Water-gas shift: comparative screening of metal promoters for metal/ceria systems and role of the metal Original Research Article

In situ diffuse reflectance mode (DRIFTS) measurements for adsorption of CO and under the water-gas shift (WGS) reaction revealed that formates emerge on the surface of reduced ceria after the reaction of CO with geminal OH groups. These groups are formed after reduction of the ceria surface shell. X-ray absorption near edge spectroscopy (XANES) results demonstrated that the process of surface shell reduction was strongly catalyzed by the presence of metal, while changing very little, if at all, the catalysis of bulk ceria reduction. For 1% Pt/ceria, under steady state WGS at a high H2O/CO ratio, surface formate concentrations were strongly limited at high CO conversions, while Pt-CO was affected only slightly. Under high H2O/CO ratios, CO exhibits a first order rate dependency, and therefore, the active site is expected to move to sparser coverages of CO, which suggested that the WGS mechanism likely proceeded via formates. Later, XANES work gave no evidence for the reoxidation of ceria surface by water under a hydrogen environment, which would be necessary to substantiate an alternate mechanism, referred to as the ceria-mediated redox process. Later, isotope switching from H2O to D2O was carried out to validate the possibility that decomposition of surface formates could be the rate limiting step for the mechanism, as was proposed and demonstrated earlier by Shido and Iwasawa. In agreement with their findings, we also observed a normal isotope effect, consistent with a link between the activation energy barrier of the rate limiting step to the breaking of the CH bond of the formate.