Complete oxidation of ethylene over supported gold nanoparticle catalysts

Complete oxidation of ethylene was performed over supported noble metals or transition metals oxide catalysts and on monoliths under atmospheric pressure. Gold nanoparticles on Al2O3 or MxOy(M = Mo, Fe, Mn) were prepared by impregnation, coprecipitation, deposition, and dispersion methods. Nanoparticles prepared by impregnation method were irregular and very large above 25 nm, but those by coprecipitation and deposition method were uniformly nanosized at 4-5 nm. The gold nanoparticle were outstandingly active in catalyzing oxidation of ethylene. The activity order of these catalysts with preparation methods was deposition > coprecipitation > impregnation, and Au/Co3O4 prepared by deposition method showed the best performance in ethylene oxidation. The addition of gold particles to MxOy/Al2O3 catalyst enhanced the ethylene oxidation activity significantly. The main role of the gold nanoparticles apparently was to promote dissociative adsorption of oxygen and to enhance the reoxidation of the catalyst.     

Graphene supported platinum nanoparticle counter-electrode for enhanced performance of dye-sensitized solar cells

Composites of few layered graphene (G) and platinum (Pt) nanoparticles (NP) with different loadings of Pt were used as counter electrode (CE) in dye-sensitized solar cell (DSSC). NPs were deposited directly on to G using pulsed laser ablation method (PLD). DSSCs formed using the composite CEs show improved performance compared to conventional Pt thin film electrode (Std Pt) and unsupported Pt NPs. Composite with 27% loading of Pt shows 45% higher efficiency (η = 2.9%), greater short circuit current (J(sc) = 6.67 mA cm(-2)), and open circuit voltage (V(oc) = 0.74 V) without any loss of the fill factor (FF = 58%) as compared to the cells fabricated using Std Pt electrodes. Values of η, J(sc) and V(oc) for DSSC using Std Pt CE were 2%, 5.05 mA cm(-2) and 0.68 V, respectively. Electrochemical impedance spectroscopy using I(-)(3)/I(-) redox couple confirm lower values of charge transfer resistance for the composite electrodes, e.g., 2.36 Ω cm(2) as opposed to 7.73 Ω cm(2) of Std Pt. The better catalytic activity of these composite materials is also reflected in the stronger I(-)(3) reduction peaks in cyclic voltammetry scans.     

Nanostructure SnO2 and supported Au catalysts: Synthesis,characterization, and catalytic oxidation of CO

Nanostructure tin dioxide (SnO₂) powders prepared by sol-gel dialytic processes using tin (IV) chloride and anhydrous alcohol as start materials, ammonia gas as catalyst of the formation of colloid solution and agent of removing Cl⁻, and by introducing dialytic processes to improve and accelerate the formation of gels. From the result of TG–DTA analyses, the dried samples were calcined at 673 K in air for 3 h. Tin dioxide nanoparticles were characterized by thermogravimetry and differential thermal analyses (TG–DTA), X-ray diffraction (XRD), nitrogen adsorption–desorption, X-ray photoelectron spectroscopy (XPS). The average particle size of the as-prepared tin dioxide was about 5 nm. The as-prepared SnO₂ possessed mesoporous structure and large surface area. The Au/SnO₂ catalysts for low-temperature CO oxidation were prepared by the deposition–precipitation method using as-prepared SnO₂ powders as the support. The Au/SnO₂ catalysts exhibited high catalytic activity for low-temperature CO oxidation. The nanostructure SnO₂ has promising applications in sensor, catalyst, catalytic support, mesoporous membranes, etc.     

Synthesis and characterization of supported heteropolymolybdate nanoparticles between silicate layers of Bentonite with enhanced catalytic activity for epoxidation of alkenes

A new heterogeneous catalyst (PVMo/Bentonite) consisting of vanadium substituted heteropolymolybdate with Keggin-type structure Na₅[PV₂Mo₁₀O₄₀]·14H₂O (PVMo) supported between silicate layers of bentonite has been synthesized by impregnation method and characterized using X-ray diffraction, Fourier-transformed infrared spectroscopy, scanning electron microscopy, UV–vis diffuse reflectance spectroscopy, transmission electron microscopy and elemental analysis. X-ray diffraction and scanning electron microscopy analysis indicated that PVMo was finely dispersed into layers of bentonite as support. The PVMo/Bentonite used as an efficient heterogeneous catalyst for epoxidation of alkenes. Various cyclic and linear alkenes were oxidized into the corresponding epoxides in high yields and selectivity with 30% aqueous H₂O₂. The catalyst was reused several times, without observable loss of activity and selectivity. The obtained results showed that the catalytic activity of the PVMo/Bentonite was higher than that of pure heteropolyanion (PVMo).     

