Gold catalysis in southern Italy

Mesoporous SBA-15 silica modified with cerium oxide: Effect of ceria loading on support modification

Abstract The present work investigates the effect of ceria loading on silica SBA-15. Five CeO2/SBA-15 samples with CeO2 content equal to 5, 10, 15, 20 and 30 wt% were prepared by wetness-impregnation of the support with cerium nitrate hexahydrate, as precursor, dissolved in ethanol. After drying at room temperature, the resulting samples were calcined at 400 °C for 2h. Characterizations by BET surface area and pore-size distribution, XRD, NH3-TPD and H2-TPR were performed.

Catalytic activity of supported cobalt oxide for SCR of NO by C3H6 in the presence of excess O2,

Supported Au catalysts for low-temperature abatement of propene and toluene, as model VOCs: Support effect

3-4 Ousmane, M. Liotta, L. F. Di Carlo, G. Pantaleo, G. Venezia, A. M. Deganello, G. Retailleau, L. Boreave, A. Giroir-Fendler, A.; In this work gold nanoparticles supported over ceria (Au/CeO2), titania (Au/TiO2), alumina (Au/Al2O3) and Ce doped alumina (Au/7.5Ce/Al2O3) were prepared by deposition-precipitation (DP) method with NaOH solution and characterized by BET, XRD, H-2-TPR, TEM and XPS techniques. The catalytic activity was evaluated in the total oxidation of propene and toluene, chosen as model VOC molecules. The attention was focused on the catalyst stability. To this aim, three consecutive catalytic cycles in propene and toluene oxidation were performed for each catalyst. The act…

Combined CO/CH4 oxidation tests over Pd/Co3O4 monolitic catalyst: effects of high reaction temperature and SO2 exposure on the deactivation process

Abstract CO and CH 4 combined oxidation tests were performed over a Pd (70 g/ft 3 )/Co 3 O 4 monolithic catalyst in conditions of GHSV = 100,000 h −1 and feed composition close to that of emission from bi-fuel vehicles. The effect of SO 2 (5 ppm) on CO and CH 4 oxidation activity under lean condition ( λ  = 2) was investigated. The presence of sulphur strongly deactivated the catalyst towards methane oxidation, while the poisoning effect was less drastic in the oxidation of CO. Saturation of the Pd/Co 3 O 4 catalytic sites via chemisorbed SO 3 and/or sulphates occurred upon exposure to SO 2 . A treatment of regeneration to remove sulphate species was attempted by performing a heating/coolin…

Catalytic performances of Co3O4/CeO2 and Co3O4/CeO2-ZrO2Composite oxides for methane combustion: influence of catalyst pretreatment temperature and oxygen concentration in the reaction mixture

Abstract The influence of catalyst pre-treatment temperature (650 and 750 °C) and oxygen concentration ( λ  = 8 and 1) on the light-off temperature of methane combustion has been investigated over two composite oxides, Co 3 O 4 /CeO 2 and Co 3 O 4 /CeO 2 –ZrO 2 containing 30 wt.% of Co 3 O 4 . The catalytic materials prepared by the co-precipitation method were calcined at 650 °C for 5 h (fresh samples); a portion of them was further treated at 750 °C for 7 h, in a furnace in static air (aged samples). Tests of methane combustion were carried out on fresh and aged catalysts at two different WHSV values (12 000 and 60 000 mL g −1  h −1 ). The catalytic performance of Co 3 O 4 /CeO 2 and Co 3…

Oxidation of CH4 over Pd supported on TiO2-doped SiO2: Effect of Ti(IV) loading and influence of SO2

Titania-modified silicas with different weight% of TiO2 were prepared by sol-gel method and used as supports for Pd (1 wt%) catalysts. The obtained materials were tested in the oxidation of methane under lean conditions in absence and in presence of SO2. Test reactions were consecutively performed in order to evaluate the thermal stability and poisoning reversibility. Increasing amounts of TiO2 improved the catalytic activity, with an optimum of the performance for 10 wt% TiO2 loading. Moreover, the titaniacontaining catalysts exhibited a superior tolerance towards SO2 by either adding it to the reactants or feeding it as a pure pretreatment atmosphere at 350 8C. Catalysts were characterize…

