Vapor phase hydroformylation of ethene over Co/SiO2 promoted by noble metals: dynamic in situ diffuse reflectance FT-IR study of surface species

An in situ diffuse reflectance FT-IR technique was employed to investigate the active surface species and the reaction mechanism of the oxygenate formation in the vapor phase hydroformylation of ethene on Co/SiO₂ promoted with various noble metals such as Ir, Rh, Pt, Re, Ru, and Pd. Co(A)/SiO₂ and Ir(CO)/SiO₂ which were derived from cobalt(II) acetate and Ir₄(CO)₁₂, respectively, were quite inactive in the reaction, and showed only quite small peaks of adsorbed CO under the conditions of 1.1 MPa of C₂H₄/CO/H₂ at 298 K. In contrast, Co(A)-Ir(CO)/SiO₂, which were very active in the reaction, exhibited strong absorption bands of linear and bridged CO species. At 423–463 K, propanal adsorbed on the catalyst and acyl species which is suggested as the intermediate for the formation of propanal were also observed on this catalyst. By exposing CO preadsorbed on this catalyst to C₂H₄/H₂ at 289 K and 0.1 MPa, the intensity of the linear CO band decreased, and the bands of propanal and acyl species emerged simultaneously, whereas that of the bridged CO band remained constant after the initial drop. These results suggested that the oxygenates are formed via the CO insertion into adsorbed ethyl species, and linear CO species plays a major role in the CO insertion on these noble metal-promoted cobalt catalysts.     

Color and Vanadium Valency in V-Doped ZrO2

The distribution and chemical states of vanadium in V-doped ZrO₂ were studied to clarify the origin of the color of vanadium-zirconium yellow pigment in comparison with vanadium-tin yellow pigment. ESCA data and measurements of lattice constants of V-doped ZrO₂ revealed that vanadium was dissolved mainly as V⁴⁺ substituting for Zr in ZrO₂ lattice, and its solubility limit was 0.5 wt% as V₂O₅. It was found that the yellow color of vanadium-zirconium yellow was produced predominantly by the dissolved vanadium and that the contribution of vanadium oxide on ZrO₂ grains to the yellow color was about 1/30 of that of the dissolved vanadium when compared on the basis of equimolar quantity of vanadium. Most of the undissolved vanadium oxide was in an amorphous or a poorly crystallized state.     

Influence of the nigrosine dye on the thermal behavior of polyamide 66

To reveal the effect of the nigrosine dye, that the addition of the dye lowers the crystallization point (T_c) of molten polyamide resins with substantially no shift in the melting point (T_m), thus suppressing the crystallization enhancement of the crystalline nucleation agents, the characteristics of polyamide 66 (PA‐66) containing nigrosine dye EX (N‐EX) were investigated. Differential scanning calorimetry (DSC) analysis showed that the addition of N‐EX reduced the crystallization rate and T_c of molten PA‐66 with substantially no shift in T_m, and the crystallization enthalpy per unit of weight of PA‐66 was substantially constant. T_c of molten PA‐66 was lowered with an increase in the amount of N‐EX and reached its maximum at 13 wt % N‐EX. Dynamic mechanical analysis showed that the glass‐transition temperature and the secondary glass‐transition temperature increased with an increasing amount of the dye. On the other hand, the DSC and X‐ray diffraction results indicated that no dye molecule was present in the crystal structure of PA‐66. This effect of the nigrosine dye on PA‐66 is in contrast to those of crystalline nucleation agents, plasticizers, and antiplasticizers. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 3270–3274, 2006     

On-chip fabrication of magnetic alginate hydrogel microfibers by multilayered pneumatic microvalves

Alginate hydrogel has widespread applications in tissue engineering, cancer therapy, wound management and drug/cell/growth factor delivery due to its biocompatibility, hydrated environment and desirable viscoelastic properties. However, the lack of controllability is still an obstacle for utilizing it in the fabrication of 3D tissue constructs and accurate targeting in mass delivery. Here, we proposed a new method for achieving magnetic alginate hydrogel microfibers by dispersing magnetic nanoparticles in alginate solution and solidifying the magnetic alginate into hydrogel fiber inside microfluidic devices. The microfluidic devices have multilayered pneumatic microvalves with hemicylindrical channels to fully stop the fluids. In the experiments, the magnetic nanoparticles and the alginate solution were mixed and formed a uniform suspension. No aggregation of magnetic nanoparticles was found, which is crucial for flow control inside microfluidic devices. By regulating the flow rates of different solutions with the microvalves inside the microfluidic device, magnetic hydrogel fibers and nonmagnetic hydrogel fibers were fabricated with controlled sizes. The proposed method for fabricating magnetic hydrogel fiber holds great potential for engineering 3D tissue constructs with complex architectures and active drug release.     

