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.     

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.     

Mechanism of heterogeneous catalytic ozonation of nitrobenzene in aqueous solution with modified ceramic honeycomb

The degradation efficiencies of nitrobenzene in aqueous solution were investigated by semi-continuous experiments in the processes of ozone alone, ozone/ceramic honeycomb (CH) and ozone/modified ceramic honeycomb (MCH). MCH with 1.0% Mn and 0.5% Cu had more pronounced catalytic ability than CH to accelerate the degradation of nitrobenzene, to increase the utilization efficiency of ozone, to improve the concentrations of hydrogen peroxide (H₂O₂) formation and hydroxyl radical (OH) initiation, and to enhance the removal efficiency of TOC. The modification process of CH with the metals enhanced the density of surface hydroxyl groups, which determines the initiation of OH from ozone decomposition and the generation of intermediate species on heterogeneous catalytic surface, yielding the acceleration of the degradation of nitrobenzene in aqueous solution. Possible reaction mechanism of ozone with heterogeneous catalytic surface in aqueous solution was proposed, and the formation mechanism of H₂O₂ and OH was also discussed according to the combined reactions in heterogeneous and homogeneous catalytic systems.     

Novel synthesis of -caprolactam from cyclohexanone-oxime via Beckmann rearrangement over mesoporous molecular sieves MCM-48

Vapor-phase synthesis of -caprolactam (-C) from cyclohexanone-oxime (CHO) has been studied at 1 atm and 300–400 °C using SiMCM-48 and AlMCM-48(X) with Si/Al molar ratios X in a fixed-bed, continuous flow reactor. The catalysts were characterized with ICP-AES, XRD, TEM, FT-IR, N₂-adsorption, ²⁷Al and ²⁹Si MAS NMR and TPD of ammonia. An increase of X value in AlMCM-48(X) enhances both the BET surface area and the unit cell parameter but diminishes the acid amount. In the reaction of CHO, benzene, toluene, ethanol and 1-hexanol were utilized as solvents. The CHO conversion increases with the reaction temperature, whereas the -C selectivity exhibits the opposite trend due to side reactions. The catalyst stability is greatly enhanced by using ethanol and 1-hexanol as the solvents due to their production of water vapor via dehydration. Excellent catalytic performance of AlMCM-48(10) is attained at 1 atm, 350 °C and W/Fc 74.6 g h/mol by using 1-hexanol in the feed; the CHO conversion and the -C selectivity exhibit higher than 99% and 90%, respectively, during at least 130 h process time.     

Novel synthetic strategy toward shape memory polyurethanes with a well-defined switching temperature

Shape memory polyurethanes (SMPUs) have been synthesised via a novel synthetic methodology, resulting in an improvement of the phase separation in the multi-block structure of the polyurethane and in its shape memory properties. ABA block copolymers based on semi-crystalline poly(-caprolactone) and amorphous poly(propylene oxide) (PPO) were used as precursor for the SMPUs. For their synthesis, poly(-caprolactone) diols have been converted into isocyanate end-capped prepolymers by using a mixture of 3(4) isocyanato-1-methyl-cyclohexylisocyanate isomers, after which a coupling with low-T_g poly(propylene oxide) oligomers is done. The shape memory polymers are obtained by reaction of the ABA block copolymers with hexamethylenediisocyanate and 1,4-butanediol as chain extender. Using this new strategy, a flexible segment (PPO) was introduced between the hard and the switching segments of the SMPU. For comparison, SMPUs without flexible segment have also been prepared with the conventional synthetic route. DSC, isostrain experiments and cyclic shape memory tests revealed narrower switching temperatures for the SMPUs including a flexible segment.     

Preparation of poly(-caprolactone) grafted titanate nanotubes

This work reported for the first time the surface functionalization of titanate nanotubes (TNTs) with biodegradable poly(-caprolactone) (PCL). A “grafting from” approach based on in situ ring-opening polymerization of -caprolactone from TNTs with a special surface modification was adopted to prepare the PCL-g-TNTs. The thickness of the grafted PCL shell can be controlled by increasing reaction time. After grafted with PCL, both the dissolubility and flexibility of the tubes were greatly improved. The obtained PCL-g-TNTs can easily disperse in several organic solvents, and the dispersal stability depends on solvent polarity and PCL shell thickness. Furthermore, the PCL immobilized on the surface of TNTs still possessed a good biodegradable capacity and could be completely decomposed in the presence of Pseudomonas (PS) lipase. The PCL-g-TNTs reported here are promising in biotechnology applications due to good dissolubility, flexibility, biocompatibility and the tubular nano-structure.     

