English
 
Help Privacy Policy Disclaimer
  Advanced SearchBrowse

Item

ITEM ACTIONSEXPORT

Released

Journal Article

Activation and Isomerization of n-Butane on Sulfated Zirconia Model Systems - An Integrated Study Across the Materials and Pressure Gaps

MPS-Authors
/persons/resource/persons21820

Lloyd,  Rhys
Inorganic Chemistry, Fritz Haber Institute, Max Planck Society;

/persons/resource/persons22257

Wrabetz,  Sabine
Inorganic Chemistry, Fritz Haber Institute, Max Planck Society;

/persons/resource/persons21673

Jentoft,  Friederike C.
Inorganic Chemistry, Fritz Haber Institute, Max Planck Society;

External Resource
No external resources are shared
Fulltext (restricted access)
There are currently no full texts shared for your IP range.
Fulltext (public)
Supplementary Material (public)
There is no public supplementary material available
Citation

Breitkopf, C., Papp, H., Li, X., Olindo, R., Lercher, J. A., Lloyd, R., et al. (2007). Activation and Isomerization of n-Butane on Sulfated Zirconia Model Systems - An Integrated Study Across the Materials and Pressure Gaps. Physical Chemistry Chemical Physics, 9(27), 3600-3618. doi:10.1039/b701854a.


Cite as: https://hdl.handle.net/11858/00-001M-0000-0011-021C-A
Abstract
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.