Synthesis and support composition effects on CH4 partial oxidation over Ni–CeLa oxides
Abstract Two series of Ni (6 wt%) catalysts supported over CeO 2 , La 2 O 3 and mixed CeO 2 –La 2 O 3 were prepared by co-precipitation and by wet-impregnation. The effect of the two Ni loading procedures on the catalyst structural properties was investigated by XRD, TPR and XPS. The catalytic behavior of the catalysts was tested in the methane partial oxidation reaction performed at 1 atm in a temperature range of 400–800 °C using dilute feed gas mixture with CH 4 /O 2 = 2 and gas hourly space velocity of 60,000 ml g −1 h −1 . Total methane combustion was observed within the 450 °C ≤ T ≤ 650 °C temperature range. Above 650 °C partial oxidation of methane started to occur, reaching at 80…
Coupled Semiconductor Systems for Photocatalysis. Preparation and Characterization of Polycrystalline Mixed WO3/WS2 Powders
Mixed WO3/WS2 powders were prepared by oxidation of WS2. The physical properties of the samples were characterized by X-ray diffraction, diffuse reflectance spectroscopy, and scanning electron microscopy; they were strongly dependent upon the time and temperature of oxidation. The chemical state and the elemental distribution of the sample surface were investigated by X-ray photoelectron spectroscopy. The photocatalytic results have showed that the aqueous suspensions of the mixed WO3/WS2 systems have significantly higher activities than pure WS2 and WO3 for the photodegradation of phenol. The enhanced performance can be related to the presence of heterojunctions WO3/WS2 on the single parti…
Gold catalysis in southern Italy
Interaction of Gold with Co-Condensed and Grafted HMS-SH Silica: A 29Si {1H} CP-MAS NMR Spectroscopy, XRD, XPS and Au LIII EXAFS Study
Hexagonal mesoporous silica (HMS) is functionalised with mercaptopropyl groups by adopting two different procedures ; co-condensation and grafting. In both cases tetraethylorthosilicate (TEOS) and 3-mercaptopropyltriethoxysilane (3-MPTES) are used as the silicon and sulfur precursors, respectively. The obtained materials are analysed by several techniques such as N 2 sorption, TG-DTA, XRD, SAXS and-solid state 29 Si { 1 H} CP-MAS NMR spectroscopy. By taking advantage of the chemical interaction between gold and the -SH groups, the effect of the thiol addition procedure on the supporting capability of the functionalised silica is evaluated by depositing gold through the incipient wet impregn…
Synthesis and physico-chemical characterization of gold nanoparticles softly coated by AOT
Size-controlled gold nanoparticles/surfactant stable systems were prepared by the combined action of the solvated metal atom dispersion (SMAD) technique and confinement in anhydrous sodium bis(2-ethylhexyl)sulfosuccinate (AOT) micellar solution. From liquid samples, by evaporation of the organic solvent, solid gold nanoparticle-surfactant liquid crystals composites were obtained. Sample characterization was performed by X-ray diffraction (SAXS and WAXS), XPS spectroscopy and UV-vis-NIR spectroscopy. All experimental data consistently revealed the coexistence of two gold nanoparticle size populations: bigger nanoparticles (size 20-50 angstrom) and smaller ones (size of few angstrom). The two…
Pd and PdAu on mesoporous silica for methane oxidation: Effect of SO2
Abstract Palladium and gold–palladium catalysts supported on mesoporous silica were prepared by incipient wetness impregnation. They were characterized by XPS, XRD, BET, and FTIR acidity measurements. The activity was tested in the oxidation of methane under lean conditions. The effect of adding SO 2 to the reactant mixture was investigated. Test reactions were consecutively performed to evaluate the thermal stability and poisoning reversibility. The palladium catalyst performed quite well in terms of the light-off temperature ( T 50 300 °C) and SO 2 tolerance. Moreover, the activity, which decreased after a night treatment in SO 2 at 350 °C, was completely recovered in subsequent cycles. …
Structure and the metal-support interaction of the Au/Mn oxide catalysts
