Investigation of alumina-supported Au catalyst for CO oxidation by isotopic transient analysis and X-ray absorption spectroscopy.
Alumina-supported Au particles (1.16 wt %) were prepared by a deposition-precipitation method involving a HAuCl4 precursor. X-ray absorption spectroscopy at the Au L(III) edge was used to monitor the evolution of the Au oxidation state and atomic structure during pretreatment in He up to 623 K. Although the as-prepared material had Au present in a +3 oxidation state, thermal treatment at 623 K facilitated autoreduction of Au cations to metal particles. Analysis of the EXAFS revealed a coordination number (Au-Au) of 7.2, which is consistent with spherical particles of 1.2 nm in average diameter. Steady-state isotopic transient kinetic analysis was used to evaluate the intrinsic turnover frequency (TOF intr) and the surface coverage of carbon-containing species (theta COx) on the gold catalyst during CO oxidation at 1.2 atm total pressure and 296 K. The artifacts in the kinetic parameters caused by re-adsorption of product carbon dioxide were removed by varying the total flow rate. The values of TOF intr and theta COx determined from the intrinsic lifetime of surface intermediates at infinite flow rate were 1.6 s(-1) and 4.9%, respectively. The intrinsic turnover frequency was nearly independent of temperature, indicating a very low activation energy for the reaction. However, the rate was significantly accelerated by the presence of water.
Calla
Jason T
JT
Department of Chemical Engineering, University of Virginia, Charlottesville, Virginia 22904-4741, USA.
Davis
Robert J
RJ