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

Abstract

This study investigates the effect of commonly used support materials (MgO, C, CeO2) on small gold particles using dispersion corrected density functional theory (DFT-D).

The influence of oxygen vacancy and Ce3+ ion positions on the properties of small gold clusters supported on CeO2−x(111)

“…36 It was shown that PBE-D3 is in good agreement with the vdW-DF optB88 for the structure of Au clusters. 24 The projector-augmented wave (PAW) formalism 32,37 implemented in VASP was employed to describe the core electrons. A plane-wave kinetic cut-off was set at 500 eV.…”

“…A Hubbard approach correction (DFT+U) using the method of Liechtenstein et al was used on the Ce 4forbitals. [39][40][41][42][43][44][45] The parameters were set to Ueff = 4 eV (U = 5 eV and J = 1 eV), which better reproduce the reduction of CeO2 as shown in our benchmarking calculations 24 and previous reports. 46,47 Dipole corrections were applied perpendicular to the surfaces upon adsorption of gold clusters.…”

“…As in our previous study, two different slab models of the CeO2-X(111) were used in this work. 24 A three-trilayered oxygenterminated slab (3×3×3) with 27 Ce and 53 O atoms (surface area = 116.5 Å 2 ) was chosen for clusters with up to four Au atoms. Larger clusters were calculated on a two-trilayered surface (6×6×2; surface area = 466.0 Å 2 ) with 72 Ce and 143 O atoms.…”

“…The structures of the supported gold clusters were based on those obtained in our previous study on stoichiometric CeO2. 24 We chose to investigate structures with 1, 2, 3, 7, 8, 10, and 11 Au atoms, which represent a cross-section through the previously investigated range of cluster sizes including odd-and even-numbered clusters. As we have noted, the structures we generate after adsorption on the surface may not be global minima, but they will still give us the insights needed on the effect of the vacancies on cluster geometry, electronic properties and reactivity.…”

“…[21][22][23] We recently performed a comparative study on the structural and electronic effects of different support materials, namely magnesium oxide (MgO), cerium (IV) oxide (CeO2) and graphene (C), on small Au clusters with particular focus on the interface mismatch. 24 We limited that study to defect-free surfaces to reduce the complexity of the investigated systems. While the most stable surface of MgO, i.e.…”