No abstract

We study catalyst-support and catalyst-carbon interactions during the chemical vapor deposition of singlewalled carbon nanotubes by combining environmental transmission microscopy and in situ, time-resolved X-ray photoelectron spectroscopy. We present direct evidence of what constitutes catalyst functionality by comparing the behavior of Ni, Fe, Pd, and Au model catalyst films on SiO 2 during preannealing in O 2 and NH 3 and during C 2 H 2 decomposition. The catalyst metal surface supplies sites to dissociate the hydrocarbon precursor and then guides the formation of a carbon lattice and the liftoff of a carbon cap. The catalysts are sharply distinguished by their reactivity toward activation of the hydrocarbon precursor, following trends known from heterogeneous catalysis. For Fe and Ni, the active state of the catalyst is a crystalline metallic nanoparticle. Graphitic networks do not form on oxidized Fe. Pd forms a silicide on SiO 2 under our reducing conditions. Pd (silicides) and Au nanocrystals are catalytically less efficient in terms of precursor dissociation, while the low adhesion of C on Au surfaces impedes nanotube nucleation.

Effects of framework and near surface composition of quinternary, phase-pure M1 MoVTeNb oxide catalysts on their catalytic performance in selective oxidation of propane to acrylic acid have been studied. The catalysts were prepared by hydrothermal synthesis, spray-drying, and superheated water vapor treatment. Electron microscopy, chemical analysis, nitrogen physisorption, and in situ photoelectron spectroscopy have been used to characterize the materials. The yield of acrylic acid normalized to the specific surface area of the catalyst increases with decreasing percentage of Mo and increasing molar ratio of Te/V at the surface. The metal stoichiometry at the surface differs from the stoichiometry in the crystalline bulk and changes in response to the composition of the gas phase. In situ valence band spectroscopy at 623 K in the presence of all reactants revealed a substantial covalent character of the metal−oxygen bonds in M1. The surface restructuring under formation of V- and Te-containing clusters anchored on crystalline, semiconducting M1 is, therefore, considered to establish structurally and electronically isolated active sites. The mobility of Te especially in the presence of water vapor may contribute to the development of site isolation under reaction conditions and to the enhanced selectivity to acrylic acid in the presence of steam in the feed

One of the prerequisites for the detailed understanding of heterogeneous catalysis is the identification of the dynamic response of the catalyst surface under variable reaction conditions. The present study of methanol oxidation on different model Ru pre-catalysts, performed approaching the realistic catalytic reaction conditions, provides direct evidence of the significant effect of reactants' chemical potentials and temperature on the catalyst surface composition and the corresponding catalytic activity and selectivity. The experiments were carried out for three regimes of oxygen potentials in the 10(-1) mbar pressure range, combining in situ analysis of the catalyst surface by synchrotron-based photoelectron core level spectroscopy with simultaneous monitoring of the products released in the gas phase by mass spectroscopy. Metallic Ru with adsorbed oxygen and transient 'surface oxide', RuO(x), with varying x have been identified as the catalytically active states under specific reaction conditions, favouring partial or full oxidation pathways. It has been shown that the composition of catalytically active steady states, exhibiting different activity and selectivity, evolves under the reaction conditions, independent of the crystallographic orientation and the initial pre-catalyst chemical state, metallic Ru or RuO(2).