Hydrated supported metal oxide, Raman

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. 

As more Raman spectra of supported metal oxide catalysts appeared in the literature, many contradictory models for the dispersed metal oxide structure were proposed. It was observed in 1983-1984 by Wang and Hall (1983), Chan et al. (1984), and Stencel et al. (1984) that supported Re207, M0O3, and WO3-V2O5 were in hydrated states during ambient Raman measurements. However, the molecular structures of the various hydrated dispersed metal oxide species on oxide supports were not fully understood at that time. 

The Raman investigation of niobium species in aqueous solutions of niobium oxalate (Jehng and Wachs, 1991) nicely showed the dependence of their constitution on pH and concentration. The PZC theory was successfully applied to predict the hydrated, molecular structures of multicomponent supported metal oxide species, such as iron-molybdenum, iron-vanadium, molybdenum-vanadium, tungsten-vanadium, and sodium-vanadium oxide species (Vuurman et al., 1991 Wachs et al., 1993). 

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. ... 

This dynamic behavior of the catalyst, depending on the degree of hydration, is typical of many supported transition metal oxides, as evidenced by the changes in their Raman modes (Brown et al., 1977, Brown et al., 1977), as discussed below. The transformations are usually reversible. 

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