Synthesis, characterization, and catalytic phenol hydroxylation of a novel complex oxide HxV2Zr2O9.H2O

A novel type of complex oxide H_xV₂Zr₂O_9.H _2O with V⁴⁺ and V⁵⁺ mixed valence has been hydrothermally synthesized in a V₂O₅-ZrO₂-H₂O system at 240°C for 5 days in presence of NaF. The catalytic data over these complex oxides show that these complex oxides are catalytically very active in phenol hydroxylation by 30% aqueous hydrogen peroxide, and their catalytic activity is dependent on crystal size of the catalysts. The phenol conversion over the catalyst with crystal size of 7 μm is twice that over the catalyst with crystal size of 35 μm. The V⁵⁺ species are suggested to be the catalytic active sites. Some other factors which influence the catalytic activity were also investigated. This revised version was published online in July 2006 with corrections to the Cover Date.     

The effect of catalyst film thickness on the electrochemical promotion of ethylene oxidation on Pt

The effect of catalyst film thickness on the magnitude of the effect of electrochemical promotion of catalysis (EPOC or NEMCA effect) was investigated for the model catalytic reaction of C₂H₄ oxidation on porous Pt paste catalyst-electrodes deposited on YSZ. It was found that the catalytic rate enhancement ρ is up to 400 for thinner (0.2 μm) Pt films (40,000% rate enhancement) and gradually decreases to 50 for thicker (1 μm) films. The results are in good qualitative agreement with model predictions describing the diffusion and reaction of the backspillover O²⁻ species which causes electrochemical promotion.     

Influence of intracrystalline diffusion on the selective catalytic reduction of NO by hydrocarbon over Cu-MFI zeolite

The influence of intracrystalline diffusion on the selective catalytic reduction of NO by hydrocarbons (propane, ethene) was investigated by using Cu-MFI catalysts of different zeolite crystal sizes. The influence of hydrocarbon as a reductant on the diffusion process was also investigated, employing kinetic and temperature-programmed desorption studies. In the NO–C₃H₈–O₂ reaction, the apparent reaction rate of NO conversion into N₂ did not depend on the zeolite crystal size, which indicates that the reaction is not controlled by intracrystalline diffusion. In the NO–C₂H₄–O₂ reaction, on the other hand, the apparent reaction rate evidently depended on the zeolite crystal size; the reaction rate over large crystal Cu-MFI (1.29 μm) was significantly less than that over a small one (0.09 μm), which indicates that the reaction is controlled by intracrystalline diffusion. The larger diffusion resistance in the NO–C₂H₄–O₂ reaction was attributed to the slower diffusion rate of ethene in zeolite channels than propane, which was due to much stronger interaction of ethene with Cu-MFI catalyst. Thus, the adsorption property of hydrocarbon on the Cu-MFI catalyst is revealed to play an important role in determining intracrystalline diffusivity and the diffusion influence on the selective reduction of NO over zeolite catalysts.     

The effect of catalyst film thickness on the magnitude of the electrochemical promotion of catalytic reactions

The effect of catalyst film thickness on the magnitude of the effect of electrochemical promotion was investigated for the model catalytic reaction of C₂H₄ oxidation on porous Pt paste catalyst-electrodes deposited on YSZ. It was found that the catalytic rate enhancement ρ is up to 400 for thinner (0.2 μm) Pt films (40,000% rate enhancement) and gradually decreases to 50 for thicker (1 μm) films. The Faradaic efficiency Λ was found to increase moderately with increasing film thickness and to be described semiquantitatively by the ratio 2Fr _o/I ₀, where r _o is the unpromoted rate and I ₀ is the exchange current of the catalyst–electrolyte interface. The results are in good qualitative agreement with model predictions describing the diffusion and reaction of the backspillover O^2- species, which causes electrochemical promotion.     

Electrochemical promotion of the oxidation of propane on Pt/YSZ and Rh/YSZ catalyst-electrodes

