Characterization and activity of vanadia-promoted Pt/ZrO2 catalysts for the water–gas shift reaction

Pt/ZrO₂ catalysts for the water–gas shift (WGS) were promoted with various amounts of vanadia. Analyses by XRD, N₂ adsorption, Raman, and UV–vis DRS showed that vanadia is present below monolayer coverage as monovanadate and polyvanadate, with the former dominating at lower loadings, and that following monolayer formation, VO₅ species appear, with the eventual generation of V₂O₅ and ZrV₂O₇ for a vanadia weight loading of 13%. Though in all cases vanadia induced an enhancement in WGS activity, the best catalyst, that contained 3 wt.% of vanadia, gave a rate that was nearly double that of the unpromoted Pt/ZrO₂. That superior global activity probably results from the monovanadate that is the main species at low loadings. It is believed that monovanadate promotes the WGS by rendering the support's surface more oxidizing through its VOZr bonds.     

Adsorption and oxidation of NH3 over V2O5/AC surface

V₂O₅/AC has been reported to be active for selective catalytic reduction (SCR) of NO with NH₃ at around 200 °C and resistant to SO₂ deactivation. To elucidate its SCR mechanism, adsorption and oxidation of NH₃ over V₂O₅/AC are studied in this paper using TG, MS and DRIFTS techniques. It is found that the adsorption and oxidation of NH₃ take place mainly at VO bond of V₂O₅. A higher V₂O₅ loading results in more NH₃ adsorption on the catalyst. V₂O₅ contains both Brnsted and Lewis acid sites; NH₄⁺ on Brnsted acid sites is less stable and easier to be oxidized than NH₃ on Lewis acid sites. Gaseous O₂ promotes interaction of NH₃ with AC and oxidation of NH₃ over V₂O₅/AC. NH₃ is oxidized into NH₂ and acylamide structures and then to isocyanate species, which is an intermediate for N₂ formation.     

Oxidative dehydrogenation of ethane to ethylene over alumina-supported vanadium oxide catalysts: Relationship between molecular structures and chemical reactivity

The influence of vanadium oxide loading in the supported VO_x/Al₂O₃ catalyst system upon the dehydrated surface vanadia molecular structure, surface acidic properties, reduction characteristics and the catalytic oxidative dehydrogenation (ODH) of ethane to ethylene was investigated. Characterization of the supported VO_x/Al₂O₃ catalysts by XPS surface analysis and Raman spectroscopy revealed that vanadia was highly dispersed on the Al₂O₃ support as a two-dimensional surface VO_x overlayer with monolayer surface coverage corresponding to 9 V/nm². Furthermore, Raman revealed that the extent of polymerization of surface VO_x species increases with surface vanadia coverage in the sub-monolayer region. Pyridine chemisorption-IR studies revealed that the number of surface Brønsted acid sites increases with increasing surface VO_x coverage and parallels the extent of polymerization in the sub-monolayer region. The reducibility of the surface VO_x species was monitored by both H₂-TPR and in situ Raman spectroscopy and also revealed that the reducibility of the surface VO_x species increases with surface VO_x coverage and parallels the extent of polymerization in the sub-monolayer region. The fraction of monomeric and polymeric surface VO_x species has been quantitatively calculated by a novel UV–Vis DRS method. The overall ethane ODH TOF value, however, is constant with surface vanadia coverage in the sub-monolayer region. The constant ethane TOF reveals that both isolated and polymeric surface VO_x species possess essentially the same TOF value for ethane activation. The reducibility and Brønsted acidity of the surface VO_x species, however, do affect the ethylene selectivity. The highest selectivity to ethylene was obtained at a surface vanadia density of 2.2 V/nm², which corresponds to a little more than 0.25 monolayer coverage. Below 2.2 V/nm², exposed Al support cations are responsible for converting ethylene to CO. Above 2.2 V/nm², the enhanced reducibility and surface Brønsted acidity appear to decrease the ethylene selectivity, which may also be due to higher conversion levels. Above monolayer coverage, crystalline V₂O₅ nanoparticles are also present and do not contribute to ethane activation, but are responsible for unselective conversion of ethylene to CO. The crystalline V₂O₅ nanoparticles also react with the Al₂O₃ support at elevated temperatures via a solid-state reaction to form crystalline AlVO₄, which suppresses ethylene combustion of the crystalline V₂O₅ nanoparticles. The molecular structure–chemical characteristics of the surface VO_x species demonstrate that neither the terminal VO nor bridging VOV bonds influence the chemical properties of the supported VO_x/Al₂O₃ catalysts, and that the bridging VOAl bond represents the catalytic active site for ethane activation.     

