Oxidation of dodecane on vanadium-molybdenum catalysts

The catalytic oxidation of dodecane with air oxygen on individual and mixed vanadium-molybdenum (1 ? x)V₂O₅ · xMoO₃ oxide is studied over a temperature range of 250 to 400°C. It is shown that oxidation of dodecane to organic acids at 250°C produces undecylic acid C₁₁H₂₆COOH and carbon oxides, as products of the subsequent oxidation of formic acid. The most effective catalyst is a mixed oxide containing 75 mol % MoO₃ and 25 mol % V₂O₅. At 275–300°C, this catalyst provides the maximum yield of acids and a relatively low fraction of complete-oxidation products. Above 250°C, a mixture of acids and carbon oxides is formed, the yield of which increases with the temperature up to 300°C. As the temperature is increased still further, the yield of acids decreases due to their subsequent oxidation. The catalytic oxidation is accompanied by changes in the phase composition, morphology, and degree of crystallinity of the mixed-oxide catalysts. A possible mechanism of the catalytic process is considered.     

Oxidation of benzene on a vanadium-molybdenum catalyst in the presence of thiophene

The catalytic oxidation of benzene by air oxygen on a vanadium-molybdenum mixed oxide (1 ? x)V₂O₅ · xMoO₃ (x = 0.25) over a temperature range of 200–320°C is studied. It is shown that the introduction of small amounts of thiophene into benzene inhibits the oxidation to maleic anhydride in this temperature range. It is established that the operation of the catalyst is accompanied by significant changes in its phase composition and morphology, with a few first operation cycles being characterized by a high conversion of benzene. A possible mechanism of the process is proposed.     

The oxidation of methanol on a silver (110) catalyst

The oxidation of methanol was studied on a Ag(110) single-crystal by temperature programmed reaction spectroscopy. The Ag(110) surface was preoxidized with oxygen-18, and deuterated methanol, CH₃OD, was used to distinguish the hydroxyl hydrogen from the methyl hydrogens. Very little methanol chemisorbed on the oxygen-free Ag(110) surface, and the ability of the silver surface to dissociatively chemisorb methanol was greatly enhanced by surface oxygen. CH₃OD was selectively oxidized upon adsorption at 180 K to adsorbed CH₃O and D₂¹⁸O, and at high coverages the D₂¹⁸O was displaced from the Ag(110) surface. The methoxide species was the most abundant surface intermediate and decomposed via reaction channels at 250, 300 and 340 K to H₂CO and hydrogen. Adsorbed H₂CO also reacted with adsorbed CH₃O to form H₂COOCH₃which subsequently yielded HCOOCH₃ and hydrogen. The first-order rate constant for the dehydrogenation of D₂COOCH₃ to DCOOCH₃ and deuterium was found to be (2.4 ± 2.0) × 10¹¹ exp(?14.0 ± 0.5 $\text{kcal}\text{mole}$ · RT)sec^?1. This reaction is analogous to alkoxide transfer from metal alkoxides to aldehydes in the liquid phase. Excess surface oxygen atoms on the silver substrate resulted in the further oxidation of adsorbed H₂CO to carbon dioxide and water. The oxidation of methanol on Ag(110) is compared to the previous study on Cu(110).     

Oscillatory oxidation of Co over a Pt catalyst

We report measurements of the temporal oscillatory oxidation rates of CO over a polycrystalline Pt wire. The experiments were conducted near atmospheric pressure in a clean flow reactor system. Reproducible oscillations in both the temperature of the Pt wire and in the rate of CO₂ production were found over a wide range of gas compositions, $\text{0.001 <}\text{P}{}_{\mathrm{CO}}\text{P}{}_{\mathrm{O}}{}_2\text{< 0.045,}$ and temperatures, 150°C < T_g < 350°C, where PCO and po₂ are the respective partial pressures of carbon monoxide and oxygen in the gas stream, and T_g is the temperature of the gas. The oscillations are believed to occur between two branches of a Langmuir-Hinshelwood reaction mechanism. It is suggested that the slow formation and removal of subsurface oxygen drives the reaction between the two branches. A simple kinetic model based on this hypothesis gives excellent qualitative agreement with the observed oscillations.     