UV- and thermal-curing behaviors of dual-curable adhesives based on epoxy acrylate oligomers

Dual-curable adhesives were prepared using various epoxy acrylate oligomers, a reactive diluent, photoinitiators, a thermal-curing agent and a filler. The UV- and thermal-curing behaviors of the dual-curable adhesives were investigated using photo-differential scanning calorimetry (photo-DSC), Fourier transform infrared-attenuated total reflection (FTIR-ATR) spectroscopy, and the determination of the gel fraction, pendulum hardness and adhesion strength.The reaction rate and extent of UV curing were found to be strongly dependent on the concentration of CC bonds in the epoxy acrylate oligomers. The FTIR-ATR absorption peak areas representing the relative concentration of CC bonds in the epoxy acrylate oligomers and trifunctional monomer decreased with increase in UV dose because of photopolymerization. When the dual-curable adhesives were irradiated with UV light, the gel fraction increased with increase in CC bond contents in the epoxy acrylate oligomers. Also, after thermal curing, the gel fraction was highly enhanced due to the cross-linking reaction of the unreacted glycidyl groups in epoxy acrylate oligomers induced by the thermal-curing agent. This cross-linked structure of the dual-curable adhesives affects the pendulum hardness and adhesion strength.     

Facile functionalization by π-stacking of macroscopic substrates made of vertically aligned carbon nanotubes: Tracing reactive groups by electrochemiluminescence

We report a simple, fast and reliable non-covalent route of functionalization of macroscopic carbon nanotubes (CNTs) surfaces based on the π-stacking of CNTs sidewall with fluorescein derivatives (i.e., amino- and isothiocyanate-). The electrochemiluminescent emission of Ru(bpy)₃²⁺ labels bearing –COOH and –NH₂ side groups coupled with colorimetric and XPS measurements allowed to estimate the quantity of –NH₂ and –NCS functions obtained. The evaluation of reactivity suggests that functionalized CNTs substrates, in particular those carrying –NCS groups, are suitable to covalently bind probe molecules such as proteins and oligonucleotides, thus opening up the possibility of future application in genomics and proteomics fields.     

Development of mesoporous Al,B-MCM-41 materials: Effect of reaction temperature on the catalytic performance of Al,B-MCM-41 materials for the cyclohexanone oxime rearrangement

A series of aluminum–boron–silicate MCM-41 mesoporous materials and their counterparts treated with NH₄F aqueous solution were synthesized and characterized by using XRD, MAS NMR, nitrogen physisorption, DRIFT, TG-DTA, TP/MS and pyridine adsorption. All of the samples showed typical MCM-41 structural and textural properties. ²⁷Al MAS NMR showed that the aluminum environment was mainly four-coordinated and six-coordinated aluminum for non-fluorinated samples and fluorinated ones, respectively. Boron was in the trigonal framework environment at ca. catalytic reaction temperatures and the NH₄F treatment did not affect the boron environment in our Al,B-MCM-41 materials. All of the Al,B-MCM-41 materials studied contained both Brønsted and Lewis acid sites. However, the strong acid Brønsted/Lewis ratios decreased in the fluorinated catalysts. Moreover, the influence of temperature was studied on the cyclohexanone oxime conversion and the product selectivity in the 623–798 K range. Results indicated that temperatures lower than 748 K favored Beckmann rearrangement to -caprolactam, whereas, at higher temperatures the main reaction was cyclohexanone oxime hydrolysis to cyclohexanone. The aluminum–boron–silicate MCM-41 mesoporous materials treated with NH₄F improved both the selectivity to -caprolactam (related mainly to boron content) and their life span (related to their lower ratios of strong Brønsted/Lewis acid sites).     

