Studies on electrocatalytic performance of titanium oxide electrode modified with Pt toward the oxidation of methanol

Electrocatalytic performance of the Pr-TiOx/Ti electrode prepared with electrochemical reduction-oxidation method toward the oxidation of methanol has been studied, The experimental results showed that the Pt-TiOx/Ti electrode has a high electrocatalytic activity and good stability for the electrocatalytic oxidation of methanol, By means of electrochemical, XPS, STM and in-situ FTIR techniques, it was found that one reason for the electrode to exhibit an excellent performance is attributed to the high dispersion between nanosized Pt and TiOx particles, The low adsorption ability of the intermediate derived from methanol, such as linearly adsorbed CO species on the electrode surface due to the interaction between Pt and TiOx, also results in the excellent performance.

Low-temperature oxidation of methane to form formaldehyde: role of Fe and Mo on Fe-Mo/SiO2 catalysts, and their synergistic effects

The partial oxidation of methane with molecular oxygen was performed on Fe-Mo/SiO2 catalysts. Iron was loaded on the Mo/SiO2 catalyst by chemical vapor deposition of Fe-3(CO)(12). The catalyst showed good low-temperature activities at 723-823 K. Formaldehyde was a major condensable liquid product on the prepared catalyst. There were synergistic effects between iron and molybdenum in Fe-Mo/SiO2 catalysts for the production of formaldehyde from the methane partial oxidation. The activation energy of Mo/SiO2 decreased with the addition of iron and approached that of the Fe/SiO2. The concentration of isolated molybdenum species (the peak at 1148 K in TPR experiments) decreased as the ion concentration increased and had a linear relationship with the selectivity of methane to formaldehyde. The role of Fe and Mo in the Fe-Mo/SiO2 catalyst was proposed: Fe is the center for the C-H activation to generate reaction intermediates, and Mo is the one for the transformation of intermediates into formaldehyde. Those phenomena were predominant below 775 K.

Oxidation of ascorbic acid by rutin at a glassy carbon electrode modified with lipid films

A stable film was prepared by casting dipalmitoylphosphatidylcholine (DPPC) and rutin onto the surface of a glassy carbon (GC) electrode. The electrochemistry behavior of rutin in the DPPC film was investigated. The modified electrode coated with rutin shows a quasi-reversible reduction-oxidation peak on the cyclic voltammogram in phosphate buffer (pH 7.4). This model of biological membrane was not only used to provide biological environment but also to investigate the oxidation of ascorbic acid by rutin. The DPPC-rutin modified electrode behaves as electrocatalytic oxidation to ascorbic acid. The oxidation peak current of ascorbic acid increases drastically and the peak potential of 4 x 10(-4) mol L-1 ascorbic acid shifts negatively about 100 mV compared with that obtained at a bare glassy carbon electrode. The catalytic current increased linearly with the ascorbic acid concentration in the range of 2 x 10(-4) mol L-1 and 1.4 x 10(-3) mol L-1 at a scan rate of 50 mV s(-1).

The development in oxidation of olefins to ketones catalyzed by palladium compounds

The development in the oxidation of olefins to ketones catalyzed by palladium compounds was reviewed. Some improved methods for the oxidation of olefins catalyzed by Wacker-type catalyst systems are also summarized. For this reaction, some new catalyst systems and the reaction mechanism are described. Emphasis has been given to the applications of Pd(I)/HPA(heteropoly acid), Pd(I)/FePc (iron phthalocyanine), Pd (I)/HQ (hydroquinone)/FePc, Pd (I)/HQ/HPA, Pd (I)/CuSO4/HPA catalyst systems in the oxidation of olefins to ketones; the application of Pd(I)/LCoNO2, PdCl2 (MeCN)(2)/CuCl, Pd(OAc)(2)/ pyridine, fluorous biphasic catalyst systems in the oxidation of olefins to ketones is also surveyed.

Electrocatalytic oxidation of ascorbic acid by ferrocene in lipid film cast on a glassy carbon electrode

A ferrocene-dimyristoyl phosphatidylcholine (DMPC) film electrode was prepared by casting the solution of ferrocene and DMPC in chloroform onto a glassy carbon electrode surface. Ferrocene retained in the biological membrane gave a couple of irreversible peaks of cyclic voltammogram. The electrode exhibited good electrocatalytic activity for the oxidation of ascorbic acid (H(2)A) in phosphate buffer (pH 6.64) with an anodic peak potential of +340 mV (vs. Ag/AgCl). The anodic current was directly proportional to the square root of the scan rate below 150 mV s(-1). The influence of the pH value was investigated and it was observed that pH 6.64 was the suitable value to the anodic peak potential and current. The thickness of the film and the interference of uric acid were also studied. The electrode can be used to determine H(2)A in the presence of equimolar uric acid. The catalytic peak current increased linearly with the concentration of H(2)A in the range of 1 X 10(-4)-5 X 10(-3) mol L-1.

