G. Pantaleo

Co3O4 nanocrystals and Co3O4–MOx binary oxides for CO, CH4 and VOC oxidation at low temperatures: a review

Among the possible substitutes for noble metals, cobalt-based catalysts represent promising alternative systems. In recent years, many articles have been devoted to the synthesis, characterization and reactivity of cobalt oxides. This article provides a comprehensive review of the state-of-the-art activities that concentrate on the synthesis, structural properties and catalytic applications of Co3O4 nanocrystals and Co3O4–MOx binary oxides in CO, CH4 and VOC oxidation at low temperatures. It begins with the major synthetic approaches and basic properties of Co3O4 nanocrystals and Co3O4–MOx binary oxides and subsequently highlights the relationship between the peculiar structure of Co3O4 nanocrystals and their catalytic activity (or between the redox properties of Co3O4–MOx binary oxides and their catalytic activity). Finally, the active sites and key factors determining the catalytic oxidation over Co3O4 and Co3O4–MOx are discussed. The perspective with respect to future research on Co3O4 nanocrystals and Co3O4–MOx binary oxides is considered.

Co3O4 particles grown over nanocrystalline CeO2: influence of precipitation agents and calcination temperature on the catalytic activity for methane oxidation

Crystalline cobalt oxides were prepared by a precipitation method using three different precipitation agents, (NH4)2CO3, Na2CO3 and CO(NH2)2. Cobalt oxide nanoparticles corresponding to a Co3O4 loading of 30 wt% were also deposited over high-surface area nanocrystalline ceria by the same precipitation agents. The effect of calcination temperature, 350 or 650 °C, on the morphological and structural properties was evaluated. Characterization by BET, XRD, SEM, TEM, Raman spectroscopy, H2-TPR, XPS and NH3-TPD was performed and the catalytic properties were explored in the methane oxidation reaction. The nature of the precipitation agent strongly influenced the textural properties of Co3O4 and the Co3O4–CeO2 interface. The best control of the particle size was achieved by using CO(NH2)2 that produced small and regular crystallites of Co3O4 homogeneously deposited over the CeO2 surface. Such a Co3O4–CeO2 system precipitated by urea showed enhanced low-temperature reducibility and high surface Co3+ concentration, which were identified as the key factors for promoting methane oxidation at low temperature. Moreover, the synergic effect of cobalt oxide and nanocrystalline ceria produced stable full conversion of methane in the entire range of investigated temperature, up to 700–800 °C, at which Co3O4 deactivation usually occurs.

Combined sulfating and non-sulfating support to prevent water and sulfur poisoning of Pd catalysts for methane combustion

The appropriate combination of titania and silica, sulfating and non-sulfating support, respectively, results in Pd catalysts with improved water and sulfur tolerance in methane combustion. For the first time the catalyst recovers the initial activity after one cycle under lean-burn conditions without additional regenerating treatments.

Ceria-zirconia nanostructured materials for catalytic applications: Textural characteristics and redox properties

Highly dispersed solid solutions of ceria-zirconia with nominal composition Ce0.6Zr0.4O2 were prepared by sol-gel technique and the influence of the gel aging time (1 day–3 weeks) on the morphological and textural properties of the materials was investigated. The samples were calcined at 923 K for 8 h, then characterized by XRD, BET surface area and pore size measurements by gas adsorption and by mercury porosimetry. DTA, TEM and SEM analyses were also carried out. The aging of the gel seems to have a remarkable influence on the morphology of the materials, whose surface area and porosity increase by increasing aging time. The phase composition of the solid solutions of ceria-zirconia, as determined by XRD analysis, seems to be independent from the synthetic procedure; in any case a cubic phase (space group Fm-3m) was identified as the main component. XRD and TEM characterizations show the presence of highly dispersed crystallites, with diameters in the range 60–80 Å. The redox properties and hydrogen chemisorption capacity have been studied by TPR/TPD/TPO experiments. Oxygen storage capacity measurements were carried out by a pulse technique, to determine the overall reducibility of the solid, OSCC (Oxygen storage capacity complete). OBC (Oxygen buffering capacity) measurement were also performed to determine the ability of the ceria-zirconia oxides to attenuate fast oscillations (0.1 Hz) of oxygen partial pressure. The correlation between textural, structural and redox properties of the oxides is discussed.

