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| ID:
315346.0,
Fritz-Haber-Institut / Inorganic Chemistry |
| Activation and Isomerization of n-Butane on Sulfated Zirconia Model Systems - An Integrated Study Across the Materials and Pressure Gaps |
| Authors: | Breitkopf, Cornelia; Papp, Helmut; Li, Xuebing; Olindo, Roberta; Lercher, Johannes A.; Lloyd, Rhys; Wrabetz, Sabine; Jentoft, Friederike C.; Meinel, Klaus; Förster, Stefan; Schindler, Karl-Michael; Neddermeyer, Henning; Widdra, Wolf; Hofmann, Alexander; Sauer, Joachim | | Language: | English | | Research Context: | Project 1: Acid-base & redox properties of promoted sulfated zirconia, Project 3: Zirconium oxide model systems | | Date of Publication (YYYY-MM-DD): | 2007 | | Title of Journal: | Physical Chemistry Chemical Physics | | Journal Abbrev.: | Phys. Chem. Chem. Phys. | | Volume: | 9 | | Start Page: | 3600 | | End Page: | 3618 | | Review Status: | Peer-review | | Audience: | Experts Only | | Intended Educational Use: | No | | Abstract / Description: | Butane activation has been studied using three types of sulfated zirconia materials, single-crystalline epitaxial films, nanocrystalline films, and powders. A surface phase diagram of zirconia in interaction with SO3 and water was established by DFT calculations which was verified by LEED investigations on single-crystalline films and by IR spectroscopy on powders. At high sulfate surface densities a pyrosulfate species is the prevailing structure in the dehydrated state; if such species are absent, the materials are inactive. Theory and experiment show that the pyrosulfate can react with butane to give butene, H2O and SO2, hence butane can be activated via oxidative dehydrogenation. This reaction occurred on all investigated materials; however, isomerization could only be proven for powders. Transient and equilibrium adsorption measurements in a wide pressure and temperature range (isobars measured via UPS on nanocrystalline films, microcalorimetry and temporal analysis of products measurements on powders) show weak and reversible interaction of butane with a majority of sites but reactive interaction with < 5 µmol/g sites. Consistently, the catalysts could be poisoned by adding sodium to the surface in a ratio S/Na=35. Future research will have to clarify what distinguishes these few sites. | | External Publication Status: | published | | Document Type: | Article |
| Communicated by: | Robert Schlögl | | Affiliations: | Fritz-Haber-Institut/Inorganic Chemistry/Functional Characterization
| | External Affiliations: | Universität Leipzig, Instititut für Technische Chemie,
Linnestraße 3, 04103 Leipzig, Germany
Technische Universität München, Lehrstuhl für Technische Chemie II, Lichtenbergstraße 4, 85747 Garching, Germany
Martin-Luther-University Halle-Wittenberg, Institute of Physics, Hoher Weg 8, 06099 Halle, Germany
Institut für Chemie, Humboldt-Universität zu Berlin,
Unter den Linden 6, D-10099 Berlin, Germany
| | Identifiers: | URL:http://dx.doi.org/10.1039/b701854a |
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