Gold catalysts with loading 1 and 10 wt % were-prepared by deposition precipitation method with urea over mesoporous manganese oxide, obtained through a surfactant-assisted procedure by using cetyltrimethylammonium bromide (CTAB), followed by treatment with sulphuric acid. For comparison, Au(10 wt %) was also deposited over commercial CeO2 and SiO2 supports. The materials were characterized by XRD and EXAFS at the Mn K and Au L-III edges and XPS. Moreover, the analyses were performed on the samples treated under 1%CO/He, at 250 degrees C for 90 min. The structural and surface results of the as prepared manganese oxide confirmed the formation of gamma-MnO2 along with some amorphous Mn3O4 upo…
Effect of Ti(IV) loading on CO oxidation activity of gold on TiO2 doped amorphous silica
Abstract Amorphous SiO 2 , doped with various amount of TiO 2 , was used as support for gold nanoparticles. Gold was deposited through the controlled sol formation technique. The effect of the TiO 2 loading on the structural and surface properties was investigated by transmission electron microscopy, X-ray diffraction, Raman and X-ray photoelectron spectroscopy. The catalytic behavior was tested in the oxidation of CO. A significant enhancement in the activity was observed for the gold supported on mixed oxide with low TiO 2 loading. On the basis of characterization data, the positive effect is assigned to the electronic modification of the Ti(IV) of the newly formed Ti O Si bonds.
Ni-Based Catalysts for Low Temperature Methane Steam Reforming: Recent Results on Ni-Au and Comparison with Other Bi-Metallic Systems
Steam reforming of light hydrocarbons provides a promising method for hydrogen production. Ni-based catalysts are so far the best and the most commonly used catalysts for steam reforming because of their acceptably high activity and significantly lower cost in comparison with alternative precious metal-based catalysts. However, nickel catalysts are susceptible to deactivation from the deposition of carbon, even when operating at steam-to-carbon ratios predicted to be thermodynamically outside of the carbon-forming regime. Reactivity and deactivation by carbon formation can be tuned by modifying Ni surfaces with a second metal, such as Au through alloy formation. In the present review, we su…
Post-synthesis alumination of MCM-41: Effect of the acidity on the HDS activity of supported Pd catalysts
Abstract Siliceous MCM-41 with different amount of alumina, from 0.25 up to 4.0 wt%, were prepared by impregnation of the MCM-41 with aqueous solution of Al(NO) 3 ·9H 2 O. The modified mesoporous silicas were then used as supports for Pd catalysts prepared by wet-impregnation from PdCl 2 precursor. Supports and corresponding Pd catalysts were characterized by XRD, XPS and NH 3 -TPD. The catalytic behavior was tested in the hydrodesulfurization (HDS) reaction of thiophene. An increase of the hydrodesulfurization activity with increasing alumina amount up to 0.5 wt% was observed. On the basis of the acidity change of the support and the structural modification underwent by the deposited palla…
Structure of the Metal–Support Interface and Oxidation State of Gold Nanoparticles Supported on Ceria
An Au/CeO2 model catalyst was prepared by deposition–precipitation, with the aim of obtaining a sample suitable for a detailed X-ray absorption fine structure (XAFS) analysis of the gold–ceria interface structure. The results demonstrate the existence of a large interface between the gold particle and the support oxide, characterized by well-defined Au–O and Au–Ce interactions extending up to ∼6.4 A. The complex interface structure is retained after CO treatment up to 250 °C and subsequent reoxidation at 400 °C. The analysis of the XANES spectra, and the Au–O distance of 2.21 A, longer than Au–O bond lengths previously reported for Au/ceria catalysts, suggest a low oxidation state for the g…
Surface characterisation of metal ions loaded TiO2 photocatalysts: structure–activity relationship
Abstract Transition metal loaded TiO 2 powders were characterised and tested for the photodegradation of some organic acids. Both Lewis and Bronsted surface acid sites were present in the samples containing large amounts of Mo, V and W. The Bronsted sites are associated to the presence of the transition metals as they do not exist in the unloaded support, and in particular to the presence of these metals in high oxidation states. The trend of the pzc values of the various powders matches rather well both with the surface acidity of the samples experimentally determined by NH 3 adsorption and with a scale of acidity/basicity for bulk binary oxides. XPS investigation indicates that only the p…