Electrocatalytic oxidation of ascorbic acid by norepinephrine embedded in lipid cast film at glassy carbon electrode

A stable lipid cast film was made by casting a lipid in chloroform onto a glassy carbon electrode. We imbedded a new mediator norepinephrine into this lipid cast film, which was considered as a biological membrane model. Through electro catalytic oxidation of ascorbic acid by this system, the anodic overpotential was reduced by about 250 mV compared with that obtained at a bare glassy carbon electrode. The electrochemical behavior of norepinephrine in the cast film was controlled by diffusion. The obtained diffusion coefficient of ascorbic acid was 1.87 x 10(-5) cm 2 s(-1). The catalytic current increased linearly with the concentration of ascorbic acid in the range from 0.5 to 10 mM. Using cyclic voltammetry, we obtained two peaks for ascorbic acid and uric acid in the same solution. The separation between the two peaks is about 147 mV. (C) 2001 Elsevier Science Ltd. All rights reserved.

Oxidation of ascorbic acid by dopamine incorporated in mimetic biomembrane

A kind of mimetic biomembrane-cast lipid film was made onto a glassy carbon electrode. Dopamine can be incorporated into the film. The oxidation of 2.0 x 10(-3) mol/L ascorbic acid with dopamine in the film was investigated. The oxidation overpotential of ascorbic acid was reduced by about 260 mV.

Renewable manganous hexacyanoferrate-modified graphite organosilicate composite electrode and its electrocatalytic oxidation of L-cysteine

Manganous hexacyanoferrate (MnHCF) supported on graphite powder was dispersed into methyltrimethoxysilane-derived gels to yield a conductive composite, which was used as electrode material to construct a renewable three-dimensional MnHCF-modifed electrode. MnHCF acts as a catalyst, graphite powder ensures conductivity by percolation, the silicate provides a rigid porous backbone, and the methyl groups endow hydrophobicity and thus limit the wetting section of the modified electrode. Cyclic voltammetry was exploited to investigate the dependence of electrochemical behavior on supporting electrolytes containing various cations. The chemically modified electrode can electrocatalytically oxidize L-cysteine, and exhibits a distinct advantage of polishing in the event of surface fouling, as well as simple preparation, good chemical and mechanical stability, and good repeatability of surface renewal.

Effect of FePc structure on the activity in the oxidation of cyclohexene catalyzed by pd (OAc)(2)/HQ/FePc

In an acidic aqueous solution of acetonitrile, the catalytic activity of the catalysts consisted of Pd(OAc)(2)/hydroquinone(HQ) with iron phthalocyanine (FePc) from various sources was obviously different in the oxidation of cyclohexene to cyclohexanone, The analysis of the FePc using IR spectroscopy, Mossbauer spectroscopy, X-ray photoelectron spectroscopy (XPS), X-ray powder diffraction (XRD), scanning electron microscopy(SEM) and BET surface area measurement indicated that the catalytic activity of the multicomponent catalytic system composed of iron phthalocyanines depends on the amount of mu -oxo FePc, the crystallinity and the surface structure of iron phthalocyanine.

In situ infrared spectroelectrochemical studies on adsorption and oxidation of nucleic acids at glassy carbon electrode

The adsorption and oxidation of yeast RNA and herring sperm DNA (HS DNA) at glass carbon (GC) electrode are studied by differential pulse voltammetry (DPV) and in situ FTIR spectroelectrochemistry. Two oxidation peaks of yeast RNA are obtained by DPV, whose peak potentials shift negatively with increasing pH. The peak currents decrease gradually in successive scans and no corresponding reduction peaks occur, thus indicating that the oxidation process of yeast RNA is completely irreversible. The IR bands in the 1200-1800 cm-l range, attributed to the stretching and ring vibrations of nucleic acid bases, show the main spectral changes when the potential is shifted positively, which gives evidence that the oxidation process takes place in the base residues. The oxidation process of HS DNA is similar to that of yeast RNA. The results both from DPV and in situ FTIR spectroelectrochemistry confirm that the guanine and adenine residues can be oxidized at the electrode surface, which is consistent with the oxidation mechanism of nucleic acids proposed previously. (C) 2001 Elsevier Science B.V. All rights reserved.

