The interaction of water with ZnO nanoparticles has been studied by means of diffuse reflectance infrared spectroscopy (DRIFTS) and ultra-high vacuum FTIR spectroscopy (UHV-FTIRS). Exposing clean ZnO powder to water at 323 K leads to both molecular and dissociative adsorption of H2O forming a number of hydroxyl species. All the OH bands are clearly identified by the adsorption of D2O showing the expected isotopic shifts. According to the vibrational and thermal stability data obtained from single crystal surfaces, the OH species observed on ZnO nanoparticles are identified as follows: (1) OH group (3620 cm(-1)) on the polar O-ZnO(0001[combining macron]) surface formed via dissociation of water on oxygen vacancy sites; (2) partial dissociation of water on the mixed-terminated ZnO(101[combining macron]0) surface yielding coexistent H2O ( approximately 3150 and 3687 cm(-1)) and OH species (3672 cm(-1)), where the molecularly adsorbed H2O is further identified by the characteristic scissoring mode at 1617 cm(-1); (3) isolated OH species (3639 and 3656 cm(-1)) formed on the mixed-terminated ZnO(101[combining macron]0) surface; (4) interaction of water with defects forming hydroxyl (or O-HO) species (3564 and 3448 cm(-1)).
The oxidation of CO over Ru/MgO and Ru/SiO2 catalysts was used as a simple model reaction to derive
turnover frequencies at atmospheric pressure, which were observed to agree with kinetic data obtained under
high-vacuum conditions with supported ruthenium catalysts and the RuO2(110) single-crystal surface. Thus,
it was possible to bridge both the pressure and the materials gap. However, a partial deactivation was observed
initially, which was identified as an activated process, both under net reducing and net oxidizing conditions.
Temperature-programmed reduction (TPR) experiments were performed subsequently in the same reactor, to
monitor the degree of oxidation, as a function of the reaction temperature and the CO/O2 reactant feed ratio.
Using in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) measurements, the structural
changes of the ruthenium catalysts during the oxidation of CO were confirmed, under relevant reaction
conditions. Under net reducing conditions, only domains of RuO2 seem to exist on the metallic ruthenium
particles, whereas, under net oxidizing conditions, the ruthenium particles were fully oxidized to bulk RuO2
particles, which may expose less-active facets, such as the RuO2(100)−c(2 × 2) surface.
A systematic series of binary and ternary copper catalysts was investigated using the methanol synthesis reaction at atmospheric pressure. Strong metal-support interactions between copper and zinc oxide induced by strongly reducing conditions were probed by the adsorption of carbon monoxide, which was monitored qualitatively and quantitatively by a combination of microcalorimetry, temperature-programmed desorption experiments and Fourier transform infrared spectroscopy. For the zinc oxide-containing catalysts, the pretreatment in flowing carbon monoxide at 493 K resulted in a severe decoration of the copper metal particles with ZnOx adspecies, whereas after methanol synthesis at 493 K the state of the copper was essentially identical to that seen after hydrogen reduction. Copper was always found to be present in its zero-valent state.
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