Synthesis,characterization, and enhanced formic acid electrooxidation activity of carbon supported MnOx promoted Pd nanoparticles

Formic acid (HCOOH) is one of the promising fuels for direct liquid fed fuel cells. However, CO poisoning is a major challenge for the development of effective catalytic system for formic acid electrooxidation (FAEO). Herein, a novel CO-resistive activated carbon supported Pd-MnO_x bimetallic catalyst (Pd-MnO_x/C) was presented for FAEO. Pd-MnO_x/C catalyst was prepared via simple and reproducible surfactant-free deposition-reduction technique. The characterization of this novel Pd-MnO_x/C catalyst was performed by inductively coupled plasma-optical emission spectroscopy (ICP-OES), powder X-ray diffraction (PXRD), X-ray photoelectron spectroscopy (XPS), bright field transmission electron microscopy (BFTEM), high resolution transmission electron microscopy (HRTEM), scanning transmission electron microscopy (STEM), and scanning transmission electron microscope-energy dispersive X-ray spectroscopy (STEM-EDX). The characterization results revealed that Pd and MnO_x nanoparticles (NPs) were well dispersed and separately nucleated with a mean diameter of 2.9?nm on the surface of active carbon. FAEO studies were performed on both Pd-MnO_x/C and Pd/C catalysts to comprehend the effect of separately formed MnO_x on the electrocatalytic activity of Pd NPs. The electrochemical measurements were carried out by using Cyclic Voltammetry (CV) and Chronoamperometry (CA), CO-Strriping Voltammetry, Lineer Sweep Voltammetry (LSV), Electrochemical impedance spectroscopy (EIS) techniques. Electrochemical results revealed that FAEO was activated by the addition of MnOx. Pd_0.6-Mn_0.4 exhibited the optimum catalytic activity with 1.05?A/mg Pd current density. The sum of their results clearly points that the existence of MnO_x NPs enhances the electrocatalytic activity of Pd NPs by increasing their CO-resistivity and durability throughout the FAEO.     

Synthesis and magnetic characterization of MnAs nanoparticles via nanoparticle conversion

We report on the synthesis of ferromagnetic manganese arsenide (MnAs) nanoparticles via the conversion of primary Mn particles which are generated in an aerosol process in a spark discharge generator. After sintering and size selection in an aerosol setup, the particles are deposited on GaAs(100)B and Si(111) substrates. Subsequent conversion to MnAs particles takes place in an annealing process under a hydrogen atmosphere with an arsine background pressure. The magnetic properties are studied using a SQUID magnetometer. The annealed MnAs particles exhibit hexagonal facets and show anisotropic magnetic behaviour on GaAs(100)B substrates, whereas on Si(111) they remain spherical and show isotropic magnetic behaviour. Scanning transmission electron microscopy studies are used to confirm the conversion from Mn to MnAs.     

Synthesis and characterization of WS2 nanotube supported cobalt catalyst for hydrodesulfurization

WS₂ nanostructures hold structural characteristics which suggest they will be suitable for heterogeneous catalysis in the hydrodesulfurization (HDS) process. In this work, WS₂ nanotubes (INT-WS₂) were coated with cobalt nanoparticles using electroless plating method. Prior to cobalt deposition, the nanotubes surface was activated using palladium seeding process. The deposited cobalt nanoparticles had hcp crystal structure and formed non-uniform layer on the nanotubes surface. The catalytic reactivity of the produced cobalt coated nanotubes toward thiophene decomposition was characterized by an atmospheric flow reactor. The coated nanotubes revealed good catalytic reactivity toward thiophene mineralization. Further, the adsorption kinetics of thiophene on coated INT-WS₂ was studied by thermal desorption spectroscopy (TDS). The cobalt coated system was found to be more catalytically active than the pristine INT-WS₂ system. This result is promising since further optimization of the nanofabrication process of the catalyst should increase the conversion rates even further.     

Synthesis and characterization of lower size,laurylamine protected palladium nanoparticles

A procedure to synthesize lower size mono dispersed palladium nanoparticles is described. The nanoparticles are stabilized by lauryl amine and are isolable as dispersible solids. The particles are characterized by UV–Vis, FT-IR, XRD, STM and TEM techniques.     

Synthesis,characterization and catalytic activity studies of Pd-based supported nanoparticle catalyst anchoring on poly(N-vinyl-2-pyrrolidone) modified CMK-3

Pd nanoparticle-poly(N-vinyl-2-pyrrolidone)/CMK-3 (Pd-PVP/CMK-3) composite was prepared by in situ polymerization method which was effectively employed as a novel heterogeneous catalyst for the Suzuki–Miyaura cross-coupling reaction. The physical and chemical properties of Pd nanoparticle-PVP/CMK-3 were investigated using FT-IR, XRD, BET, UV–vis, TEM and TGA techniques. The reaction was carried out between aryl halides and phenylboronic acid in the presence of water at room temperature. The stability of the catalyst was good and could be reused 10 times without much loss of activity in Suzuki–Miyaura reaction.     

