Support effects on structure and activity of molybdenum oxide catalysts for the oxidative dehydrogenation of ethane

The structural and catalytic properties of MoO₃ catalysts supported on ZrO₂, Al₂O₃, TiO₂ and SiO₂ with Mo surface densities, n_s, in the range of 0.5–18.5 Mo/nm² were studied for the oxidative dehydrogenation (ODH) of ethane by in situ Raman spectroscopy and catalytic activity measurements at temperatures of 400–540 °C. The molecular structure of the dispersed surface species evolves from isolated monomolybdates (MoO₄ and MoO₅, depending on the support) at low loadings to associated MoO_x units in polymolybdate chains at high loadings and ultimately to bulk crystalline phases for loadings exceeding the monolayer coverage of the supports used. The nature of the oxide support material and of the Mo–O–support bond has a significant influence on the catalytic behaviour of the molybdena catalysts with monolayer coverage. The dependence of reactivity on the support follows the order ZrO₂ > Al₂O₃ > TiO₂ > SiO₂. The oxygen site involved in the anchoring Mo–O–support is of relevance for the catalytic activity.     

Structure–activity relationships in alumina-supported molybdena–vanadia catalysts for propane oxidative dehydrogenation

The interactions between Mo and V on alumina are studied for the oxidative dehydrogenation (ODH) of propane. Dispersed surface molybdena and vanadia species share alumina support but show no interaction below Mo + V monolayer coverage. Vanadia and molybdena species react on alumina into mixed Mo–V–(Al)–O above Mo + V monolayer coverage, which nature depends on environmental conditions. Molybdena sites may form Al₂(MoO₄)₃ or Mo–V–O phases depending on loading and temperature. The Mo–V–O phases spread on the support as separate surface oxides at lower coverage, such trend appears promoted by ODH reaction conditions.     

Structural and optical properties of MoO3 and V2O5 thin films prepared by Spray Pyrolysis

MoO₃ and V₂O₅ thin films were prepared on glass substrates by Spray Pyrolysis technique at a substrate temperature of 423 K. The precursor solutions were obtained by varying the concentrations of MoCl₅ and VCl₃ in bi-distilled water. The structural investigation conducted by X-ray diffraction showed that MoO₃ and V₂O₅ thin films were polycrystalline with orthorhombic structure. The optical properties studied in the 300–2500 nm range suggest that the thin film behaviours are related to bound electronic states. The optical band gaps have been estimated from slopes of ln(hν) versus hν plots of MoO₃ and V₂O₅ films were 3.35 and 2.44 eV, respectively. The electrical conductivity was measured using four probes method.     

The structure analysis of MoOx/TiO2(110) by polarization-dependent total-reflection fluorescence X-ray absorption fine structure

The surface structure analysis of a model catalyst MoO_x/TiO₂(110) was for the first time performed by polarization-dependent total-reflection fluorescence X-ray absorption fine structure (PTRF-XAFS) in three different directions of the crystal surface. Two samples of MoO_x/TiO₂(110) were prepared by an impregnation of (NH₄)₆Mo₇O₂₄·4H₂O using ultra high purity water and normal distilled water. The PTRF-XAFS analysis revealed that anisotropic Mo dimer species was preferentially formed on the TiO₂(110) surface, with Mo–Mo bond (0.335 nm) parallel to the direction when the ultra high purity water was used as the solvent. On the other hand, the Mo oxide on the surface prepared using normal distilled water had a symmetric tetrahedral structure (MoO₄) with Mo–O of 0.176 nm, which was due to the coexistence of alkaline metals at the surface.     

