LIQUID-CHROMATOGRAPHY AMPEROMETRIC DETECTION OF CATECHOL, RESORCINOL, AND HYDROQUINONE WITH A COPPER-BASED CHEMICALLY MODIFIED ELECTRODE

A copper-based chemically modified electrode (CME) has been constructed and characterized for flow-through amperometric detection of catechol, resorcinol, and hydroquinone. Novel potential dependence of the detector response was first obtained for these analytes at the Cu CME, where negative peaks together with positive ones were observed in one definite chromatogram using amperometric detection. Its advantages in chromatographic applications were demonstrated. From these observations it is proposed that the detector response was governed by formation of copper complexes with the solutes. A dynamic linear range over two orders of magnitude was obtained, when operating the detector at +0.10 V vs. SCE, from which ng detection limits were achieved.

LIQUID-CHROMATOGRAPHY AMPEROMETRIC DETECTION OF CARBOXYLIC-ACIDS AND PHENOLIC-ACIDS WITH A COPPER-BASED CHEMICALLY-MODIFIED ELECTRODE

A copper-based chemically-modified electrode has been constructed and characterized by various experimental parameters in flow-through amperometric detection of carboxylic acids and phenolic acids. Novel hydrodynamic voltamperograms were first obtained in flow-through amperometric detection with the Cu-based CME and subsequently negative and positive peaks were observed in a single chromatogram. This unique and flexible potential dependence could be of great benefit in chromatographic speciation and quantification. These observations suggest that the detector response was governed by the complexation reaction of copper ions with the solutes.

Liquid phase oxidation of toluene to benzaldehyde with molecular oxygen over copper-based heterogeneous catalysts

We conducted the liquid phase oxidation of toluene with molecular oxygen over heterogeneous catalysts of copper-based binary metal oxides. Among the copper-based binary metal oxides, iron-copper binary oxide (Fe/Cu = 0.3 atomic ratio) was found to be the best catalyst. In the presence of pyridine, overoxidation of benzaldehyde to benzoic acid was partially prevented. As a result, highly selective formation of benzaldehyde (86% selectivity) was observed after 2 h of reaction (7% conversion of toluene) at 463 K and 1.0 MPa of oxygen atmosphere in the presence of pyridine. These catalytic performances were similar or better than those in the gas phase oxidation of toluene at reaction temperatures higher than 473 K and under 0.5-2.5 MPa. It was suggested from competitive adsorption measurements that pyridine could reduce the adsorption of benzaldehyde. At a long reaction time of 4 It, the conversion increased to 25% and benzoic acid became the predominant reaction product (72% selectivity) in the absence of pyridine. The yield of benzoic acid was higher than that in the Snia-Viscosa process, which requires corrosive halogen ions and acidic solvents in the homogeneous reaction media. The catalyst was easily recycled by simple filtration and reusable after washing and drying.

Elucidating the mechanism and active site of the cyclohexanol dehydrogenation on copper-based catalysts: A density functional theory study

Abstract The dehydrogenation of cyclohexanol to cyclohexanone is very important in the manufacture of nylon. Copper-based catalysts are the most popular catalysts for this reaction, and on these catalysts the reaction mechanism and active site are in debate. In order to elucidate the mechanism and active site of the cyclohexanol dehydrogenation on copper-based catalysts, density functional theory with dispersion corrections were performed on up to six facets of copper in two different oxidation states: monovalent copper and metallic copper. By calculating the surface energies of these facets, Cu(111) and Cu2O(111) were found to be the most stable facets for metallic copper and for monovalent copper, respectively. On these two facets, all the possible elementary steps in the dehydrogenation pathway of cyclohexanol were calculated, including the adsorption, dehydrogenation, hydrogen coupling and desorption. Two different reaction pathways for dehydrogenation were considered on both surfaces. It was revealed that the dehydrogenation mechanisms are different on these two surfaces: on Cu(111) the hydrogen belonging to the hydroxyl is removed first, then the hydrogen belonging to the carbon is subtracted, while on Cu2O(111) the hydrogen belonging to the carbon is removed followed by the subtraction of the hydrogen in the hydroxyl group. Furthermore, by comparing the energy profiles of these two surfaces, Cu2O(111) was found to be more active for cyclohexanol dehydrogenation than Cu(111). In addition, we found that the coordinatively unsaturated copper sites on Cu2O(111) are the reaction sites for all the steps. Therefore, the coordinatively unsaturated copper site on Cu2O(111) is likely to be the active site for cyclohexanol dehydrogenation on the copper-based catalysts.