Combined effect of noble metals (Pd, Au) and support properties on HDS activity of Co/SiO2 catalysts
Abstract Cobalt-based catalysts supported on different types of SiO 2 are studied in the hydrodesulfurization of thiophene. Amorphous silica and siliceous MCM-41 and HMS, characterized by different texture and surface acidity are used as carriers. The effects due to the modification of the support by impregnation with palladium precursor and to the co-impregnation of cobalt and gold are considered. The catalysts are characterized by N 2 physisorption (BET), XRD, TPR and XPS techniques. The use as supports of the ordered mesoporous silica with higher surface area with respect to amorphous silica, produces a better dispersion of the cobalt oxides particles. Moreover, the addition of palladium…
Preparation of N-doped TiO2: characterization and photocatalytic performance under UV and visibile light
Nanocrystalline N-doped TiO(2) samples were prepared by using TiCl(4) or TiOSO(4) as precursors. The powders were characterized by X-ray diffraction, BET specific surface area measurements, scanning electron microscopy, diffuse reflectance spectroscopy, Raman spectroscopy and X-ray photoelectron spectroscopy. The photocatalytic activity was tested using the photodegradation of 4-nitrophenol under UV and visible light.Some samples were more active than commercial Degussa P25. A shift of the absorption edge to a lower energy and a stronger absorption in the visible light region were observed in the samples obtained from TiCl(4). Two absorption edges were observed in the samples derived from T…
Nature of cobalt active species in hydrodesulfurization catalysis: combined support and preparation method effects
Abstract Co/γ-Al2O3, Co/SiO2, Co/MCM-41, Co/ASA and Co/S2 (amorphous aluminosilicate with Al/Si = 0.13 and with Al/Si ≈ 2, respectively) were prepared by the method of wet impregnation and by the method of precipitation in the presence of sodium carbonate. The samples were characterised by XPS, XRD and TPR. The catalytic activity was tested in the hydrodesulfurization of thiophene using a continuous flow reactor. Among the wet impregnated catalysts those supported on the amorphous and ordered mesoporous silica exhibited higher HDS activity as compared to the alumina containing supports. Particularly, the use of the mesoporous, high surface area MCM-41 support, determined the best performing…
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…
Influence of Sodium on the Structure and HDS Activity of Co–Mo Catalysts Supported ON Silica and Aluminosilicate
Abstract Structural changes and catalytic performances of hydrodesulfurization (HDS) Co–Mo catalysts, supported on amorphous aluminosilicate (ASA) and amorphous SiO 2 were investigated as a function of the amount of sodium ions added to the supports. The catalysts were prepared according to the incipient wet impregnation method using (NH 4 ) 6 Mo 7 O 24 as molybdenum precursor and CoCl 2 or Co(NO 3 ) 2 as cobalt precursor. Structural and morphological characterisations of the materials were performed with X-ray diffraction (XRD) and surface area measurements (BET). In the case of the ASA-supported catalysts, increasing the amount of sodium resulted in a gradual decrease of the catalyst surf…
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…
Physicochemical investigation of cobalt?iron cyanide nanoparticles synthesized by a novel solid?solid reaction in confined space
Cobalt–iron cyanide (Cox[Fe(CN)6]) nanoparticles have been synthesized by a novel solid–solid reaction in the confined space of dry sodium bis(2-ethylhexyl)sulfosuccinate (AOT) reversed micelles dispersed in n-heptane. The reaction has been carried out by mixing two dry AOT/n-heptane solutions containing CoCl2 and K4Fe(CN)6 or K3Fe(CN)6 nanoparticles in the micellar core, respectively. By UV-Vis spectroscopy it was ascertained that, after the mixing process, the formation of stable nanoparticles is fast and complete. Microcalorimetric measurements of the thermal effect due to the Cox[Fe(CN)6] nanoparticle formation allowed the determination of the stoichiometric ratio (x) and of the molar e…
Influence of fluorine on the synthesis of anatase TiO2for photocatalytic partial oxidation: Are exposed facets the main actors?