Aerobic oxidation of alcohols over novel crystalline MoVO oxide

Novel crystalline MoVO oxide was employed as the catalyst in the aerobic oxidation of alcohols to the corresponding carbonyl compounds. Reactions were mainly conducted at 353 K in pure oxygen or air (1 atm). The selectivities for benzaldehydes were more than 95% in all cases. The conversions of benzyl alcohols varied from 10% to 99% depending on the substituent. A Hammett plot gave a moderate ρ-value of −0.249 (r² = 0.98), suggesting that the reaction processes may involve hydride abstraction. The oxidation of primary alkanols afforded aldehydes, and secondary alcohols were mainly dehydrated to olefins. It was found that the conversion of linear alkanols decreased with the length of alkanols. Kinetic analysis showed that catalytic reaction rate was first-order dependent on the concentrations of substrate and of catalyst. The apparent activation energy was estimated to be 45.7 kJ mol⁻¹. Catalytic reactions took place on the 6- or 7-member rings on the a–b basal plane, where highly dense unsaturated metal cation centers and oxygen anion might serve as catalytic active sites.     

Preparation and photocatalytic activity of hierarchically mesoporous-macroporous TiO2−xNx

Hierarchically mesoporous-macroporous N-doped titania materials were fabricated by the thermal treatment of spontaneously formed hierarchical mesoporous-macroporous titanias with urea solution, in order to extend their photocatalytic applications from ultraviolet to visible-light range. The resultant meso-macroporous TiO_2−xN_x exhibited a bicrystalline (anatase and brookite) framework with high surface area and large porosity. The content of the doped nitrogen increased with the urea solution and the nitridation temperature, and the band gaps narrowed from 3.14 to 2.48 eV. The formation of OTiN bonds in the meso-macroporous TiO_2−xN_x was confirmed by the XPS and FT-IR spectra. The photocatalytic activity was evaluated by the photodegradation of methyl orange and rhodamine B under UV and visible-light irradiation, respectively. The significant improvement of photocatalytic activity for water contaminant decomposition under both UV and visible-light irradiation was observed, which is due to the incorporation of nitrogen into the titania lattice and the presence of the hierarchical meso-macroporous structure.     

Enhancing effect of S and F moieties on the performance of Fenton system in the selective oxidation of propane

The selective oxidation of propane to oxygenated products (isopropanol, n-propanol, propionic aldehyde and acetone) mediated by the Fe(II)/H₂O₂ Fenton system at 80 °C in the presence of solid acid and superacid promoters containing S and F moieties has been studied. The occurrence of a radical reaction pathway accounting for the activation of the CH bonds of the propane molecule by OH radicals has been proved by assessing the inhibiting effect of both Cl⁻ and NO₃⁻ radical scavengers and organic (CH₃COOH, CH₃CN, DMSO) reaction media on the reaction pattern. S and F functionalities of several solid agents promote the electron transfer processes controlling the H₂O₂ activation. Any effect of the Brönsted acid features of the solid promoters on the reaction kinetics and pathway has been disregarded.     

