The oxidation of dodecane on a vanadium-molybdenum catalyst

The catalytic oxidation of dodecane by air oxygen on a mixed vanadium-molybdenum oxide (V₂O₅ · MoO₃, 40 mol % MoO₃) was studied over the temperature range 300–350°C. The reaction at 300–330°C occurred on oxygen vacancies with the rupture of C-H bonds and formation of α-acid. Oxidation above 350°C occurred with the splitting of the C-C bond and formation of two and more acids. Singlet oxygen ¹O₂ generated in the oxidation of oxide catalyst lattice oxygen participated in the reaction. A possible mechanism of the process was 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.     

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.     

The partial catalytic oxidation of toluene on vanadium and molybdenum oxides

The partial catalytic oxidation of toluene on pure and mixed vanadium and molybdenum oxides was studied over the temperature range 300–500°C. The main reaction products were maleic anhydride (MA), benzaldehyde (BA), and carbon oxides (CO _x ) depending on the catalyst composition and reactor temperature. The samples containing more than 50% vanadium were characterized by conversion and selectivity close to those of pure vanadium oxide V₂O₅. Reaction temperature was found to influence the amount of products formed, primarily the amounts of MA and BA. The role played by the generation of the singlet molecular oxygen form in the samples and its influence on the selectivity of the reaction is considered.     

Effect of Co substitution for Fe in Sr2FeMoO6 on electrocatalytic properties for oxygen reduction in alkaline medium

Double perovskites Sr₂Fe_1???x Co _x MoO₆ (x?=?0, 0.25, 0.5, 0.75 and 1) have been investigated as cathode material for oxygen reduction reaction (ORR) in 0.5 M NaOH at 25 °C using the rotating disk electrode. The electrocatalytic powders were prepared by a solid-state process and characterised by X-Ray powder diffraction, scanning electron microscopy and infrared spectroscopy. The electrochemical techniques considered are linear voltammetry, steady-state polarization and impedance spectroscopy. The electrocatalysts Sr₂Fe_1???x Co _x MoO₆/C consisting of the double perovskite oxides and carbon (Vulcan XC-72) were mixed and spread out into a thin layer on a glassy carbon substrate. The electrocatalytic activity was strongly influenced by the Co substitution at room temperature. The relation between catalytic performance and the degree of Co content was examined. The Co-containing catalysts exhibited lower activity attributed to their high resistivity, and the highest activity toward oxygen reduction was observed for Sr₂CoMoO₆.     

Spectroscopy of mixed molybdenum-vanadium oxides and catalytic oxidation of toluene

The EPR, FTIR, and XRD techniques are used to examine individual and mixed vanadiummolybdenum oxides of composition (1 ? x)V₂O₅: xMoO₃ prepared by coprecipitation. The phase and structural heterogeneity of these oxides is characterized. The oxidation of toluene with air oxygen to maleic anhydride on V₂O₅ and mixed oxides involves singlet oxygen ¹O₂. A correlation between the content of V(IV) ions in the mixed catalysts and the amount desorbed ¹O₂ is observed. It is demonstrated that the oxidation of toluene causes changes in the spatial distribution of the V(IV) ions in the matrix and the phase composition of the samples.     

Preparation and characterization of hybrid nanoparticles based on chitosan and poly(methacryloylglycylglycine)

CeO₂–MnO _x composites possessing rod-like morphology (fixed mole proportion of Ce/Mn) were synthesized through hydrothermal method and chosen as supporters to load PdO nanoparticles (PdO/Ce _x Mn_1–x ). The size of loaded PdO nanoparticles is about 2 nm. The catalytic behaviors of supported catalysts were examined through the complete catalytic oxidation of benzene. The results illustrated that the activities of supported catalysts were enhanced greatly as compared to unsupported, and the completely conversion temperature of benzene was reduced to ca. 250 °C. The effect of noble metal species (PdO) addition on the catalytic property and crystal structure of composites was researched in detail. The data revealed that the interaction between PdO and supporter, and intrinsic properties of supporter resulted in the enhancement of catalytic abilities.     