Synthesis and characterization of silver nanoparticle composite with poly(p-Br-phenylsilane)

The one-pot synthesis and characterization of silver nanoparticle-poly(p-Br-phenylsilane) composites have been carried out. The conversion of silver(+1) salt to stable silver(0) nanoparticles is promoted by poly(p-Br-phenylsilane), Br-PPS possessing both possible reactive Si-H bonds in the polymer backbone and C-Br bonds in the substituents. The composites were characterized using XRD, TEM, FE-SEM, and solid-state UV-vis analytical techniques. TEM and FE-SEM data show the formation of the composites where large number of silver nanoparticles (less than 30 nm of size) are well dispersed throughout the Br-PPS matrix. XRD patterns are consistent with that for fcc-typed silver. The elemental analysis for Br atom and the polymer solubility confirm that the cleavage of C-Br bond and the Si-Br dative bonding were not occurred appreciably at ambient temperature. Nonetheless, TGA data suggest that some sort of cross-linking was occurred at high temperature. The size and processability of such nanoparticles depend on the ratio of metal to Br-PPS. In the absence of Br-PPS, most of the silver particles undergo macroscopic aggregation, which indicates that the polysilane is necessary for stabilizing the silver nanoparticles.     

Synthesis and characterization of CeO2 supported ZSM-5 zeolite for organic dye degradation

Journal of Materials Science: Materials in Electronics - ZSM-5:CeO2 nanocomposites were prepared by two-step hydrothermal method in combination with the wet impregnation method. The synthesized...     

Preparation and characterization of hollow carbon nanospheres supported metallic catalysts by using one-step pyrolysis method

A versatile one-step pyrolysis method is successfully employed to fabricate hollow carbon nanospheres (HCNs, ca. 60 nm in diameter) supported with metallic nanoparticle catalyst. The resultant catalyst hybrid was characterized by using TEM, FTIR, TGA measurements. It is confirmed that, as the carbon precursor and hollow core/shell structure template, hollow chitosan nanospheres provide the important adsorption sites for the metallic precursor. The one-step pyrolysis process at 750 degrees C under nitrogen atmosphere results in the simultaneous decomposition of the chitosan nanospheres to HCNs and the adsorbed metal salt complex to metallic nanoparticles. It is found that metallic nanoparticles with an average diameter of ca. 4 nm highly dispersed in the carbon shell of HCNs, and no aggregation phenomenon occurs under the high deposition temperature. As a demonstration, the HCNs-supported Pt catalyst for the electrochemical methanol oxidation was studied.     

Nanostructural and chemical characterization of supported metal oxide catalysts by aberration corrected analytical electron microscopy

The performance of catalyst materials are usually governed by the precise atomic structure and composition of very specific catalytically active sites. Therefore, structural and chemical characterization at the atomic scale becomes a vital requirement in order to identify any structure-performance relationships existing in heterogeneous catalyst systems. Aberration-corrected scanning transmission electron microscopy (STEM) represents an ideal means to probe the atomic scale structural and chemical information via a combination of various imaging and spectroscopy techniques. In particular, high-angle annular dark-field (HAADF) imaging provides directly interpretable atomic number (Z) contrast information; while X-ray energy dispersive spectroscopy (XEDS) and electron energy-loss spectroscopy (EELS) spectrum imaging can be used to identify the chemical composition and oxidation state. Here we review some applications of aberration-corrected STEM to catalyst research, firstly in the context of supported metal catalysts, which serve as ideal material systems to illustrate the power of these techniques. Then we focus our attention on more recent progress relating to the characterization of supported metal oxide catalysts using aberration-corrected STEM. We demonstrate that it is now possible to directly image supported surface oxide species, study oxide wetting characteristics, identify the catalytic active sites and develop new insights into the structure-activity relationships for complex double supported oxide catalysts. Future possibilities for in situ and gentle low voltage electron microscopy studies of oxide-on-oxide materials are also discussed.     

Synthesis and characterization of super-microporous material with enhanced hydrothermal stability

Super-microporouos silicon material with high hydrothermal stability denoted as MCM-41-T has been prepared from mesoporous MCM-41 by high temperature treatment. The structural and chemical property of MCM-41-T has been characterized by X-ray diffraction, transmission electron microscopy, N₂ adsorption-desorption, infrared spectroscopy and ²⁹Si MAS NMR. The characteristic results show that Si-OH groups are forced to condense by high temperature treatment, and the pore size of MCM-41-T is around 1.5 nm in the super-microporous range. Compared with the original material MCM-41, the hydrothermal stability of MCM-41-T has been significantly enhanced.     