Adsorption mechanism and property of novel composite material PMAA/SiO2 towards phenol

In this paper, functional macromolecule poly(methacrylic acid) (PMAA) was grafted on the surface of silica gel particles using 3-methacryloxypropyl trimethoxysilane (MPS) as intermedia, and the grafted particle PMAA/SiO₂ with strong adsorption ability for phenol was prepared. The adsorption mechanism and properties of PMAA/SiO₂ for phenol were researched by static and dynamic methods. The experimental results showed that PMAA/SiO₂ possesses strong adsorption ability for phenol with interaction of three kinds of hydrogen bonds including peculiar O–Hπ hydrogen bond (aromatic hydrogen bond) and O–HOC π hydrogen bond. The saturated adsorption amount could reach up to 162.88 mg g⁻¹. The empirical Freundlich isotherm was found to describe well the equilibrium adsorption data. pH and temperature were found to have great influence on the adsorption amount. Finally, PMAA/SiO₂ was observed to possess excellent reusability properties as well.     

Contribution of intermolecular interactions to constructing supramolecular architecture: Synthesis, structure and Hirshfeld surface analysis of a new hybrid of polyoxomolybdate and ((1H-tetrazole-5-yl) methyl)morpholine

A new soluble organic–inorganic hybrid based on polyoxomolybdate, [C₆H₁₂N₅O]₃[(PO₄)Mo₁₂O₃₆]·6H₂O (1), has been successfully synthesized and characterized by using elemental analysis, IR, UV spectroscopies, ¹H NMR technique, and single-crystal X-ray diffraction. According to the results of X-ray crystallography the anion [(PO₄)Mo₁₂O₃₆]³⁻ has a typical Keggin structure and the Mo–O distances of Mo–O–Mo bonds are alternately short and long in the polyoxoanion structure. Hirshfeld surface analyses, especially d_norm surface and fingerprint plots, are used for decoding intermolecular interactions in the crystal network and contribution of component units for the construction of the 3D architecture. The results indicate that in 1 the hydrogen bond interaction play a main role in the construction of the 3D architecture, especially the CHO interaction which overruns the classic NHO, NHO hydrogen bond interactions; van der Waals force between the peripheral atoms of component units cannot be ignored.     

HDS of benzothiophene and dihydrobenzothiophene over sulfided Mo/γ-Al2O3

The hydrodesulfurization (HDS) of benzothiophene (BT) and dihydrobenzothiophene (DHBT) was studied over a sulfided Mo/γ-Al₂O₃ catalyst at 5 MPa and 280 and 300 °C. In the absence of H₂S, benzothiophene reacted by hydrogenation to dihydrobenzothiophene and by hydrogenolysis to ethylbenzene (EB), and dihydrobenzothiophene reacted by hydrogenolysis to ethylbenzene. H₂S inhibited both hydrogenation and hydrogenolysis, but the latter much more strongly. The reverse inhibition was observed for 2-methylpiperidine (MPi). In the presence of H₂S and/or 2-methylpiperidine, dihydrobenzothiophene reacted to ethylbenzene as well as by total hydrogenation to octahydrobenzothiophene, and on to ethylcyclohexenes and ethylcyclohexane. Dihydrobenzothiophene did not react back to benzothiophene at and below 300 °C, while the equivalent tetrahydrodibenzothiophene reacted fast to an equilibrium with tetrahydrodibenzothiophene, due to stabilization of the vinylic bond by the alkyl groups. The observed products and kinetic results were explained by a model in which the CS bonds were mainly broken by hydrogenolysis.     