MgO-supported Mo, CoMo and NiMo sulfide hydrotreating catalysts

The most common preparation of high surface area MgO (100–500 m² g⁻¹) is calcination of Mg(OH)₂ obtained either by precipitation or MgO hydration or sol–gel method. Preparation of MoO₃/MgO catalyst is complicated by the high reactivity of MgO to H₂O and MoO₃. During conventional aqueous impregnation, MgO is transformed to Mg(OH)₂, and well soluble MgMoO₄ is easily formed. Alternative methods, that do not impair the starting MgO so strongly, are non-aqueous slurry impregnation and thermal spreading of MoO₃. Mo species of MoO₃/MgO catalyst are dissolved as MgMoO₄ during deposition of Co(Ni) by conventional aqueous impregnation. This can be avoided by using non-aqueous impregnation. Co(Ni)Mo/MgO catalysts must be calcined only at low temperature because Co(Ni)O and MgO easily form a solid solution. Literature data on hydrodesulfurization (HDS) activity of MgO-supported catalysts are often contradictory and do not reproduced well. However, some results suggest that very highly active HDS sites can be obtained using this support. Co(Ni)Mo/MgO catalysts prepared by non-aqueous impregnation and calcined at low temperature exhibited strong synergism in HDS activity. Co(Ni)Mo/MgO catalysts are much less deactivated by coking than their Al₂O₃-supported counterparts. Hydrodenitrogenation (HDN) activity of Mo/MgO catalyst is similar to the activity of Mo/Al₂O₃. However, the promotion effect of Co(Ni) in HDN on Co(Ni)Mo/MgO is lower than that on Co(Ni)Mo/Al₂O₃.     

Solid state chemistry of bulk mixed metal oxide catalysts for the selective oxidation of propane to acrylic acid

Syntheses of Mo–V–Sb–Nb–O bulk materials, which are candidate catalyst systems for the selective oxidation of propane to acrolein and acrylic acid, were made using soluble precursor materials. The products were characterized by X-ray powder diffraction and Raman spectroscopic studies. The objectives of this work were to explore the utility of liquid phase automated synthesis for the preparation of bulk mixed metal oxides, and the identification of the oxide phases present in the system. This is the first published study of the phase composition for these materials. After calcination of these bulk oxides under flowing nitrogen at 600°C, and using stoichiometric ratios of Mo–V–Sb–Nb (1:1:0.4:0.4) and Mo–V–Sb–Nb (3.3:1:0.4:0.4) it was demonstrated that a mixture of phases were obtained for the syntheses. X-ray powder diffraction studies distinguished SbVO₄, Mo₆V₉O₄₀, MoO₃, and a niobium-stabilized defect phase of a vanadium-rich molybdate, Mo_0.61–0.77V_0.31–0.19Nb_0.08–0.04O_x, as the major phases present. Complementary data were provided by the Raman spectroscopic studies, which illustrated the heterogeneity of the phases present in the mixture. Raman also indicated bands attributable to the presence of phases containing terminal M=O bonds as well as M–O–M polycrystalline phases. Previous studies on this system have identified SbVO₄ and niobium-stabilized vanadium molybdate species as the active phases necessary for the selective oxidation of alkanes.     

High temperature calcined K–MoO3/γ-Al2O3 catalysts for mixed alcohols synthesis from syngas: Effects of Mo loadings

One series of oxidized K–MoO₃/γ-Al₂O₃ samples with different Mo loadings (MoO₃/Al₂O₃ (wt ratio)=0.05–0.45) was prepared by impregnating K and Mo compounds and successive calcination in air at 800°C. The oxidized samples were sulfided and then utilized for mixed alcohols synthesis from syngas. The structural information from laser Raman spectroscopy (LRS), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), ammonia saturation, temperature programmed desorption (TPD) and ethanol decomposition were studied to elucidate the reaction properties.

The results indicated that with Mo loading increased from MoO₃/Al₂O₃=0.05 to 0.25, the total yields of mixed alcohols and hydrocarbons decreased, but the selectivity to mixed alcohols was enhanced sharply from 3% to 50%. With Mo loading increased from MoO₃/Al₂O₃=0.25 to 0.45, the CO conversion was enhanced, but the selectivity to mixed alcohols leveled off. On these catalysts, Fischer–Tropsch (FT) synthesis to linear alcohols and the condensation reaction of low alcohols to form branched i-C₄OH occurred at the same time. With increased Mo loading, activity of the alcohols condensation became high.