Surface-renewable cobalt(II) hexacyanoferrate-modified graphite organosilicate electrode and its electrocatalytic oxidation of thiosulfate

Cobalt(II) hexacyanoferrate (CoHCF) was deposited on graphite powder by an in situ chemical deposition procedure and then dispersed into methyltrimethoxysilane-derived gels to prepare a surface-renewable CoHCF-modified electrode. The electrochemical behavior of the modified electrode in different supporting electrolyte solutions was characterized by cyclic voltammetry. In addition, square-wave voltammetry was employed to investigate the pNa-dependent electrochemical behavior of the electrode. The CoHCF-modified electrode showed a high electrocatalytic activity toward thiosulfate oxidation and could thus be used as an amperometric thiosulfate sensor.

In-situ FTIR study on adsorption and oxidation of native and thermally denatured calf thymus DNA at glassy carbon electrodes

In-situ Fourier transform infra-red (FTIR) spectra of native and thermally denatured calf thymus DNA (CT DNA) adsorbed and/or oxidized at a glassy carbon (GC) electrode surface are reported. The adsorption of native DNA occurs throughout the potential range (-0.2 similar to 1.3 V) studied, and the adsorbing state of DNA at electrode surface is changed from through the C=O band of bases and pyrimidine rings to through the C=O of cytosine and imidazole rings while the potential shifts negatively from 1.3 V to -0.2 V. An in-situ FTIR spectrum of native CT DNA adsorbed at GC electrode surface is similar to that of the dissolved DNA, indicating that the structure of CT DNA is not distorted while it is adsorbed at the GC electrode surface. In the potential range of -0.2 similar to 1.30 V, the temperature-denatured CT DNA is adsorbed at the electrode surface first, then undergoes electrochemical oxidation reaction and following that, diffuses away from the electrode surface. (C) 2001 Elsevier Science B.V. All rights reserved.

Synthesis of monodisperse pheyl-capped oligoaniline pentamer and hexamer in the leucoemeraldine oxidation state and EB state and its UV studies

Aniline pentamer and hexamer in the leucoemeraldine oxidation state were synthesized through a novel method. The method was accomplished by the reaction of parent aniline tetramer in the pernigraniline oxidation state with diphenylamine and N-phenyl-1,4-phenylenediamine in the leucoemeraldine oxidation state respectively. The oligomers in the leucoemeraldine oxidation state were characterized by IR, NMR, elemental analysis and MALDI-MS. Aniline pentamer and hexamer in the emeraldine oxidation state were synthesized by the oxidation of Ag2O in DMF. It was found that some fragmentation occurred when the pentamer and hexamer were oxidized by (NH4)(2)S2O8 and FeCl3. 6H(2)O. The pentamer and hexamer in the emeraldine oxidation state was studied by UV/Vis spectra. The relative intensity of exciton peak for pentaaniline showed a little increase compared with that of hexaaniline.

Oxidation of NADH by dopamine incorporated in lipid film cast onto a glassy carbon electrode

Stable lipid film was made by casting lipid in chloroform onto a glassy carbon electrode. This model of a biological membrane was used to investigate the oxidation of dihydronicotinamide adenine dinucleotide (NADH) by dopamine. After this electrode had been immersed in dopamine solution for 10 h, it was found that some dopamine had been incorporated in the film. The cyclic voltammogram was obtained for the oxidation of 2.0 X 10(-3) mol 1(-1) NADH with dopamine incorporated in the films. All electrochemical experiments were performed in 0.005 mol 1(-1) phosphate buffer (pH 7.0) containing 0.1 mol 1(-1) NaCl without oxygen. The oxidation current increased gradually with successive sweeps and reached steady state. It was a different phenomenon from previous results. The anodic overpotential was reduced by about 130 mV compared with that obtained at a bare glassy carbon electrode. The diffusion coefficient for 2.0 X 10(-3) mol 1(-1) NADH was 6.7 X 10(-6) cm(2) s(-1). (C) 1999 Elsevier Science S.A. All rights reserved.

A mechanistic study of electrochemical oxidation processes of (OEP)Mg(II) in the presence of anions

In the presence of F-, OH-, Cl-, electrochemical redox of (OEP)Mg(II) [2,3, 7,8,12,13,17,18 octaethyl-21H, 23H-porphine magnesium (II)] are investigated in DCE/0.1 mol/L solution by cyclic voltammetry and spectroelectrochemistry, In the presence of anions, anions are axially coordinated to (OEP)Mg(II) generate (OEP)Mg(II)Y, the E-1/2 of (OEP)MS(II)Y oxidation are negatively shifted. A chemical reaction following the second oxidation step is observed, the E-1/2 of the reaction product is obtained. Mechanism of (OEP)Mg(II) in the halogen and OH- anions titration process has been proposed.