STUDY ON ELECTROCATALYTIC OXIDATION OF NADH BY FERROCENE DERIVATIVES AND DETERMINATION OF CATALYTIC RATE-CONSTANT AT MICRODISK ELECTRODE

The electrocatalytic oxidation of NADH by ferrocene derivatives and the influence of complexation with beta-cyclodextrin (beta-CD) were investigated at a microdisk electrode in a buffer solution. The cyclic voltammetric behavior of the ferrocene derivatives on the microdisk electrode was used to determine the electron-transfer rate constant from NADH to the ferricinium species. The heterogeneous rate constants and the diffusion coefficient of ferrocene derivatives were determined with the microdisk electrode. The effect of temperature and pH on the electrocatalytic oxidation of NADH were assessed.

INFLUENCE ON THE THIN-LAYER SPECTROELECTROCHEMISTRY - DIFFUSION WITHIN A THIN-LAYER CELL

The potential step and cyclic voltammetric experiments in the thin layer cell were studied by the digital simulation method in this work. A relationship between the time needed for exhaustive electrolysis of the electroactive species and the thickness of the thin layer cell was obtained. On the basis of this formula, the lower time limit for a kinetic plot of the following chemical reaction can be estimated. For the cyclic voltammetry, a semiempirical formula was derived for the peak-peak potential difference (Delta Ep) in terms of the sweep rate (v), thickness of the cell (d), diffusion coefficient (D) and electron transfer number (n) 59 - n Delta Ep/n Delta Ep = 0.328(RT D/nF vd(2))(1.20).

ELECTRODEPOSITION OF PLATINUM PARTICLES ON GLASSY-CARBON MODIFIED WITH COBALT PORPHYRIN AND NAFION FILM AND THEIR ELECTROCATALYTIC REDUCTION OF DIOXYGEN

In this paper, five types of chemically modified electrode (CMEs) prepared with the deposition of platinum particles on various surfaces of glassy carbon (GC) modified with cobalt porphyrin and Nafion(R) solution are characterized using the electron scanning microscope (SEM). Their activities in the four-electron reduction of dioxygen to water on the basis of their electrochemical data from cyclic voltammetric and rotating ring-disk electrode (RRDE) experiments are examined and compared. Platinum particles dispersed on the GC surface adsorbed with the cobalt porphyrin exhibit the highest activity for the electrocatalytic reduction of dioxygen. However it is interesting that the cobalt ion is lost from the center of the porphyrin ring during the preparation of the cobalt porphyrin + Nafion mixture solution, while the porphyrin ring still remains in the Nafion film, as shown by EDX analysis. The incorporation of the porphyrin may change the structure of the Nafion film into a looser form, since the platinum particles dispersed in the film are more readily exposed, resulting in more favourable mass transfer and higher activity for the electrocatalytic reduction of dioxygen.

Unusual voltammetry of the reduction of O-2 in [C(4)dmim][N(Tf)(2)] reveals a strong interaction of O-2(center dot-) with the [C(4)dmim](+) cation

Voltammetric studies of the reduction of oxygen in the room temperature ionic liquid [C(4)dmim][N(Tf)(2)] have revealed a significant positive shift in the back peak potential, relative to that expected for a simple electron transfer. This shift is thought to be due to the strong association of the electrogenerated superoxide anion with the solvent cation. In this work we quantitatively simulate the microdisc electrode voltammetry using a model based upon a one-electron reduction followed by a reversible chemical step, involving the formation of the [C(4)dmim](+)center dot center dot center dot O-2(center dot-) ion-pair, and in doing so we extract a set of parameters completely describing the system. We have simulated the voltammetry in the absence of a following chemical step and have shown that it is impossible to simultaneously fit both the forward and reverse peaks. To further support the parameters extracted from fitting the experimental voltammetry, we have used these parameters to independently simulate the double step chronoamperometric response and found excellent agreement. The parameters used to describe the association of the O-2(center dot-) with the [C(4)dmim](+) were k(f) = 1.4 x 10(3) s(-1) for the first-order rate constant and K-eq = 25 for the equilibrium constant.