Kinetic study of trichloroethylene combustion on exchanged zeolites catalysts

In this paper is presented a kinetic study of the catalytic combustion of trichloroethylene (TCE) over Y-zeolites exchanged with several cations. The catalysts, based on zeolite, were prepared by ion exchange and characterized by means of physico-chemical techniques and then tested under kinetic conditions. The kinetic results obtained were interpreted using kinetic models of power-law type and Eley-Rideal. The results obtained indicate that catalyst Y-Cr is more active than Y-Co catalyst. The greater activity of catalyst exchanged with Cr can be attributed to the higher acidity that presented these catalysts.     

Catalytic hydrodechlorination of 2,4-dichlorophenol on Pd/Rh/C catalysts

Catalytic hydrodechlorination of 2,4-dichlorophenol was studied over 0.97% Pd/C, 0.98% Rh/C and 0.8% Pd-0.19% Rh/C catalysts. The catalysts were prepared by incipient wetness impregnation of support and characterized by BET surface area, temperature programmed reduction (TPR) and X-ray diffraction (XRD). The 0.97% Pd/C catalyst, which had the largest crystallite size, was the most active and selective towards the formation of 2- and 4-chlorophenols among three catalysts in liquid phase. Hydrodechlorination activity of carbon-supported catalysts were in the order of Pd/C>Pd/Rh/C>Rh/C. The kinetic equation explained experimental data well and kinetic parameters of three catalysts were provided and discussed.     

Preparation and characterization of nanosized gold catalysts supported on Co3O4 and their activities for CO oxidation

Gold catalysts supported on Co3O4 were prepared by co-precipitation (CP), deposition-precipitation (DP), and impregnation (IMP) methods. The Au/Co3O4 catalysts were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), and temperature programmed reduction (TPR) to understand the different activities for CO oxidation with different preparation methods. Gold particles below 5 nm supported on Co3O4 by DP method were found to be more exposed to the surface than those by CP and IMP methods, and this catalyst was highly active and stable in CO oxidation. Finally, catalytic activity of Au/Co3O4 catalyst for CO oxidation was strongly dependent on the gold particle size.     

Synthesis and characterization of carbon nanotubes grown on montmorillonite clay catalysts

Multiwall carbon nanotubes have been grown on montmorillonite clay catalysts through anchoring on FeCo nanoparticles. The starting clay is a commercial sodium-rich montmorillonite in which the intercalated sodium ion was exchanged for cobalt(II) and iron(III) ions via mechanical agitation or sonication, both with and without subsequent centrifugation. The cobalt-iron intercalate clay was used as a catalyst for the synthesis of carbon nanotubes via decomposition of ethylene at 700 °C. The largest carbon deposit was obtained for catalysts prepared with 3 or 4 cation exchange equivalents. X-ray diffraction indicates both that the basal spacing of the clay increases from 12.43 Å to 16.4 Å upon intercalation of cobalt and iron. Atomic absorption analysis of the catalysts indicates that virtually all of the sodium ions originally present in the clay have been replaced by iron(III) and cobalt(II). Transmission electron micrographs show the presence of multiwall carbon nanotubes with inner and outer diameters of ca. 10 nm and 20 nm grown on metal particles present on the plates of catalysts. The iron-57 Mössbauer spectra indicate that the intercalated clay contains iron(III) in octahedral and tetrahedral sites and iron(II) in octahedral sites, the catalysts contain an extensive amount of small superparamagnetic particles of α-Fe₂O₃ and that the carbon-nanotube catalyst composites show the presence of iron(II) and iron(III) paramagnetic doublets, characteristic of a reduced montmorillonite, and of sextets that are characteristic of an FeCo alloy and of Fe₃C cementite. The Mössbauer spectra indicate that the carbon nanotubes grow on FeCo metallic nanoparticles and bond to these particles through the formation of cementite.     

Iron supported clay as catalysts for oxidation of cyclooctane

Iron supported bentonite clay catalysts have been prepared by the ion exchange of bentonite with iron²⁺ and iron³⁺ solution and immobilization with iron compounds using ligands: acetylacetonate, picolinate, pyrazinate and bipyridine. The catalysts were characterized by FT-IR spectroscopy, X-ray diffraction, X-ray fluorescence analysis and scanning electron microscopy. They were used as catalyst in the oxidation reaction of cyclooctane with tert-butyl hydroperoxide as oxidant. The experimental results show that activity of the catalysts is influenced by ligand, it decreases in the following order: acetylacetonate > picolinate > pyrazinate ∼ bipyridine. Bentonite supported with iron³⁺ acetylacetonate gave 17% yield with 80% selectivity to cyclooctanone at 70°C for 24 h. The mechanism of the cyclooctane oxidation with tert-butyl hydroperoxide was proposed to occur via alkyl hydroperoxide intermediate in radical pathway.