We report that alkali ions (sodium or potassium) added in small amounts activate platinum adsorbed on alumina or silica for the low-temperature water-gas shift (WGS) reaction (H(2)O + CO → H(2) + CO(2)) used for producing H(2). The alkali ion-associated surface OH groups are activated by CO at low temperatures (~100°C) in the presence of atomically dispersed platinum. Both experimental evidence and density functional theory calculations suggest that a partially oxidized Pt-alkali-O(x)(OH)(y) species is the active site for the low-temperature Pt-catalyzed WGS reaction. These findings are useful for the design of highly active and stable WGS catalysts that contain only trace amounts of a precious metal without the need for a reducible oxide support such as ceria.

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We compare the activity and relevant gold species of nanostructured gold-cerium oxide and gold-iron oxide catalysts for the CO oxidation by dioxygen and water. Well dispersed gold nanoparticles in reduced form provide the active sites for the CO oxidation reaction on both oxide supports. On the other hand, oxidized gold species, strongly bound on the support catalyze the water-gas shift reaction. Gold species weakly bound to ceria (doped with lanthana) or iron oxide can be removed by sodium cyanide at pH ‡12. Both parent and leached catalysts were investigated. The activity of the leached gold-iron oxide catalyst in CO oxidation is approximately two orders of magnitude lower than that of the parent material. However, after exposure to H 2 up to 400°C gold diffuses out and is in reduced form on the surface, a process accompanied by a dramatic enhancement of the CO oxidation activity. Similar results were found with the gold-ceria catalysts. On the other hand, pre-reduction of the calcined leached catalyst samples did not promote their water-gas shift activity. UV-Vis, XANES and XPS were used to probe the oxidation state of the catalysts after various treatments.

Combined in situ X-ray absorption near-edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) studies have been conducted to follow gold structural changes of low-content (<1%Au) gold-ceria catalysts in water-gas shift (WGS) reaction tests at 100 and 200 °C; and after heating the used catalysts in oxygen gas at 150 °C. Gold in the fresh (400 °C-calcined) material was atomically dispersed in cerium oxide. Under WGS reaction conditions, reduction of the oxidized gold species was observed, accompanied by gradual gold aggregation. The Au-Au coordination number is zero for the fresh material, but increases with the reaction temperature, to 6.5 ( 2.4 (after use at 100 °C) and to 8.7 ( 1.5 (after 200 °C) in a gas mixture containing 5% CO-3% H 2 O in helium. The second important parameter is the reaction gas composition which determines the extent of Au-O reduction. The lower the reduction potential of the reaction gas mixture, the more oxidized the gold is in the used catalyst, and the higher its activity. The maximum activity of Au-CeO 2 was that of the fully dispersed Au-O-Ce fresh material. Loss of surface oxygen took place during reaction, as measured by H 2 -TPR of the used samples, and it was commensurate with the activity loss. Attempts to reoxidize and redisperse the gold by heating in oxygen gas at 150 °C were not effective. However, we report here that complete recovery of the surface oxygen amount and redispersion of gold in ceria was possible after a 400 °Coxygen treatment of both the 100 °Cand 200 °Cused catalyst samples, with concomitant recovery of the initial catalyst activity. These tests were conducted by consecutive H 2 -TPR/steady-state catalyst activity measurements in the same microreactor.