Electrochemical ammonia gas sensing in nonaqueous systems: A comparison of propylene carbonate with room temperature ffonc liquids

First, the direct and indirect electrochemical oxidation of ammonia has been studied by cyclic voltammetry at glassy carbon electrodes in propylene carbonate. In the case of the indirect oxidation of ammonia, its analytical utility of indirect for ammonia sensing was examined in the range from 10 and 100 ppm by measuring the peak current of new wave resulting from reaction between ammonia and hydroquinone, as function of ammonia concentration, giving a sensitivity 1.29 x 10(-7) A ppm(-1) (r(2)=0.999) and limit-of-detection 5 ppm ammonia. Further, the direct oxidation of ammonia has been investigated in several room temperature ionic liquids (RTILs), namely 1-butyl-3-methylimidazolium tetrafluoroborate ([C(4)mim] [BF4]), 1-butyl-3-methylimiclazolium trifluoromethylsulfonate ([C4mim] [OTf]), 1-Ethyl -3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([C(2)mim] [NTf2]), 1-butyl-3-methylimidazolium bis(tritluoromethylsulfonyl)imide ([C4mim] [NTf2]) and 1-butyl-3-methylimidazolium hexafluorophosphate ([C4mim] [PF6]) on a 10 put diameter Pt microdisk electrode. In four of the RTILs studied, the cyclic voltammetric analysis suggests that ammonia is initially oxidized to nitrogen, N-2, and protons, which are transferred to an ammonia molecule, forming NH4+ via the protonation of the anion(s) (A(-)). However, in [C4mim] [PF6], the protonated anion was formed first, followed by NH4+. In all five RTILs, both HA and NH4+ are reduced at the electrode surface, forming hydrogen gas, which is then oxidized. The analytical ability of this work has also been explored further, giving a limit-of-detection close to 50 ppm in [C(2)mim] [NTf2], [C(4)mim] [OTf], [C(4)mim] [BF4], with a sensitivity of ca. 6 x 10(-7) A ppm(-1) (r(2) = 0.999) for all three ionic liquids, showing that the limit of detection was ca. ten times larger than that in propylene carbonate since ammonia in propylene carbonate might be more soluble in comparison with RTILs when considering the higher viscosity of RTILs.

Alkynyl-Bridged Ruthenium(II) 4 '-Diferroceny1-2,2 ':6 ',2 ''-terpyridine Electron Transfer Complexes: Synthesis, Structures, and Electrochemical and Spectroscopic Studiese

The novel ligand 4'-diferrocenylallcyne-2,2':6',2 ''-terpyridine (7; Fc-C C-Fc-tpy; tpy = terpyridyl; Fc = ferrocenyl) and its Ru2+ complexes 8-10 have been synthesized and characterized by single-crystal X-ray diffraction, cyclic voltammetry, and UV-vis and luminescence spectroscopy. Electrochemical data and UV absorption and emission spectra indicate that the insertion of an ethynyl group causes delocalization of electrons in the extended pi* orbitals. Cyclic voltammetric measurements of 7 show two successive reversible one-electron-oxidation processes with half-wave potentials of 0.53 and 0.78 V. The small variations of the E-1/2 values for the Fe2+/Fe3+ redox couples after the coordination of the Ru2+ ion suggest a weak interaction between the Ru2+ and Fe2+ centers. After insertion of an ethynyl group, UV-vis absorption spectra show a red shift of the absorption peak of the (1)[(d(pi)(Fe))(6)]->(1)[(d(pi)(Fe))(5)(pi*(Ru)(tpy))(1)] MMLCT of the Ru2+ complexes. The Ru2+ complex 8 exhibits the strongest luminescence intensity (lambda(em)(max) 712 nm, Phi(em) = 2.63 x 10(-4), tau = 323 ns) relative to analogous ferrocene-based terpyridine Ru(II) complexes in H2O/CH3CN (4/1 v/v) solution.

