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The intermetallic compounds PdGa and Pd3Ga7 are introduced as selective catalysts for the hydrogenation of acetylene. Single phase PdGa and Pd3Ga7 can readily be prepared by the appropriate thermal treatment of the stoichiometric mixtures of the corresponding elements. The initial low surface areas of the as-prepared materials can be increased by careful mechanical treatment without decomposition. Detailed investigations of PdGa and Pd3Ga7 by DSC/TG, in situ powder X-ray diffraction and in situ X-ray absorption spectroscopy during thermal treatment under various inert or reactive gas atmospheres showed a high thermal stability. The long-range and short-range order in the crystal structures remained intact up to temperatures of about 600 K. Neither phase transitions nor decomposition were detectable. In addition to high thermal stability—preserving the active-site isolation under reaction conditions—no incorporation of hydrogen or carbon in the intermetallic compounds under reducing conditions was observed. Besides being interesting model systems, palladium–gallium intermetallic compounds are promising candidates for the application as highly selective hydrogenation catalysts.

Mn-promoted sulfated zirconia (0.5 or 2 wt% Mn) was investigated during activation (in inert or oxidizing atmosphere at 703–773 K), during n-butane isomerization (323–333 K, 1 kPa n-butane) and during regeneration (see activation conditions) using in situ UV–vis–NIR, diffuse reflectance IR, and X-ray absorption spectroscopies. While the activation atmosphere did not influence the degree of hydration and the state of the sulfate, manganese—which was always present as a mixture of Mn2+ and higher oxidation states—was slightly reduced in the absence of oxygen. Catalytic data did not give a clear picture as to whether activation in oxygen-containing atmosphere is advantageous or not. The catalysts deactivated within hours, but complete recovery in O2 was possible. Heating of a deactivated catalyst in N2 produced an inactive material and unsaturated compounds on the surface.

Two different sulfated zirconia catalysts were produced through precipitation from zirconyl nitrate solutions, followed by aging of the precipitate either at 298 K for 1 h (SZ-1) or 373 K for 24 h (SZ-2). After drying, the samples were sulfated with ammonium sulfate and calcined for 3 h at 873 K. SZ-1 had a smaller surface area (90 m2 g-1) than SZ-2 (140 m2 g-1) but displayed a one order of magnitude higher maximum n-butane isomerization rate (373–423 K, 1–5 kPa n-butane at 101.3 kPa total pressure). Both materials consisted predominantly of tetragonal ZrO2, contained 9 wt% of sulfate, and adsorbed about 0.5 mmol g-1 NH3. Measurements of adsorption isotherms and differential heats for propane and iso-butane at 313 K reveal a larger number of adsorption sites on SZ-1 than on SZ-2, extrapolated to 1 kPa, 42 vs. 20 µmol g-1 (propane) and 120 vs. 44 µmol g-1 (iso-butane). At coverages > 2 µmol g-1 the heats were similar for both samples with both probes and decreased from 60 to 40 kJ mol-1. Temporal analysis of products measurements indicated shorter residence times for n-butane than for iso-butane, and SZ-1 retained both of these molecules longer than SZ-2. The activation energy for n-butane desorption was 45 kJ mol-1 for both samples. Interaction with pulses of CO2 suggested that non-sulfated, basic ZrO2 surface is exposed on SZ-2, consistent with the larger surface area at the same sulfate content as SZ-1. The results suggest that only a fraction of the sulfate groups participates in adsorption and that product desorption may be of importance.

Report of preliminary XAS results on Cu/ZrO2 obtained at HASYLAB in 2001