The effect of electrochemical promotion (EP) or non-faradaic electrochemical modification of catalytic activity (NEMCA) was studied in the catalytic reaction of the total oxidation of propane on Pt and Rh films deposited on Y₂O₃-stabilized-ZrO₂ (or YSZ), an O²⁻ conductor, in the temperature range 420–520 °C. In the case of Pt/YSZ and for oxygen to propane ratios lower than the stoichiometric ratio it was found that the rate of propane oxidation could be reversibly enhanced by application of both positive and negative overpotentials (“inverted volcano” behavior), by up to a factor of 1350 and 1130, respectively. The induced rate increase Δr exceeded the corresponding electrochemically controlled rate I/2F of O²⁻ transfer through the solid electrolyte, resulting in absolute values of the apparent faradaic efficiency Λ=Δr/(I/2F) up to 2330. The Rh/YSZ system exhibited similar EP behavior. Abrupt changes in the oxidation state of the rhodium catalyst, accompanied by changes in the catalytic rate, were observed by changing the O₂ to propane ratio and catalyst potential. The highest rate increases, by up to a factor of 6, were observed for positive overpotentials with corresponding absolute values of faradaic efficiency Λ up to 830. Rate increases by up to a factor of 1.7 were observed for negative overpotentials. The observed EP behavior is explained by taking into account the mechanism of the reaction and the effect of catalyst potential on the binding strength of chemisorbed reactants and intermediates and on the oxidative state of the catalyst surface.     

Electrogeneration of Hydrogen Peroxide in Acid Medium using Pyrolyzed Cobalt-based Catalysts: Influence of the Cobalt Content on the Electrode Performance

Cobalt tetramethoxyphenyl porphyrin (CoTMPP) adsorbed on a high area carbon support (Vulcan XC72-R) and heat-treated at 900 °C under inert atmosphere was studied as electrocatalyst for the reduction of O₂ to H₂O₂ in acid medium. Experiments performed on rotating ring-disc electrode (RRDE) and gas diffusion electrode (GDE) show that the catalyst performance depends on the cobalt loading, going through a maximum at 0.2 wt. % Co. For higher cobalt loadings, a growing part of oxygen is reduced into water, decreasing therefore the selectivity of the catalyst. These results are interpreted in terms of a further reduction of H₂O₂ on Co-based catalytic sites before leaving the catalytic layer. For a GDE polarized at −150 mV vs. saturated calomel electrode (SCE) and loaded with 0.9 μg cm⁻² of 0.2 wt. % Co-based catalyst, a H₂O₂ production rate of 300 μmol h⁻¹ cm⁻² was obtained which is five times higher than the H₂O₂ production rate measured with Vulcan. In these conditions, the selectivity of the Co-based catalyst for H₂O₂ production is 92%. The good agreement observed between RRDE and GDE results confirms the relevance of using RRDE experiment for screening these non-precious metal catalysts for further GDE applications.     

Mathematical model for a direct propane phosphoric acid fuel cell

A mathematical model was developed and used to predict the performance of direct propane phosphoric acid (PPAFC) fuel cells, utilizing both Pt/C state-of the-art electrodes and older Pt black electrodes. It was found that the overpotential caused by surface processes on the platinum catalyst in the anode is much greater than the potential losses caused by either ohmic resistance or propane diffusion in gas-filled and liquid-filled pores. In one comparison, the anode overpotential (0.5 V) was larger than the cathode overpotential (0.3 V) at a current density of 0.4 A cm⁻² for Pt loadings 4 mg Pt cm⁻². The need for sufficient water concentration at the anode, where water is a reactant, was indicated by the large effect of H₃PO₄ concentration. In another comparison, the model predicted that at 0.2 A cm⁻², modern carbon supported Pt catalysts would produce 0.35 V compared to 0.1 V for unsupported Pt black catalysts that were used several decades ago, when the majority of the research on direct hydrocarbon fuel cells was performed. The propane anode and oxygen cathode catalyst layers were modeled as agglomerates of spherical catalyst particles having their interior spaces filled with liquid electrolyte and being surrounded by gas-filled pores. The Tafel equation was used to describe the electrochemical reactions. The model incorporated gas and liquid-phase diffusion equations for the reactants in the anode and cathode and ionic transport in the electrolyte. Experimental data were used for propane and oxygen diffusivities, and for their solubilities in the electrolyte. The accuracy of the predicted electrical potentials and polarization curves were normally within ±0.02 V of values reported in experimental investigations of temperature and electrolyte concentration. Polarization curves were predicted as a function of temperature, pressure, electrolyte concentration, and Pt loading. A performance of 0.45 V at 0.5 A cm⁻² was predicted at some conditions.     

Simultaneous removal of particulates and NO by the catalytic bag filter containing MnOx catalysts

A catalytic bag filter which can remove particulates and NOx simultaneously was prepared and tested in a laboratory and a pilot plant. Manganese oxides (MnOx), active for the selective NO reduction with NH₃ at low temperatures, was utilized as the catalyst. This MnOx-coated bag filter showed 92.6% NOx conversion at 423 K with a space velocity of 400,000 h⁻¹.     