Structural organization of catalytic functions in Mo-based oxides for propane selective oxidation

Several single phasic MoVO-based mixed oxides, all of which have a layer structure in the direction of c-axis and a high dimensional arrangement of metal octahedra in a–b plane, were synthesized by hydrothermal method and their catalytic performance in the selective oxidation of propane to acrylic acid were compared in order to elucidate structure effects on catalytic property and roles of constituent elements. It was clearly demonstrated that the catalyst with the particular arrangement of MO₆ (M = Mo, V) octahedra forming slabs with pentagonal, hexagonal and heptagonal rings in (0 0 1) plane of orthorhombic structure was exclusively superior both in the propane oxidation activity and in the selectivity to acrylic acid to the other related Mo- and V-based layer oxide catalysts consisting of either pentagonal or hexagonal ring unit. The role of constituent elements was clarified by the comparison of catalytic performance of MoVO, MoVTeO and MoVTeNbO, all of which have the same orthorhombic structure. Mo and V, which were indispensable elements for the structure formation, were found to be responsible for the catalytic activity for propane oxidation. Te located in the central position of the hexagonal ring promoted the conversion of intermediate propene effectively, resulting in a high selectivity to acrylic acid. The introduced Nb occupied the same structural position of V and the resulting catalyst clearly showed the improved selectively to acrylic acid particularly at high conversion region, because the further oxidation of acrylic acid to CO_x was suppressed.     

A new type of supramolecular assembly consisting of crown ether complex cation and a polyoxometalate anion: Synthesis and crystal structure of [Na(C20H24O6)(CH3CN)2]2[Mo6O19] · 4CH3CN

A novel supramolecular assembly consisting of sodium-dibenzo-18-crown-6(DB18C6) complex cation [Na(C₂₀H₂₄O₆)(CH₃CN)₂]²⁺ and isopolyanion [Mo₆O₁₉]²⁻ has been demonstrated in the 3D structure of [Na(C₂₀H₂₄O₆)(CH₃CN)₂]₂[Mo₆O₁₉] · 4CH₃CN (1). Weak intermolecular forces (C–HO hydrogen bonds) between isopolyanion and crown ether play a significant role in the construction of supramolecular framework in the crystal structure of 1. Compound 1 has been characterized in the solid state by single crystal X-ray diffraction, IR, CHN analysis, and TGA.     

Synthesis and magnetic properties of nanoporous Co3O4 nanoflowers

Nanoporous Co₃O₄ hierarchical nanoflowers have been prepared through sequential process of a hydrothermal reaction and heat treatment. These nanoflowers consisting of a great deal of Co₃O₄ nanofibers have bimodal pore structures and Brunauer–Emmett–Teller surface area of 34.61 m²/g. The temperature dependence curves of magnetization in zero-field-cooled and field-cooled exhibit main antiferromagnet and weak ferromagnet of Co₃O₄ nanoflowers at blocking temperature of 34 K, respectively. In addition, analysis of their optic properties obviously indicates red shift of absorption peaks, exhibiting quantum-confined effect and traits of semiconductor.     

The effect of crystallographic orientation and solution aging on the electrical properties of sol–gel derived Pb(Zr0.45Ti0.55)O3 thin films

Lead zirconate titanate—Pb(Zr_0.45Ti_0.55)O₃ thin films are grown on Pt_1 1 1/Ti/SiO₂/Si_1 0 0 substrates by a sol–gel method with 1 0 0/0 0 1 and 1 1 1 preferred orientations. Film orientation was controlled mainly by the annealing process and temperature. Films with 1 0 0/0 0 1 orientation consist of a uniform microstructure with micron size grains, whereas films with 1 1 1 orientation contain sub-micron grains. The electrical properties were influenced markedly by the microstructure and orientation of the films. The 1 1 1 oriented films exhibit a square-like hysteresis loop with remnant polarization (P_r) reaching 46 μC/cm² under 550 kV/cm, whereas 1 0 0/0 0 1 oriented films have a P_r of 20 μC/cm² with more slim hysteresis curves. Aging of the precursor solutions resulted in films growing with 1 0 0/0 0 1 texture and displaying inferior electrical properties.     

