Oxide‐Supported Gold Clusters and Nanoparticles in Catalysis: A Computational Chemistry Perspective

Abstract

This review provides an insight into the simulation of gold nanoparticles supported on oxide surfaces, with particular emphasis on the applications in heterogeneous catalysis. Some important methodological issues are firstly addressed: the polymorphism of small gold clusters, the difficulty in determining the actual charge state of adsorbed gold atoms, the relevance of long‐range dispersion and relativistic effects and the size‐effects in modelling Au nanoparticles. Then, the adsorption of Au species on oxides is addressed by comparing bulk oxides to ultrathin oxide films supported on metals. The role of defects as nucleation centres is also discussed. Finally, this review addresses the contribution from computational studies on the mechanisms involving Au‐based heterogeneous catalysts in important reactions such as the CO oxidation, the water‐gas shift reaction and the CO2 hydrogenation to methanol.

The influence of support materials on the structural and electronic properties of gold nanoparticles – a DFT study

“…The transition between planar and three-dimensional Au clusters in the gas phase has been discussed controversially and is strongly dependent on the computational method. 133 DFT methods predict higher stability of planar Au n clusters over three-dimensional ones compared to correlated ab initio methods due to the lack of long-range interactions. Therefore, we recalculated the 2D-3D transition using literature-known structures 84, with our dispersion-corrected PBE-D3 method and compared it to plain PBE and the vdW-DF optB88 134 (see ESI ‡).…”

On the Real Nature of Rh Single‐Atom Catalysts Dispersed on the ZrO2 Surface

“…Heterogeneous catalysts often consists of highly dispersed precious metal clusters deposited on more or less inert oxide supports and are used in various catalytic reactions, from oxidation, [1,2,3] to water-gas shift, [4,5] and CO 2 activation, [6] just to mention a few. The chemical activity of these systems is due to the metal centers that are able to activate, and often break, chemical bonds at low energetic cost.…”

Pt8 cluster on alumina under a pressure of hydrogen: Support-dependent reconstruction from first-principles global optimization

“…In several of these processes, supported metal clusters and nanoparticles are used as catalysts, where the clusters/nanoparticles are the active components, and high surface area materials are used as supports. [1][2][3] Usual support materials are metal oxides, such as alumina or silica. Oxide supports are primarily used for stabilizing metal clusters, but extensive studies also show that the oxide can influence the catalytic properties of metal clusters 4 .…”