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

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

Acid-Base Catalyzed Activation of n-Alkanes: Isomerization of n-Butane

Due to its unique activity for skeletal isomerization of short alkanes at low temperature, sulfated zirconia (SZ) is generally recognized as the most promising alternative for the zeolite based hydroisomerization catalysts. However, despite the large amount of investigations, several important topics related to SZ are still discussed controversially. Here we report on our detailed investigation of the mechanism of butane skeletal isomerization on SZ. Typically, SZ had an induction period followed by a period of virtually constant activity. The selectivity to isobutene was higher than 96%, the byproducts being propane and pentanes. The induction period can be related to the formation and accumulation of reactive intermediates on the catalyst surface. We show that the alkane activation is initiated via stoichiometric oxidative dehydrogenation of butane by sulphate species to butane, water and SO2. For the first time, direct experimental evidence is given for all reaction products formed by oxidative dehydrogenation. In situ IR spectroscopy and density functional calculations indicate that pyrosulfate or re-adsorbed SO3 species are the active species for the oxidation. Butene formed interacts with Bronsted acid sites and forms sec-butoxy groups which isomerize mono-molecularly to tert-butoxy groups, as deduced from the 100% selectivity to isobutane at zero conversion. The tert-butoxy group undergoes hydride transfer from n-butane, forming a new sec-butoxy group and isobutane. The lower selectivity to isobutane with increasing conversion is explained by the higher isobutene concentration which triggers a bimolecular pathway. Note that isobutane is kinetically a primary product, while propane and pentanes are secondary products formed in sequential reactions. The larger amount of propane with respect to pentanes for conversion above 40% is attributed to multiple alkylation reactions followed by cracking. Transient experiments showed conclusively that the isomerization of the carbenium ion is the rate-determining step in the chain sequence and that hydride transfer is in quasi equilibrium. A kinetic model for butane isomerization under differential conditions is presented showing that the overall rate of butane conversion is proportional to the rate constant of the monomolecular isomerization of the carbenium ion, the concentration of Bronsted acid sites, the partial pressure of the alkane and the concentration of the labile sulfate-based redox sites. We show here that the key to successful catalysts for skeletal isomerization does not lie in high acid strength, but that a subtle balance between redox and acid sites is necessary

Statistical Mechanical Calculation of Anisotropic Step Stiffness of a Two-Dimensional Hexagonal Lattice Gas Model with Next-Nearest-Neighbor Interactions: Application to Si(111) Surface

We study a two-dimensional honeycomb lattice gas model with both nearest- and next-nearest-neighbor interactions in a staggered field, which describes the surface of stoichiometrically binary crystal. We calculate anisotropic step tension, step stiffness, and equilibrium island shape, by an extended random walk method. We apply the results to Si(111) 7$\times$7 reconstructed surface and high-temperature Si(111) 1$\times$1 surface. We also calculate inter-step interaction coefficient.Comment: revised on May 29 1999: RevTeX v3.1, 10 pages with 9 figures (one figure added

Effect Sizes in Experimental Pain Produced by Gender, Genetic Variants and Sensitization Procedures

Background: Various effects on pain have been reported with respect to their statistical significance, but a standardized measure of effect size has been rarely added. Such a measure would ease comparison of the magnitude of the effects across studies, for example the effect of gender on heat pain with the effect of a genetic variant on pressure pain. Methodology/Principal Findings: Effect sizes on pain thresholds to stimuli consisting of heat, cold, blunt pressure, punctuate pressure and electrical current, administered to 125 subjects, were analyzed for 29 common variants in eight human genes reportedly modulating pain, gender and sensitization procedures using capsaicin or menthol. The genotype explained 0–5.9% of the total interindividual variance in pain thresholds to various stimuli and produced mainly small effects (Cohen's d 0–1.8). The largest effect had the TRPA1 rs13255063T/rs11988795G haplotype explaining >5% of the variance in electrical pain thresholds and conferring lower pain sensitivity to homozygous carriers. Gender produced larger effect sizes than most variant alleles (1–14.8% explained variance, Cohen's d 0.2–0.8), with higher pain sensitivity in women than in men. Sensitization by capsaicin or menthol explained up to 63% of the total variance (4.7–62.8%) and produced largest effects according to Cohen's d (0.4–2.6), especially heat sensitization by capsaicin (Cohen's d = 2.6). Conclusions: Sensitization, gender and genetic variants produce effects on pain in the mentioned order of effect sizes. The present report may provide a basis for comparative discussions of factors influencing pain

Epitaxial fe/cu superlattices on Si(111)

We report on the successful epitaxial growth of Fe/Cu superlattices on Si( 111) wafers at room temperature. The superlattices were characterized with x-ray diffraction, conversion electron Mossbauer spectrometry, and selected area electron diffraction experiments. The epitaxial growth is crucially dependent on which element is deposited first on the bare Si( 111)