L. Ilieva

Low-temperature water-gas shift reaction over Au/CeO2 catalysts

A high and stable activity for gold/ceria catalyts has been established for the water-gas shift reaction. The relationship between gold loading and catalytic activity was studied over a wide temperature range. The influence of space velocity and H2O/CO ratio at different temperatures on the catalytic activity and stability was also investigated. The reduction/oxidation processes of ceria in the presence of gold was readily followed by TPR measurements. It was shown that ceria plays the role of an active support capable of producing oxygen. The high and stable activity of gold/ceria catalysts could arise from the high and stable gold dispersion present during the catalytic operation.

Nanosize gold catalysts promoted by vanadium oxide supported on titania and zirconia for complete benzene oxidation

Abstract The complete benzene oxidation reaction was used to test the reactivity of the Au-V 2 O 5 /TiO 2 and Au-V 2 O 5 /ZrO 2 catalytic systems. A strong synergistic effect between gold and vanadia was established when molecular oxygen was used as an oxidizing agent. This effect was more pronounced for titania than for the zirconia support. In the presence of gold, predominantly polyvanadate structures are formed on the surface which are more active in the reaction of complete benzene oxidation in comparison with monovanadate species and bulk V 2 O 5 . The deposition of gold leads to a relative lengthening of the Vue605O bond and to a higher electron delocalization. The B and C parameters calculated from ESR spectra showed no differences for the fresh and spent gold-containing samples, i.e. the catalytic systems seemed to be “stabilized” under the working conditions. The effect of gold on the vanadium oxide reducibility, which could be related to the strength of the Vue5f8O-support bond, results in a considerable lowering of the temperature of the V 5+ → V 3+ transition. With ozone as the oxidizing agent, an additional lowering of the reaction temperature was achieved and very close values of the catalytic activity on all investigated samples were registered. Upon oxidation by molecular oxygen the oxidant activation takes place on the nanosize gold particles while the vanadium oxide surface species are responsible for the activation of benzene. This is in agreement with synergistic effect between the finely dispersed gold and the surface vanadium structures.

Complete benzene oxidation over gold-vanadia catalysts supported on nanostructured mesoporous titania and zirconia

Abstract The new generation of gold-vanadia catalysts supported on mesoporous titania and zirconia for complete benzene oxidation were explored. The catalysts were characterized by X-ray, TEM, SEM, N2 adsorption analysis, TPR and ESR spectroscopy. The vanadia loading stabilized structure of the both mesoporous supports and this effect is stronger for zirconia comparing to titania. The presence of gold enhanced the V5+→V3+ reduction step and depending on the preparation method, differences in the reduction behavior were established. The catalytic activity of the catalysts also strongly depends on the preparation techniques. For the both series of the studied catalysts when the gold is loaded firstly the activity in complete benzene oxidation is higher than when the vanadia is deposited firstly (VAT>AVT and VAZ>AVZ). A strong synergistic effect between gold and vanadia supported on titania was observed and the catalysts on titania exhibit higher catalytic activity than the catalysts based on zirconia. Comparing the activity of the gold-vanadia/zirconia and gold/zirconia catalysts, it was established for the both catalysts high and equal activity in the reaction studied. The observed differences in the structural and catalytic properties of the both series of the studied catalysts were connected with the nature of the supports used.

Nanosize gold-ceria catalysts promoted by vanadia for complete benzene oxidation

New gold-vanadia-ceria catalysts for complete benzene oxidation were synthesized. A high and stable catalytic activity was established. The influence of the preparation method and the vanadia loading on the catalytic activity was studied. The presence of gold enhances the reducibility and the reactivity of VOx and ceria surface layers which results in the lowering of the reaction temperature. The observed strong synergistic effect between gold and vanadia, when they present simultaneously on ceria, could be related to the specific interaction between gold, vanadia and ceria and the possibility to obtain nanosize gold and ceria particles, being able to produce more active oxygen species.

Gold catalysts on ceria doped with MeOx (Me = Fe, Mn, Co and Sn) for complete benzene oxidation: effect of composition and structure of the mixed supports

Gold catalysts supported on ceria doped with different metal oxides (Fe, Mn, Co and Sn) were synthesized using two techniques: CP and mechanochemical activation. The catalytic activity in complete benzene oxidation (CBO) was studied. The samples were characterized by means of XRD and high resolution transmission electron microscopy, and non-significant differences in the average size and the distribution of gold particles were observed. This means that the main reason for the different catalytic behavior in CBO has to be searched in the composition and structure of the supports. In spite of the higher hydrogen consumption (e.g., higher oxygen mobility) estimated by means of TPR, the gold catalysts on ceria doped with transition metal oxides generally are less active than gold/ceria catalyst. This observation could be explained taking into consideration that the key factor for the high oxidation activity is not the oxygen supplying but the activation of the very stable benzene molecule. The higher catalytic activity in comparison with that of the gold/ceria catalyst was observed only using a mixed ceria–CoOx support mechanochemically prepared. Very high and stable catalytic activity in CBO was obtained over this sample.