On highly active partially oxidized platinum in carbon monoxide oxidation over supported platinum catalysts

• Published in: Journal of catalysis Vol. 263; no. 2; pp. 228 - 238
• Main Authors: Alayon, E.M.C., Singh, J., Nachtegaal, M., Harfouche, M., van Bokhoven, J.A.
• Format: Journal Article
• Language: English
• Published: Amsterdam Elsevier Inc 25.04.2009; Elsevier; Elsevier BV
• Subjects: Active phase; Analytical chemistry; Carbon monoxide; Carbon monoxide oxidation; Catalysis; Catalysts; Chemistry; Exact sciences and technology; General and physical chemistry; In situ XAS; Oxidation; Platinum; Supported platinum catalysts; Theory of reactions, general kinetics. Catalysis. Nomenclature, chemical documentation, computer chemistry; Carbon monoxide oxidation; Active phase; Supported platinum catalysts; In situ XAS; Binary compound; Bond length; In situ; Ignition; High temperature; Silica; Supported catalyst; Particle; Dynamics; Platinum; Defect; Oxidation; Carbon monoxide; Structure; Low temperature; Platinum oxide; Oxygen; Extinction; Transition element compounds; Transition metal; Heterogeneous catalysis; Silicon oxides; Gas phase; Titanium oxide; Catalyst activity; Alumina; X ray absorption
• ISSN: 0021-9517; 1090-2694
• DOI: 10.1016/j.jcat.2009.02.010

In situ X-ray absorption spectroscopy identified the role of oxidized platinum species in generating a high-activity state in the oxidation of carbon monoxide over Pt/Al 2O 3, Pt/TiO 2 and Pt/SiO 2. Two activity regimes were identified: low-activity at high carbon monoxide concentration and low temperature, and high activity at low carbon monoxide concentration and high temperature. The change between the two regimes occurred suddenly; there was ignition when going from low to high activity, and extinction from high to low activity. Ignition only occurred when the concentration of oxygen was higher than that of carbon monoxide. The catalyst was metallic and covered with carbon monoxide at low activity and partially oxidic at high activity. Carbon monoxide poisoned the catalyst at low activity. The partially oxidized platinum catalysts showed high activity. The partially oxidized catalyst had a lower oxygen coordination number and shorter Pt–O bond length as expected for bulk PtO 2, suggesting that a strongly defected platinum oxide was formed with a possibly square planar coordination. The catalyst structure showed a dynamic behavior and the amount of oxide depended on the concentration of reactants in the gas phase. Smaller particles of Pt/Al 2O 3 reached high activity at lower temperature than the larger particles. Pt/TiO 2 reached high activity at the lowest temperature while Pt/SiO 2 required the highest temperature. Parallel with the temperature of ignition, Pt/SiO 2 was the most oxidized while Pt/TiO 2 was the least oxidized. In situ XAS identified surface-oxidized platinum as the active species at high activity during carbon monoxide oxidation over supported platinum catalysts. At low activity, the platinum catalysts were metallic and poisoned by carbon monoxide.