Activity and stability of low-content gold–cerium oxide catalysts for the water–gas shift reaction

Abstract

We report here on the high activity and stability of low-content gold–cerium oxide catalysts for the water–gas shift reaction (WGS). These catalysts are reversible in cyclic reduction–oxidation treatment up to 400°C, are non-pyrophoric, and are thus potential candidates for application to hydrogen generation for fuel cell power production. Low-content (0.2–0.9at.%) gold–ceria samples were prepared by single-pot synthesis by the urea gelation/coprecipitation method; and by sodium cyanide leaching of high-content (2–8at.%) gold–ceria materials prepared by various techniques. The low-content gold–ceria catalysts are free of metallic gold nanoparticles. Gold is present in oxidized form, as verified by a variety of analytical techniques. However, these materials display the same WGS activity as the high-content gold ones, and remain free of gold nanoparticles after use in a reaction gas stream composed of 11% CO–26% H2O–26% H2–7% CO2–balance He up to 300°C. We show that the determining factor for the retention of active gold in ceria is the surface properties of the latter. Measurements of lattice constant expansion indicate gold ion substitution in the ceria lattice. The turnover frequency of WGS under the assumption of fully dispersed gold is the same for a variety of low-content gold–ceria preparations. The stability of gold–ceria in various gas compositions and temperatures was good. The most serious stability issue is formation of cerium hydroxycarbonate in shutdown operation.