<Emphasis Type="Italic">In situ</Emphasis> electrochemical modification of catalytic activity for propane combustion of Pt/β′′-Al<Subscript>2</Subscript>O<Subscript>3</Subscript> catalyst-electrodes

The effect of electrochemical promotion (EP) of propane combustion was studied over a platinum film catalyst deposited on sodium β′′-Al₂O₃, a Na⁺ conductor, in the temperature range 320–440 °C. It was found that electrochemical pumping of sodium to the platinum surface markedly modifies its catalytic properties. For stoichiometric oxygen to propane ratio the system exhibited electrophobic behavior, i.e., addition of sodium resulted in decrease of the CO₂ production rate. Relative changes in the catalytic rate by up to 60 times larger than the corresponding change in sodium coverage were measured. The observed behavior is explained by taking into account the reaction mechanism and the effect of the electrochemically controlled sodium coverage on the bonding of coadsorbed reactant species.     

Characterizing cocoa butter seed crystals by the oil-in-water emulsion crystallization method

Unambiguous quantitative evidence for the catalytic action of seed crystals in cocoa butter is presented. We used an ultrasound velocity technique to determine the isothermal growth of solid fat content in cocoa butter oil-in-water emulsions, in which the probability of finding a seed crystal in any one droplet was around 0.37 at 14.2°C. The upper limit for the size of seed crystals in West African cocoa butter was around 0.09 μm, the Gibbs free energy for nucleation was 0.11 mj m⁻², and the concentration of seed crystals was in the range of 10¹⁶ to 10¹⁷ m⁻³. X-ray diffraction measurements showed that emulsified cocoa butter crystallizes in the α polymorph and does not appear to transform to the β′ form within the first 25 min of crystallization. Primary nucleation events in cocoa butter emulsions are accounted for by seed crystals. Collision-mediated nucleation, a secondary nucleation mechanism, in which solid droplets (containing seed crystals) catalyze nucleation in liquid droplets, is shown to account for subsequent crystallization. This secondary nucleation mechanism is enhanced by stirring.     

Shear and longitudinal ultrasonic measurements of solid fat dispersions

Dispersions of coating fat in corn oil (2.5–12.5 wt%) were prepared following two different protocols: Type A dispersions had an average crystal size of 30–36 μm, whereas type B dispersions were less than 1 μm. In both dispersions the fat crystals were aggregated into larger structures (up to 80 μm). The longitudinal ultrasonic properties (i.e., velocity, attenuation, and reflectance) were linearly related to the solid fat content, but only attenuation was sensitive to the different microstructures. The velocity and reflectance measurements were modeled using the Urick equation. Shear ultrasonic reflectance and oscillatory viscometry were used to measure the dynamic viscosity of all dispersions. According to both methods, type B samples were always more viscous than type A at a similar solids content. The correlation between the two techniques was good (r ²>0.99), but the numeric agreement was different for both systems.     

Response of spontaneously hypertensive rats to inhalation of fine and ultrafine particles from traffic: experimental controlled study

Background  

Many epidemiological studies have shown that mass concentrations of ambient particulate matter (PM) are associated with adverse health effects in the human population. Since PM is still a very crude measure, this experimental study has explored the role of two distinct size fractions: ultrafine (<0.15 μm) and fine (0.15- 2.5 μm) PM. In a series of 2-day inhalation studies, spontaneously hypersensitive (SH) rats were exposed to fine, concentrated, ambient PM (fCAP) at a city background location or a combination of ultrafine and fine (u+fCAP) PM at a location dominated by traffic. We examined the effect on inflammation and both pathological and haematological indicators as markers of pulmonary and cardiovascular injury. Exposure concentrations ranged from 399 μg/m³ to 3613 μg/m³ for fCAP and from 269μg/m³ to 556 μg/m³ for u+fCAP.     

Pd/γ-Al<Subscript>2</Subscript>O<Subscript>3</Subscript> catalysts on cellular supports for VOC vapor neutralization

