Impact of co-adsorbed oxygen on crotonaldehyde adsorption over gold nanoclusters:a computational study

Abstract

Crotonaldehyde (2-butenal) adsorption over gold sub-nanometer particles, and the influence of co-adsorbed oxygen, has been systematically investigated by computational methods. Using density functional theory, the adsorption energetics of crotonaldehyde on bare and oxidised gold clusters (Au , d = 0.8 nm) were determined as a function of oxygen coverage and coordination geometry. At low oxygen coverage, sites are available for which crotonaldehyde adsorption is enhanced relative to bare Au clusters by 10 kJ mol. At higher oxygen coverage, crotonaldehyde is forced to adsorb in close proximity to oxygen weakening adsorption by up to 60 kJ mol relative to bare Au. Bonding geometries, density of states plots and Bader analysis, are used to elucidate crotonaldehyde bonding to gold nanoparticles in terms of partial electron transfer from Au to crotonaldehyde, and note that donation to gold from crotonaldehyde also becomes significant following metal oxidation. At high oxygen coverage we find that all molecular adsorption sites have a neighbouring, destabilising, oxygen adatom so that despite enhanced donation, crotonaldehyde adsorption is always weakened by steric interactions. For a larger cluster (Au, d = 1.1 nm) crotonaldehyde adsorption is destabilized in this way even at a low oxygen coverage. These findings provide a quantitative framework to underpin the experimentally observed influence of oxygen on the selective oxidation of crotyl alcohol to crotonaldehyde over gold and gold-palladium alloys.

Publication DOI: https://doi.org/10.1039/c3cp53691b
Divisions: College of Engineering & Physical Sciences > School of Infrastructure and Sustainable Engineering > Chemical Engineering & Applied Chemistry
College of Engineering & Physical Sciences > Energy and Bioproducts Research Institute (EBRI)
Additional Information: This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. Funding: EPSRC (EP/E046754/1; EP/G007594/3 and award of a Leadership Fellowship and studentship; UK’s National high-performance computing service, HECToR (EP/F067496) through the materials consortium, ARCCA and HPC-Wales super-computer facilities.
Publication ISSN: 1463-9084
Last Modified: 04 Jan 2024 08:20
Date Deposited: 06 Aug 2014 10:35
Full Text Link: http://pubs.rsc ... 1b#!divAbstract
Related URLs: http://www.scop ... tnerID=8YFLogxK (Scopus URL)
PURE Output Type: Article
Published Date: 2014-06-21
Authors: Zeinalipour-Yazdi, Constantinos D.
Willock, David J.
Machado, Andreia
Wilson, Karen (ORCID Profile 0000-0003-4873-708X)
Lee, Adam F. (ORCID Profile 0000-0002-2153-1391)

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