Anatase TiO2 samples were synthesized in the presence of different amounts of HF acid with the aim of understanding the effect of the presence of fluorine on the photocatalytic activity. It is well known that the presence of fluoride ions influences the photocatalytic performance by adsorption on the surface of TiO2 and that they are capping agents in the control of specific exposed facets. The samples were characterized by X-ray diffraction (XRD), Raman spectroscopy, nitrogen adsorption–desorption measurements, scanning electron microscopy (SEM), transmission electron microscopy (TEM), UV-vis spectrophotometry, and X-ray photoelectron spectroscopy (XPS). The photocatalytic activity was eva…
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…
Structural characterisation of silica supported CoMo catalysts by UV Raman spectroscopy, XPS and X-ray diffraction techniques
The structure of Co-Mo catalysts supported on commercial silica, doped with various amounts of sodium ions, was investigated by means of X-ray diffraction (XRD), UV-Raman spectroscopy and X-ray photoelectron spectroscopy (XPS). Two series of samples were considered. One series was prepared by classic incipient wet impregnation (WI) and the other series by co-impregnation in the presence of nitrilotriacetic acid (NTA). The effect of sodium on the catalyst structure depended on the preparation procedure: in the case of the WI catalysts, sodium promoted the transformation of the polymolybdate species into monomolybdate Na2MoO4; in the case of the NTA prepared samples, sodium induced transforma…
Activity of SiO2 supported gold-palladium catalysts in CO oxidation
Abstract Bimetallic Au-Pd catalysts supported on silica with different Au/Pd atomic ratios were prepared by simultaneous reduction of palladium and gold precursors by ethanol in the presence of the polymer, polyvinylpyrrolidone (PVP). Formation of alloyed particles was detected by means of X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM) and CO chemisorption measurements. The catalysts were tested in the catalytic oxidation of CO using a plug–flow reactor. The CO conversion was determined as a function of temperature. The monometallic palladium and the palladium-rich catalysts behaved quite similarly and were the most active catalysts. …
EXAFS and XRD study of Pd–Ag bimetallic catalysts supported on pumice from organometallic precursors
Abstract Silver–palladium bimetallic catalysts were supported on pumice following different procedures, based on mild treatments of organometallic precursors. The experiments for the structural characterization of the synthesized samples, wide angle X-ray diffraction (XRD) and X-ray absorption spectroscopy, were carried out at the beamline GILDA of the European Synchrotron Radiation Facility. The analysis of the data demonstrated that alloying took place with a degree of homogeneity depending on the different preparation routes.
