The effect of SiO_2 particle size on iron based F–T synthesis catalysts

The effect of particle size of silica, as catalyst binder, on the chemical and mechanical properties of iron based FT catalyst was studied in this work. The samples were characterized using XRD, BET, TEM, FT-IR, and H2-TPR, respectively. The attrition resistance and the FT activity were tested. Si-8–Si-15 catalysts prepared with 8–15 nm silica sol show good attrition resistance(attrition loss b 4%), especially Si-13 with an attrition loss of 1.89%. Hematite appeared in XRD patterns when silica sol above 15 nm is used. TEM micrographs show that no obvious Si O_2 particles appear when silica sol particle with size less than 8 nm was used, but Si O_2 particles coated with small ferrihydrite particles appear when silica sol above 8 nm was used. Si–O–Si vibration peak in FT-IR spectra increases with increasing silica sol size. Samples prepared with silica sol show good stability of FT reactions, and the average molecular weight of FT products increases with the increase of Si O_2 particle.     

Pd/polyaniline as the catalysts for 2‐ethylanthraquinone hydrogenation. The effect of palladium dispersion

By doping of polyaniline (PANI) in PdCl₂ aqueous and ethanol solutions the catalysts containing crystalline and colloidal Pd particles of different sizes were prepared. The size of palladium particles present in Pd/PANI catalysts (characterised by SEM and XRD methods) influenced the course of 2‐ethylanthraquinone (eAQ) hydrogenation, a key step in the industrial production of H₂O₂. The presence of large palladium particles promotes reactions leading to the formation of the so‐termed “degradation products” not capable of hydrogen peroxide formation. This revised version was published online in July 2006 with corrections to the Cover Date.     

Novel Pd–Au/TiO2 catalyst for the selective catalytic reduction of NOx by H2

Novel Pd–Au/TiO₂ catalyst exhibited high catalytic activity with a wide temperature window for the selective catalytic reduction of NO_x by H₂ in the presence of oxygen. The synergetic effect between Pd and Au contributes to the formation of Pd⁰ and Pd–Au alloy, thus promoting the NO_x reduction to proceed.     

The effect of the change of the structure on oxidative dehydrogenation of propane over cerium–zirconium catalysts

A series of pure CeO₂, ZrO₂, and CeZrO_x mixed metal oxide catalysts were prepared by a wetness impregnation method and were applied to the dehydrogenation of propane to propylene at 500°C and 0.1 MPa. The prepared catalysts were characterized by thermal gravimetric analysis (TGA), Brunauer, Emmett, and Teller (BET), X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), scanning electron microscope (SEM), transmission electron microscopes (TEM), Raman spectroscopy, and H₂-TPR. It was observed that the zirconium content of the solid solution of the mixed metal oxide catalyst was 5%–25%, while the zirconium content of the material with phase segregation was higher (50%). The addition of zirconium was proven to decrease the oxygen vacancy concentration on the catalyst surface and change the intensity of (111) crystal of cerium oxide in the catalysts. Among the prepared catalysts, the Ce_0.90Zr_0.10O_x catalyst with the maximum strength of the (111) crystal plane of cerium oxide exhibited the better catalytic oxidation performance for the dehydrogenation of propane to propylene. Compared with ZrO₂ in the blank experiment, the average propane conversion and propylene selectivity of the Ce_0.90Zr_0.10O_x catalyst were increased by 10.78% and 17.95%, respectively.     

The effect of particle size on the formation and structure of carbide-derived carbon on β-SiC nanoparticles by reaction with chlorine

Carbide-derived carbon (CDC) coatings were produced by reaction with pure chlorine gas on the surface of β-SiC nanoparticles. Various CDC thicknesses were obtained using moderate temperatures (565–635 °C) associated with a short time (30 min) of chlorination under atmospheric pressure. Such conditions enable controlled layer-by-layer silicon extraction from SiC material. Kinetics of CDC formation were assessed using three SiC laser pyrolysis-produced nanopowders of different average size. Under the same conditions, the smallest particle size material is more prone to chlorination and exhibits a thicker carbon coating. Effect of particle size distribution on reactivity with chlorine is also discussed. After achieving carbide to carbon partial conversion, tem observations show good covering and adherent carbon coatings on remaining SiC material, N₂ adsorption analysis show that CDC coating is microporous and has a specific surface area exceeding 1000 m² g⁻¹. Thermogravimetric analysis coupled with mass spectroscopy under He gas flow, is used to determine the thermal stability and the nature of volatile species trapped in the microporosity. Under an O₂ gas flow, the amount of CDC formed is measured by burning it off at temperatures of 400–750 °C, before the onset of oxidation of the remaining SiC.     