Synthesis of tadpole-shaped copolyesters based on living macrocyclic poly(-caprolactone)

Synthesis of an asymmetric tadpole-shaped aliphatic copolyester consisting of a poly(-caprolactone) ring and two poly(l-lactide) tails was reported for the first time. First, a high molecular weight cyclic PCL macroinitiator (M_n = 31,000) was prepared by intramolecular photocross-linking of “living” chains. Polymerization of l-lactide was resumed by the tin dialkoxide containing macrocycles, thus making the targeted tadpole-shaped copolyester available. A preliminary investigation of the crystallization of these copolyesters was carried out by differential scanning calorimetry and polarized optical microscopy.     

Catalytic ozonation for the degradation of nitrobenzene in aqueous solution by ceramic honeycomb-supported manganese

Catalytic ozonation of nitrobenzene in aqueous solution has been carried out in a semi-continuous laboratory reactor where ceramic honeycomb and Mn–ceramic honeycomb have been used as the catalysts. The presences of the two catalysts significantly improve the degradation efficiency of nitrobenzene, the utilization efficiency of ozone and the production of oxidative intermediate species compared to the results from non-catalytic ozonation, and the improvement of them is even more pronounced in the presence of Mn–ceramic honeycomb. Adsorptions of nitrobenzene on the two catalytic surfaces have no remarkable influence on the degradation efficiency. Addition of tert-butanol causes the obvious decrease of degradation efficiency, suggesting that degradation of nitrobenzene follows the mechanism of hydroxyl radical (OH) oxidation. Some of the main operating variables like amount of catalyst and reaction temperature exert a positive influence on the degradation efficiency of nitrobenzene. Initial pH also presents a positive effect in the ozonation alone system while the optimum working initial pH is found to be around 8.83 and 10.67 to the processes of ozonation/ceramic honeycomb and ozonation/Mn–ceramic honeycomb, respectively. The surface characteristics measurement of the two catalysts indicates that the loading of Mn increases the specific surface area, the pH at the point of zero charge (pH_PZC) and the density of surface hydroxyl groups, and results in the appearance of new crystalline phase of MnO₂. The results of mechanism research confirm that the loading of Mn promotes the initiation of OH.     

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.     

Modification of electrodes with nanostructured functionalized thiadiazole polymer film and its application to the determination of ascorbic acid

We report the electropolymerization of 2-amino-1,3,4-thiadiazole (ATD) on glassy carbon (GC) and indium tin oxide (ITO) electrodes in 0.10 M H₂SO₄. The electropolymerized ATD (p-ATD) film was characterized by cyclic voltammetry, attenuated total reflectance (ATR)-FT-IR spectroscopy, X-ray photoelectron spectroscopy (XPS) and atomic force microscopy (AFM). The AFM image showed that the p-ATD formed a spherical-like structure with a thickness of 25 nm. XPS of the p-ATD film showed binding energies at 398.7, 400.3 and 401.3 eV in the N 1s region corresponding to –N, –NH– and –N⁺H–, respectively, and at 285.5 and 287.0 eV in the C 1s region corresponding to C–N and CN, respectively. The appearance of binding energies at 285.5 and 287.0 eV confirmed that the p-ATD film proceeded via C–N and CN linkages and not via C–C or CC linkages. The p-ATD film deposited on the GC electrode was successfully used for the determination of ascorbic acid (AA) at physiological pH. The amperometric current was increased linearly from 7.5 × 10⁻⁸ to 2.0 × 10⁻⁵, and the detection limit was found to be 0.28 nM (S/N = 3).     

Cs exchanged phosphotungstic acid as an efficient catalyst for liquid-phase Beckmann rearrangement of oximes

Cs exchanged phosphotungstic acid is a highly efficient and environmentally benign solid acid catalyst for the liquid-phase Beckmann rearrangement of ketoximes to the corresponding amides. The catalysts Cs_xH_3−xPW₁₂O₄₀ (x = 1.5, 2, 2.5 and 3) were prepared by a titration method. The characterization results indicated that the primary Keggin structure remained intact after exchanging the protons with Cs ions. Moreover, the Cs exchanged catalysts were insoluble and exhibited larger BET surface area than the parent acid. The catalysts exhibited high reactivity and selectivity for the formation of -caprolactam, the precursor of Nylon 6, from cyclohexanone oxime. The catalyst can be recovered after reaction without any structural transformation.     

