Water-gas shift reaction over supported Au nanoparticles

[Display omitted] •Reaction orders and rates for the water-gas shift reaction on Au catalysts as a function of Au particle size and support.•DFT calculations performed on the catalyst with the lowest (alumina) and highest (titania) rates allowed us to understand the catalytic role that the support plays in activating water.•Non-porous, high surface area supports have permitted preparation of samples with tight Au particle distributions fully accessible by TEM.•Full reaction kinetics presented to understand the relation between the chemical and physical characteristics of the catalysts and their performance.•DFT calculations to examine the adsorption and reaction of CO, water and relevant intermediates over a range of different sites on model unsupported cubo-octahedral Au clusters (Au55) as well as on model Au nano-rods supported on rutile TiO2(110) and α-Al2O3(0001) surfaces. The water–gas shift (WGS) reaction rates per total mole of Au at 120 °C, 7% CO, 22% H2O, 8.5% CO2, 37% H2 decrease in the order Au/Anatase ∼ Au/Anatase001 (uniform anatase TiO2 single crystals with 64 per cent of the more {001} facets) ∼ Au/P25 ∼ Au/P25-WGC (obtained from the World Gold Council) ∼ Au/Rutile > Au/ZrO2 > Au/CeO2 > Au/ZnO when compared at the same number average Au particle size (d) and vary as ∼ d-3. From high resolution transmission electron microscopy images, the geometry of Au nanoparticles on these catalysts resembled truncated cubo-octahedra. A physical model of Au nanoparticles as truncated cubo-octahedra was used to calculate that the fractions of surface, perimeter and corner sites to the total Au sites vary as d-0.7, d-1.8 and d-2.9, respectively. Thus, the variation in the WGS reaction rate per total mole of Au (∼d-3) correlates well with the corner sites (d-2.9) allowing us to determine that the dominant active sites for these catalysts are the low coordinated metallic corner Au sites. In addition, as the apparent H2O order increases and the apparent activation energy decreases, the WGS reaction rate per total mole of Au systematically decreases for Au nanoparticles supported on anatase, anatase001, P25, rutile, ZrO2, CeO2, ZnO and Al2O3 at near 120 °C. Density functional theory calculations were carried out over Au nano-rods supported on rutile TiO2(100) and α-Al2O3(0001) surfaces to elucidate the differences in reactivity for the most reactive (Au/TiO2) and least reactive (Au/Al2O3) catalysts. Water preferentially adsorbs and dissociates at the Lewis acid-