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Oxidation of Propylene over Pd(5 5 1): Temperature Hysteresis Induced by Carbon Deposition and Oxygen Adsorption Full article

Journal Catalysis Today
ISSN: 0920-5861 , E-ISSN: 1873-4308
Output data Year: 2015, Volume: 244, Pages: 29-35 Pages count : 7 DOI: 10.1016/j.cattod.2014.08.023
Tags Heterogeneous catalysis, Palladium, Propylene oxidation, Temperature hysteresis
Authors Matveev Andrey V. 1 , Kaichev Vasily V. 1,2 , Saraev Andrey A. 1 , Gorodetskii Vladimir V. 1 , Knop-Gericke Axel 3 , Bukhtiyarov Valerii I. 1,2 , Nieuwenhuys Bernard E. 4
Affiliations
1 Boreskov Institute of Catalysis of the Siberian Branch of the Russian Academy of Sciences, Pr. Acad. Lavrentieva 5, 630090 Novosibirsk, Russia
2 Novosibirsk State University, Pirogova Str. 2, 630090 Novosibirsk, Russia
3 Department of Inorganic Chemistry, Fritz Haber Institute of the Max Plank Society, Faradayweg 4-6, D-14195 Berlin, Germany
4 Leiden Institute of Chemistry, Leiden University, P.O. Box 9502, Einsteinweg 55, 2333 CC Leiden, The Netherlands

Funding (2)

1 Russian Foundation for Basic Research 12-03-00766
2 The Ministry of Education and Science of the Russian Federation

Abstract: The oxidation of propylene over a Pd(5 5 1) single crystal surface has been studied by X-ray photoelectron spectroscopy (XPS) and temperature-programmed reaction spectroscopy during both heating and cooling in various oxygen/propylene mixtures. In all the experiments, the partial pressure of propylene was approximately 1 × 10−7 mbar and the partial pressure of oxygen was varied to achieve molar oxygen/propylene ratios of 1, 3, 10, and 100. Under all these conditions, we observed a temperature hysteresis: temperature dependences of the catalyst activity and product distribution were different during heating and cooling. It was shown that the temperature hysteresis was due to concurrent accumulation of carbon and oxygen atoms on the palladium surface. At low temperatures, a high concentration of carbonaceous deposits detected by XPS resulted in a low catalytic activity due to blocking of the palladium surface. Increasing temperature led to full dehydrogenation of the carbonaceous species and dissolution of carbon atoms into subsurface palladium layers. As a result, even under oxygen-rich conditions, the formation of a PdCx phase was detected by XPS at 373 K. This process had no influence on the selectivity in the oxidation of propylene at least under UHV conditions. A shift of selectivity toward CO2 was found to result from an increase in the oxygen concentration on the palladium surface. The state with a low catalytic activity in the oxidation of propylene was associated with palladium in the metallic state covered by carbon deposits. The high-active state of palladium was associated with palladium in the metallic state with a high concentration of chemisorbed oxygen and a moderate concentration of a surface oxide. Bulk PdO was not detected by XPS under all conditions used.
Cite: Matveev A.V. , Kaichev V.V. , Saraev A.A. , Gorodetskii V.V. , Knop-Gericke A. , Bukhtiyarov V.I. , Nieuwenhuys B.E.
Oxidation of Propylene over Pd(5 5 1): Temperature Hysteresis Induced by Carbon Deposition and Oxygen Adsorption
Catalysis Today. 2015. V.244. P.29-35. DOI: 10.1016/j.cattod.2014.08.023 WOS Scopus РИНЦ ANCAN OpenAlex
Files: Full text from publisher
Dates:
Submitted: Mar 31, 2014
Accepted: Aug 19, 2014
Published online: Sep 12, 2014
Published print: Apr 1, 2015
Identifiers:
Web of science: WOS:000349088000005
Scopus: 2-s2.0-84922879246
Elibrary: 24008328
Chemical Abstracts: 2014:1510748
Chemical Abstracts (print): 162:286988
OpenAlex: W2022352502
Citing:
DB Citing
Web of science 33
Scopus 35
OpenAlex 35
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