Oxidative dehydrogenation of ethane over vanadium-based hexagonal mesoporous silica catalysts

Vanadium-containing hexagonal mesoporous silica catalysts were tested in oxidative dehydrogenation of ethane. V-HMS catalysts (0.3–9.0 wt.% V) were prepared by impregnation with solution of vanadyl acetylacetonate, and by incorporation of vanadium in the synthesis process. The prepared catalysts achieved a different distribution of vanadium species (isolated monomeric units with tetrahedral coordination, oligomeric units connected by VOV bonds up to distorted tetrahedral coordination, two-dimensional polymeric units in octahedral coordination, and bulk vanadium oxides). The contribution deals with the understanding of the relationship between the distribution of vanadium species and their activity in ODH of ethane. It has been found that both monomeric and oligomeric vanadium species play important role in ODH of ethane. The activity correlated with the population of oligomeric tetrahedrally coordinated vanadium species, which were evidenced by the UV–vis band at 315 nm. To analyze this effect, V-HMS catalysts were characterized by means of UV–vis spectroscopy, H₂-TPR and N₂-adsorption.     

A novel route to α,ω-telechelic poly(-caprolactone) diols, precursors of biodegradable polyurethanes, using catalysis by decamolybdate anion

A new convenient route for the synthesis of poly(-caprolactone) (PCL) with α,ω-telechelic diols' end-groups is presented. Synthesis of α,ω-telechelic PCL diols (HOPCLOH) was achieved by ring-opening polymerization (ROP) of -caprolactone (CL) catalyzed with ammonium decamolybdate (NH₄)₈[Mo₁₀O₃₄] and using diethylene glycol (DEG) as initiator. Obtained HOPCLOH was characterized by ¹H and ¹³C NMR, FT-IR, GPC and MALDI-TOF. Comparative studies demonstrate that ammonium decamolybdate (NH₄)₈[Mo₁₀O₃₄] is better catalyst than Sn-octanoate (SnOct₂) toward CL polymerization in presence of DEG, under the conditions tested. A biodegradable poly(ester-urethane-urea) derivative was efficiently prepared from synthesized HOPCLOH. Obtained polymer shows minor differences with respect to the properties recorded for a poly(ester-urethane-urea) obtained from commercial HOPCLOH.     

Analysis of the formation of Ta2O5 passive films in acid media through mechanistic modeling

Electrochemical impedance spectroscopy (EIS) analyses are carried out to evaluate the passive features of tantalum oxide films (Ta₂O₅) formed at different potentiostatic conditions (0.5, 1.0, 1.5 and 2.0 V vs SSE). A supporting electrolyte of 0.1 M H₂SO₄ (pH 1) has been used to emulate acidic corrosive conditions for the growth of films with an n-type electronic character. A modification of the point defect model (PDM) accounting for the formation of molecular hydrogen (blistering damage) is used to fit the experimental EIS diagrams, and obtain the kinetic parameters that best describe the semiconductive behavior of the passive films. After this analysis, diffusivities in the order of 5.37 ± 1.6 × 10⁻¹⁷ and 1.98 ± 1.4 × 10⁻²⁰ cm² s⁻¹ were obtained for the oxygen (DVO) and hydroxyl vacancies (DVOH), respectively. These findings show the capabilities of the EIS and the physicochemical modeling to account for the formation of valve-metal oxide films on a different range of conditions.     

Zero-strain insertion mechanism of Li[Li1/3Ti5/3]O4 for advanced lithium-ion (shuttlecock) batteries

Zero-strain insertion mechanism of Li[Li_1/3Ti_5/3]O₄ Å) was examined by ex situ XRD. Change in oxygen positional parameter at 32(e) sites was observed to be from 0.266 for Li[Li_1/3Ti_5/3]O₄ to 0.257 for Li₂[Li_1/3Ti_5/3]O₄ while the cubic lattice dimension remains virtually constant. This indicates that bond length of TiO elongates from 1.96 to 2.03 Å due to the change in oxygen parameter, when Li[Li_1/3Ti_5/3]O₄ is reduced to Li₂[Li_1/3Ti_5/3]O₄. Relationship among the cubic crystallographic unit cell dimension, mean bond length of TiO, and oxygen parameter is given for space group symmetry of in order to understand the zero-strain insertion scheme, and an origin of the zero-strain insertion scheme is discussed from the analytical results.     

