Shape and Crystal-Plane Effects of Nanoscale Ceria on the Activity of Au-CeO2 Catalysts for the Water-Gas Shift ReactionGrant support from the DOE/BES-Hydrogen Fuel Initiative program (DE-FG02-05ER15730) and the NSF-NIRT program (grant 0304515) is gratefully acknowledged

The water–gas shift (WGS) reaction (CO+H2OQCO2+H2) plays an important role in fuel processing for polymer electrolyte membrane (PEM) fuel-cell applications. The hydrogen in the reformate gas is upgraded by removal of the carbon monoxide, which is a strong poison of the anode catalysts in current PEM fuel cells. Active shift catalysts that are also stable under the operating conditions of practical fuel-cell systems are under intense study, and nanostructured Au-CeO2, first reported by Fu et al. as a promising lowtemperature shift catalyst, holds a prominent position. This catalyst exploits the strong interaction of ceria with finely dispersed and stabilized gold atoms and clusters on the surface of ceria. Gold nanoparticles and clusters that interact strongly with oxide supports were first described by Haruta et al. to be extremely active CO oxidation catalysts. Numerous studies since then have reaffirmed the activity of well-dispersed gold for CO oxidation and many other reactions. While a full mechanism of this catalytic process still needs to be established, even for the simplest of these reactions (CO oxidation), a careful investigation of the reported strong metal–support interaction through structural studies may provide further mechanistic insights as well as rationalize the design of practical catalysts. For the WGS reaction on Au-CeO2, the importance of nanoscale ceria as a support that stabilizes active gold species has been demonstrated recently. Hydrolysis methods for the synthesis of ceria nanocrystals have proven to be powerful for controlling particle size and crystal shape. For example, Yan et al. have obtained single-crystalline CeO2 nanopolyhedra ({111} and {100}), nanorods ({110} and {100}), and nanocubes ({100}) by hydrolysis of cerium(III) salts, combined with a hydrothermal treatment, and have further found that oxygen storage takes place both at the surface and in the bulk for nanorods and nanocubes but is restricted to the surface for nanopolyhedra, just like its bulk ceria counterpart. Trovarelli et al. have studied the rearrangement of CeO2 crystallites under airaging and the exposure of more reactive {100} surfaces for CO oxidation. Very little is known for Au-CeO2 composite polycrystalline nanomaterials with respect to the shape/crystal plane effect of CeO2 on the gold species< activity/stabilization as highly active catalysts for the WGS reaction. Herein, we present activity correlations with the shape (rod, cube, polyhedron) and crystal plane of nanoscale ceria as a support for gold catalysts for this reaction. The interaction between deposited gold and different crystal orientations is investigated at ambient pressure andmonitored by several analytical techniques, including transmission electron microscopy (TEM), high-resolution TEM (HRTEM), X-ray photoelectron spectroscopy (XPS), and temperature-programmed reduction by hydrogen (H2-TPR). Figure 1 depicts our two-step preparation process, which includes hydrothermal synthesis of ceria nanorods, nano-