Evaluation of a simple disposable microband electrode device for amperometric gas sensing

We report a simple and facile methodology for constructing Pt (6.3 mm x 50 mu m) and Cu (6.3 mm x 30 mu m) annular microband electrodes for use in room temperature ionic liquids (RTILs) and propose their use for amperometric gas sensing. The suitability of microband electrodes for use in electrochemical analysis was examined in experiments on two systems. The first system studied to validate the electrochemical responses of the annular microband electrode was decamethylferrocene (DmFc), as a stable internal reference probe commonly used in ionic liquids, in [Pmim][NTf2], where the diffusion coefficients of DmFc and DmFc(+) and the standard electron rate constant for the DmFc/DmFc(+) couple were determined through fitting chronoamperometric and cyclic voltammetric responses with relevant simulations. These values are independently compared with those collected from a commercially available Pt microdisc electrode with excellent agreement. The second system focuses on O-2 reduction in [Pmim][NTf2], which is used as a model for gas sensing. The diffusion coefficients of O-2 and O-2(-) and the electron transfer rate constant were again obtained using chronoamperometry and cyclic voltammetry, along with simulations. Results determined from the microbands are again consistent to those evaluated from the Pt microdisc electrode when compared these results from home-made microband and commercially available microdisc electrodes. These observations indicate that the fabricated annular microband electrodes are suitable for quantitative measurements. Further the successful use of the Cu electrodes in the O-2 system suggests a cheap disposable sensor for gas detection. (C) 2013 Elsevier B.V. All rights reserved.

Electrochemical determination of the herbicide bentazone using a carbon nanotube b-Cyclodextrin modified electrode

An electrochemical sensor has been developed for the determination of the herbicide bentazone, based on a GC electrode modified by a combination of multiwalled carbon nanotubes (MWCNT) with b-cyclodextrin (b-CD) incorporated in a polyaniline film. The results indicate that the b-CD/MWCNT modified GC electrode exhibits efficient electrocatalytic oxidation of bentazone with high sensitivity and stability. A cyclic voltammetric method to determine bentazone in phosphate buffer solution at pH 6.0, was developed, without any previous extraction, clean-up, or derivatization steps, in the range of 10–80 mmolL 1, with a detection limit of 1.6 mmolL 1 in water. The results were compared with those obtained by an established HPLC technique. No statistically significant differences being found between both methods.

Multistep electrochemical reduction path of clusters [Os3(CO)10(α-diimine)]: comparison of electrochemical and photochemical Os-Os(α-diimine) bond cleavage

Electrochemical reduction of the triangular clusters [Os-3(CO)(10)(alpha-dimine)] (alpha-dimine = 2,2'-bipyridine (bpy), 2,2'-bipyrimidine (bpym)) and [Os-3(CO)(10)(mu-bpym) ReBr(CO)(3)] produces primarily the corresponding radical anions. Their stability is strongly determined by the pi acceptor ability of the reducible alpha-dimine ligand, which decreases in the order mu-bpym > bpym >> bpy. Along this series, increasing delocalisation of the odd electron density in the radical anion over the Os(alpha-dimine) chelate ring causes weakening of the axial (CO)(4)Os-Os(CO)(2)(alpha-dimine) bond and its facile cleavage for alpha-diimine = bpy. In contrast, the cluster radical anion is inherently stable for the bridging bpym ligand, the strongest pi-acceptor in the studied series. In the absence of the partial delocalisation of the unpaired electron over the Re( bpym) chelate bond, the Os-3-core of the radical anion remains intact only at low temperatures. Subsequent one-electron reduction of [Os-3(CO)(10)(bpym)](center dot-) at T = 223 K gives the open-triosmium core (= Os-3*) dianion, [Os-3*(CO)(10)(bpym)](2-). Its oxidation leads to the recovery of parent [Os-3(CO)(10)( bpym)]. At room temperature, [Os-3*( CO)(10)(bpym)](2-) is formed along a two-electron (ECE) reduction path. The chemical step (C) results in the formation of an open- core radical anion that is directly reducible at the cathodic potential of the parent cluster in the second electrochemical (E) step. In weakly coordinating tetrahydrofuran, [Os-3*(CO)(10)( bpym)](2-) rapidly attacks yet non- reduced parent cluster molecules, producing the relatively stable open- core dimer [Os-3*(CO)(10)(bpym)](2)(2-) featuring two open- triangle cluster moieties connected with an ( bpym) Os - Os( bpym) bond. In butyronitrile, [Os-3*( CO)(10)(bpym)](2-) is stabilised by the solvent and the dimer [Os-3*(CO)(10)(bpym)](2)(2-) is then mainly formed by reoxidation of the dianion on reverse potential scan. The more reactive cluster [Os-3(CO)(10)(bpy)] follows the same reduction path, as supported by spectroelectrochemical results and additional valuable evidence obtained from cyclic voltammetric scans. The ultimate process in the reduction mechanism is fragmentation of the cluster core triggered by the reduction of the dimer [Os-3*(CO)(10)(alpha- diimine)](2)(2-). The products formed are [Os-2(CO)(8)](2-) and {Os(CO)(2)(alpha- diimine)}(2). The latter dinuclear fragments constitute a linear polymeric chain [Os( CO)(2)(alpha-dimine)] n that is further reducible at the alpha-dimine ligands. For alpha-dimine = bpy, the charged polymer is capable of reducing carbon dioxide. The electrochemical opening of the triosmium core in the [Os-3( CO)(10)(alpha-dimine)] clusters exhibits several common features with their photochemistry. The same Os-alpha-dimine bond dissociates in both cases but the intimate mechanisms are different.