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)(2)CO3, 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 degrees C, on the morphological and structural properties was evaluated. Characterization by BET, XRD, SEM, TEM, Raman spectroscopy, H-2-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…

“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 …

"Design and catalytic performances of Co3O4/CeO2 and Co3O4/Ce0.6Zr0.4O2 composite oxides for methane combustion",

Alumina supported Pt(1%)/Ce0.6Zr0.4O2 monolith: Remarkable stabilization of ceria–zirconia solution towards CeAlO3 formation operated by Pt under redox conditions

Abstract A structured Pt(1 wt%)/ceria–zirconia/alumina catalyst and the metal-free ceria–zirconia/alumina were prepared, by dip-coating, over a cordierite monolithic support. XRD analyses and Rietveld refinements of the structural data demonstrate that in the Pt supported catalysts ceria–zirconia is present as a Ce 0.6 Zr 0.4 O 2 homogeneous solid solution and that the deposition over the cordierite doesn’t produce any structural modification. Moreover no Pt sintering occurs. By comparing the XRD patterns recorded on Pt/ceria–zirconia/alumina and ceria–zirconia/alumina after three redox cycles, it results that Pt, favouring the structural reorganization of the ceria–zirconia into one cubic …

Pd/Co3O4 catalyst for CH4 emissions abatement: study of SO2 poisoning effect

A catalyst with 0.7 wt% Pd load supported over Co3O4 oxide was investigated in the methane oxidation by operating under CH4/O2 stoichiometric conditions. The effect of the noble metal addition on the activity of bare Co3O4 was evaluated. Samples were characterized by BET, XRD, TPR and XPS analyses. The SO2 poisoning of Pd catalyst and Co3O4 was studied by performing CH4 oxidation tests under stoichiometric conditions in SO2 (1 ppm or 10 ppm). Experiments evidenced that in our conditions the low amount of SO2 doesn’t influence the Pd behaviour, whereas in presence of 10 ppm of SO2 some deactivation occurs that becomes more evident above 450 °C at which the catalyst doesn’t reach 100% of meth…

Total oxidation of propene at low temperature over Co3O4–CeO2 mixed oxides: Role of surface oxygen vacancies and bulk oxygen mobility in the catalytic activity

Liotta, L. F. Ousmane, M. Di Carlo, G. Pantaleo, G. Deganello, G. Marci, G. Retailleau, L. Giroir-Fendler, A.; Co3O4, CeO2 and Co3O4-CeO2 mixed oxides with Co/Ce nominal atomic ratio 0.1:5, prepared by co-precipitation method with sodium carbonate, were tested in the oxidation of propene under lean condition and the catalyst stability was checked by performing three consecutive heating-cooling cycles. Characterization of the textural properties were performed by surface area measurement BET, X-ray diffraction (XRD) and scanning electron microscopy (SEM) measurements. Among the Co3O4-CeO2 mixed oxides, Co3O4 (30 Wt%)-CeO2 (70 wt%) gives the best activity attaining full propene conversion at …

Support effect on the catalytic performance of Au/Co3O4–CeO2 catalysts for CO and CH4 oxidation

Gold-based catalysts supported on Co3O4, on CeO2 and on mixed Co3O4-CeO2 oxides were prepared by co-precipitation. They were tested in the catalytic oxidation of CO and CH4, in separate tests, and their activities were compared with that of the bare oxides. Tests of CH4 oxidation were performed in two consecutive runs in order to evaluate the catalysts stability. The effect of SO2 in the reactant mixture was investigated. The fresh and spent catalysts were analsed by XRD, BET, TPR and XPS techniques. Among the fresh catalysts, Au supported on CeO2 was the most active in CO oxidation whereas Au supported on Co3O4 was the most active for methane total oxidation. Synergy between the two oxides…

Oxidative degradation properties of Co-based catalysts in the presence of ozone

Four series of cobalt-based catalysts, such as bare Co3O4 and CoO, CoOx-CeO2 mixed oxides, CoOx supported over alumina and alumina-baria and CoMgAl and CoNiAl hydrotalcites have been synthesized and investigated for the oxidative degradation of phenol in the presence of ozone. Characterizations were obtained by several techniques in order to investigate the nature of cobalt species and their morphological properties, depending on the system. Analyses by XRD, BET, TPR, UV-visible diffuse reflectance spectroscopy and TG/DT were performed. The CoNiAl hydrotalcite exhibits, after 4 h of reaction, the highest phenol ozonation activity followed by Co(3 wt%)/Al2O3-BaO and CoMgAl. The samples Co(1 …