Structural studies demonstrated that on oxidized samples with increased Mo loading the same K–Mo–O species was formed, but the dispersion of these K–Mo species decreased. The catalyst's acidity decreased remarkably with Mo loading up to MoO₃/Al₂O₃=0.25, and stayed unchanged as Mo loading was further increased to MoO₃/Al₂O₃=0.45. With increased Mo loading, the activity for ethanol dehydration changed parallel to the acidity. Results of the activity experiments for mixed alcohols' synthesis and the structural measurements indicated that the dispersion state of Mo species and the content of unreduced Mo species influenced the total CO conversion, and that the acidity of the catalyst controlled the selectivity to mixed alcohols.     

Characterization of Mo–Sn–O system by means of Raman spectroscopy and electrical conductivity measurements

Mo–Sn–O systems were characterized by Raman spectroscopy and electrical conductivity measurements. The catalysts were obtained from precipitation of SnCl₄ by ammonia in the presence of (NH₄)₂Mo₇O₂₄ using four different levels of Mo concentration. The electrical conductivity measurements showed that particles are formed by agglomeration of SnO₂ crystals aggregated by polymolybdate. Raman spectroscopy suggested that four-coordinated species are dispersed at the external surface while six-coordinated species are inside the particles. For high Mo concentration (Mo >10%), octahedral coordinated species are also on the surface. Bulk MoO₃ oxide was not observed. These results confirm the model previously proposed.     

Preparation of Porous Anatase Coating from Sol-Gel-Derived Titanium Dioxide and Titanium Dioxide-Silica by Water-Vapor Exposure

The effects of water vapor on the crystallization behavior of sol-gel-derived titanium dioxide (TiO₂) thin films that contained 0-50 mol% silica (SiO₂) were investigated. Anatase formed on exposure to water vapor at 60°-180°C, with a simultaneous decrease in the concentration of OH groups. An increase in the SiO₂ content of the exposed films led to an increase in the average crystalline size. Because crystallization of the exposed films of the films was not accompanied by shrinkage, porous anatase coatings were obtained via exposure at a relatively low temperature. Phase separation of the immiscible TiO₂-SiO₂ system was induced with water vapor, which resulted in acceleration of the crystallization of the sol-gel films.     

Evaluation of the role played by bismuth molybdates in Bi2Sn2O7–MoO3 catalysts used for partial oxidation of isobutene to methacrolein

The catalytic behaviour of multiphasic catalysts based on -bismuth pyrostannate, Bi₂Sn₂O₇, was investigated in the selective oxidation of isobutene into methacrolein. When -Bi₂Sn₂O₇ is mixed with MoO₃, strong cooperation effects on the yield and selectivity in methacrolein occur. However, XRD analyses performed on samples after test revealed the formation of a low quantity of -bismuth molybdate, -Bi₂Mo₃O₁₂, when the reaction temperature exceeded 673 K. Additional experiments were therefore carried out on the “Bi–Sn–Mo–O” catalysts in order to shed light on the role of Bi₂Mo₃O₁₂ in the synergetic effects observed in the Bi₂Sn₂O₇–MoO₃ system. The experimental results are discussed in terms of several hypotheses. First, the intrinsic activity of Bi₂Mo₃ O₁₂ is probably the simplest explanation for the synergetic effects, although experiments have shown that this phase present in a low quantity is only poorly active. Second, catalytic tests made on Bi₂Sn₂O₇–Bi₂Mo₃O₁₂ mechanical mixtures have evidenced a cooperation between these two ternary oxides, particularly when Bi₂Sn₂O₇ was the major component of the mixture. Consequently, it is likely that a synergy between Bi₂Sn₂O₇ and the in situ generated Bi₂Mo₃O₁₂ might play a role in the synergy observed in the Bi₂Sn₂O₇–MoO₃ association. Third, as bismuth pyrostannate was previously shown to behave as an oxygen donor phase with respect to WO₃, a remote control mechanism could therefore occur between Bi₂Sn₂O₇ and MoO₃, independently from the formation of -Bi₂Mo₃O₁₂.     