The selective oxidation of glycerol over model Au/TiO2 catalysts — The influence of glycerol purity on conversion and product selectivity

The activity and selectivity of a model Au/TiO₂ catalyst was studied in the selective oxidation of glycerol as a function of the purity of the glycerol source. A reasonable conversion was noted when reagent grade starting materials were used. When crude glycerol from a FAME production facility was used, the activity of the catalyst was severely compromised and the selectivity of the reaction changed. Several low-cost approaches to purifying the crude glycerol were attempted but none resulted in the formation of a glycerol substrate whose conversion under reaction conditions matched that of the pure reagent grade substrate.     

The effect of the Ce content on the oxidative dehydrogenation of propane over CrOy-CeO2/γ-Al2O3 catalysts

A series of CrO_y (17.5 wt%)-CeO₂ (X wt%)/γ-Al₂O₃ catalysts (X = 0, 0.5, 2, 5, 8) with various Ce contents were prepared by a wetness impregnation method and were applied to the dehydrogenation of propane to propylene at 550 °C and 0.1 MPa. The prepared catalysts were characterized by BET, H₂-TPR, O₂-TPD, XPS, XRD, SEM-EDS and Raman spectroscopy. Among the prepared catalysts, the 17.5Cr-2Ce/Al catalyst with the largest amount of lattice oxygen exhibited the best catalytic performance for the dehydrogenation of propane to propylene with lattice oxygen. The decreased presence of oxygen defects and reducibility were the factors responsible for the improved dehydrogenation activity of the catalysts. The CeO₂ layer could inhibit the evolution of lattice oxygen (O²⁻) to electrophilic oxygen species (O₂⁻), and the oxygen defects on the catalyst surface were reduced. The inhibited lattice oxygen evolution prevented the deep oxidation of propane or propylene, the average CO_x selectivity decreased from 24.41% (17.5Cr/Al) to 5.71% (17.5Cr-2Ce/Al), and the average propylene selectivity increased from 60.15% (17.5Cr/Al) to 85.05% (17.5Cr-2Ce/Al).     

The effect of the Ce content on the oxidative dehydrogenation of propane over CrOy-CeO2/γ-Al2O3 catalysts

A series of CrO_y (17.5 wt%)-CeO₂ (X wt%)/γ-Al₂O₃ catalysts (X=0, 0.5, 2, 5, 8) with various Ce contents were prepared by a wetness impregnation method and were applied to the dehydrogenation of propane to propylene at 550℃ and 0.1 MPa. The prepared catalysts were characterized by BET, H₂-TPR, O₂-TPD, XPS, XRD, SEM-EDS and Raman spectroscopy. Among the prepared catalysts, the 17.5Cr-2Ce/Al catalyst with the largest amount of lattice oxygen exhibited the best catalytic performance for the dehydrogenation of propane to propylene with lattice oxygen. The decreased presence of oxygen defects and reducibility were the factors responsible for the improved dehydrogenation activity of the catalysts. The CeO₂ layer could inhibit the evolution of lattice oxygen (O^2-) to electrophilic oxygen species (O₂^-), and the oxygen defects on the catalyst surface were reduced. The inhibited lattice oxygen evolution prevented the deep oxidation of propane or propylene, the average CO_x selectivity decreased from 24.41% (17.5Cr/Al) to 5.71% (17.5Cr-2Ce/Al), and the average propylene selectivity increased from 60.15% (17.5Cr/Al) to 85.05% (17.5Cr-2Ce/Al).     