Structural and morphological properties of Co-La catalysts supported on alumina/lanthana for hydrocarbons oxidation

Abstract Two Al 2 O 3 (24 wt%)–La 2 O 3 (76 wt%) supported Co–La oxides with Co loading 4 wt% and different La content (1 and 9 wt%) were prepared by co-impregnation of the support, the aluminum–lanthanum oxide, with cobalt and lanthanum nitrates in aqueous solution and successive calcination at 800 °C for 4 h. The alumina–lanthana was synthesized by the sol–gel method. The samples were characterized by X-ray diffraction (XRD) and Rietveld refinement in order to identify the crystalline phases and their relative weight. H 2 -TPR (Temperature Programmed Reduction) experiments were recorded with the aim to identify the different Co phases present. Co 3 O 4 and LaCoO 3 were formed for La loadi…

“Preferential oxidation (PROX) of CO in the presence of H2 over gold catalysts: support effect”

Co3O4/CeO2 and Co3O4/CeO2–ZrO2 composite catalysts for methane combustion: Correlation between morphology reduction properties and catalytic activity

Abstract Co3O4/CeO2 and Co3O4/CeO2–ZrO2 composite catalysts have been prepared by two different techniques, co-precipitation by citrate method and impregnation with cobalt nitrate of pre-formed ceria and ceria–zirconia oxides. The materials, as prepared and after ageing at 750 °C 7 h, were tested for methane combustion and the catalytic performances were compared with those of a commercial Co3O4, used as reference. A significant improvement of the activity was observed in the composite oxide Co3O4(30 wt%)/CeO2(70 wt%), prepared by citrate method, which exhibits the lowest light-off temperature of methane (T50 = 400 °C) and does not suffer deactivation after calcination at 750 °C 7 h.

CoOx catalysts supported on alumina and alumina-baria: influence of the support on the cobalt species and their activity in NO reduction by C3H6 in lean conditions

Abstract CoO x catalysts (Co 1 and 3 wt.%) were prepared by incipient-wetness impregnation of the supports, Al 2 O 3 and Al 2 O 3 (80 wt.%)-BaO (20 wt.%), and calcined at 500 and 800 °C. The samples were characterized by X-ray diffraction (XRD) and BET techniques. H 2 -temperature programmed reduction (TPR) and UV-Vis diffuse reflectance spectroscopy (DRS) spectra were recorded with the aim to identify the different Co species formed. The presence of Co 2+ species tetrahedrally and octahedrally coordinated appears strongly influenced by the nature of the support and the cobalt content. Co 3 O 4 particles were detected after calcination at 500 °C, a successive treatment at 800 °C promotes th…

Honeycomb supported Co3O4/CeO2 catalysts for CO/CH4 emissions abatement: effect of low Pd-Pt content on the catalytic activity

Abstract A structured Co3O4–CeO2 composite oxide, containing 30% by weight of Co3O4, has been prepared over a cordieritic honeycomb support. The bimetallic, Pd–Pt catalyst has been obtained by impregnation of the supported Co3O4–CeO2 with Pd and Pt precursors in order to obtain a total metal loading of 50 g/ft3. CO, CH4 combined oxidation tests were performed over the catalyzed monoliths in realistic conditions, namely GHSV = 100,000 h−1 and reaction feed close to emission from bi-fuel vehicles. The Pd–Pt un-promoted Co3O4–CeO2 is promising for cold-start application, showing massive CO conversion below 100 °C, in lean condition. A strong enhancement of the CH4 oxidation activity, between 4…

Colonisation process of vegetative fragments of Posidonia oceanica (L.) Delile on rubble mounds

Seagrass colonise new areas via the dispersion of seeds or vegetative fragments. Independent of the manner of colonization, habitat requirements need to be met for the successful establishment of seagrasses. Here we report on the colonization process of Posidonia oceanica in a highly disturbed area: a gas pipeline trench at Capo Feto (SW Sicily, Italy). A trench dredged through a P. oceanica bed was back-filled with rubble added from dump barges leading to the formation of a series of rubble mounds on the seabed. Over time, these mounds became colonised with P. oceanica. In order to understand the pattern of P. oceanica colonization, shoot density was quantified over 3 years (2001-2003) on …