Simultaneous removal of NO and Hg0 from flue gas over MnSmCo/Ti catalyst at low temperature

The MnSmCo/Ti catalyst was designed for the simultaneous removal of NO and Hg⁰ at low temperature. The MnSmCo/Ti catalyst exhibited 80% NO conversion, almost 100% N₂ selectivity and 100% Hg⁰ removal in the absence of HCl within the temperature range of 150–250 °C with a gas hourly space velocity of 100,000 h^?1. The influence of flue gas components on Hg⁰ oxidation was investigated and the NO and O₂ are mainly responsible for Hg⁰ oxidation. Hg balance analysis revealed that the Hg⁰ removal was achieved through chemisorption and catalytic oxidation. Furthermore, the Hg⁰ oxidation mechanism was explored using transient reaction along with temperature-programmed desorption of mercury and X-ray photoelectron spectroscopy. Hg⁰ oxidation proceeds through Mars–Maessen mechanism in which adsorbed Hg⁰ is bound to MnO_x to form weakly bonded HgMnO_x+1 species and follows Langmuir?Hinshelwood mechanism, where adsorbed Hg⁰ reacts with active NO₂ to generate HgO.     

Au-MoOx nanoparticles for LSPR hydrogen detection prepared by a facile anodizing method

Nowadays, the plasmonic properties of defective transition metal oxides, have attracted great attention in the sensing and catalyst applications. The aim of this paper is to fabricate plasmonic Au-MoO_x nanoparticles (NPs) using a facile anodizing in liquid approach to be used as localized surface plasmon resonance (LSPR) hydrogen sensor. Firstly, dark blue MoO_x nanosheets with a strong NIR (700–800 nm) LSPR band were obtained. The Au-MoO_x NPs (Au size=5–7 nm) were then obtained by adding a gold cation into the blue MoO_x liquid base. Thanks to the catalytic properties of Au NP, this system exhibited LSPR hydrogen sensing ability where the LSPR variations allowed us to detect hydrogen in the 0–3% concentration range with a good linearity and possible many data points.     

Effect of Preparation Method on the SCR Activity of Fe-Doped CoCr Oxide Catalysts

Fe-doped CoCr oxide catalysts are prepared by solid-phase mixing method, coprecipitation method, mechanical mixing method, and citric acid method, respectively, and their catalytic activity in the selective catalytic reduction of nitrogen oxides with NH₃ (NH₃-SCR) is tested. The Fe_0.5CoCrO_x catalysts prepared by all preparation methods have good water resistance and sulfur resistance when the calcination temperature is 400 °C. Fe_0.5CoCrO_x prepared by coprecipitation method by calcination at 400 °C (CP-400) is shown to have the optimum catalyst activity. In addition, the catalysts are characterized by a series of characterizations. The characterization results show that CP-400 has the largest specific surface area, which makes the active and acidic sites highly dispersed on the surface of CP-400, resulting in stronger redox and acidity and improved SCR activity. The removal of NO by NH₃-SCR over CP-400 at 150 °C follows the Eley-Rideal (E R) and Langmuir-Hinshelwood (L H) mechanisms.     

Aes study of the segregation behaviour of silicon in high-silicon steel during oxidation

The segregation behaviour of silicon during oxidation of a high-silicon steel has been investigated by AES. The results show that silicon seems to have two states of oxidation: one leading to the formation of SiO_x and iron oxides when the oxidation and the following heat treatments in vacuum are performed below 500°C and the other occurring at temperatures higher than 500°C, leading to the formation of SiO₂ and segregation of this species toward the surface without oxidation of iron.     

Stabilizing the triclinic structure of Mn2V2O7 via isovalent cationic substitution

The thermal expansion of Mn₂V₂O₇ in the temperature range of ?190 to 1030°C is studied. The volumetric thermal expansion coefficients for triclinic (α) and monoclinic (β) modifications are 2.57 × 10^?5 and 3.86 × 10^?5 1/deg, respectively. It is shown that as the Ni²⁺ concentration in Mn_2?2x Ni_2x V₂O₇ rises, the point of the α → β phase transition point moves from room temperature for Mn₂V₂O₇ to 155 ° 5°C for Mn_1.46Ni_0.54V₂O₇ (27 mol % Ni₂V₂O₇).     