Oxidation of benzene and thiophene on a nanostructured vanadium-molybdenum mixed oxide

The catalytic oxidation of benzene and thiophene by air oxygen on a nanostructured vanadium-molybdenum mixed oxide with 50 mol % MoO₃ and 50 mol % V₂O₅ prepared by the solvothermal method is studied. It is shown that, in the temperature range 200–350°C, the catalyst efficiently oxidizes thiophene (with a degree of conversion of up to 40 mol %) and poorly oxidizes benzene. This enables to consider nanostructured molybdenum-vanadium oxides as promising for the low-temperature catalytic desulfurization of hydrocarbons. It is demonstrated that the reaction causes a change in the structure and morphology of the oxide system.     

Sono-photo-Fenton oxidation of bisphenol-A over a LaFeO3 perovskite catalyst

In this study, oxidation of bisphenol-A (IUPAC name – 2,2-(4,4-dihydroxyphenyl, BPA), which is an endocrine disrupting phenolic compound used in the polycarbonate plastic and epoxy resin industry, was investigated using sono-photo-Fenton process under visible light irradiation in the presence of an iron containing perovskite catalyst, LaFeO₃. The catalyst prepared by sol–gel method, calcined at 500 °C showed a catalytic activity in BPA oxidation using sono-photo-Fenton process with a degradation degree and a chemical oxygen demand (COD) reduction of 21.8% and 11.2%, respectively. Degradation of BPA was studied by using individual and combined advanced oxidation techniques including sonication, heterogeneous Fenton reaction and photo oxidation over this catalyst to understand the effect of each process on degradation of BPA. It was seen, the role of sonication was very important in hybrid sono-photo-Fenton process due to the pyrolysis and sonoluminescence effects caused by ultrasonic irradiation. The prepared LaFeO₃ perovskite catalyst was a good sonocatalyst rather than a photocatalyst. Sonication was not only the effective process to degrade BPA but also it was the cost effective process in terms of energy consumption. The studies show that the energy consumption is lower in the sono-Fenton process than those in the photo-Fenton and sono-photo- Fenton processes.     

Transient studies of carbon monoxide oxidation over platinum catalyst

The applicability of transient techniques to the study of the catalytic oxidation of carbon monoxide is discussed. It is shown that at 100–150°C adsorption and desorption equilibria between the gas phase and catalyst cannot be assumed, and an elementary step formulation may be used to predict both multiple steady states and transient behaviour.     

Monte Carlo simulation of temperature programmed reaction and surface explosion during CO oxidation on a Pt catalyst

A Monte Carlo model of CO oxidation on a Pt(111) surface that includes finite rates of adsorption-desorption and reaction and the effect of the catalyst temperature is presented. The results show that, as expected from the reaction-adsorption probabilities, the surface coverage changes from being almost completely covered by CO at low temperature (60°C), to being completely covered by oxygen at high temperature (160°C). Furthermore, it was found that an unstable state occurs when cooling down the oxygen covered surface from 160°C to 60°C. It is shown that if a site for CO adsorption is created under this metastable state, a surface explosion that propagates spatially occurs. Thus the MC simulations provide a method to describe a catalytic reaction on surfaces with strongly non-linear spatio-temporal dynamics.     

In situ controlled promotion of catalyst surfaces via solid electrolytes: Ethylene oxidation on Rh and propylene oxidation on Pt

The kinetics of C₂H₄ oxidation on Rh and C₃H₆ oxidation on Pt were investigated on polycrystalline metal films interfaced with ZrO₂(8mol%Y₂O₃) solid electrolyte in galvanic cells of the type:

One-step synthesis of Pt-Pd catalyst nanoparticles supported on few-layer graphene for methanol oxidation

In this study, Pt-Pd nanoparticles (NPs) supported on few-layer graphene (FLG) have been firstly prepared by one-step arc discharge evaporation of carbon electrodes containing both Pt and Pd elements. The few-layer graphene and Pt-Pd nanoparticles were achieved simultaneously through the evaporation process. After a high-temperature hydrogen treatment, the Pt-Pd/graphene was applied in the study of methanol oxidation in direct methanol fuel cell. The total weight of electrocatalyst keeps 2 wt% of the electrode. The sample with a mass ratio of Pt:Pd = 3:1 (H-Pt₃Pd₁/G) exhibits better electrocatalytic activity (198 mA mg-1 pt) and better tolerance to carbon monoxide(CO) poisoning (I_f/I_b = 1.26). It is noteworthy that the value of I_f/I_b can reach to 1.55 for the sample with the mass ratio of Pt:Pd = 2:1 (H-Pt₂Pd₁/G),which implies its excellent ability of CO tolerance. The introduction of Pd element may open a new strategy to improve the CO tolerance by arc discharge evaporation.     