Effect of hydrophilic group on thin film formation using redox-active surfactants with an azobenzene group

Thin films of organic pigments were prepared at higher than pH 1 by the contact plating method using an anionic surfactant (AZNa, first figure of this article (part c) (n = 4)) containing an azobenzene moiety. The effects of hydrophilic group of the surfactants on the rate of following reaction of the reduction product were studied by cyclic voltammetry. The positive shift of the reduction peak potential of AZNa compared to those of cationic and non-ionic surfactants was ascribed to higher rate of following reaction of reduction product due to the presence of the anionic hydrophilic group of the surfactant. The present investigation revealed that the anionic hydrophilic group accelerates the cleavage of the NN bond of the azobenzene group. This phenomenon enabled us to prepare the organic thin film at higher pH condition.     

Cathodic deposition of molybdenum and vanadium mixed oxyhydroxide films from V-substituted polymolybdophosphate

We report a new electrochemical route for fabricating molybdenum and vanadium mixed oxyhydroxide films on Au electrode from Keggin-type vanadium-substituted polymolybdophosphate. The process involves a potentiodynamic reduction of aqueous 9-molybdo(VI)-3-vanadophosphosphate(V) ([PMo₉V₃O₄₀]⁶⁻) in the potential region between 0 and −0.7 V versus Ag/AgCl. The resulting MoV oxyhydroxide film electrode gave a stable redox behavior in Na₂SO₄ electrolyte of pH 3. X-ray photoelectron spectroscopy revealed that this results from oxidation/reduction of Mo⁵⁺/Mo⁶⁺ in the film which accompanies extraction/insertion of protons for charge compensation. The deposited V ions remained in the film upon repetitive potential cycling without affecting their oxidation state. Voltammetric data in the presence of sodium nitrite showed electrocatalytic activity of the MoV oxyhydroxide toward the electroreduction of nitrite.     

Electro-oxidation of chlorophenols at glassy carbon electrodes modified with polyNi(II)complexes

The effect of the ligand macrocycle (phenylporphyrin (PP) or phthalocyanine (Pc)) and of the ligand substituent (NH₂ or SO₃⁻) on the catalytic activity for the electro-oxidation in a pH 11 buffer electrolyte of 2- and 4-chlorophenol (2-CP and 4-CP), 2,4- and 2,6-dichlorophenol (2,4-DCP and 2,6-DCP), 2,4,6-trichlorophenol (2,4,6-TCP), and pentachlorophenol (PCP) at glassy carbon electrodes modified with electropolymerized Ni(II) macrocycles was studied. The polyphenolic residue deposited at the electrode surface was characterized by cyclic voltammetry, impedance measurements, ex situ Fourier transform infrared spectroscopy (FT-IR) and X-ray Photoelectron Spectroscopy (XPS). A band of aliphatic CO stretching in the IR spectrum of the fouling film produced by potential cycling in 2,4,6-TCP indicated that the aromatic ring had been broken, yielding ketones, aldehydes and/or carboxylic acids. The sulphonated Ni(II) polymers, which showed the Ni(III)/Ni(II) process in the CV, had XP spectra typical of paramagnetic Ni(II), indicating that they contained Ni(OH)₂ clusters. On the contrary, the CVs of the amino Ni(II) did not show the Ni(III)/Ni(II) process at all, this process appearing only after previous activation by potential cycling, and only to a small extent. As was to be expected, the XP spectra of activated amino films corresponded to diamagnetic Ni(II), showing that the concentration of Ni(OH)₂ clusters was very small. The amino films were less active than the sulpho films for the oxidation of chlorophenols, in agreement with the lower concentration of Ni(OH)₂ clusters in the former films. For all electrodes the highest activity was observed for 2,4,6-TCP, since its oxidation yields a phenolic residue which is much more porous than those produced by the other CPs.