RESUMEN
The present study illustrates the importance of the oxidation state of iron within the mesoporous iron trimesate [{Fe(3)O(H(2)O)(2)F(0.81)(OH)(0.19)}{C(6)H(3)(CO(2))(3)}(2)] denoted MIL-100(Fe) (MIL= Material from Institut Lavoisier) during adsorption of molecules that can interact with the accessible metal sites through π-back donation. Adsorption of CO has been first followed by FTIR spectroscopy to quantify the Lewis acid sites in the dehydrated Fe(III) sample, outgassed at 150 °C, and on the partially reduced Fe(II/III), outgassed at 250 °C. The exposure of MIL-100(Fe) to CO(2), propane, propene and propyne has then been studied by FTIR spectroscopy and microcalorimetry. It appears that π-back donating molecules are strongly adsorbed on reduced iron(II) sites despite the weaker Lewis acidity of cus Fe(2+) sites compared to that of Fe(3+) ones, as shown by pyridine adsorption.
Asunto(s)
Alquenos/química , Alquinos/química , Dióxido de Carbono/química , Monóxido de Carbono/química , Hierro/química , Propano/química , Adsorción , Oxidación-Reducción , Porosidad , Piridinas/química , Espectroscopía Infrarroja por Transformada de FourierRESUMEN
The combination of several probe molecules has enabled the construction of a detailed picture of the surface of aluminium hydroxyl fluoride, AlF(2.6)(OH)(0.4), which has the hexagonal tungsten bronze (HTB) structure. Using pyridine as a probe leads to features at 1628 cm(-1), ascribed to very strong Lewis acid sites, and at 1620-1623 cm(-1), which is the result of several different types of Lewis sites. This heterogeneity is indicated also from CO adsorption at 100 K; the presence of five different types of Lewis site is deduced and is suggested to arise from the hydroxylated environment. Brønsted acid sites of medium strength are indicated by adsorption of lutidine and CO. Adsorption of lutidine occurs at OH groups, which are exposed at the surface and CO reveals that these OH groups have a single environment that can be correlated with their specific location inside the bulk, assuming that the surface OH group may reflect the bulk OH periodicity. A correlation between the data obtained from CO and pyridine molecules has been established using co-adsorption experiments, which also highlight the inductive effect produced by pyridine. Adsorption of the strong Brønsted acid, anhydrous hydrogen chloride, detected by monitoring the beta(-) emission of [(36)Cl]-HCl at the surface, indicates that surface hydroxyl groups can behave also as a Brønsted base and that H(2)O-HCl interactions, either within the hexagonal channels or at the surface are possible. Finally, the formation of strongly bound H(36)Cl as a result of the room temperature dehydrochlorination of [(36)Cl]-labelled tert-butyl chloride provides additional evidence that HTB-AlF(2.6)(OH)(0.4) can behave as a Lewis acid.