Very low friction state of a dodecane film confined between mica surfaces

The existence of a very low friction state of a lubrication film is demonstrated in nonequilibrium molecular dynamics simulations of a six-layer dodecane film between mica walls. We argue that this low friction state is thermodynamically stable with respect to the well documented high friction film, the latter being a metastable state. These results are in striking accord with the recent report of Zhu and Granick [Phys. Rev. Lett. 93, 096101 (2004).]. The extreme low friction is the result, not of wall slip, but of layer sliding throughout the film, a mechanism similar to solid lubrication.     

Electrocatalytic oxidation of methanol on Pt catalyst supported on nitrogen-doped graphene induced by hydrazine reduction

Hydrazine is often used to reduce graphene oxide (GO) to produce graphene. Recent observations suggested that when hydrazine is used to reduce GO, the resulting reduced graphene actually contains certain amounts of nitrogen dopants, which may influence the properties of the obtained material, and in some cases may be deployed for beneficial advantage. In this work, we prepared graphene oxide by the chemical oxidation method, then used either hydrazine or sodium borohydride (as a control) to reduce the graphene oxide to graphene and to explore the nature of the nitrogen functionalities introduced by hydrazine reduction. Pt nanoparticles were then deposited on the nitrogen doped (hydrazine-reduced) and undoped (control) graphene substrates, and the morphology, structure, and electrocatalytic methanol oxidation activity were characterized and evaluated. The results show that the nitrogen functional groups introduced into the graphene by hydrazine reduction greatly improve the electrocatalytic activity of the underlying Pt nanoparticles towards the methanol oxidation reaction.     

Platinum catalyst on ordered mesoporous carbon with controlled morphology for methanol electrochemical oxidation

Ordered mesoporous carbons CMK-3 with various morphologies are synthesized by using various mesoporous silica SBA-15 as template and then support to prepare Pt/CMK-3 catalyst. The obtained catalysts are compared in terms of the electrocatalytic activity for methanol oxidation in sulfuric acidic solutions. The structure characterizations and electrochemical analysis reveal that Pt catalysts with the CMK-3 support of large particle size and long channel lengths possess larger electrochemical active surface area (ECSA) and higher activity toward methanol oxidation than those with the other two supports. The better performance of Pt/CMK-3 catalyst may be due to the larger area of electrode/electrolyte interface and larger ECSA value of Pt catalyst, which will provide better structure in favor of the mass transport and the electron transport.     

Monte Carlo simulations of FTIR studies during CO oxidation on a Pt/SiO2 catalyst

A Monte Carlo (MC) simulation of the reaction of CO with an oxygen covered Pt surface and oxygen with a CO covered Pt surface is presented in this paper. The effect of the adsorption, desorption, reaction, and surface migration rates on the formation of CO clusters is analyzed in terms of the CO frequency shift in the IR spectrum. The MC simulation calculates the CO frequency shifts according to a dipole-dipole interaction model. The IR frequency shifts predicted by the simulation depend on the value of the various kinetic processes considered. The simulation indicates that the CO migration on the surface is important at low pressure but is inhibited at high pressure. The IR frequency shifts predicted by the simulation agree qualitatively with experimental values obtained during CO oxidation on a Pt catalyst.     

Electrochemical codeposition of Pt/graphene catalyst for improved methanol oxidation

Pt/graphene electrocatalyst was uniformly deposited on a glassy carbon substrate using a pulsed galvanostatic electrodeposition method, which facilitated the simultaneous electrochemical reduction of graphene oxide and formation of Pt nanoparticles. Compared to the commercial carbon-supported Pt electrocatalyst, the electrochemically reduced Pt/graphene (Pt/ERG) catalyst exhibited improved electrocatalytic activity for methanol oxidation due to the synergistic effects of an increase in the number of catalytic reaction sites and an enhancement of the charge transfer rate.     

Sensitivity of styrene oxidation reaction to the catalyst structure of silver nanoparticles

This study shows how different morphologies of silver nanoparticles affect the selective oxidation of styrene in the gas phase using oxygen as oxidant. Silver nanoparticles (nanowires and nanopolyhedra), prepared using the polyol process, were supported on α-Al₂O₃. For comparison, a conventional catalyst obtained by wet impregnation was also prepared. Phenylacetaldehyde (Phe) and styrene oxide (SO) were the main products for nanoparticles catalysts. The promotion effect on the catalytic activity of potassium and cesium on the silver nanowires catalysts was also studied. At 573 K, the styrene conversion and selectivity to styrene oxide with the silver nanowires catalyst were 57.6 and 42.5%, respectively. Silver nanopolyhedra catalyst showed 57.5% conversion and 30.8% selectivity to styrene oxide. The promotion by cesium played an important role in improving the epoxidation of styrene. The samples were structurally characterized using X-ray diffraction (XRD), ultraviolet-visible spectroscopy (UV-vis), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). X-ray photoelectron spectroscopy (XPS) and temperature programmed reduction (TPR) were applied to characterize the oxygen species detected (O_β, O_γ) on the silver surface.     