Correlation between equation of state and temperature and pressure dependence of self-diffusion coefficient of polymers and simple liquids

Correlation between the equation of state and the temperature dependence of the self-diffusion coefficient D for polymers such as polystyrene (PS) and polydimethyl siloxane (PDMS) and simple liquids such as argon, methane and benzene and the pressure dependence of D for oligomers such as dimethyl siloxane (DMS) and simple liquids such as cyclohexane and methanol has been examined based on the equation of state derived previously. The experimental data used were published by Antonietti et al. and McCall et al. for polymers, by McCall for linear dimethylsiloxanes and by Jonas et al. and Woolf et al. for simple liquids. The expression for D in this work is given by

where A₁(M) is a function of molecular weight M_w, C₁(T) and P₁(T) are functions of temperature and B₁, n₁ and m₁ are constants determined experimentally. For simple liquids, the values of n₁ obtained range from 0.3 to 1.2, with an average , and m₁ is in the range 0.5–1.2, with . For polymers, values of n₁ are in the range 2.5–7.0 for PS and 0.5–1.3 for PDMS and m₁ for DMS is in the range 0.8–1.0. The relation Dη/T = f(M) is found to be useful for simple liquids over a wide range of temperature including the critical region and for pressures up to ≈5 kbar

1 kbar = 100 MPa There is a close correlation between ln(D/T) and _p and β_T through ln(D/T)ln D_c−⁻¹_p−β⁻¹_T, where D_c is D at the critical temperature and _p and β_T are the thermal expansion coefficient and compressibility, respectively. The molecular weight dependence of D for polymers and simple liquids is discussed based on the experimental data and recent theory of Doi and Edwards. A new model for the mechanism of self-diffusion in the liquid state is proposed.     

Effect of electro-chemical properties of sodium salts of various anions on their diffusional parameters in symmetrical cellulose acetate membranes

A relation was obtained between electro-chemical properties of sodium salts (NaCl, NaBr, and Na₂SO₄), and the thermodynamic property of permeability in symmetrical cellulose acetate membranes, the distribution coefficient K and the kinetic property, the overall diffusion coefficients D. K and D were obtained by the method we proposed using measured unsteady- and steady-state dialysis data. The K values increase with the increase of water content and are in the range of 10⁻² for sodium halides and 10⁻³ for Na₂SO₄. D is found to increase with the increase of the solute concentration, and the extrapolated values of D to zero concentration D⁽⁰⁾ are obtained as 0.015–0.03 μm²/s and increase with the increase of water content in the membrane. D can be divided into the concentration independent diffusion coefficients in the dense part of the membrane D_d and in the porous D_p, applying a two-part (perfect or dense and imperfect or porous) model of the membrane. Contrary to D_d, D_p increases with the increase of W_w and can be correlated as D_p,c = _d exp (γ × W_w). It is shown that the averaged D_d, _D increases with the increase of the quantity of the ionic mobility u of the solutes at infinite dilution divided by valence, and that the parameter γ increases with the increase of the ionic mobility u. The value of K increases slightly with the increase of water content and decreases with the increase of the Flory—Huggins parameter χ. The Flory—Huggins parameter χ is calculated from the measured values of distribution coefficients and data obtained from the literature. And it was found that the gradient of linear decrease of χ (λ_cation) depends on equivalent ionic conductivity of anion of salt, λ_an.     

Direct evidence for purely silver ion conduction in CuI-doped silver oxysalt superionic systems: Combined electrolysis and EDS studies

Maiden attempt has been made for the direct estimation of the contributions of silver and copper ions to the ionic conductivity in superionic solids obtained in CuI-doped silver oxysalt systems. The application of the combined electrolysis and EDS techniques towards qualitative and quantitative analyses of the mobile ionic species in solid electrolyte systems having more than one possible mobile ion is reported. These studies confirmed that these electrolyte materials are purely Ag⁺ conducting up to 50 mol% CuI in xCuI–(100 − x)[2Ag₂O–0.7V₂O₅–0.3B₂O₃] and xCuI–(100 − x)[Ag₂O–0.7MoO₃–0.3WO₃] systems and small fraction of t_Cu+ exists above 60 mol% CuI. These solid electrolyte materials exhibited a high ionic transport numbers (t_i) of >0.985 and the t_i increases when two glass formers are used.     

