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: | 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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