Effect of Pd loading and precursor on the catalytic performance of Pd/WO3–ZrO2 catalysts for selective oxidation of ethylene

The structure and properties of Pd/WO₃–ZrO₂ (W/Zr = 0.2) catalysts with different Pd loadings and precursors were investigated. The results indicate that Pd/WO₃–ZrO₂ prepared from a PdCl₂ precursor was optimum for high activity and selectivity. Moreover, ethylene conversion increased with the Pd loading. The structure and nature of the catalysts were characterized using X-ray diffraction, BET N₂ adsorption, H₂ temperature-programmed reduction and H₂ pulse adsorption techniques. The results reveal that the higher catalytic performance of Pd/WO₃–ZrO₂ prepared from PdCl₂ could be related to the formation of polytungstate species and the existence of well-dispersed Pd particles.     

Fischer–Tropsch synthesis: effect of small amounts of boron,ruthenium and rhenium on Co/TiO2 catalysts

The effect of the addition of small amounts of boron, ruthenium and rhenium on the Fischer–Tropsch (F–T) catalyst activity and selectivity of a 10 wt.% Co/TiO₂ catalyst has been investigated in a continuously stirred tank reactor (CSTR). A wide range of synthesis gas conversions has been obtained by varying space velocities over the catalysts. The addition of a small amount of boron (0.05 wt.%) onto Co/TiO₂ does not change the activity of the catalyst at lower space times and slightly increases synthesis gas conversion at higher space times. The product selectivity is not significantly influenced by boron addition for all space velocities investigated. Ruthenium addition (0.20 wt.%) onto Co/TiO₂ and CoB/TiO₂ catalysts improves the catalyst activity and selectivity. At a space time of 0.5 h-g cat./NL, synthesis gas conversion increases from 50–54 to 68–71% range and methane selectivity decreases from 9.5 to 5.5% (molar carbon basis) for the promoted catalyst. Among the five promoted and non-promoted catalysts, the rhenium promoted Co/TiO₂ catalyst (0.34 wt.% Re) exhibited the highest synthesis gas conversion, and at a space time of 0.5 h-g cat./NL, synthesis gas conversion was 73.4%. In comparison with the results obtained in a fixed bed reactor, the catalysts displayed a higher F–T catalytic activity in the CSTR.     

The effect of rippled graphene sheet roughness on the adhesive characteristics of a collagen–graphene system

A great amount of effort has been made in order to reach a more precise understanding of the adhesion phenomenon that happens as a vital component of several biological systems. Therefore, a firm understanding of the important factors that influence this phenomenon is of special importance in triggering the adhesive characteristics of different biological, bio-inspired and synthetic materials in fields such as tissue engineering.In this study the adhesive characteristics of a multi-material system consisting of the frequently used synthetic material, graphene, in the form of armchair-configuration sheets, and an important biological filament which is type 1 Collagen consisting of 3 alpha helices, has been studied in detail. The main emphasis of this study is placed on understanding the effects of the roughness characteristics of the inorganic elements which are the graphene sheets on the overall adhesive features of the system which are quantified within the framework of two main criteria: adhesion energy and peeling force. At first, the methodology used in order to obtain graphene sheets with various roughness values is described in detail. The abovementioned criteria are then evaluated through Molecular Dynamics (MD) modeling of the system in the NAMD simulation software environment and various simulation scenarios are studied.     

The effect of the addition of Y2O3 to Ni/α-Al2O3 catalysts on the autothermal reforming of methane

The addition of Y₂O₃ to Ni/α-Al₂O₃ catalysts was investigated by BET surface area measurements, hydrogen chemisorption, X-ray diffraction, UV–vis diffuse reflectance spectroscopy, X-ray fluorescence, temperature programmed reduction, temperature programmed oxidation and cyclohexane dehydrogenation. Autothermal reforming experiments were performed in order to evaluate the methane conversion and proceeded through an indirect mechanism consisting of total combustion of methane followed by CO₂ and steam reforming generating the synthesis gas. The Y₂O₃·Al₂O₃ supported catalysts presented better activity and stability in autothermal reforming reaction. Temperature programmed oxidation analysis demonstrated that the addition of Y₂O₃ resulted in a change of the type or the location of coke formed during reaction. None of the prepared catalyst presented deactivation by sintering under the tested conditions. The improved stability of supported catalysts Y₂O₃·Al₂O₃ was the result of minimizing the formation of coke on the surface of nickel particles.     