The value of diagnostic ultrasound for detecting occult inguinal hernia in patients with groin pain

Aims: chronic groin pain caused by an occult hernia can be a difficult clinical diagnosis and may require additional investiga- tive modalities. The aim of this study was to demonstrate the accuracy of ultrasound in diagnosing occult hernia in patients with recurrent inguinal pain and a negative clinical examination. Patients and methods: over a period of three years, a total of 76 patients were referred for ultrasound examination with clini- cally suspected occult inguinal hernia. Patients with positive US scans were offered surgery, while those with negative US findings were offered further imaging or other diagnostic tests. The ultrasound examination of the inguinal region was conducted …

Co3O4/CeO2 composite oxides for methane emissions abatement: Relationship between Co3O4–CeO2 interaction and catalytic activity

Abstract Co 3 O 4 /CeO 2 composite oxides with different cobalt loading (5, 15, 30, 50, 70 wt.% as Co 3 O 4 ) were prepared by co-precipitation method and investigated for the oxidation of methane under stoichiometric conditions. Pure oxides, Co 3 O 4 and CeO 2 were used as reference. Characterization studies by X-ray diffraction (XRD), BET, temperature programmed reduction/oxidation (TPR/TPO) and X-ray photoelectron spectroscopy (XPS) were carried out. An improvement of the catalytic activity and thermal stability of the composite oxides was observed with respect to pure Co 3 O 4 in correspondence of Co 3 O 4 –CeO 2 containing 30% by weight of Co 3 O 4 . The combined effect of cobalt oxide…

Co3O4 – based CeO2 and CeO2-ZrO2 oxides for methane oxidation”,

Nature of the cobalt species in a Co (1%)/Al2O3-BaO catalyst upon redox cycles and their effectiveness in the CO+NO reaction

Heterogeneous catalytic degradation of phenolic substrates: catalysts activity

This review article explored the catalytic degradation of phenol and some phenols derivates by means of advanced oxidation processes (AOPs). Among them, only the heterogeneous catalyzed processes based on catalytic wet peroxide oxidation. catalytic ozonation and catalytic wet oxidation were reviewed. Also selected recent examples about heterogeneous photocatalytic AOPs; will be presented. In details, the present review contains: (i) data concerning catalytic wet peroxide oxidation of phenolic compounds over metal-exchanged zeolites, hydrotalcites, metal-exchanged clays and resins. (ii) Use of cobalt-based catalysts, hydrotalcite-like compounds, active carbons in the catalytic ozonation proc…

Structural and morphological investigation of a cobalt catalyst supported on alumina-baria: effects of redox treatments on the activity in the NO reduction by CO

Abstract Temperature-programmed reduction (TPR) and temperature-programmed oxidation (TPO) have been used to study the various cobalt species formed in a cobalt catalyst (Co 1 wt.%) supported on alumina-baria, with composition Al2O3(80 wt.%)–BaO (20 wt.%). The catalyst was synthesized by incipient-wetness impregnation of the support with a water solution of cobalt acetylacetonate and calcined at 550 °C for 5 h. In order to investigate the structure and morphology of the sample, XRD, BET and SEM analyses were performed. Depending on the temperature and nature of pre-treatment (reductive or oxidative) different Co species (Co3O4, Co3+, surface Co2+, CoAl2O4) were formed. Activity tests in the…

Synthesis of high-surface area CeO2 through silica xerogel template: influence of cerium salt precursor”;

Abstract Ceria nanosized oxides with high surface area were synthesized by means of a templating approach, using a porous silica xerogel with surface area as high as 718 m2/g. After impregnation of the silica template with the cerium salt solution and further calcination at 600 °C, the final ceria oxide was recovered by dissolving the silica framework in NaOH solution. The effect of cerium counteranion, nitrate or chloride, on the textural and reduction properties of the ceria oxide was examined. Characterizations by BET and pore size distribution, XRD, TPR and SEM/EDX techniques were performed. The silica xerogel templated approach resulted in the preparation of ceria with surface area of …