Nanoparticulate TiO2-promoted PtRu/C catalyst for methanol oxidation

To improve the electrocatalytic properties of PtRu/C in methanol electrooxidation, nanoparticulate TiO₂-promoted PtRu/C catalysts were prepared by directly mixing TiO₂ nanoparticles with PtRu/C. Using cyclic voltammetry, it was found that the addition of 10 wt% TiO₂ nanoparticles can effectively improve the electrocatalytic activity and stability of the catalyst during methanol electrooxidation. The value of the apparent activation energy (E _a) for TiO₂-PtRu/C was lower than that for pure PtRu/C at a potential range from 0.45 to 0.60 V. A synergistic effect between PtRu and TiO₂ nanoparticles is likely to facilitate the removal of CO-like intermediates from the surface of PtRu catalyst and reduce the poisoning of the PtRu catalysts during methanol electrooxidation. Therefore, we conclude that the direct introduction of TiO₂ nanoparticles into PtRu/C catalysts offers an improved facile method to enhance the electrocatalytic performance of PtRu/C catalyst in methanol electrooxidation.     

Variation of the vanadium oxidation state within a VPO catalyst layer in a membrane reactor: XPS mapping and modelling

Recently, the feasibility of butane oxidation in an electrochemical membrane reactor (EMR) using a vanadium phosphorus oxide (VPO) catalyst layer on a tubular anodic electrode has been reported. This novel application of EMR gives rise to questions about the vanadium oxidation state (V_ox) under working conditions and about its spatial distribution in the catalyst layer. It has now been determined by means of position-resolved XPS measurements. In addition, model calculations on the spatial V_ox distribution have been performed for the first time. The simulations reveal a non-uniform 3D distribution of V_ox due to the relative rate of reduction and re-oxidation processes in the catalyst layer, in good agreement with the experimental XPS data.     

Microwave assisted oxidation of some aromatics by hydrogen peroxide at supported tungsten catalyst

Summary The oxidation of some arenes with the alkyl side groups by means of hydrogen peroxide is been presented. As the activator of hydrogen peroxide tungstoboric acid was chosen. The catalyst was examined under both homogeneous and heterogeneous conditions. The reactions under conventional conditions were compared with the microwave assisted reactions.     

Surface characterization study of a Pd/Co3O4 methane oxidation catalyst

A surface characterization study using X-ray photoelectron spectroscopy (XPS) and ion scattering spectroscopy (ISS) has been performed on a 5 wt.% Pd/Co₃O₄ methane oxidation catalyst before and after exposure to a mixture of CH₄ and O₂ in N₂ at 250 °C for a period of 6 days. The primary peaks observed in the XPS survey spectra are the Co 2p, Pd 3d, O 1s and C 1s, along with Co, Pd and O Auger peaks. High-resolution Pd 3d spectra reveal that Pd exists on the surface predominantly as PdO, with no apparent change in chemical state during reaction. High-resolution XPS Co 2p and O 1s spectra reveal an accumulation of CoOOH and a depletion of CoO in the near-surface region during reaction. ISS analysis with intermittent 1-keV Ar⁺ sputtering was used to obtain depth profiles from the catalyst before and after reaction. The results indicate that the Pd/Co concentration ratio decreases with sputtering and that this ratio is larger for the as-prepared catalyst indicating that morphological changes occur during reaction. The ISS depth profile spectra obtained from the catalyst after reaction indicates the presence of an oxyhydroxide layer throughout the near-surface region. This observation is consistent with the XPS data indicating accumulation of hydroxide and oxyhydroxide species at the surface during reaction.Based on these data and the results of related studies, a reaction mechanism is proposed. In this mechanism, methane dissociatively chemisorbs to form a surface methoxy species and CoOOH. The remaining hydrogen atoms are stripped from the methoxy species leaving an active adsorbed C species which reacts with surface oxygen and a hydroxyl group to form an adsorbed bicarbonate ion which then decomposes to form CO₂ and a surface hydroxyl group. These hydroxyl groups also react to form H₂O and then more O₂ adsorbs dissociatively at the vacant sites.