doi:10.1016/j.jcat.2004.01.001
Copyright © 2004 Elsevier Inc. All rights reserved.
Priority Communication
On the origin of the catalytic activity of gold nanoparticles for low-temperature CO oxidation
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N. Lopez a, T. V. W. Janssens b, B. S. Clausen b, Y. Xu c, M. Mavrikakis c, T. Bligaard d and J. K. Nørskov
,
, d
a Departement de Quimica Fisica, Universitat de Barcelona, c/Marti i Franques 1, 08028, Barcelona, Spain
b Haldor Topsøe A/S, Nymøllevej 55, DK-2800, Lyngby, Denmark
c Department of Chemical and Biological Engineering, University of Winconsin-Madison, Madison, WI 53706, USA
d Center for Atomic-Scale Materials Physics, Department of Physics, Technical University of Denmark, DK-2800, Lyngby, Denmark
Received 19 December 2003;
accepted 8 January 2004.
Available online 11 March 2004.
Abstract
It is suggested that there may be several effects contributing to the special catalytic properties of supported nanosized gold particles, and that it is useful to order them in a hierarchy. The most important effect is related to the availability of many low-coordinated gold atoms on the small particles. Effects related to the interaction with the support may also contribute, but to a considerably smaller extent. We base the analysis on a new set of experimental results comparing the CO oxidation rates over gold supported on different reducible and nonreducible oxides, on an analysis of a large number of published activity data, and on an analysis of density-functional calculations of the effect of metal coordination numbers in comparison to the role of charge transfer, layer thickness, and interactions with the support.
Author Keywords: Author Keywords: Gold; Nanoparticles; CO oxidation
Fig. 1. Measured activities (in mmol CO/(gAus)) for CO oxidation at 273 K over different Au-based catalysts as a function of the average particle size (d, in nm). Supports are indicated by the symbol shape. Open symbols are used for reducible supports; solid symbols for irreducible supports. The curve shows a 1/d3 guide to the eye, showing that the activity of gold catalysts is approximately proportional with the number of low-coordinated atoms at the corners of the gold particles. The three points marked by an arrow are from our measurements, and the rest are collected from Refs. [1, 6, 23, 24, 25, 26, 27, 28 and 29] as described in the text. A full account of the data and references can be found at http://www.fysik.dtu.dk/CooxidationGoldNano.pdf.
Fig. 2. (Top) The correlation between the binding energies, for CO molecules and O atoms, with respect to the coordination number of Au atoms in a series of environments. Binding energies, in eV, reported are referred to gas-phase CO and O2, for O2 the energies are given per O atom. The kink configuration falls outside the general trend as noted in Ref. [43]. (Bottom) The dependence of the binding energy of O atoms with the position of the d band of Au atoms in different environments.
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