Catalytic CO oxidation over pumice supported Pd–Ag catalysts
Abstract Results on the catalytic oxidation of CO at 523 K over bimetallic Pd–Ag catalysts supported on pumice are reported and compared with those obtained from the monometallic Pd and Ag catalysts. The catalysts were prepared by organometallic precursors and were characterized by X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) after different treatments with air and with hydrogen. The activity of the catalysts decreases with increasing Ag/Pd atomic ratio, the monometallic palladium exhibiting the highest activity. Furthermore, the treatment with air and with hydrogen always results in a better catalytic performance. On the basis of the structural characterization by XRD…
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…
Highly stable defective TiO2-x with tuned exposed facets induced by fluorine: Impact of surface and bulk properties on selective UV/visible alcohol photo-oxidation
Abstract Titanium dioxide samples were prepared in the presence of different amounts of fluorine via hydrothermal method. It has been found that the presence of fluoride influenced the physico-chemical properties of TiO2 in various ways as polymorphic form stability, surface hydroxylation, generation of hydroxyl radicals under irradiation and formation of Ti3+ centers and oxygen vacancies. The generation rate of OH radicals was investigated by the photoluminescence technique in the presence of terephthalic acid. X-ray diffractometry indicated that fluorine stabilized the anatase TiO2. X-Ray photoelectron spectroscopy (XPS) revealed the presence of fluorine on the surface and the shift of th…
NO reduction by CO in the presence of water over gold supported catalysts on CeO2-Al2O3 mixed support, prepared by mechanochemical activation
Abstract The reduction of NO by CO was studied on gold catalysts supported on ceria-alumina, prepared by mechanochemical activation. The samples were characterized by means of XRD, TPR, XPS and Raman spectroscopy. The influence of water in the feed on the catalytic activity was evaluated as well. It was established that the addition of hydrogen and water improves NO reduction activity by CO. The role of water was connected to the hydrogen production by WGS. The role of oxygen vacancies created in ceria structure in the presence of alumina was also discussed. The 100% selectivity to N2 at about 200 8C was kept in all cases of catalytic measurements, making the studied gold catalysts promisin…
Gold catalysts supported on CeO2 and CeO2–Al2O3 for NO reduction by CO
Abstract The reduction of NO x by CO was studied over gold catalyst supported on ceria and ceria–alumina. The mixed supports with different CeO 2 /Al 2 O 3 ratios were prepared by co-precipitation. The catalysts were characterized by means of XRD, TPR, XPS and Raman spectroscopy. The addition of alumina led to a slight enlargement of the gold particles, while the ceria particle size was decreased. Deeper oxygen vacancies formation in the presence of alumina was detected by TPR, XPS and Raman spectroscopy, compared to the pure ceria support. The samples exhibited a high and stable activity and 100% selectivity towards N 2 was reached at 200 °C.
CoMo catalysts supported on aluminosilicates: synergy between support and sodium effects
Abstract The structural properties and the hydrodesulfurization (HDS) activity of sodium doped and sodium free CoMo catalysts supported on amorphous aluminosilicates (ASA) were investigated as a function of different SiO2:Al2O3 ratios. The support yielding the most active catalyst, (66% alumina) doped with different amounts of sodium, was used for a series of similar catalysts in order to study the effect of the alkali ion on the catalytic performance. The supports were prepared by sol–gel method and the catalysts were prepared by incipient wet impregnation method. The structure and the surface of the various samples were investigated by X-ray diffraction (XRD), temperature-programmed reduc…
“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 …
Influence of the preparation method on the thiophene HDS activity of silica supported CoMo catalysts
Abstract The effect of the preparation method of CoMo/SiO2 catalysts with and without sodium ions, on the hydrodesulfurization (HDS) of thiophene was investigated by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and N2 physisorption (BET). The samples were prepared by total sol–gel route, by classic wetness impregnation and by co-impregnation, in the presence of nitrilotriacetic acid (NTA), of commercial and sol–gel prepared silica. The influence of sodium ions added to the sol mixture and to the silica before the impregnation with Co and Mo salt solution, was also considered. The presence of sodium favoured the phase transition of amorphous silica to cristobalite with con…
Photoactivity under visible light of metal loaded TiO2 catalysts prepared by low frequency ultrasound treatment
Abstract Visible-light responsive bare and metal loaded (Pt, Ag, Rh, Pd) TiO 2 photocatalysts were prepared by using a simple ultrasound treatment. This method induced bulk oxygen deficiency resulting in a narrowing bandgap (from 3.18 to 3.04 eV) and in visible light absorption. The samples were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), BET specific surface area (SSA) and pore size distribution (PSD), UV–vis diffuse reflectance spectroscopy (DRS), Raman spectroscopy and X-ray photoelectron spectroscopy (XPS). The photocatalytic activity of the samples was evaluated by using the 4-nitrophenol oxidation reaction and the photocatalytic oxidation of glucose w…
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…
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…
Characterization of Pumice-Supported Ag–Pd and Cu–Pd Bimetallic Catalysts by X-Ray Photoelectron Spectroscopy and X-Ray Diffraction
Bimetallic Ag–Pd and Cu–Pd catalysts supported on pumice have been prepared in order to be used in the selective hydrogenation of dienes. The catalysts were obtained by the classical impregnation method and in the case of the Cu–Pd system also by organometallic precursors. They were analysed by X-ray photoelectron spectroscopy (XPS) and X-ray diffraction (XRD). XPS allowed us to determine the surface distribution and chemical state of the two elements; XRD yielded the lattice parameters and allowed us to establish the possible formation of alloys. The two bimetallic systems behave differently. In the case of the Ag-Pd catalysts, Pd particles covered by silver atoms along with highly dispers…
Structural characterization of Pd-Ag and Pd-Cu bimetallic catalysts by means of EXAFS, WAXS and XPS
Bimetallic Pd-Ag and Pd-Cu pumice-supported catalysts have been synthesized following different preparation procedures with the aim of improving the selectivity and reactivity of monometallic Pd/pumice systems. The structural characterization, carried out by X-ray Diffraction, X-ray Absorption and X-ray Photoelectron Spectroscopy, allowed to investigate the importance of the preparation procedures in the alloy formation.
