Title

Reshaping of Truncated Pd Nanocubes: Energetic and Kinetic Analysis Integrating Transmission Electron Microscopy with Atomistic-Level and Coarse-Grained Modeling

Publication Date

7-28-2020

Department

Chemistry; Ames Laboratory; Mathematics; Physics and Astronomy

Campus Units

Ames Laboratory, Chemistry, Mathematics, Physics and Astronomy

OSTI ID+

1638689

Report Number

IS-J 10188

DOI

10.1021/acsnano.0c02864

Journal Title

ACS Nano

Volume Number

14

Issue Number

7

First Page

8551

Last Page

8561

Abstract

Stability against reshaping of metallic fcc nanocrystals synthesized with tailored far-from-equilibrium shapes is key to maintaining optimal properties for applications such as catalysis. Yet Arrhenius analysis of experimental reshaping kinetics, and appropriate theory and simulation, is lacking. Thus, we use TEM to monitor the reshaping of Pd nanocubes of ∼25 nm side length between 410 °C (over ∼4.5 h) and 440 °C (over ∼0.25 h), extracting a high effective energy barrier of Eeff ≈ 4.6 eV. We also provide an analytic determination of the energy variation along the optimal pathway for reshaping that involves transfer of atoms across the nanocube surface from edges or corners to form new layers on side {100} facets. The effective barrier from this analysis is shown to increase strongly with the degree of truncation of edges and corners in the synthesized nanocube. Theory matches experiment for the appropriate degree of truncation. In addition, we perform simulations of a stochastic atomistic-level model incorporating a realistic description of diffusive hopping for undercoordinated surface atoms, thereby providing a visualization of the initial reshaping process.

DOE Contract Number(s)

AC02-07CH11358; CHE-1566445; AC02-05CH11231; ACI-1548562

Language

en

Publisher

Iowa State University Digital Repository, Ames IA (United States)

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