Segregation effects on the properties of (AuAg)147

Catlow, Charles Richard ORCID: https://orcid.org/0000-0002-1341-1541, Gould, A.L., Heard, C.J. and Logsdail, Andrew ORCID: https://orcid.org/0000-0002-2277-415X 2014. Segregation effects on the properties of (AuAg)147. Physical Chemistry Chemical Physics -Cambridge- Royal Society of Chemistry 16 (39) , pp. 21049-21061. 10.1039/C4CP00753K

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Abstract

AuAg nanoclusters are promising supported co-catalysts for photocatalytic hydrogen reduction. However, beyond the quantum regime (N > 100) little is known about how the electronic properties of these nanoparticles are affected by chemical ordering. We investigate the effects of chemical ordering on the properties of 147-atom cuboctahedral AuAg nanoclusters, using empirical potentials coupled with an atomic-swap basin-hopping search to optimise the elemental distribution, with the lowest energy arrangements then reminimised using Density Functional Theory (DFT). Force-field calculations show Au atoms preferentially occupy sub-surface positions in the bimetallic structures, which results in the formation of a pseudo-onion structure for Ag-rich compositions. At the DFT-level, however, an Ag core surrounded by an Au shell (Ag@Au) is energetically favoured, as electron density can be drawn more readily when Au atoms are positioned on the nanocluster surface, thus resulting in a partial negative charge. Core@shell configurations are analogous to structures that can be chemically synthesised, and further detailed electronic analysis is discussed in the context of nanocluster applications to co-catalysed photocatalysis.

Item Type:	Article
Date Type:	Published Online
Status:	Published
Schools:	Chemistry
Subjects:	Q Science > QD Chemistry
Publisher:	Royal Society of Chemistry
ISSN:	1463-9076
Date of First Compliant Deposit:	2 June 2016
Date of Acceptance:	14 April 2014
Last Modified:	17 Dec 2023 16:17
URI:	https://orca.cardiff.ac.uk/id/eprint/83881

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