Au/CeO2-SBA-15 catalysts for CO oxidation: Effect of ceria loading on physic-chemical properties and catalytic performances
In this work gold catalysts supported over SBA-15 with different CeO 2 loadings (5-30 wt%) were prepared, characterized by N 2 physisorption analyses, SAXS, XRD, STEM and XPS techniques and their catalytic performances were evaluated in the CO oxidation, chosen as reaction test. Over a selected catalyst, Au/CeO 2(20 wt%)-SBA-15, the effect of CO 2 and of the mixture (CO 2 + H 2O) on the CO conversion to CO 2 was also evaluated. Characterizations by SAXS, XRD, STEM and XPS were carried out on selected spent catalysts after CO oxidation. The results were discussed in terms of relationship between morphological, structural, electronic and catalytic properties as a function of the ceria loading…
Effect of Alkali Ions on the Amorphous to Crystalline Phase Transition of Silica
Abstract The effect of the addition of alkali ions to commercial amorphous silica, generally used as support for heterogeneous catalysts, has been investigated from the point of view of morphological and structural changes. Samples of alkali-doped silica were prepared by impregnation and subsequent calcination at various temperatures. The structural effect of Li, Na, K, and Cs was determined by use of techniques such as wide-angle (WAXS) and small-angle X-ray scattering (SAXS). The WAXS diffractograms, analyzed with the Rietveld method using the GSAS program, allowed qualitative and quantitative identification of the fraction of the different silica polymorphs like quartz, tridymite, and cr…
Support effect on the structure and CO oxidation activity of Cu-Cr mixed oxides over Al2O3 and SiO2
Abstract Cu-Cr based catalysts supported on silica and alumina with 5 wt% total loading of (CuO + Cr2O3), in different molar ratios, were prepared by wet impregnation. The samples were studied by nitrogen adsorption isotherms (BET), temperature-programmed reduction (TPR), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). Their catalytic activity was tested in the CO oxidation reaction. Different structures were obtained in dependence of the support, the atomic ratio and the calcination temperature. In particular, whereas on Al2O3 there was no experimental evidence for interaction between Cu and Cr, over the silica supported systems formation of new phases CuCr2O4 and CuCrO…
ChemInform Abstract: Coupled Semiconductor Systems for Photocatalysis. Preparation and Characterization of Polycrystalline Mixed WO3/WS2 Powders.
