Two oxygen species, which are constituents of the active centers for ethylene epoxidation over silver, have been characterized by a number of physical methods sensitive to adsorbate electronic structure such as XPS, UPS, Auger and XANES spectroscopy. One of the species denoted as nucleophilic oxygen due to its activity in total oxidation only exhibits spectroscopic characteristics close to those of bulk Ag2O. This allows us to describe this species as atomically adsorbed oxygen in the structure of surface silver (I) oxide. Considerable extent of the covalency in bonding of this oxide-like oxygen with silver surface due to hybridization of O2p levels with Ag4d and Ag5sp orbitals should be also emphasized. Contrary to this only 5sp orbitals of silver hybridize with 2p levels of oxygen as the other oxygen species forms. As consequence, this species being also atomic oxygen is characterized by a lower oxygen-silver bonding interaction and lower charge on the oxygen. The latter causes the activity of this electrophilic species in epoxidation. Possible models of adsorption centers for these oxygen species are discussed.
A new preparative route for vanadium phosphate catalysts is described using supercritical CO2 as an antisolvent. The amorphous microspheroidal VPO produced is shown to be more active than comparable crystalline VPO catalysts for the selective oxidation of n-butane to maleic anhydride and, furthermore, does not require an extensive pre-treatment or activation period to establish full catalytic activity. VPO catalysts prepared using supercritical CO2 as an antisolvent maintain their amorphous nature throughout the catalyst test period. In contrast, amorphous VPO catalysts can also be prepared using liquid CO2 as antisolvent, or by solvent evaporation in vacuo, however, these materials are found to partially crystallise during the oxidation of n-butane. The wholly amorphous catalysts are characterised using transmission electron microscopy, X-ray absorption spectroscopy, 31 P spin echo mapping NMR spectroscopy and X-ray photoelectron spectroscopy. The role of amorphous material in vanadium phosphate catalysis is discussed in detail.
In-situ soft X-ray absorption spectroscopy (XAS) has been applied to study the iron redox behavior in overexchanged Fe/ZSM5. The Fe L 2,3 XAS and O K spectral shapes of the Fe/ZSM5 surface have been measured during heat treatments and reduction/oxidation cycles. Charge-transfer multiplet calculations provide a detailed understanding of the L 2,3 spectra of iron in Fe/ZSM5. The oxidized form of Fe/ZSM5 contains Fe III ions in an octahedral surrounding, with a total crystal field splitting of ∼1.0 eV. This value is significantly smaller than that for Fe 2 O 3 , which is indicative of a much weaker Fe-O bonding. The reduced form of Fe/ZSM5 has Fe II ions in a tetrahedral oxygen surrounding. The Fe L 2,3 spectra show that iron in calcined Fe/ZSM5 is reduced in 15 min to an average valence state of 2.65, under 10 mbar of pure helium at room temperature. This value has a relative uncertainty on the order of 0.01. Heating in helium up to 350°C under the same pressure further reduces the iron valence to 2.15. The oxygen spectra show that the autoreduction is accompanied by a loss of molecular oxygen and water. Reoxidation with 5% O 2 in helium yields a valence of >2.90 after 10 min.
In situ X-ray absorption spectroscopy (XAS) and in situ X-ray photoelectron spectroscopy (XPS) have been
applied to study the active surface of vanadium phosphorus oxide (VPO) catalysts in the course of the oxidation
of n-butane to maleic anhydride (MA). The V L3 near edge X-ray absorption fine structure (NEXAFS) of
VPO is related to the details of the bonding between the central vanadium atom and the surrounding oxygen
atoms. Reversible changes of the NEXAFS were observed when going from room temperature to the reaction
conditions. These changes are interpreted as dynamic rearrangements of the VPO surface, and the structural
rearrangements are related to the catalytic activity of the material that was verified by proton-transfer reaction
mass spectrometry (PTR-MS). The physical origin of the variation of the NEXAFS is discussed and a tentative
assignment to specific V−O bonds in the VPO structure is given. In situ XPS investigations were used to
elucidate the surface electronic conductivity and to probe the ground state of the NEXAFS spectra.
The oxidation of ammonia over polycrystalline copper was investigated by means of in situ NEXAFS (near edge X-ray absorption fine structure) spectroscopy in the soft X-ray ra nge. The reaction, carried out in a 1:12 excess of oxygen, was observed by mass spectrometry. The simultaneous detection of the surface electronic structure and its catalytic performance allows to correlate different reaction products to the current surfac e structure of the catalyst. It is shown that a change in total pressure from 0.4 mbar to 1.2 mbar severely affects the reaction path. Copper (I) nitride was identified as poison and a copper oxide was found to be the active phase for the selective oxidation of ammonia to nitrogen.
We present the V L3 near edge X-ray absorption fine structure (NEXAFS) of a vanadium phosphorus oxide (VPO) catalyst. The spe ctrum is related to the V3d-O2p hybridised unoccupied states. The overall peak position at the V L3-absorption edge is determined by the formal oxidation state of the absorbing vanadium atom. Details of the absorption fine structure are influenced by the geometric structure of the compound. Empirically we found a linear relationship between the energy position of several absorption resonances and the V -O bond length of the participating atoms. This allows to identify the contribution of specific V-O bonds to the near edge X-ray absorption fine structure. The bond length / resonance position relationship will be discussed under consideration of relations between geometric structure and NEXAFS features observed in X-ray absorption experiments and theory.
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