Electrochemical promotion of propane oxidation over Pd, Ir, and Ru catalyst-electrodes deposited on YSZ

The effect of electrochemical promotion of catalysis was investigated for the oxidation of propane using Pd, Ir, and Ru catalyst-electrodes sputter-deposited on YSZ disks in the temperature range of 250–450 °C. Electrophobic type behavior was observed, i.e., the catalytic reaction rate was found to increase with catalyst potential. The observed rate changes under polarization were strongly non-Faradaic and exceeded under anodic potential application the electrocatalytic rate of O^2? supply to the catalyst surface, I/2F, by up to a factor of 250 for Pd, 125 for Ir, and 15 for Ru catalyst-electrodes.     

Motional narrowing in the electron-spin-resonance-spectrum of pentavalent vanadium-compounds

The activation energy of the hopping frequency of the vanadium-3d ¹-electron is derived from the temperature dependence of the ESR linewidth in the following semiconducting, pentavalent vanadium-compounds: Na_xV₂O₅, Li_xV₂O₅ (x <0.02), V₂O₅ weakly doped with WO₃ or MoO₃ (E _a ≈0.07 eV). In V₂MoO₈, vanadium-3d ₁-electrons are responsible for the electronic conductivity, too.     

Synthesis of nanostructured lean-NO x catalysts by direct laser deposition of monometallic Pt-, Rh- and bimetallic PtRh-nanoparticles on SiO2 support

Monometallic Pt and Rh and bimetallic PtRh catalysts with a highly dispersed noble metal weight loading of ca. 1 wt% were produced via the direct deposition of nanoparticles on different SiO₂ supports by means of pulsed ultra-violet (248 nm) excimer laser ablation of Pt, Rh bulk metal and PtRh alloy targets. Backscattered electron microscopy (BSE), energy dispersive X-ray spectroscopy (EDX), and transmission electron microscopy (TEM) were employed to characterize the deposited nanoparticles, which were found to exhibit narrow size distribution centred around 2.5 nm. The catalytic activities for lean NO _x reduction of the monometallic and bimetallic catalyst samples were investigated in a flow reactor setup in the temperature range 100–400°C using a test gas mixture representative of oxygen rich diesel engine exhaust gas. For comparison a Rh/SiO₂ reference catalyst prepared by a conventional impregnation method was also tested. Further experiments were performed in which PtRh nanoparticles were deposited on a Rh/SiO₂ reference catalyst sample to study the possibility for controlled modification of its activity. The catalytic activity measurements revealed that among the samples solely prepared by laser deposition the PtRh–SiO₂ nanoparticle catalyst showed the highest activity for NO _x reduction at low temperatures 100–300°C. In addition, it could be demonstrated that the initially low NO _x reduction activity and the N₂ selectivity of the Rh/SiO₂ reference catalyst sample for temperatures below 250°C can be enhanced by post laser deposition of PtRh nanoparticles.     

The AC monitoring of a mixed conducting Li-Ni-Co-O catalyst during temperature programmed reactions

The temporal analysis of effluent species with temperature linearly increasing with time for two reactions, carbon dioxide hydrogenation (250° to 600°C) and the oxidative coupling of methane (400° to 800°C) have been studied. A non-stoichiometric, mixed-oxide catalyst, Li_0.9Ni_0.5Co_0.5O_2-δ, containing both mobile ions and electrons at elevated temperatures was investigated. The exit gas stream was monitored by using the multiple-ion monitoring facility of a quadrupole mass spectrometer. The AC electrical characteristics of the catalyst pellet between 100 Hz and 1 MHz were simultaneously monitored in-situ. A clear correlation between catalytic behaviour and electrical properties was obtained. Frequency-dependent AC losses due to surface dipole effects were dominant during phases of strong chemisorption and reaction, whilst reversion to thermally activated behaviour occurred during times of reduced chemical activity. In the case of carbon dioxide hydrogenation, the catalyst becomes partially reduced as a result of the chemical reaction, as shown by the changes in conductance-temperature-frequency characteristics. The original oxidised state could be recovered by re-oxidation at 700°C for 1 hour in air. For the partial oxidation of methane, mobile lattice oxygen participates in the reaction. The temporary changes in the state of oxidation of the catalyst during this reaction are correlated with changes in the electrical characteristics of the material. Paper presented at the 3rd Euroconference on Solid State Ionics, Teulada, Sardinia, Italy     

Bias voltage and annealing-temperature dependences of magnetoresistance ratio in Ir–Mn exchange-biased double tunnel junctions