Comparison of the chemical composition of boron-doped diamond surfaces upon different oxidation processes

In spite of the high stability of polycrystalline diamond, oxidation of the hydrogenated surface is relatively easy to perform. This results in the introduction of ether (C–O–C), carbonyl (CO) and hydroxyl (C–OH) groups on the surface. For further surface functionalization, it is important to quantify the presence of each group on the diamond surface when different oxidation processes are used. In this paper, we investigate the composition of oxidized boron-doped diamond surfaces using X-ray photoelectron spectroscopy (XPS) when electrochemical, photochemical or oxygen plasma methods were employed to introduce oxygen functionalities on as-deposited diamond interfaces. Cyclic voltammetry and C–V measurements were additionally performed to identify more clearly the formation of C–OH, C–O–C and/or CO functions.     

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.     

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.     

Numerical studies of a tube-in-tube helically coiled heat exchanger

In the present study a tube-in-tube helically coiled (TTHC) heat exchanger has been numerically modeled for fluid flow and heat transfer characteristics for different fluid flow rates in the inner as well as outer tube. The three-dimensional governing equations for mass, momentum and heat transfer have been solved using a control volume finite difference method (CVFDM). The renormalization group (RNG) k– model is used to model the turbulent flow and heat transfer in the TTHC heat exchanger. The fluid considered in the inner tube is compressed air at higher pressure and cooling water in the outer tube at ambient conditions. The inner tube pressure is varied from 10 to 30 bars. The Reynolds numbers for the inner tube ranged from 20,000 to 70,000. The mass flow rate in the outer tube is varied from 200 to 600 kg/h. The outer tube is fitted with semicircular plates to support the inner tube and also to provide high turbulence in the annulus region. The overall heat transfer coefficients are calculated for both parallel and counter flow configurations. The Nusselt number and friction factor values in the inner and outer tubes are compared with the experimental data reported in the literature. New empirical correlations are developed for hydrodynamic and heat-transfer predictions in the outer tube of the TTHC.     

Low temperature preparation of carbon-supported PdCo alloy electrocatalysts for methanol-tolerant oxygen reduction reaction

Carbon-supported PdCo alloy electrocatalysts of different Pd/Co atomic ratios were simply prepared in an aqueous solution at room temperature with NH₄F as a complexing agent and H₃BO₃ as a buffer, followed by NaBH₄ reduction. As-prepared PdCo bimetallic nanoparticles show a single-phase face-centered-cubic (fcc) disordered structure, and the mean particle size is found to decrease with increase in Co content. TEM images demonstrated that the as-prepared PdCo alloy nanoparticles are well dispersed on the surface of the carbon support with a small particle size and a relatively narrow particle size distribution. For example, the average particle size of a Pd₂Co₁/C catalyst is ca. 3.0 nm, which is much smaller than that of the PdCo/C bimetallic nanoparticles reported by others. An activity evaluation of the oxygen reduction reaction (ORR) on as-prepared PdCo/C catalysts with a rotating disk electrode (RDE) technique indicated that the maximum ORR mass activity was observed for a Pd:Co atomic ratio of 4:1, but the highest specific activity was found on a Pd:Co atomic ratio of 2:1. Kinetic analysis reveals that the ORR on PdCo/C catalysts follows a four-electron process leading to water. Moreover, the PdCo/C catalyst exhibited much higher methanol tolerance during the ORR than the Pt/C catalyst, assessing that it may function as a methanol-tolerant cathode catalyst in a direct methanol fuel cell (DMFC).     

Liquid–liquid equilibrium for the system n-heptane+o-xylene+triethylene glycol from 293.1 to 323.1 K

Extraction of xylenes from straight-run naphtha streams, using a suitable solvent, is an important industrial application. This study is concerned with the experimental investigation of the LLE of n-heptane+o-xylene+triethylene glycol (TEG) at 293.1, 303.1, 313.1 and 323.1 K. Results from three versions of model, as provided in (a sequential simulator), are compared to the experimental data. These versions, which differ only in the database for the mutual group interaction parameters, are the standard (with group interaction parameters extracted from vapor–liquid-equilibrium (VLE) databank), - (with group interaction parameters extracted from liquid–liquid-equilibrium databank), and - (with group interaction parameters extracted from the Dortmund Data bank). The comparison is made in terms of root-mean-square (RMS) and the average-absolute deviations (AAD) in compositions. The performance of and - in describing the experimental data has been found comparable and better than that of -