Grain refinement studies on Mg and Mg-Al based alloys

Demand on magnesium and its alloys is increased significantly in the automotive industry because of their great potential in reducing the weight of components, thus resulting in improvement in fuel efficiency of the vehicle. To date, most of Mg products have been fabricated by casting, especially, by die-casting because of its high productivity, suitable strength, acceptable quality & dimensional accuracy and the components produced through sand, gravity and low pressure die casting are small extent. In fact, higher solidification rate is possible only in high pressure die casting, which results in finer grain size. However, achieving high cooling rate in gravity casting using sand and permanent moulds is a difficult task, which ends with a coarser grain nature and exhibit poor mechanical properties, which is an important aspect of the performance in industrial applications. Grain refinement is technologically attractive because it generally does not adversely affect ductility and toughness, contrary to most other strengthening methods. Therefore formation of fine grain structure in these castings is crucial, in order to improve the mechanical properties of these cast components. Therefore, the present investigation is “GRAIN REFINEMENT STUDIES ON Mg AND Mg-Al BASED ALLOYS”. The primary objective of this present investigation is to study the effect of various grain refining inoculants (Al-4B, Al- 5TiB2 master alloys, Al4C3, Charcoal particles) on Pure Mg and Mg-Al alloys such as AZ31, AZ91 and study their grain refining mechanisms. The second objective of this work is to study the effect of superheating process on the grain size of AZ31, AZ91 Mg alloys with and without inoculants addition. In addition, to study the effect of grain refinement on the mechanical properties of Mg and Mg-Al alloys. The thesis is well organized with seven chapters and the details of the studies are given below in detail.

Insight into Copper-Based Catalysts: Microwave-Assisted Morphosynthesis, In Situ Reduction Studies, and Dehydrogenation of Ethanol

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Kinetics of eutectoid decomposition in Cu-Al and Cu-Al-Ag alloys

The kinetics of eutectoid decomposition beta(1)' --> gamma(2) + (alpha + gamma(2)) in Cu-12.86 wt% Al and Cu-12.84 wt% Al-1.98 wt% Ag alloys was studied by hardness measurements, using the Johnson-Mehl-Avrami equation. The results indicate that the presence of silver seems to influence the nucleation rate and the activation energy of the reaction.

Thermal behavior of alpha-(Cu-Al-Ag) alloys

Thermal behavior of alpha-(Cu-Al-Ag) alloys, i.e. alloys with composition less than about 8.5 mass% Al, was studied using differential scanning calorimetry (DSC), differential thermal analysis (DTA), scanning electron microscopy (SEM), energy dispersive X-ray analysis (EDX) and X-ray diffractometry (XRD). The results indicated that the presence of silver introduces new thermal events ascribed to the formation of a silver-rich phase and, after addition higher amounts than 8 mass% Ag to the Cu-8 mass% Al alloy it is possible to observe the formation of the gamma(1) phase (Al4Cu9), which is only observed in alloys containing minimum of 9 mass% Al. These results may be attributed to some Ag characteristics and its interaction with Cu and Al.

Diffusion of oxygen in some binary Ti-Based alloys used as biomaterials

Ti and its alloys are widely used as biomaterials. Their main properties are excellent corrosion resistance, relatively low elastic modulus, high specific strength, and good biocompatibility. The development of new Ti alloys with properties favorable for use in the human body is desired. To this end, Ti alloys with Mo, Nb, Zr, and Ta are being developed, because these elements do not cause cytotoxicity. The presence of interstitial elements (such as oxygen and nitrogen) induces strong changes in the elastic properties of the material, which leads to hardening or softening of the alloy. By means of anelastic spectroscopy, we are able to obtain information on the diffusion of these interstitial elements present in the crystalline lattice. In this paper, the effect of oxygen on the anelastic properties of some binary Ti-based alloys was analyzed with anelastic spectroscopy. The diffusion coefficients, pre-exponential factors, and activation energies were calculated for oxygen and nitrogen in these alloys.

The Rate of Precipitation of Copper Aluminide in the Silver Rich Silver-Copper-Aluminum Alloys

In order to determine the best annealing temperature at which to age-harden the alloys, hardness tests on speci­men annealed for different lengths of time at different temperatures were made.

The Electrical Conductivity of the Copper-Aluminum Alloys.

Among the many aluminum alloys which have been studied are the binary copper-aluminum alloys. These have proven to be among the most useful of the alumi­num alloys thus far worked upon.

Age Hardening of Copper Antimony Alloys

A large number of alloys of varying percentages of copper and antimony were prepared. These alloys were treated in various ways which might be expected to produce age hardening. The effect of cold working was studied in the range where the alloys were malleable.