Hydrated surface metal oxide species

Supported metal oxide species are hydrated when exposed to moist environments and low temperatures (<230°C). Thus, all calcined supported metal oxide species are hydrated at ambient conditions (room temperature and air exposed) [34,35]. The hydrated surface layer corresponds to a thin aqueous film that corresponds to multiple layers of moisture [32]. The hydrated surface metal oxide species equilibrate with the pH of the aqueous layer. The pH of the aqueous film is determined by the pH at point zero charge (PZC) of the hydrated surface [36,37]. The net pH at PZC is defined as the equilibrated pH of a hydrated surface when the net charge is zero (protonated positive surface sites are balanced by an equal number of depro-tonated negative surface sites). At pH values above the PCZ, the hydrated surface becomes negatively charged, while for pH values below the PCZ, the hydrated surface becomes positively charged. Thus, hydrated surfaces always equilibrate at the pH at PZC in order to preserve charge balance. 

The molecular structures of the hydrated surface metal oxides on oxide supports have been determined in recent years with various spectroscopic characterization methods (Raman [34,37,40 3], IR [43], UV-Vis [44,45], solid stateNMR [32,33], and EXAFS/XANES [46-51]). These studies found that the surface metal oxide species possess the same molecular strucmres that are present in aqueous solution at the same net pH values. The effects of vanadia surface coverage and the different oxide supports on the hydrated surface vanadia molecular structures are shown in Table 1.2. As the value of the pH at F ZC of the oxide support decreases, the hydrated surface vanadia species become more polymerized and clustered. Similarly, as the surface vanadia coverage increases, which decreases the net pH at PZC, the hydrated surface vanadia species also become more polymerized and clustered. Consequently, only the value of the net pH at PZC of a given hydrated supported metal oxide system is needed to predict the hydrated molecular structure(s) of the surface metal oxide species. 

The finding that only one parameter, the net pH at PZC, controls the hydrated molecular structures of surface metal oxide species also has very... 

The vanadium oxide species is formed on the surface of the oxide support during the preparation of supported vanadium oxide catalysts. This is evident by the consumption of surface hydroxyls (OH) [5] and the structural transformation of the supported metal oxide phase that takes place during hydration-dehydration studies and chemisorption of reactant gas molecules [6]. Recently, a number of studies have shown that the structure of the surface vanadium oxide species depends on the specific conditions that they are observed under. For example, under ambient conditions the surface of the oxide supports possesses a thin layer of moisture which provides an aqueous environment of a certain pH at point of zero charge (pH at pzc) for the surface vanadium oxide species and controls the structure of the vanadium oxide phase [7]. Under reaction conditions (300-500 C), moisture desorbs from the surface of the oxide support and the vanadium oxide species is forced to directly interact with the oxide support which results in a different structure [8]. These structural... 

Under dehydrated conditions, the adsorbed moisture is removed and the in situ Raman spectra of the surface metal oxides differ markedly showing that the structures of the dehydrated species are very different from those of their hydrated counterparts (see references above in Section 6.2.2). These changes are not surprising since the influence of the net zero surface charge of the oxide support can only be exerted in an aqueous medium. For the dehydrated surface metal oxides, however, essentially the same molecular structures are seen on all the oxide supports for each supported metal oxide. ... 

The corrosion of iron is one of the most widespread and technologically important examples of metallic corrosion. In the presence of water and oxygen, the corrosion of iron proceeds to form a complicated mixture of hydrated iron oxides and related species a complete description is beyond the scope of the present discussion, and the interested reader is referred to the previously cited general references on corrosion as well as to the well known descriptions of electrochemical equilibria in aqueous solution given by Pourbaix (8, 9,). Iron is a base metal, subject to corrosion in aqueous solutions. In the presence of oxidizing species, iron surfaces can be passivated by the formation of an oxide layer if the oxide layer formed is Imperfect, rapid corrosion may occur. In simplest form, the reaction of iron to form iron oxide can be written as ... 

Acidity and basicity are relative properties. Many compounds are amphoteric and behave as acids or as bases according to a partner. Metal oxides are classified as acidic, amphoteric or basic. Experimentally, this classification corresponds to the adsorption of probe molecules[7, 8]. NH3 is a base probe molecule that reacts with the electron deficient metal atoms (Lewis acid) or the protons adsorbed on the hydrated surface, CO2 is usually considered as acidic and thus it is expected to adsorb more strongly on basic sites. According to this classification, Ti02 belongs to an amphoteric species and MgO to a basic species. A general difficulty for such classifications is that the order can vary with the choice of the probe. The Hard and Soft Bases and Acids theory[9, 10] responds to the necessity to refine the model with a second scale it is better to couple... 

The surface reaction of impregnated mixed metal cluster complexes may be analogous to that of homometallic clusters on hydrated and dehydrated metal oxides as described in Sections III and IV. Bimetallic clusters are converted to anionic surface species by simple deprotonation via 0 on dehydrated MgO or AI2O3 surfaces these species have been characterized by IR spectroscopy (119). The ionic interaction with surface cations such as AF and Mg is demonstrated by IR and NMR measurements. The surface polynuclear carbonyl anions are stable up to about 373 K. If heated in vacuo at higher temperature, extensive decomposition takes place to give a mixture of Ru (or Os) metal particles and Fe oxides, accompanied by the evolution of H2, CO, and CO2. 

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