Synthesis, characterization and photocatalytic reactivity of Ti-containing micro- and mesoporous materials

Ti-oxides incorporated within the framework of microporous zeolites and mesoporous molecular sieves were found to exhibit high and unique photocatalytic activity for the decomposition of NO into N₂ and O₂ as well as the reduction of CO₂ with H₂O to produce CH₄ and CH₃OH. Spectroscopic investigations of these catalytic systems using photoluminescence, UV-vis, XAFS (XANES and FT-EXAFS) and IR analyses revealed that the charge transfer excited state of the isolated tetra-coordinated Ti-oxides plays a vital role in these photocatalytic reactions. The reactivity of such Ti-oxides was found to depend strongly on their local structures which were controlled by the unique framework structures of the micro- and mesoporous material supports.     

Selective vapor phase hydroformylation of ethylene over cluster-derived cobalt catalyst

Vapor phase hydroformylation of ethylene was studied with silica-supported metal catalysts. A cobalt metal catalyst derived from Co₂(CO)₈ gave propanal and its derivatives in as high selectivity of about 36% as Rh/SiO₂ catalyst under the reaction conditions of 1.1 MPa of a gas-mixture of ArCOC₂H₄H₂ = 1333 at 423–503 K. On the other hand, conventional cobalt catalysts derived from cobalt nitrate, chloride, or acetate, and other noble metal catalysts (Pd/SiO₂ and Ir/SiO₂) produced mainly ethane.     

Structural characterization of 1,2-polybutadiene by 13C-n.m.r. spectroscopy: 2. Sequence distribution of 1,2-unit in hydrogenated polybutadienes

The configurational sequences of 1,2-unit in a series of hydrogenated syndiotactic 1,2-polybutadienes were determined in relation to the sequence distribution of 1,2- and 1,4-units on the basis of the ¹³C-n.m.r. signal assignment of the methyl carbons. The observed triad distributions of 1,2- and 1,4-units and configurational distributions of the 1,2-unit are in good agreement with the calculated distributions from transition probabilities. The number average sequence lengths of the 1,2-unit and the 1,2-unit in the racemic addition are 5.7 to 8.0 and 4.1 to 5.4, respectively. From the extrapolation of the plot of the number average sequence length against the crystallinity of the starting 1,2-polybutadienes, the minimum sequence length for crystallization is estimated to be 3.7 for the 1,2-unit in the racemic addition.     

Applying MHD technology to the continuous casting of steel slab

The application of magnetohydrodynamics (MHD) in the continuous casting process started with the electromagnetic stirring of the stand pool with a traveling magnetic field. It has now advanced to the electromagnetic stirring of molten steel in the mold and the control of molten steel flow by an in-mold direct current magnetic field brake. These applied MHD techniques are designed to further improve the continuous casting process capability. They improve the surface quality of cast steel by homogenizing the meniscus temperature, stabilizing initial solidification, and cleaning the surface layer. They also improve the internal quality of cast steel by preventing inclusions from penetrating deep into the pool and promoting the flotation of argon bubbles. Applied MHD technology is still advancing in scope and methods in addition to the improvement of conventional continuously cast slab qualities. The continuous casting of bimetallic slab by suppressing mixing in the pool is one example of this progress.     

Corrosion protection of NdFeB magnets by phosphating with tungstate incorporation

In this investigation the effect of surface treatments on the corrosion resistance of a commercial NdFeB sintered magnet has been investigated. A solution of 10 g L^− 1 NaH₂PO₄, acidified to pH 3.8 has been used for phosphating this magnet. The corrosion resistance of the phosphated magnet was investigated in a 0.10 mol L^− 1 Na₂SO₄ solution by electrochemical impedance spectroscopy and cyclic voltammetry with rotating disc electrode. The obtained results reveal that the resistance decreases with exposure time due to the development of pores and/or defects in the conversion coating exposing the substrate to corrosive attack. The effect of tungstate incorporation into the phosphate conversion coating resulting from a phosphating treatment prior to immersion in the tungstate solution was evaluated. The proposed treatment consists of re-immersing the phosphated samples in a 0.1 mol L^− 1 Na₂WO₄ solution during 72 h at the open circuit potential (OCP). Under these conditions, the corrosion resistance of the magnet was improved and this was attributed to the formation of a protective layer due to the adsorption of tungstate anions at the metallic substrate exposed in the coating, decreasing metal dissolution.