Passivity behavior of melt-spun Mg–Y Alloys

Several Mg–Y binary ribbons with Y content up to 17.9 at.% were fabricated by melt-spinning. X-ray diffraction (XRD) revealed that the phase structure changes with increasing Y content from extended solid solution to partially amorphous, and then fully intermetallic Mg₂₄Y₅. Anodic potentiodynamic polarization performed in 0.01 M NaCl electrolyte (pH=12) revealed improved anodic passivity behavior compared to pure Mg for all the Mg–Y alloys. X-ray photoelectron spectroscopy (XPS) revealed that the improved passivity of Mg–Y was more related to the elemental oxidation state rather than the concentration of the surface components. To study the effect of Cl⁻ ion on the passivity behavior, anodic potentiodynamic and potentiostatic polarization were performed on Mg–17.9 at.% Y in alkaline (pH=12) NaCl electrolytes containing Cl⁻ ion in the concentration range from 0.00 to 0.50 M. The passive films formed in 0.01 M NaCl electrolyte were similar to the native film, which were composed of MgO and Y₂O₃. No CO₃²⁻ and Cl⁻ ions were incorporated into the passive film. The passivity was significantly degraded in the electrolytes containing higher Cl⁻ concentration (0.1 and 0.5 M). Detailed XPS revealed that the surface films under these conditions were composed of much hydrated species Mg(OH)₂ and YOOH and/or Y(OH)₃ and CO₃²⁻ was incorporated into the surface film. The incorporation of Y₂O₃ in the passive film was given as the reason for the enhanced passivity properties of Mg–Y ribbons. The mechanism of Cl⁻ and CO₃²⁻ ions to the degradation of the passivity was discussed.     

Selective oxidative dehydrogenation of propane over surface molybdenum-enriched MgMoO4 catalyst

Drastic activity increases were observed by the treatments of the magnesium-rich MgMo_0.99O_y catalysts, which are poorly active for the oxidative dehydrogenation of propane, with inorganic or organic acid to remove excess magnesium on the surface. MoO₃ loading on magnesium-rich MgMo_0.99O_y catalysts also resulted in drastic activity increases. The activity increases followed non-effective loadings of MoO₃ in the range 0–2 wt%, because it is necessary to neutralize the surface magnesium with MoO₃ before the formation of molybdenum-rich surface. The pH of the aqueous (NH₄)₆Mo₇O₂₄ solution for the MoO₃ loading apparently influenced the activity. Under the acidic conditions the MoO₃ loading resulted in the drastic activity increase but under the basic conditions the effect of the MoO₃ loading was poor, suggesting that a cluster-type MoO₃ on MgMoO₄ surface is responsible for the activity of propane oxidative dehydrogenation.     

Structural Changes of Sol–Gel-Derived TiO2–SiO2 Coatings in an Environment of High Temperature and High Humidity

Structural changes in sol–gel-derived TiO₂–SiO₂ coatings were found to proceed in an environment of high temperature and high humidity as follows: (1) dissociation of Si–O–Ti bonds in the coating by the attack of water vapor, (2) formation of Ti–O–Ti bonds, and (3) nucleation and growth of anatase TiO₂. The coating obtained with the addition of poly(ethylene glycol), PEG, reacts with water vapor more easily than the coating obtained without PEG, since the former is more porous than the latter due to the decomposition of PEG during heat treatment.     

TiO2 coating types influencing the role of water vapor on the photocatalytic oxidation of methyl ethyl ketone in the gas phase

Four TiO₂-based materials, named A, B, C and D, are used to investigate the influence of water vapor on the gas–solid adsorption and heterogeneous photocatalytic oxidation of gaseous methyl ethyl ketone (MEK). Two of the photocatalysts (A and B) are constituted of powdered TiO₂ deposited onto two different supports (ordinary glass and non-woven cellulose fibers). The other ones (C and D) are composed of a thin film of TiO₂ coated on glass substrates. The effect of water vapor on MEK initial conversion rates is studied for the four photocatalytic materials using the Langmuir–Hinshelwood model at the initial time. On the concentrations range where the model hypotheses are verified, adsorption constants K and kinetics constants k are calculated for experiments under both dry and humid atmosphere. When the relative humidity is increased, the evolution of these constants shows that water vapor acts differently depending on the form of deposited TiO₂ (powder and film).     

