Oxidative activation electronic structure

The turnover frequency (TOP) based on surface-exposed atoms significantly increases with a decrease in the diameter of the gold particle from 5 nm [66]. This feature is unique to gold, because other noble metals usually show TOFs that decrease or remain the same with a decrease in the diameter [7]. The decrease in particle size gives rise to an increase in corner or edge and perimeter of NPs and change in electronic structure however, the origin of size effects on catalytic activity for CO oxidation is not clear. 

The different classes of Ru-based catalysts, including crystalline Chevrel-phase chalcogenides, nanostructured Ru, and Ru-Se clusters, and also Ru-N chelate compounds (RuNj), have been reviewed recently by Lee and Popov [29] in terms of the activity and selectivity toward the four-electron oxygen reduction to water. The conclusion was drawn that selenium is a critical element controlling the catalytic properties of Ru clusters as it directly modifies the electronic structure of the catalytic reaction center and increases the resistance to electrochemical oxidation of interfacial Ru atoms in acidic environments. 

Recent studies [193] of the CO oxidation activity exhibited by highly dispersed nano-gold (Au) catalysts have reached the following conclusions (a) bilayer structures of Au are critical (b) a strong interaction between Au and the support leads to wetting and electron rich Au (c) oxidative environments deactivate Au catalyst by re-ox-idizing the support, which causes the Au to de-wet and sinter. Recent results have shown that the direct intervention of the support is not necessary to facilitate the CO oxidation reaction therefore, an Au-only mechanism is sufficient to explain the reaction kinetics. 

PEMFC)/direct methanol fuel cell (DMFC) cathode limit the available sites for reduction of molecular oxygen. Alternatively, at the anode of a PEMFC or DMFC, the oxidation of water is necessary to produce hydroxyl or oxygen species that participate in oxidation of strongly bound carbon monoxide species. Taylor and co-workers [Taylor et ah, 2007b] have recently reported on a systematic study that examined the potential dependence of water redox reactions over a series of different metal electrode surfaces. For comparison purposes, we will start with a brief discussion of electronic structure studies of water activity with consideration of UHV model systems. 

In contrast, for the NO8- species the N—O bond is elongated, only slightly polarized, and the stretching frequency, vNO, decreases below 1850 cm-1. Such changes indicate that the activation consists in redistribution of the electron and spin densities within the M—NO unit, which accumulates on the nitrogen atom. Among the first series TMI, the oxidative adsorption is less common and includes only the tj1 CuNO] 11 and 171 3CrNO 6 adducts. The mechanistic implications of the electronic structures for both type of the nitrosyl complexes are discussed in the next section. 

Table VIII records the Arrhenius parameters and the activity of four alloy films and the two pure metals the results are insufficient to provide a neat correlation with bulk electronic structure such as observed for CO oxidation over Pd-Au wires 129), but the familiar pattern is discernible. The rate of CO oxidation is approximately constant for Ag and Ag-rich films but decreases by a factor of 104 over pure Pd and a Pd-rich film.

The model shown in Scheme 2 indicates that a change in the formal oxidation state of the metal is not necessarily required during the catalytic reaction. This raises a fundamental question. Does the metal ion have to possess specific redox properties in order to be an efficient catalyst A definite answer to this question cannot be given. Nevertheless, catalytic autoxidation reactions have been reported almost exclusively with metal ions which are susceptible to redox reactions under ambient conditions. This is a strong indication that intramolecular electron transfer occurs within the MS"+ and/or MS-O2 precursor complexes. Partial oxidation or reduction of the metal center obviously alters the electronic structure of the substrate and/or dioxygen. In a few cases, direct spectroscopic or other evidence was reported to prove such an internal charge transfer process. This electronic distortion is most likely necessary to activate the substrate and/or dioxygen before the actual electron transfer takes place. For a few systems where deviations from this pattern were found, the presence of trace amounts of catalytically active impurities are suspected to be the cause. In other words, the catalytic effect is due to the impurity and not to the bulk metal ion in these cases. 

C-Nitroso compounds, oximes, N-hydroxyguanidines and N-hydroxyureas each contain an N-O bond and release nitric oxide (NO) or one of its redox forms under some conditions. The nitrogen atom of a C-nitroso compound formally exists in the +1 oxidation state, the same oxidation state as nitroxyl (HNO), the one-electron reduced form of N O. The nitrogen atoms of oximes, N-hydroxyguanidines, and N-hydroxyureas each formally exist in the -1 oxidation state, the same oxidation state as hydroxylamine. Consequently, the direct formation of NO (formal oxidation state = +2) from any of these species requires oxidation, one electron for a C-nitroso compound and three electrons for an oxime, N-hydroxyguanidine or N-hydroxyurea. This chapter summarizes the syntheses and properties, NO-releasing mechanisms and the known structure-activity relationships of these compounds. 

Authors [143] suppose that sulfur atoms are not affected by oxidation and only act as activating double bond substituents. However, the analysis of the electronic structure of tetrathiofulvalene shows that, resulting from the interaction of tt CC) and 7t(S) orbitals, HOMO of this molecule is an antibonding combination of jr and riji orbitals with the predominant contribution being from the latter. Indeed, the substitution of one or more S atoms with Se results in a less conjugated system and, as a consequence, in higher oxidation potentials [144]. 

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