266559 Water-Gas Shift Catalysis Over Supported Gold Nanoparticles

Wednesday, October 31, 2012: 2:30 PM
319 (Convention Center )
Mayank Shekhar1, Jun Wang1, Wen-Sheng Lee1, M. Cem Akatay2, Wenjie Tang3, Matthew Neurock3, W. Nicholas Delgass1 and Fabio H. Ribeiro1, (1)School of Chemical Engineering, Purdue University, West Lafayette, IN, (2)School of Materials Engineering and Birck Nanotechnology Center, Purdue University, West Lafayette, IN, (3)Chemical Engineering, University of Virginia, Charlottesville, VA

The water-gas shift (WGS) reaction (CO + H2O → CO2 + H2) is an important industrial chemical process for hydrogen production. Our work focuses on determining the (1) active sites and (2) the effect of the support for supported Au nanoparticles.

The WGS reaction rate per total mole of Au varies with the average Au particle size (d) as ~ d-3 for Au/TiO2, Au/ZrO2, Au/CeO2, Au/ZnO, and Au/Al2O3 catalysts. The variations of reaction rate and apparent reaction orders with particle size were used to show that the active sites are low coordinated metallic corner and perimeter Au atoms. The addition of Br at a level of 16% of the surface moles of Au to a 2.3%Au/TiO2 catalyst decreased its WGS reaction rate by six times but did not result in an appreciable change in the average Au particle size, apparent activation energy, or the reaction orders. From operando Fourier transform infrared (FTIR) spectroscopy experiments, we found that the WGS reaction rate is proportional to the normalized peak area of CO adsorbed on metallic Au (IR peak at 2100 cm‑1). Corner Au atoms were counted as the active sites by transient isotopic switch experiments. Thus, it was confirmed that metallic corner Au atoms are the dominant active sites for Au/TiO2catalysts.

The WGS reaction rate per total mole of Au and H2O order (in parenthesis) vary as Au/Al2O3 (~ 0.6) < Au/CeO2 (~ 0.3) < Au/ZrO2 (~ 0.0) < Au/TiO2 (~ -0.3) at the same Au particle size at 120 °C. The CO, CO2 and H2 orders do not vary with the support. Density functional theory (DFT) results show that the H2O activation barrier on rutile sites adjacent to Au is lower than on corner sites of unsupported Au nanoparticles and clean rutile TiO2 (110) surface. We interpret these data to show that the support plays a direct role in activating H2O. Thus, the supported Au catalysts are bifunctional in nature, where CO activation occurs on Au and the H2O activation occurs on the support.

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