Dual-spin-valve-type double tunnel junctions (DTJs) of sputtered Ir–Mn/Co–Fe/AlO_x/Co₉₀Fe₁₀/AlO_x/Co–Fe/Ir–Mn were fabricated using photolithography and ion-beam milling. The DTJs were annealed at various temperatures (150–400°C) to introduce interdiffusion. The magnetoresistance (MR) ratio and DC bias voltage value at which the MR ratio decreases in half value (V_1/2) were measured before and after annealing. A maximum MR ratio and V_1/2 obtained after annealing at ∼320°C was 42.4% and 952 mV, respectively, at room temperature. There is a correlation between the loss of the MR ratio and that of V_1/2 above 320°C. The loss of the MR ratio and that of V_1/2 are well explained by considering two phenomena, i.e., interdiffusion of O and Mn at the AlO_x/Co–Fe/Ir–Mn interfaces. The mechanism for the loss of MR ratio is not only related to the loss of interface polarization, but is also related to the barrier properties, taking into account the spin-independent two-steps tunneling via defect states in the barrier. These results are consistent with the X-ray photoelectron spectroscopy and cross-sectional transmission electron spectroscopy measurements, which indicate the existence of an Al–Mn–O barrier above 320°C.     

Synthesis and electrochemical performance of Li1+xV3O8 as cathode material prepared by citric acid and tartaric acid assisted sol–gel processes

Lithium-ion battery cathode material Li_1+xV₃O₈ is synthesized by a citric acid/tartaric acid assisted sol–gel method and sintered at 350 °C, 450 °C and 550 °C for 3 h for the formation of Li_1+xV₃O₈ phase. The synthesized samples were fully characterized by FTIR, TG/DTA, XRD, SEM, EIS and charge–discharge tests. Li_1+xV₃O₈ material synthesized by tartaric acid assisted route and sintered at 450 °C for 3 h shows best electro-chemical performance. It shows a high initial capacity of 249 mAh g^?1 and still reserves a discharge capacity of 260 mAh g^?1 after 50 cycles. Moreover, in the case of tartaric assisted products, no capacity decadence is observed in 50 cycles. XRD together with TG/DTA measurements reveal that compared with citric acid assisted products, the adoption of tartaric acid as chelating agent effectively lowers the crystallization temperature of amorphous Li_1+xV₃O₈. Therefore, precursors obtained by tartaric acid route calcinated at 450 °C for 3 h exhibit lower crystallinity and smaller grain size, which contributes to the better electrochemical performance of the cathode electrodes. From EIS measurements, the bulk resistance is reduced, which favors the intercalation and de-intercalation of lithium ions while cycling.     

钴改性Fe3O4-MnO2催化转化生物质合成气制备液体燃料

本文制备了用于费托合成反应的钴改性Fe₃O₄-MnO₂双功能催化剂,并探究了钴负载量对Fe-Co协同效应的影响以及Fe₁Co_xMn₁催化剂的费托合成反应性能. 实验发现,在Fe₃O₄-Mn催化剂中加入Co可促进铁氧化物的还原、增加反应过程中铁位点的活性. 此外,Co的加入可增强Fe-Co金属间的电子转移,加强两者的协同作用,提高催化性能. Co负载较高的Fe₁Co_xMn₁催化剂可进一步促进加氢反应能力,使产品分布向短链烃方向转移. 在280 ^°C、2.0 MPa和3000 h^-1的最佳工况条件下,Fe₁Co₁Mn₁催化剂的液体燃料收率最高.     

Phase transition in a NaBi(MoO<Subscript>4</Subscript>)<Subscript>2</Subscript> crystal: Acoustic investigations

This paper reports on the results of acoustic investigations of a NaBi(MoO₄)₂ crystal in the temperature range from 20 to 70°C. The temperature dependences of the velocity of longitudinal ultrasonic waves propagating along the crystallographic axes z and x are measured at a frequency of 4 MHz. The results obtained demonstrate that a structural phase transition occurs in the NaBi(MoO₄)₂ crystal at a temperature of 309 K. The experimental findings are consistent with the assumption that the observed phase transition is either a second-order ferroelastic transition or a first-order ferroelastic transition that is very close to being a second-order phase transition.