(583b) Determination of the Active Site for Nanoparticle Gold Water-Gas Shift Catalysts Using a Model Support

Authors: 
Williams, W. D., Purdue University
Shekhar, M., Purdue University
Lee, W., Purdue University
Kispersky, V., Purdue University
Wang, J., Purdue University
Delgass, W. N., Purdue University
Ribeiro, F. H., Purdue University
Kim, S. M., Purdue University
Stach, E. A., Purdue University
Miller, J. T., Argonne National Laboratory
Allard, Jr., L. F., Oak Ridge National Laboratory


The rate per mole of
gold for the water-gas shift (WGS) reaction was measured for a series of gold
catalysts supported on model rutile TiO2.  The use of a model support provides an enhanced ability in
resolving supported gold nanoclusters using Transmission Electron Microscopy
(TEM).  A physical model of the gold
clusters as truncated cubo-octahedra was used to determine the fraction of
atoms in a gold cluster that have a specific number of gold neighbors.  The rate of each sample was then obtained by
assuming a constant rate per active site on each cluster imaged by TEM and
obtaining a value for the constant rate to best fit the experimental data.  Results indicate that the number of active
sites on each cluster is constant irrespective of the gold nanocluster size in
the range of samples studied.  DRIFTS
and transmission FTIR experiments were used to show how different surface
intermediates are related to the WGS rate under in situ conditions and during
isotope switching experiments.  The rate
on a Au/TiO2 catalyst with a 1.2 nm average particle size (1.4x10-1
s-1) is two orders of
magnitude higher than the rate on an industrial Cu/ZnO/Al2O3
catalyst (5x10-4s-1) (moles CO reacted per surface mole of Au or Cu at 120oC,
6.8% CO, 21.9% H2O, 8.5% CO2, 37.4% H2, and
balance Ar) further emphasizing the potential practical and scientific interest
of nanogold WGS catalysts.

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