The effect of Si–Bi2O3 on the ignition of the Al–CuO thermite

The ignition temperature of the Al–CuO thermite was measured using DTA at a scan rate of 50 °C min^?1 in a nitrogen atmosphere. Thermite reactions are difficult to start as they require very high temperatures for ignition, e.g. for Al–CuO thermite comprising micron particles it is ca. 940 °C. It was found that the ignition temperature is significantly reduced when the binary Si–Bi₂O₃ system is added as sensitizer. Further improvement is achieved when the reagents are nano-sized powders. For the composition Al + CuO + Si + Bi₂O₃ (65.3:14.7:16:4 wt.%), with all components nano-sized, the observed ignition temperature is ca. 613 °C and a thermal runaway reaction is observed in the DTA.     

Oxidation and reduction effects of propane–oxygen on Pd–chlorine/alumina catalysts

Pd–chloride precursor salt was used to prepare Pd/Al₂O₃ catalysts. TPSR measurements showed three distinct reactions for the oxidation of propane on palladium surface under excess of hydrocarbon: complete oxidation, steam reforming and propane hydrogenolysis. Propane oxidation on palladium catalysts was related to the Pd²⁺ sites observed on Pd/Al₂O₃ through infrared of adsorbed carbon monoxide. In fresh catalysts reduced by H₂, the IR spectra showed the linear and bridge adsorbed CO species on the Pd⁰ surface. After propane reaction, a new band at 2130 cm^-1 related to CO adsorption on Pd²⁺ species was noted. Carbon monoxide species adsorbed on Pd⁰ were also observed in all samples after reaction. Our results suggest surface ratios of Pd⁰/PdO during the propane oxidation. On the other hand, time on stream conversions of the complete oxidation of propane were affected by either the water generated during the reaction or added as a reactant at 10 vol%. The water generated by the reaction helped to eliminate chlorine residues in the form of oxychloride species leading to an increasing of the activity. However, the presence of water into the reaction mixture caused a strong decreasing of the activity. The inhibition mechanism of propane oxidation in the presence of water consisted in the dissociative adsorption of water on palladium sites with the possible formation of palladium hydroxide (Pd–OH) at the surface, diminishing the number of active surface sites. Dynamic fluctuations into the reaction conditions supported the idea that a pseudo‐equilibrium adsorption–desorption of water was reached. After water removal or increasing in the reaction temperature the equilibrium was shifted to the direction of OH–Pd decomposition. This behavior suggests that the inhibitory effect of water is a reversible phenomenon, being a function of the amount of water and the reaction temperature. This revised version was published online in July 2006 with corrections to the Cover Date.     

The effect of Cl− on the kinetics of the anodic dissolution of Pd in H2SO4 solutions

The electrodissolution kinetics of palladium have been studied in deoxygenated

solutions at 25°C. The chloride concentration was varied between 0.01 and 0.5 M and the ionic strength was maintained at 1 M. For all the chloride concentrations an anodic Tafel slope of approximately 58 mV decade⁻¹ and an electrochemical anodic reaction order of 1.1 were obtained. The kinetic equation consistent with the experimental results is

which is consistent with the theoretical equation derived from the proposed mechanism, with the assumption that the adsorbed intermediate, (PdCl⁻₂)_ad follows Temkin adsorption behavior.     