An FTIR/ATR in situ study of sorption and transport in corrosion protective organic coatings: Paper 2. The effects of temperature and isotopic dilution

A detailed temperature variation (18–50 °C) FTIR/ATR study of sorption and desorption of water into a series of cured epoxy resins has been reported. For higher temperatures (35–50 °C) the data were modelled with a single Fickian diffusion equation, giving an increased D as the temperature increased and an activation energy (E_A) in the 55–60 kJ mol⁻¹ region. At lower temperatures (18–35 °C)—well-below the T_g—a two-stage sorption equation was needed and the apparent E_A was negative. This is probably associated with changes in water clustering among the distributed ‘voids’ in the glassy polymer associated with chain relaxation at extended times. The use of D₂O as a penetrant allowed diffusion coefficient measurements for highly dense epoxy matrices, where FTIR/ATR cannot detect the ν(OH) band of water over and above the residual polymer–OH groups (in the dry state). The data for the D₂O studies were notably influenced by isotopic exchange; which was found to be a diffusion controlled process, even in a polymer matrix.     

Structural studies of reaction products between paramolybdate anion and some cationic [metal(II) and (III)-(ethylenediamine)n] complexes utilized as new photocatalysts under UV–VIS light illumination

Five cationic transition metal (ethylenediamine) complexes (M=Cr(III), Co(III), Ni(II), and Cu(II)):paramolybdate anion (Mo₇O₂₄⁶⁻) have been synthesis and characterized via their elemental analysis, magnetic susceptibility (μ_eff), thermal analysis (TG and DTA), FTIR spectra, and X-ray diffraction (XRD). The FTIR study suggests that the compounds prepared be of the ion-pair type ([M(en)_n]_m·Mo₇O₂₄). Thermal study showed that molybdenum in the Cr(III), and Co(III) compounds is reduced from oxidation state (VI) to (V) at high temperature. The stoichiometries of the resulting mixed oxides at elevated temperatures (500–750°C) are: Cr₂O₃·7MoO_2.5, Co₂O₃·7MoO_2.5, 6CoOCl·7MoO_2.5, 3NiO·7MoO₃ and 3CuO·7MoO₃. Above 750°C the molybdenum oxide in the ion-pair compounds start the sublimation process. X-ray diffraction of [Cr(en)₃]·Mo₇O₂₄, [Co(en)₃]·Mo₇O₂₄, and [Cu(en)₂(H₂O)₂]₃·Mo₇O₂₄ shows that these complexes are crystalline solids with a similar structure, while the [Ni(en)(H₂O)₄]₃·Mo₇O₂₄, and [Co(en)(H₂O)₂Cl₂]₆·Mo₇O₂₄ ion-pair compounds display a different structure.

A novel technique based on photocatalysis to eliminate Cr(VI) ions, a toxic pollutant in the environment, was applied. The photoreduction of Cr(VI) to Cr(III) ion in aqueous suspensions using new-mixed oxides as photocatalysts (Cr₂O₃·MoO_2.5, Co₂O₃·MoO_2.5, NiO·MoO₃, and CuO·MoO₃) under air-equilibration and irradiation by a medium pressure mercury lamp (UV–VIS) was investigated.     

Effect of Phosphorus Ions on the Proton Conductivity in the Sol–Gel-Derived Porous Glasses

The effect of phosphorus ions on the proton conductivity was examined for the sol–gel-derived glasses. The porous glasses were prepared through hydrolysis of PO(OCH₃)₃ and Si(OC₂H₅)₄, in which the phosphorus ions consisted of the POH bonds and were dissolved into the silica matrix without any P-O-Si bond. The electrical conductivity increased in a humid atmosphere and reached ∼30 mS/cm at 50°C under 70% RH. High conductivity is achieved by both the POH bonds and the molecular water bonded to the POH bonds. The conductivity increased with a change in humidity from 40% to 80% RH. The phosphorus ions were selectively dissolved in water, resulting in a lower conductivity.