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

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

doi:10.1038/s41467-023-37212-6

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

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

Research output: Contribution to journal › Article › peer-review

21 Scopus citations

Abstract

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.

Original language	English
Article number	1754
Journal	Nature Communications
Volume	14
Issue number	1
DOIs	https://doi.org/10.1038/s41467-023-37212-6
State	Published - Dec 2023

Bibliographical note

Publisher Copyright:
© 2023, The Author(s).

Funding

This work was performed as part of the Engineering and Physical Science Research Council grant numbers EP/R023522/1, and EP/R023603/1. The in situ STEM research was supported by the Center for Nanophase Materials Sciences at Oak Ridge National Laboratory, which is a US Department of Energy Office of Science User Facility, and this work was supported in part by the National Science Foundation under DMR 1455154 (M.P.T., B.S.G.). J.W. and S.C.P. gratefully acknowledge support from the ARCHER2 UK National Supercomputing Service and YOUNG HPC (supported by the UK Materials and Molecular Modelling Hub, which is partially funded by EPSRC (EP/T022213)) for providing computation resources, accessed through the U.K. Materials Chemistry Consortium (funded by the EPSRC grants: EP/R029431). The authors are grateful to all the members of the Emergent Nanomaterials (EPSRC Critical Mass Proposal) project for useful discussion.

Funders	Funder number
ARCHER2 UK National Supercomputing Service
Center for Nanophase Materials Sciences
National Science Foundation Arctic Social Science Program	DMR 1455154
National Science Foundation Arctic Social Science Program
Office of Science Programs
Oak Ridge National Laboratory
Engineering and Physical Sciences Research Council	EP/R029431, EP/T022213, EP/R023522/1, EP/R023603/1
Engineering and Physical Sciences Research Council

ASJC Scopus subject areas

General Chemistry
General Biochemistry, Genetics and Molecular Biology
General Physics and Astronomy

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abstract = "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.",

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AU - Wu, Ji

AU - Gavalda-Diaz, Oriol

AU - Marquardt, Katharina

AU - Saiz, Eduardo

AU - Neagu, Dragos

AU - Unocic, Raymond R.

AU - Parker, Stephen C.

AU - Guiton, Beth S.

AU - Payne, David J.

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

Abstract

Bibliographical note

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ASJC Scopus subject areas

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