TY - JOUR
T1 - Adsorption–desorption equilibrium investigations of n-butane on nanocrystalline sulfated zirconia thin films
AU - Lloyd, Rhys
AU - Hansen, Thomas Willum
AU - Ranke, Wolfgang
AU - Jentoft, Friederike C.
AU - Schlögl, Robert
PY - 2011
Y1 - 2011
N2 - Nanocrystalline thin films of the alkane skeletal isomerisation catalyst sulfated zirconia were successfully deposited on a silicon substrate in order to allow the application of surface science techniques. Thermal treatment of the films was optimised to chemically mimic the powder preparation process, resulting in films possessing the essential features (including tetragonal phase, nanocrystallinity and sulfur content of ∼3 at.%) of active powder catalysts. The n-butane adsorption–desorption equilibrium under isobaric conditions (10−8–10−6 h Pa) over the temperature range 300–100 K was monitored by photoelectron spectroscopy. Analysis of the isobars revealed strong and weak n-butane chemisorption sites, releasing heats of between 59–40 and 47–34 kJ/mol, corresponding to 5 and 25% of a monolayer coverage, respectively. The total amount of chemisorbed n-butane coincides with the estimated number of surface sulfate groups. An increase in adsorption heat was observed between coverages of ∼5–8% of a monolayer, indicating adsorbate–adsorbate interactions. It follows that adjacent sites are present and isomerisation by a bimolecular surface reaction is feasible. Physisorption on the films generates heats of ∼28 kJ/mol, for coverages from 30% up to a complete monolayer. Multilayer adsorption results in the formation of an electrically insulating adsorbate structure. It is proposed that the strong chemisorption sites correspond to an interaction with a minority disulfate species.
AB - Nanocrystalline thin films of the alkane skeletal isomerisation catalyst sulfated zirconia were successfully deposited on a silicon substrate in order to allow the application of surface science techniques. Thermal treatment of the films was optimised to chemically mimic the powder preparation process, resulting in films possessing the essential features (including tetragonal phase, nanocrystallinity and sulfur content of ∼3 at.%) of active powder catalysts. The n-butane adsorption–desorption equilibrium under isobaric conditions (10−8–10−6 h Pa) over the temperature range 300–100 K was monitored by photoelectron spectroscopy. Analysis of the isobars revealed strong and weak n-butane chemisorption sites, releasing heats of between 59–40 and 47–34 kJ/mol, corresponding to 5 and 25% of a monolayer coverage, respectively. The total amount of chemisorbed n-butane coincides with the estimated number of surface sulfate groups. An increase in adsorption heat was observed between coverages of ∼5–8% of a monolayer, indicating adsorbate–adsorbate interactions. It follows that adjacent sites are present and isomerisation by a bimolecular surface reaction is feasible. Physisorption on the films generates heats of ∼28 kJ/mol, for coverages from 30% up to a complete monolayer. Multilayer adsorption results in the formation of an electrically insulating adsorbate structure. It is proposed that the strong chemisorption sites correspond to an interaction with a minority disulfate species.
U2 - 10.1016/j.apcata.2010.06.028
DO - 10.1016/j.apcata.2010.06.028
M3 - Journal article
SN - 0926-860X
VL - 391
SP - 215
JO - Applied Catalysis A - General
JF - Applied Catalysis A - General
IS - 2-2
ER -