We addressed the interaction of oxygen with silver by synchrotron based near ambient pressure X-ray photoelectron spectroscopy at temperatures relevant for industrial oxidation reactions performed with silver catalysts. For silver single crystals, polycrystalline foils and powders in equilibrium with gas phase O 2 , we observed the dynamics of the formation of five different atomic oxygen species with relative abundances depending on the temperature and time. Correlation of their formation kinetics with spectroscopic features and thermal stability indicates that these are distinct species with different electronic structures, which might relate to the different roles of silver in oxidation reactions.
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.
In this study we combine density-functional theory (DFT) calculations on oxygen core excitations in vanadia-silica model clusters with experimental in situ X-ray absorption fine structure (NEXAFS) near the oxygen K edge of vanadia model catalysts supported by SBA-15 silica in order to identify structural details of the vanadia species. The silica support is found to contribute to the NEXAFS spectrum in an energy range well above that of the vanadium oxide units allowing a clear separation between the corresponding contributions. Further, differently coordinated oxygen which is characteristic for particular vanadia species, monomeric or polymeric, can be clearly identified in the theoretical spectra in agreement with the oxygen K-edge NEXAFS measurements. The comparison of the theoretical and experimental NEXAFS spectra provides clear evidence that under in situ conditions different molecular vanadia species, in particular polymeric VO x , exist at the catalyst surface and the exclusive presence of monomeric vanadia groups can be clearly ruled out. The present analysis goes beyond earlier work applying vibrational spectroscopy to the present systems where, as a result of extended vibrational coupling, a separation between vanadia, silica, and interface contributions is less successful.
The structure and magnetic properties of CuCo alloys electrodeposited in aqueous solution on n-type Si(100) substrates were investigated as a function of the trisodium citrate concentration in the electrolyte. The compositional analysis show that percentage of Co has a non-monotonic dependence on the increase in concentration of sodium citrate, with a maximum at 300 mM followed by a significant decrease The magnetic measurements in similar samples in terms of composition and thickness show that the coercive field value it differs greatly, from 87 to 20 Oe without and with added citrate, respectivelly, owing to the improved morphological quality and change in crystalline structure induced by the citrate. For electrodeposited films without citrate in the electrolyte, the X-ray diffraction pattern shows two peaks at 2h = 43.298 and 44.217 typical of fcc (111) planes for copper and cobalt, respectively, while in the presence of citrate only one peak characteristic of fcc of the CuCo alloy was observed.
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