The results from investigating the influence of temperature, concentration, and flow rate on the catalytic oxidation of vapors of volatile organic compounds (VOCs) in the presence of Pd/γ-Al₂O₃ catalyst on cellular supports are presented. The activity of Pd/γ-Al₂O₃ catalysts on ceramic and metal monolith supports with a cellular structure during the catalytic neutralization of VOC (ethanol, ethyl acetate) vapors under laboratory conditions was determined, and the most stable catalyst for the preliminary study of a large batch was chosen. A pilot unit was created to test a large batch of cellular monolith catalyst in neutralizing VOC vapors under conditions of flexographic production. It was established that a high rate of conversion (> 99 %) was achieved for VOC concentrations of 0.5 g/m³ at space velocities of up to ∼10⁴ h⁻¹, and for VOC concentrations of 5.0 g/m³ at space velocities of up to ∼5 × 10⁵ h⁻¹. The change in the activity of the catalysts on metal (nickel alloyed by aluminum) and ceramic cellular supports in service was investigated. After 300–500 min of operation, virtually complete deactivation of catalyst on a metal support was observed, accompanied by the formation of nickel oxide and acetate. Pilot unit tests with catalyst on cellular supports having a volume of 14.5 l in neutralizing the ventilation exhausts of flexographic production confirmed the possibility of more than 90% conversion at VOC concentrations of ∼0.1 g/m³ and more than 97% at VOC concentrations of over 1 g/m³. A consistently high conversion of VOC was observed during a 100 h test of the pilot unit. A system for recovering the heat released during VOC oxidation lowers the operating costs of the pilot unit.     

Preparation of KF/CaO nanocatalyst and its application in biodiesel production from Chinese tallow seed oil

KF/CaO nanocatalyst was prepared by using impregnation method and used to convert Chinese tallow seed oil to biodiesel. The effects of different preparation conditions on biodiesel yield were investigated and the structure of the catalyst was characterized. Transmission electron microscopy (TEM) photograph showed that the catalyst had porous structure with the particle size of 30-100 nm. Brunauer-Emmet-Teller (BET) analysis indicated that the catalyst specific surface area was 109 m² g⁻¹ and average pore size was 97 nm. X-ray diffractometer (XRD) analysis demonstrated that the new crystal KCaF₃ was formed in catalyst, which enhanced catalytic ability. Under the optimal conditions, the biodiesel yield was 96.8% in the presence of as-prepared KF/CaO catalyst, showing potential applications of catalyst in biodiesel industry.     

Effect of oxygen mobility in solid catalyst on transient regimes of catalytic reaction of methane partial oxidation at short contact times

Mathematical modeling of the effect of the oxygen mobility in a solid oxide catalyst on the dynamics of transients of fast catalytic reactions has been carried out. The analysis was based upon the redox mechanistic scheme with a due regard for diffusion of oxygen from the bulk of catalyst to its surface. Parameters of kinetic and mathematical models were selected via fitting of the experimental data for methane selective oxidation into syngas on 1.4%Pt/Gd_0.2Ce_0.4Zr_0.4O _x catalyst. The range of the Thiele parameter (φ) where the oxygen bulk diffusion affects the most strongly reaction transients corresponds to φε [0.3 ÷ 7]. For high-surface-area oxide catalysts, the bulk oxygen diffusion coefficients corresponding to this range of the Thiele parameter are in the range of 10^–18 ÷ 10^–13cm²/s.     

Preparation of H<Subscript>5</Subscript>PMo<Subscript>10</Subscript>V<Subscript>2</Subscript>O<Subscript>40</Subscript> catalyst immobilized on spherical carbon and its application to the vapor-phase 2-propanol conversion reaction

Spherical carbon (SC) with a diameter of ca. 9 μm was synthesized by a hydrothermal method using sucrose as a carbon precursor. The spherical carbon was then modified to have a positive charge, and thus, to provide a site for the immobilization of H₅PMo₁₀V₂O₄₀ (PMo₁₀V₂) catalyst. The PMo₁₀V₂ catalyst was immobilized on the surface-modified spherical carbon by taking advantage of the overall negative charge of [PMo₁₀V₂O₄₀]⁵⁻. The PMo₁₀V₂ catalyst immobilized on the spherical carbon (PMo₁₀V₂/SC) was applied to the vapor-phase 2-propanol conversion reaction. In the catalytic reaction, the PMo₁₀V₂/SC catalyst showed a higher 2-propanol conversion than the unsupported PMo₁₀V₂ catalyst. Furthermore, the PMo₁₀V₂/SC catalyst showed enhanced oxidation catalytic activity (formation of acetone) and the suppressed acid catalytic activity (formation of propylene and isopropyl ether) compared to the unsupported PMo₁₀V₂ catalyst. The enhanced oxidation activity of PMo₁₀V₂/SC catalyst was due to the fine dispersion of [PMo₁₀V₂O₄₀]⁵⁻ on the spherical carbon formed via chemical immobilization.     