Synthesis and properties of tetra-μ-acetatodiruthenium(II,III) phenylphosphinate and phenylphosphonate complexes: X-ray crystal structures of [Ru2(μ-O2CCH3)4(HPhPO2)2]H and [Ru2(μ-O2CCH3)4(PhPO3H)2]H·H2O

Phenylphosphinic acid (HPhPO2H) and phenylphosphonic acid (PhPO3H2) react with a methanolic solution of [Ru2(μ-O2CCH3)4(O2CCH3)2]H·0.7H2O at room temperature to give [Ru2(μ-O2CCH3)4(HPhPO2)2H (1) and [Ru2(μ-O2CCH3)4 (PhPO3H)2]H·H2O (2), respectively. The X-ray crystal structures of 1 and 2 each show the RuRu core to be ligated by four bridging bidentate acetate ligands [RuRu distances: 1 = 2.272(1) Å; 2 = 2.267(2) Å] and two axial phenylphosphinate and phenylphosphonate ligands, respectively. In each complex the individual bimetallic molecules are linked together by a hydrogen ion which bridges the oxygen atoms of neighbouring axial ligands. In 2 the water molecule is also hydrogen-bonded to one of the axial phenylphosphonate groups. Spectroscopic, magnetic and cyclic voltammetric data for the complexes are given.

Facile oxidation of phenylphosphinic acid to phenylphosphonic acid using [Cu2(μ-O2CCH3)4(H2O)2]: X-ray crystal structures of monomeric [Cu(PhPO3H)2(C5H5N)4]·2CH3OH and [Cu(PhPO3H)2(C5H5N)4]

Phenylphosphinic acid (HPhPO2H) is oxidized to phenylphosphonic acid (PhPO3H2) at room temperature using a solution of [Cu2(μ-O2CCH3)4(H2O)2] in pyridine. The phenylphosphonic acid was recovered as the monomeric copper(II) complex [Cu(PhPO3H)2(C5H5N)4]·H2O (1a), and the reaction thought to proceed via a copper(I) intermediate. Recrystallization of 1a from methanol gave [Cu(PhPO3H)2(C5H5N)4]·2CH3OH (1b). The unsolvated complex [Cu(PhPO3H)2(C5H5N)4] (1c) was prepared by refluxing polymeric [Cu(PhPO3)(H2O)] (2) in pyridine. The X-ray crystal structures of 1b and 1c show that in each of these monomeric complexes the copper(II) ion is ligated by four equatorial pyridine molecules and two axial monoanionic phenylphosphonate groups. A cyclic voltammetric study of 1a revealed a quasi-reversible Cu2+/Cu+ couple with E1/2 = +228 mV (vs Ag/AgCl).

Temperature-dependent reduction pathways of complexes fac-[Re(CO)3(N-R-imidazole)(1,10-phenanthroline)]+ (R = H, CH3)