Effect of particle size on microstructural and mechanical properties of UHMWPE–TiO2 composites produced by gelation and crystallization method

In this study, Ultra-high-molecular-weight polyethylene (UHMWPE) in 0.5 wt % concentration—0.5, 1, and 2 wt % nanosized and micron-sized TiO₂ composites were produced via gelation/crystallization method in decalin + antioxidant solution at 150 °C for 45 min by using magnetic stirrer. The gel composites were cooled in an aluminum tray embedded in iced water under ambient conditions and dried in an oven at 130 °C for 90 min to remove any residual trace of decalin and to strengthen the UHWMPE matrix. Scanning electron microscopy–EDS images indicate that TiO₂ particles were integrated well with the polymer matrix. differential scanning calorimetry studies revealed that the crystallinity of pure UHMWPE was calculated as 56% and an increase of 13.32% for micron sized and 19.25% for nano sized TiO₂. Crystalline and amorphous phases of UHMWPE–TiO₂ composites confirmed by Raman are in good agreement with the literature. The elastic modulus of test materials ranged from 610 to 791 MPa for micron sized and raised from 675 to 1085 for nano sized reinforcing agents. Ultimate tensile stress increased about 35% for micron sized and 60% for nano sized weight 1% TiO₂ reinforced composites. Biomineralization tests (performed in stimulated body fluid, at 37 °C and 6.5 pH during 1 month) have shown that produced composites are compatible as acetabular liner replacement for hipjoints due to no accumulation (Ca, P, Na, etc.) on UHMWPE–TiO₂ composites. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47402.     

The flooding of a powder — the importance of particle size distribution

This paper reviews the development of a new annular shear cell for the characterisation of aerated powders, and studies in detail the flooding phenomena for an alumina powder. Results have shown a large reduction in shear stress for small quantities of air entrainment and transition from normal Coulomb-solid flow to liquid-like flow at high shear rates. Addition of fine particles is shown to enhance these effects, thereby increasing the likelihood of flooding. Addition of particles of size 40 μm and below is shown to be the main factor. An increase of 10% of particles in this size range shows a similar shear response to that obtained with a sample of alumina known to have flooded, although smaller quantities also have a significant effect. Such low quantities of additional fines could occur due to segregation, resulting in pockets of material with a high chance of flooding under normal powder handling conditions.     

Preparation and characterization of the bimetallic Pt–Au/ZnO/Al2O3 catalysts: Influence of Pt–Au molar ratio on the catalytic activity for toluene oxidation

The bimetallic Pt–Au catalysts supported on ZnO/Al₂O₃ with different Pt/Au molar ratios were prepared by impregnation (IMP) method using a mixed solution of Pt and Au precursor. These were characterized by X-ray diffraction (XRD), CO chemisorption, temperature programmed reduction (TPR), and transmission electron microscopy (TEM) equipped energy dispersive spectroscopy (EDS). Catalytic activity for complete oxidation of toluene was measured using a flow reactor under atmospheric pressure. In the results, the aggregation of Au particles depended on the molar ratio in the bimetallic Pt–Au catalyst, and Pt particles was well dispersed homogeneously even by the IMP method. The Pt₇₅Au₂₅ and Pt₆₇Au₃₃ catalysts concurrently coated with Pt and Au precursors by IMP method showed higher activity than monometallic Pt and Au catalyst for toluene oxidation. Also, in order of the catalytic activity for toluene was very good agreement compare with the TPR results. The Au particles might promote the toluene oxidation over the bimetallic catalyst concurrently coated with Pt and Au particles. Therefore, the size of Pt and Au particles and catalytic activity were confirmed to be correlated to molar ratio of Pt and Au loaded.     

The effect of heat treatment conditions on the textural and catalytic properties of nickel–titania composite aerogel catalysts

Highly dispersed nickel–titania composite aerogel catalysts have been prepared by CO₂ supercritical drying of alcogels obtained by the sol–gel process. The effect of heat treatment conditions on the textural and structural properties of the resulting aerogels was investigated by nitrogen adsorption–desorption, TG/DTA, XRD and TEM. The nickel–titania composite aerogel calcined and reduced under carefully controlled conditions exhibited an excellent catalytic performance for the liquid-phase hydrogenation of benzophenone to benzhydrol.     

On the self-similarity of the aggregation–fragmentation equilibrium particle size distribution

A rather simple (yet general) theoretical analysis is presented concerning the steady-state particle size distribution in combined aggregation–fragmentation processes. The general conditions are provided for this distribution to exhibit self-similar behaviour. The theory is applied to the case of turbulent aggregation-fragmentation of fractal particles. It is shown that by using this analysis, experimental data can be interpreted without resorting to a numerical solution of the population balance equation.