Complex oscillatory decrease with size in diffusivity of {100}-epitaxially supported 3D fcc metal nanoclusters
Abstract
Diffusion and coalescence of supported 3D metal nanoclusters (NCs) leads to Smoluchowski Ripening (SR), a key pathway for catalyst degradation. Variation of the NC diffusion coefficient, $$D_N$$, with size $N$ (in atoms) controls SR kinetics. Traditionally, a form $$D_N ~ N^{-β}$$ was assumed consistent with mean-field analysis. However, KMC simulation of a stochastic model for diffusion of {100}-epitaxially supported fcc NCs mediated by surface diffusion reveals instead a complex oscillatory decrease of $$D_N$$ with $N$. Barriers for surface diffusion of metal atoms across and between facets, along step edges, etc., in this model are selected to accurately capture behavior for fcc metals. (This contrasts standard bond-breaking prescriptions which fail dramatically.) For strong adhesion, equilibrated NCs are truncated pyramids (TP). Local minima of DN sometimes but not always correspond to sizes, $N$TP, where these have a closed-shell structure. Local maxima generally correspond to $N ≈ N$TP + 3 for $N$ = O(102). For weak adhesion, equilibrated NCs are truncated octahedra (TO), and local minima of $$D_N$$ occur for sizes close or equal to those of just a subset of closed-shell structures. Analytic characterization of energetics along the NC diffusion pathway (which involves dissolving and reforming outer layers of facets) provides fundamental insight into the behavior of $$D_N$$, including the strong variation with $N$ of the effective NC diffusion barrier.
- Authors:
-
- Division of Chemical & Biological Sciences, Ames Laboratory, USDOE and Department of Physics & Astronomy, Iowa State University, Ames IA 50011
- Publication Date:
- Research Org.:
- Ames Lab., Ames, IA (United States)
- Sponsoring Org.:
- USDOE
- OSTI Identifier:
- 1562571
- Alternate Identifier(s):
- OSTI ID: 1569740
- Report Number(s):
- IS-J 9974
Journal ID: ISSN 2040-3364; NANOHL
- Grant/Contract Number:
- AC02-07CH11358
- Resource Type:
- Published Article
- Journal Name:
- Nanoscale
- Additional Journal Information:
- Journal Name: Nanoscale Journal Volume: 11 Journal Issue: 37; Journal ID: ISSN 2040-3364
- Publisher:
- Royal Society of Chemistry (RSC)
- Country of Publication:
- United Kingdom
- Language:
- English
- Subject:
- 77 NANOSCIENCE AND NANOTECHNOLOGY
Citation Formats
Lai, King C., and Evans, James W. Complex oscillatory decrease with size in diffusivity of {100}-epitaxially supported 3D fcc metal nanoclusters. United Kingdom: N. p., 2019.
Web. doi:10.1039/C9NR05845A.
Lai, King C., & Evans, James W. Complex oscillatory decrease with size in diffusivity of {100}-epitaxially supported 3D fcc metal nanoclusters. United Kingdom. https://doi.org/10.1039/C9NR05845A
Lai, King C., and Evans, James W. Thu .
"Complex oscillatory decrease with size in diffusivity of {100}-epitaxially supported 3D fcc metal nanoclusters". United Kingdom. https://doi.org/10.1039/C9NR05845A.
@article{osti_1562571,
title = {Complex oscillatory decrease with size in diffusivity of {100}-epitaxially supported 3D fcc metal nanoclusters},
author = {Lai, King C. and Evans, James W.},
abstractNote = {Diffusion and coalescence of supported 3D metal nanoclusters (NCs) leads to Smoluchowski Ripening (SR), a key pathway for catalyst degradation. Variation of the NC diffusion coefficient, $D_N$, with size $N$ (in atoms) controls SR kinetics. Traditionally, a form $D_N ~ N^{-β}$ was assumed consistent with mean-field analysis. However, KMC simulation of a stochastic model for diffusion of {100}-epitaxially supported fcc NCs mediated by surface diffusion reveals instead a complex oscillatory decrease of $D_N$ with $N$. Barriers for surface diffusion of metal atoms across and between facets, along step edges, etc., in this model are selected to accurately capture behavior for fcc metals. (This contrasts standard bond-breaking prescriptions which fail dramatically.) For strong adhesion, equilibrated NCs are truncated pyramids (TP). Local minima of DN sometimes but not always correspond to sizes, $N$TP, where these have a closed-shell structure. Local maxima generally correspond to $N ≈ N$TP + 3 for $N$ = O(102). For weak adhesion, equilibrated NCs are truncated octahedra (TO), and local minima of $D_N$ occur for sizes close or equal to those of just a subset of closed-shell structures. Analytic characterization of energetics along the NC diffusion pathway (which involves dissolving and reforming outer layers of facets) provides fundamental insight into the behavior of $D_N$, including the strong variation with $N$ of the effective NC diffusion barrier.},
doi = {10.1039/C9NR05845A},
journal = {Nanoscale},
number = 37,
volume = 11,
place = {United Kingdom},
year = {2019},
month = {9}
}
https://doi.org/10.1039/C9NR05845A
Web of Science
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