Inverse gas chromatography as a technique for the characterization of the performance of Mn/Zr mixed oxides as combustion catalysts.

Adsorption of different volatile organic compounds (trichloroethylene, TCE; 1,2-dichloroethane, DCE; n-hexane) over different manganese-zirconia mixed oxides (Mn(x)Zr(1-x)O(2)) - widely used as combustion catalysts - was studied by inverse gas chromatography. Adsorption isotherms (calculated in the Henry region), adsorption enthalpies (DeltaH(ads)), and dispersive (gamma(S)(D)) and specific (I(sp)) components of the surface energy have been determined at infinite dilution for the investigated compounds. Both the adsorption enthalpy and the specificity of the interaction of TCE and DCE over Mn(x)Zr(1-x)O(2) catalysts depend strongly on manganese content. Thus, the adsorption strength of the reactants over the active sites is closely related with both the surface acidity and the accessibility of the lattice oxygen. A great influence of the specific interaction on the catalytic pattern has been also noticed. Since I(sp) depends on the redox properties, it has been proved that the specific interaction is determined by the presence of bulk Mn(3)O(4), which hinders the mobility of the oxygen lattice, and MnO(x), with the contrary effect. Finally, the selectivity to oxidation products has been correlated with both the enthalpy of adsorption and the specific interaction parameter, decreasing the selectivity to HCl with the increase of the enthalpy of adsorption.

Effect of carbon nanofiber functionalization on the adsorption properties of volatile organic compounds.

The effect of the chemical activation, using HNO3, of a commercial carbon nanofiber (CNF) on its surface chemistry and adsorption properties is studied in this work. The adsorption of different alkanes (linear and cyclic), aromatic compounds and chlorohydrocarbons on both the parent and the oxidized CNF were compared. Temperature-programmed desorption results, in agreement with X-ray photoelectron spectroscopy experiments, reveal the existence of oxygen groups on the surface of the treated CNF. Capacity of adsorption was derived from the adsorption isotherms, whereas thermodynamic properties (enthalpy of adsorption, surface free energy characteristics) have been determined from chromatographic retention data. Both the capacity and the strength of adsorption decrease after the oxidant treatment of the carbon nanofibers, although in the case of chlorinated compounds the specific component of the surface energy shows an important increase. For n-alkanes and cyclic compounds, it was demonstrated that the presence of oxygen surface groups does not affect their interaction, the morphology of the surface being the key parameter. The oxidation of the nanofiber leads to steric limitations of the adsorption. In the adsorption of aromatic compounds, these limitations are compensated by the nucleophilic interactions between the aromatic ring and surface oxygenated groups, leading to similar performances of both materials. The absence of nucleophilic groups in the chlorinated compounds hinders their adsorption on the activated nanofibers.