Journal
NANO LETTERS
Volume 13, Issue 8, Pages 3618-3625Publisher
AMER CHEMICAL SOC
DOI: 10.1021/nl401467r
Keywords
Intermetallic; Ni-Zn; Kirkendall effect; hollow nanoparticle; diffusion; moving boundary model
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Funding
- American Chemical Society Petroleum Research Fund (ACS PRF) [50-794-DN15]
- U.S. Department of Energy [DE-AC02-06CH11357]
- Department of Energy
- MRCAT
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Intermetallic Ni-Zn nanoparticles (NPs) were synthesized via the chemical conversion of nickel NPs using a zerovalent organometallic zinc precursor. After the injection of a diethylzinc solution, Ni NPs progressively transformed from a solid to a hollow Ni-Zn intermetallic structure with time. During the transformation of Ni NPs to intermetallic structures, they retained their overall spherical morphology. The growth mechanism for the solid-to-hollow nanoparticle transformation is ascribed to the nanoscale Kirkendall effect due to unequal diffusion rates of Ni and Zn. We develop a diffusion model for nonreactive, homogeneous, diffusion-controlled intermetallic hollow NP formation including moving boundaries at the interfaces of void solid and solid bulk solutions. Apparent diffusion coefficients for both metals and vacancy were evaluated from modeling the time-dependent growth of the void. The apparent diffusion coefficients obtained in this system compared favorably with results from measurement at grain boundaries in bulk Ni-Zn. This study represents the first combined experimental modeling of the formation of hollow nanostructures by the nanoscale Kirkendall effect.
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