Size and support effects for the water-gas shift catalysis over gold nanoparticles supported on model Al2O3 and TiO2

J Am Chem Soc. 2012 Mar 14;134(10):4700-8. doi: 10.1021/ja210083d. Epub 2012 Feb 27.


The water-gas shift (WGS) reaction rate per total mole of Au under 7% CO, 8.5% CO(2), 22% H(2)O, and 37% H(2) at 1 atm for Au/Al(2)O(3) catalysts at 180 °C and Au/TiO(2) catalysts at 120 °C varies with the number average Au particle size (d) as d(-2.2±0.2) and d(-2.7±0.1), respectively. The use of nonporous and crystalline, model Al(2)O(3) and TiO(2) supports allowed the imaging of the active catalyst and enabled a precise determination of the Au particle size distribution and particle shape using transmission electron microscopy (TEM). Further, the apparent reaction orders and the stretching frequency of CO adsorbed on Au(0) (near 2100 cm(-1)) determined by diffuse reflectance infrared spectroscopy (DRIFTS) depend on d. Because of the changes in reaction rates, kinetics, and the CO stretching frequency with number average Au particle size, it is determined that the dominant active sites are the low coordinated corner Au sites, which are 3 and 7 times more active than the perimeter Au sites for Au/Al(2)O(3) and Au/TiO(2) catalysts, respectively, and 10 times more active for Au on TiO(2) versus Al(2)O(3). From operando Fourier transform infrared spectroscopy (FTIR) experiments, it is determined that the active Au sites are metallic in nature. In addition, Au/Al(2)O(3) catalysts have a higher apparent H(2)O order (0.63) and lower apparent activation energy (9 kJ mol(-1)) than Au/TiO(2) catalysts with apparent H(2)O order of -0.42 to -0.21 and activation energy of 45-60 kJ mol(-1) at near 120 °C. From these data, we conclude that the support directly participates by activating H(2)O molecules.