Issue 7, 2015

How to determine accurate chemical ordering in several nanometer large bimetallic crystallites from electronic structure calculations

Abstract

Chemical and physical properties of binary metallic nanoparticles (nanoalloys) are to a great extent defined by their chemical ordering, i.e. the pattern in which atoms of the two elements are located in a given crystal lattice. The reliable determination of the lowest-energy chemical ordering is a challenge that impedes in-depth studies of several-nm large bimetallic particles. We propose a method to efficiently optimize the chemical ordering based solely on results of electronic structure (density functional) calculations. We show that the accuracy of this method is practically the same as the accuracy of the underlying quantum mechanical approach. This method, due to its simplicity, immediately reveals why one or another chemical ordering is preferred and unravels the nature of the binding within the nanoparticles. For instance, our results provide very intuitive understanding of why gold and silver segregate on low-coordinated sites in Pd70Au70 and Pd70Ag70 particles, while Pd70Cu70 exhibits matryoshka-like structure and Pd70Zn70 features Zn and Pd atoms arranged in layers. To illustrate the power of the new method we optimized the chemical ordering in much larger Pd732Au731, Pd732Ag731, Pd732Cu731, and Pd732Zn731 nanocrystals, whose size ∼4.4 nm is common for catalytic applications.

Graphical abstract: How to determine accurate chemical ordering in several nanometer large bimetallic crystallites from electronic structure calculations

Supplementary files

Article information

Article type
Edge Article
Submitted
29 Oct 2014
Accepted
01 Apr 2015
First published
02 Apr 2015
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY-NC license

Chem. Sci., 2015,6, 3868-3880

Author version available

How to determine accurate chemical ordering in several nanometer large bimetallic crystallites from electronic structure calculations

S. M. Kozlov, G. Kovács, R. Ferrando and K. M. Neyman, Chem. Sci., 2015, 6, 3868 DOI: 10.1039/C4SC03321C

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