4.2 Article

Evolution of surface and sub-surface morphology and chemical state of exsolved Ni nanoparticles

Journal

FARADAY DISCUSSIONS
Volume 236, Issue -, Pages 141-156

Publisher

ROYAL SOC CHEMISTRY
DOI: 10.1039/d1fd00123j

Keywords

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Funding

  1. Laboratory Directed Research and Development (LDRD) Program at Lawrence Berkeley National Laboratory
  2. U.S. DOE Office of Science User Facility [DE-AC02-05CH11231]
  3. Alexander von Humboldt Foundation, Bonn, Germany
  4. U. S. Department of Energy, Office of Science [DE-AC02-06CH11357]

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Nanoparticles can be generated by dopant migration from bulk host lattices. In this study, Ni dopants were found to migrate to the surface of strontium titanate lattices, forming metallic Ni nanoparticles. The morphology of the nanoparticles was observed to change during the migration process.
Nanoparticle formation by dopant exsolution (migration) from bulk host lattices is a promising approach to generate highly stable nanoparticles with tunable size, shape, and distribution. We investigated Ni dopant migration from strontium titanate (STO) lattices, forming metallic Ni nanoparticles at STO surfaces. Ex situ scanning probe measurements confirmed the presence of nanoparticles at the H-2 treated surface. In situ ambient pressure X-ray photoelectron spectroscopy (AP-XPS) revealed reduction from Ni2+ to Ni-0 as Ni dopants migrated to the surface during heating treatments in H-2. During Ni migration and reduction, the Sr and Ti chemical states were mostly unchanged, indicating the selective reduction of Ni during treatment. At the same time, we used in situ ambient pressure grazing incidence X-ray scattering (GIXS) to monitor the particle morphology. As Ni migrated to the surface, it nucleated and grew into compressed spheroidal nanoparticles partially embedded in the STO perovskite surface. These findings provide a detailed picture of the evolution of the nanoparticle surface and subsurface chemical state and morphology as the nanoparticles grow beyond the initial nucleation and growth stages.

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