Mixed WO3/WS2 powders were prepared by oxidation of WS2. The physical properties of the samples were characterized by X-ray diffraction, diffuse reflectance spectroscopy, and scanning electron microscopy; they were strongly dependent upon the time and temperature of oxidation. The chemical state and the elemental distribution of the sample surface were investigated by X-ray photoelectron spectroscopy. The photocatalytic results have showed that the aqueous suspensions of the mixed WO3/WS2 systems have significantly higher activities than pure WS2 and WO3 for the photodegradation of phenol. The enhanced performance can be related to the presence of heterojunctions WO3/WS2 on the single parti…
Influence of SMSI effect on the catalytic activity of a Pt(1%)/ Ce0.6Zr0.4O2 catalyst: SAXS, XRD, XPS and TPR investigations
Abstract The steady-state activity of NO reduction by C3H6, in lean conditions, was studied on a Pt(1%)/Ce0.6Zr0.4O2 catalyst, in a plug-flow reactor, in the temperature range 100–500 °C. The influence of reductive pre-treatments on the catalytic performance at low temperature (250 °C) was investigated. Enhancement of the activity was found for the catalyst pre-treated in hydrogen at 350 °C as compared to the sample pre-treated in H2 at 800 and 1050 °C. Moreover, transient reactivity tests of NO reduction by hydrogen were also carried out. As previously observed, the sample reduced at 350 °C was the most active catalyst. In both types of reactions the temperature and the nature of pre-treat…
Effect of the Al/Si atomic ratio on surface and structural properties of sol-gel prepared aluminosilicates
Abstract A series of aluminosilicates with an Al/Si ratio ranging from 0 to ∞ (0 for pure silica and ∞ for pure alumina) was prepared by sol–gel process and characterized by surface and structure techniques. Aluminum tri sec butoxide and tetramethylorthosilicate were used as precursors for the sol–gel synthesis. The acidic properties of the oxides were studied by determination of the zero point charges, through mass titration method, and, for selected samples, by FT-IR spectroscopy of adsorbed pyridine used as a probe for both Bronsted and Lewis acidity. A dependence of the acidity on the Al/Si atomic ratio was found. According to the X-ray diffraction patterns, all the oxides have an amorp…
Chromia on silica and zirconia oxides as recyclable oxidizing system: structural and surface characterization of the active chromium species for oxidation reaction
Chromium oxide samples supported over silica and zirconia were prepared by wet impregnation of the supports with aqueous solution of CrO3. In order to investigate the influence of the preparation method on the chromium dispersion and oxidation state, one sample was prepared by sol-gel technique. The materials were structurally characterized by XRD analysis. The oxidation states of chromium species were investigated by XPS, DRS and TPR/TPO techniques. EPR analyses were also carried out for the sample Cr/SiO2, that due to the low crystalline state exhibits broad XPS signals. In this case, particular attention was paid to the presence of Cr(V) and Cr (III) species and their concentration. The …
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 incre…
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…
Characterization of the porous structure of Chilean volcanic soils by nitrogen adsorption and mercury porosimetry
Pore volume, specific surface area (SSA), and total intragranular porosity (TIP) of Chilean soils derived from volcanic materials were studied. Soil samples involving the 0-15 and 15-30 cm depth of virgin and cultivated Collipulli (Ultisol) and Diguillin (Andisol) soils at two particle size fractions (<1 mm and <2 µm) were considered. From mercury porosimetry and N2 adsorption, mainly mesopores (pore diameter, dpore, about 10 nm) were determined for <1 mm Collipulli samples. Diguillin <1 mm soil shows macroporosity with dpore from 70 nm to 7000 nm. The clay fraction of Collipulli has macropores (dpore from 2000 nm to 40000 nm) and mesopores (dpore from 3 nm to 23 nm), while for Diguillin cl…
Preparation characterization and photocatalytic activity of polycrystalline ZnO/TiO2 systems. 2. Surface, bulk characterization, and 4-nitrophenol photodegradation in liquid-solid regime
Electron spin resonance spectroscopy (ESR), Fourier transform infrared spectroscopy (FTIR), and monitoring of pyridine (py) and boric acid trimethyl ester (BATE) adsorption for determining surface acidity and basicity, respectively, were used to carry out further characterization of mixed ZnO/TiO2 polycrystalline solids prepared by different methods. Moreover, the powders were tested in a batch photoreactor for a probe reaction, i.e., 4-nitrophenol photodegradation in aqueous medium. ESR results indicated the presence of signals attributable to Zn+ species in ZnO/TiO2 (anatase) solids, while in ZnO/TiO2 (rutile) samples the presence of zinc induced only the formation of signals probably due…