadi A.; Yu, Edward T.; Wang, Deli Nano Letters, Vol. 9, Issue 5 https://doi.org/10.1021/nl900191w	journal	May 2009
Atomic-scale imaging of nanoengineered oxygen vacancy profiles in SrTiO3 Muller, David A.; Nakagawa, Naoyuki; Ohtomo, Akira Nature, Vol. 430, Issue 7000 https://doi.org/10.1038/nature02756	journal	August 2004
Switching on electrocatalytic activity in solid oxide cells Myung, Jae-ha; Neagu, Dragos; Miller, David N. Nature, Vol. 537, Issue 7621 https://doi.org/10.1038/nature19090	journal	August 2016
In situ growth of nanoparticles through control of non-stoichiometry Neagu, Dragos; Tsekouras, George; Miller, David N. Nature Chemistry, Vol. 5, Issue 11 https://doi.org/10.1038/nchem.1773	journal	October 2013
Direct observation of oxygen vacancy-driven structural and resistive phase transitions in La2/3Sr1/3MnO3 Yao, Lide; Inkinen, Sampo; van Dijken, Sebastiaan Nature Communications, Vol. 8, Issue 1 https://doi.org/10.1038/ncomms14544	journal	February 2017
Enhancing CO2 electrolysis through synergistic control of non-stoichiometry and doping to tune cathode surface structures Ye, Lingting; Zhang, Minyi; Huang, Ping Nature Communications, Vol. 8, Issue 1 https://doi.org/10.1038/ncomms14785	journal	March 2017
Nano-socketed nickel particles with enhanced coking resistance grown in situ by redox exsolution Neagu, Dragos; Oh, Tae-Sik; Miller, David N. Nature Communications, Vol. 6, Issue 1 https://doi.org/10.1038/ncomms9120	journal	September 2015
Lattice strain-enhanced exsolution of nanoparticles in thin films Han, Hyeon; Park, Jucheol; Nam, Sang Yeol Nature Communications, Vol. 10, Issue 1 https://doi.org/10.1038/s41467-019-09395-4	journal	April 2019
Electron Beam Induced Artifacts During in situ TEM Deformation of Nanostructured Metals Sarkar, Rohit; Rentenberger, Christian; Rajagopalan, Jagannathan Scientific Reports, Vol. 5, Issue 1 https://doi.org/10.1038/srep16345	journal	November 2015
Strontium vacancy clustering in Ti-excess SrTiO ₃ thin film Tokuda, Y.; Kobayashi, S.; Ohnishi, T. Applied Physics Letters, Vol. 99, Issue 3 https://doi.org/10.1063/1.3616136	journal	July 2011
Big data in reciprocal space: Sliding fast Fourier transforms for determining periodicity Vasudevan, Rama K.; Belianinov, Alex; Gianfrancesco, Anthony G. Applied Physics Letters, Vol. 106, Issue 9 https://doi.org/10.1063/1.4914016	journal	March 2015
Oxygen vacancies: The (in)visible friend of oxide electronics Gunkel, F.; Christensen, D. V.; Chen, Y. Z. Applied Physics Letters, Vol. 116, Issue 12 https://doi.org/10.1063/1.5143309	journal	March 2020
The General Utility Lattice Program ( GULP ) Gale, Julian D.; Rohl, Andrew L. Molecular Simulation, Vol. 29, Issue 5 https://doi.org/10.1080/0892702031000104887	journal	May 2003
Ab initiomolecular dynamics for liquid metals Kresse, G.; Hafner, J. Physical Review B, Vol. 47, Issue 1, p. 558-561 https://doi.org/10.1103/PhysRevB.47.558	journal	January 1993
Ab initio molecular-dynamics simulation of the liquid-metal–amorphous-semiconductor transition in germanium Kresse, G.; Hafner, J. Physical Review B, Vol. 49, Issue 20, p. 14251-14269 https://doi.org/10.1103/PhysRevB.49.14251	journal	May 1994
Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set Kresse, G.; Furthmüller, J. Physical Review B, Vol. 54, Issue 16, p. 11169-11186 https://doi.org/10.1103/PhysRevB.54.11169	journal	October 1996
Restoring the Density-Gradient Expansion for Exchange in Solids and Surfaces Perdew, John P.; Ruzsinszky, Adrienn; Csonka, Gábor I. Physical Review Letters, Vol. 100, Issue 13 https://doi.org/10.1103/PhysRevLett.100.136406	journal	April 2008
From Droplets to Nanowires: Dynamics of Vapor-Liquid-Solid Growth Schwarz, K. W.; Tersoff, J. Physical Review Letters, Vol. 102, Issue 20 https://doi.org/10.1103/PhysRevLett.102.206101	journal	May 2009
Self-consistent DFT + U + V study of oxygen vacancies in SrTiO 3 Ricca, Chiara; Timrov, Iurii; Cococcioni, Matteo Physical Review Research, Vol. 2, Issue 2 https://doi.org/10.1103/PhysRevResearch.2.023313	journal	June 2020
Probing vacancy behavior across complex oxide heterointerfaces Zhu, Jiaxin; Lee, Jung-Woo; Lee, Hyungwoo Science Advances, Vol. 5, Issue 2 https://doi.org/10.1126/sciadv.aau8467	journal	February 2019
The initial stage of growth of crystalline nanowhiskers Sibirev, N. V.; Nazarenko, M. B.; Cirlin, G. E. Semiconductors, Vol. 44, Issue 1 https://doi.org/10.1134/S1063782610010197	journal	January 2010

Similar Records

Fast Surface Oxygen Release Kinetics Accelerate Nanoparticle Exsolution in Perovskite Oxides

Journal Article · Mon Jan 09 19:00:00 EST 2023 · Journal of the American Chemical Society · OSTI ID:1924197

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
electrocatalysis
solid-state chemistry
synthesis and processing

Real-time insight into the multistage mechanism of nanoparticle exsolution from a perovskite host surface

Citation Formats

References (48)

Similar Records

Related Subjects