Structural and Morphological Investigation of Ce0.6Zr0.4O2 Oxides Synthesized by Sol-Gel Method: Influence of Calcination and Redox Treatments

Ceria-zirconia mixed oxides of nominal composition Ce0.6Zr0.4O2 were prepared by sol-gel method. The structural and morphological modifications of these materials due to calcination and redox treatments up to 1000°C were studied by X-ray diffraction (XRD) and Rietveld refinements, specific surface area measurements (BET), oxygen storage capacity (OSC), TEM and SEM analyses. The materials maintain high OSC after several hours of treatments at 1000°C in oxidizing and reducing atmosphere, showing good resistance to the thermal ageing. An improvement of the OSC is manifested after repetitive redox cycles, even though textural characterization shows that reduction/oxidation processes induce sintering of the crystallites.

Hydrodesulfurization cobalt-based catalysts modified by gold

Cobalt catalysts supported on amorphous SiO2 and ordered mesoporous silica (MCM-41) were prepared by incipient wetness impregnation. Gold was added by consecutive impregnation or by co-impregnation. The materials were characterised by XPS, XRD and TPR techniques and evaluated in the hydrodesulfurization (HDS) of thiophene in order to investigate the effect of the noble metal on the structure and on the catalytic behaviour of the supported cobalt. Co/MCM-41 exhibited higher HDS activity and higher stability than the Co/SiO2. Moreover, in contrast to silica case, the gold impregnated MCM-41, produced an enhancement of the cobalt catalytic activity, and this is likely to be related to an increased cobalt reducibility. Both the support and the addition of gold improve the cobalt dispersion.

A new cell for the study of in situ chemical reactions using X-ray absorption spectroscopy

An in situ cell for reductive and oxidative treatments at different temperatures that allows the possibility of recording data as a function of temperature has been designed and constructed for X-ray absorption experiments at the GILDA beamline BM08 of ESRF. The cell is linked to a mass quadrupole spectrometer providing control of the reaction gases and monitoring of the products. The apparatus allows measurements to be performed both in transmission and fluorescence geometry. The cell was tested by studying the CO oxidation reaction promoted by a Pt/ceria-zirconia-supported catalyst. The CO(2) yield is correlated with the structural results confirming the existence of a strong metal-support interaction between the Pt metal clusters and the ceria-zirconia support.

Surface and bulk changes of a Pt 1%/Ce0.6Zr0.4O2 catalyst during CO oxidation in the absence of O2

The reduction of a Pt 1%/Ce0.6Zr0.4O2 catalyst by CO in the absence of gaseous oxygen was studied by transient reactivity tests, temperature programmed surface reaction with CO, flow thermogravimetric tests and DRIFTS experiments, in order to obtain information generally on the OSC properties and, specifically, on the mechanism of CO oxidation over both, Pt catalyst and support-only sample (Ce0.6Zr0.4O2). The results of thermogravimetric experiments showed the presence of an induction time in the weight change % of the catalyst, depending on the CO concentration in the gas flow. This induction time could be related to the presence of two oxygen reactive sites. The first one leads to strongly chemisorbed CO2 or carbonate species, while the second, tentatively related to Pt/support interface sites, generates weakly chemisorbed CO2 species in reversible equilibrium with gaseous CO2. The concentration of CO and the presence of a co-feeding of gaseous CO2 significantly and non-linearly affected the presence and reactivity of these Pt/support interface sites, although the details of this effect should be better understood.

Supported Co3O4-CeO2 monoliths: effect of preparation method and Pd-Pt promotion on the CO/CH4 oxidation activity

Abstract Two structured composite oxides, Co3O4(30wt%)-CeO2(70wt%), have been prepared by washcoating commercial cordierite monoliths with a CeO2-γAl2O3 layer, on which the active phase Co3O4-CeO2 was added through two different methods: dip-coating from a suspension containing the preformed active oxide or impregnation with a solution of the cobalt and cerium precursors. Morphological characterizations of the monoliths have been performed by BET, and SEM-EDAX analyses. Electronic and reduction properties have been evaluated by XPS and H2-TPR, respectively. The effect of the preparation method has been investigated in the catalytic oxidation of CO, whereas the promotion by a low content of Pd-Pt has been evaluated in combined CO-CH4 oxidation tests. Four successive CO oxidation cycles performed over the structured Co3O4-CeO2 indicate that the best performing sample is the monolith prepared by dip-coating, whereas that one obtained by impregnation method manifests a certain deactivation upon two consecutive cycles. Accordingly, XPS spectra are consistent with the presence of the active phase CO3O4 in the former, while Co2+ has been identified as the main species in the latter sample.