Peculiar reduction pathways of the complexes fac-[Re(imH)(CO)3(phen)]+ and fac-[Re(imCH3)(CO)3(phen)]+ (imH = imidazole, imCH3 = N-methylimidazole and phen = 1,10-phenanthroline) have been unravelled by performing combined cyclic voltammetric and in situ IR spectroelectrochemical experiments. In the temperature range of 293–233 K, the initial reduction of the phen ligand in [Re(imH)(CO)3(phen)]+ results in irreversible conversion of the imidazole ligand to 3-imidazolate by a rapid phen•−→ imH intramolecular electron transfer coupled with N H bond cleavage. This process is followed by second phen-localized 1e− reduction producing [ReI(3-im−)(CO)3(phen•−)]−, similar to the analogous 2,2'-bipyridine complex. In contrast to the bpy analogue, the stability of the phen•−-containing complexes is significantly affected by lowering the temperature. At 233 K, a secondary reaction occurs in both [Re(3-im−)(CO)3(phen•−)]− and [Re(imCH3)(CO)3(phen•−)]. The resulting products exhibit v(CO) wavenumbers indistinguishable from those of the parent phen•− complexes; however, their oxidation occurs at a considerably more positive electrode potential. It is proposed that these species are produced by a new C C bond formation between the C(2) site of 3-im− or imCH3 and the C(2) site of the phen•−ligand.

[M(CO)4(2,2′-bipyridine)] (M = Cr, Mo, W) as efficient catalysts for electrochemical reduction of CO2 to CO at a gold electrode

Group 6 complexes of the type [M(CO)4(bpy)] (M=Cr, Mo, W) are capable of behaving as electrochemical catalysts for the reduction of CO2 at potentials less negative than those for the reduction of the radical anions [M(CO)4(bpy)].−. Cyclic voltammetric, chronoamperometric and UV/Vis/IR spectro-electrochemical data reveal that five-coordinate [M(CO)3(bpy)]2− are the active catalysts. The catalytic conversion is significantly more efficient in N-methyl-2-pyrrolidone (NMP) compared to tetrahydrofuran, which may reflect easier CO dissociation from 1e−-reduced [M(CO)4(bpy)].− in the former solvent, followed by second electron transfer. The catalytic cycle may also involve [M(CO)4(H-bpy)]− formed by protonation of [M(CO)3(bpy)]2−, especially in NMP. The strongly enhanced catalysis using an Au working electrode is remarkable, suggesting that surface interactions may play an important role, too.

Surfactant degradation by a catechol-driven Fenton reaction

The addition of 0.5 mM catechol is shown to accelerate the degradation and mineralization of the anionic surfactant DOWFaX (TM) 2A1 (sodium dodecyldiphenyloxide disulfonate) under conventional Fenton reaction conditions (Fe(II) plus H(2)O(2) at pH 3). The catalytic effect causes a 3-fold increase in the initial rate (up to ca. 20 min) of conversion of the surfactant to oxidation products (apparent first-order rate constants of 0.021 and 0.061 min(-1) in the absence and presence of catechol, respectively). Although this catalytic rate increase persists for a certain amount of time after complete disappearance of catechol itself (ca. 8 min), the reaction rate begins to decline slowly after the initial 20 min towards that observed in the absence of added catechol. Total organic carbon (TOC) measurements of net mineralization and cyclic voltammetric and high performance liquid chromatographic (HPLC) measurements of the initial rate of reaction of catechol and the surfactant provide insight into the role of catechol in promoting the degradation of the surfactant and of degradation products as the eventual inhibitors of the Fenton reaction. (C) 2010 Elsevier B.V. All rights reserved.

Carbon supported electrocatalysts prepared by the sol-gel method and their utilization for the oxidation of methanol in acid media

One of the key objectives in fuel-cell technology is to improve the performance of the anode catalyst for the alcohol oxidation and reduce Pt loading. Here, we show the use of six different electrocatalysts synthesized by the sol -gel method on carbon powder to promote the oxidation of methanol in acid media. The catalysts Pt-PbO(x) and Pt-(RuO(2)-PbO(x)) with 10% of catalyst load exhibited significantly enhanced catalytic activity toward the methanol oxidation reaction as compared to Pt-(RuO(2))/C and Pt/C electrodes. Cyclic voltammetry studies showed that the electrocatalysts Pt-PbO(x)/C and Pt-(RuO(2)-PbO(x))/C started the oxidation process at extremely low potentials and that they represent a good novelty to oxidize methanol. Furthermore, quasi-stationary polarization experiments and cronoamperometry studies showed the good performance of the Pt-PbO(x), Pt-(RuO(2)-PbO(x))/C and Pt-(RuO(2)-IrO(2))/C catalysts during the oxidation process. Thus, the addition of metallic Pt and PbO(x) onto high-area carbon powder, by the sol -gel route, constitutes an interesting way to prepare anodes with high catalytic activity for further applications in direct methanol fuel cell systems.