Physical and electrochemical properties of synthesized carbon nanotubes [CNTs] on a metal substrate by thermal chemical vapor deposition

Multi-walled carbon nanotubes were synthesized on a Ni/Au/Ti substrate using a thermal chemical vapor deposition process. A Ni layer was used as a catalyst, and an Au layer was applied as a barrier in order to prevent diffusion between Ni and Ti within the substrate during the growth of carbon nanotubes. The results showed that vertically aligned multi-walled carbon nanotubes could be uniformly grown on the Ti substrate (i.e., metal substrate), thus indicating that the Au buffer layer effectively prevented interdiffusion of the catalyst and metal substrate. Synthesized carbon nanotubes on the Ti substrate have the diameter of about 80 to 120 nm and the length of about 5 to 10 μm. The Ti substrate, with carbon nanotubes, was prepared as an electrode for a lithium rechargeable battery, and its electrochemical properties were investigated. In a Li/CNT cell with carbon nanotubes on a 60-nm Au buffer layer, the first discharge capacity and discharge capacity after the 50th cycle were 210 and 80 μAh/cm², respectively.     

Design and performance evaluation of plasma air cleaning systems for removing yellow sand dust

Yellow sand dust (Asian dust storms) causes harmful damage indoors and outdoors during the springtime, and the removal of Yellow sand dust has become an issue for suitable indoor conditions. An air cleaner is required to remove Yellow sand dust efficiently to improve indoor air quality, and the removal characteristics of Yellow sand dust should be studied. The size distribution and mass concentration of Yellow sand dust observed in China and Korea are analyzed, and the removal efficiency of a plasma air cleaning system based on the principle of electrostatic precipitation is evaluated by using Yellow sand dust. Mass median diameter of Yellow sand dust sampled in Beijing and Seoul ranges from 7.0 to 8.0 μm with a mass concentration of 300-1,462 μg/m³. For a single-pass test, the efficiency of dust removal increases with increasing particle size and decreasing flow rate. The removal efficiency of Yellow sand dust in a plasma air cleaning system at a face velocity of 1.0 m/s is higher than 80%. For a multi-pass test in occupied spaces, the operation time required to reduce Yellow sand dust concentration from an initial concentration of 300 μg/m³ to 150 μg/m³ is 10 minutes for a test room of 27 m³.     

Effects of droplet size on the oxidative stability of oil-in-water emulsions

The effects of droplet size and emulsifiers on oxidative stability of polyunsaturated TAG in oil-in-water (o/w) emulsions with droplet sizes of 0.806±0.0690, 3.28±0.0660, or 10.7±0.106 μm (mean ± SD) were investigated. Hydroperoxide contents in the emulsion with a mean droplet size of 0.831 μm were significantly lower than those in the emulsion with a mean droplet size of 12.8 μm for up to 120 h of oxidation time. Residual oxygen contents in the headspace air of the vials containing an o/w emulsion with a mean droplet size of 0.831 μm were lower compared with those of the emulsion with a mean droplet size of 12.8 μm. Hexanal developed from soybean oil TAG o/w emulsions with smaller droplet size showed significantly lower residual oxygen contents than those of the larger droplet size emulsions. Consequently, oxidative stability of TAG in o/w emulsions could be controlled by the size of oil droplet even though the origins of TAG were different. Spin-spin relaxation time of protons of acyl residues on TAG in o/w emulsions measured by ¹H NMR suggested that motional frequency of some acyl residues was shorter in o/w emulsions with a smaller droplet size. The effect of the wedge associated with hydrophobic acyl residues of emulsifiers was proposed as a possible mechanism to explain differences in oxidative stability between o/w emulsions with different droplet sizes.     

Towards the Development of Fiber-Based Oxidovanadium(IV) Catalysts for the Oxidation of Thioanisole

Abstract  

The catalytic activity of a series of bis-coordinated oxidovanadium(IV) complexes with 2-(4,5-diphenyl-1H-imidazol-2-yl)-4R-phenol ligands (R = NO₂, Br, H, MeO) was investigated for the oxidation of thioanisole by hydrogen peroxide in acetonitrile at 25°C. The substituent groups had a significant effect on the catalytic activity and followed the order NO₂ > Br > H > MeO, with the nitro (NO₂) derivative achieving >99% conversion after 10 min while the methoxy (MeO) derivative yielded the same result in 60 min. The nitro- and methoxy-substituted homogeneous catalysts were incorporated into polystyrene and electrospun to form nonwoven mats with fiber diameters in the range 0.33–1.98 μm. These vanadium incorporated fibers were subjected to a continuous flow system at a flow rate of 1 mL/h for the oxidation of thioanisole and the nitro-substituted catalyst showed excellent catalytic activity with conversions dropping from 99 to 93% in the 10th fraction while the drop was down to 88% for the methoxy-substituted catalyst.