The electrochemical reduction of hydrogen sulfide on platinum in several room temperature ionic liquids

The electrochemical reduction of I atm hydrogen sulfide gas (H2S) has been studied at a platinum microelectrode (10 mu m diameter) in five room temperature ionic liquids (RTILs): [C(2)mim][NTf2], [C(4)mpyrr][NTf2], [C(4)mim][OTf], [C(4)mim][NO3] and [C(4)mim]][PF6] (where [C(n)mim](+) = 1-alkyl-3-methylimidazolium, [NTf2](-) = bis(trifluoromethylsulfonyl)imide, [C(4)mpyrr](+) = N-butyl-N-methylpyrrolidinium, [OTf](-) = trifluoromethlysulfonate, [NO3](-) = nitrate, and [PF6](-) = hexafluorophosphate). In all five RTILs, a chemically irreversible reduction peak was observed on the reductive sweep, followed by one or two oxidative peaks on the reverse scan. The oxidation peaks were assigned to the oxidation of SH- and adsorbed hydrogen. In addition, a small reductive peak was observed prior to the large wave in [C(2)mim]][NTf2] only, which may be due to the reduction of a sulfur impurity in the gas. Potential-step chronoamperometry was carried out on the reduction peak of H2S, revealing diffusion coefficients of 3.2, 4.6, 2.4, 2.7, and 3.1 x 10(-11) m(2) s(-1) and solubilities of 529, 236, 537, 438, and 230 mM in [C(2)mim][NTf2], [C(4)mpyrr][NTf2], [C(4)mim][OTf], [C(4)mim][NO3], and [C(4)mim]][PF6], respectively. The solubilities of H2S in RTILs are much higher than those reported in conventional molecular solvents, suggesting that RTILs may be very favorable gas sensing media for H2S detection.

Oxidation of several p-phenylenediamines in room temperature ionic liquids: Estimation of transport and electrode kinetic parameters

The electrochemical oxidation of N,N,N',N'-tetramethyl-p-phenylenediamine (TMPD) has been studied by cyclic voltammetry and potential step chronoamperometry at 303 K in five ionic liquids, namely [C(2)mim] [NTf2], [C(4)mim] [NTf2] [C(4)mpyrr] [NTf2] [C(4)mim] [BF4], and [C(4)mim] [PF6] (where [C(n)mim](+) = 1-alkyl-3-methylimidazolium, [C(4)mpyrr](+) = N-butyl-N-methylpyrrolidinium, [NTf2](-) = bis(trifluoromethylsulfonyl)imide, [BF4](-) = tetrafluoroborate, and [PF6](-) = hexafluorophosphate). Diffusion coefficients, D, of 4.87, 3.32, 2.05, 1.74, and 1.34 x 10(-11) m(2) s(-1) and heterogeneous electron-transfer rate constants, k(0), of 0.0109, 0.0103, 0.0079, 0.0066, and 0.0059 cm s(-1) were calculated for TMPD in [C(2)mim] [NTf2], [C(4)mim] [NTf2], [C(4)mpyrr] [NTf2], [C(4)mim] [BF4], and [C(4)mim] [PF6], respectively, at 303 K. The oxidation of TMPD in [C4mim][PF6] was also carried out at increasing temperatures from 303 to 343 K, with an activation energy for diffusion of 32.3 kJ mol(-1). k(0) was found to increase systematically with increasing temperature, and an activation energy of 31.4 kJ mol(-1) was calculated. The study was extended to six other p-phenylenediamines with alkyl/phenyl group substitutions. D and k(0) values were calculated for these compounds in [C(2)mim] [NTf2], and it was found that k(0) showed no obvious relationship with the hydrodynamic radius, r.

Electroreduction of sulfur dioxide in some room-temperature ionic liquids

The mechanism of sulfur dioxide reduction at a platinum microelectrode was investigated by cyclic voltammetry in several room-temperature ionic liquids (RTILs)-[C(2)mim][NTf2], [C(4)mim][BF4], [C(4)mim][NO3], [C(4)mim][PF6], and [C(6)mim][Cl] where [C(2)mim] is 1-ethyl-3-methylimidazolium, [C(4)mim] is 1-butyl-3-methylimidazolium, [C(6)mim] is 1-hexyl-3-methylimidazolium, and [NTf2] is bis(trifluoromethylsufonyl)imide-with special attention paid to [C(4)mim][NO3] because of the well-defined voltammetry, high solubility, and relatively low diffusion coefficient of SO2 obtained in that ionic liquid. A cathodic peak is observed in all RTILs between -2.0 and -1.0 V versus a silver quasi-reference electrode. In [C(4)mim][NO3], the peak appears at -1.0 V, and potential step chronoamperometry was used to determine that SO2 has a very high solubility of 3100 (+/-450) mM and a diffusion coefficient of 5.0 (+/-0.8) x 10(-10) m(2) s(-1) in that ionic liquid. On the reverse wave, up to four anodic peaks are observed at ca. -0.4, -0.3, -0.2, and 0.2 V in [C(4)mim][NO3]. The cathodic wave is assigned to the reduction of SO2 to its radical anion, SO2-center dot. The peaks at -0.4 and -0.2 V are assigned to the oxidation of unsolvated and solvated SO2-center dot, respectively. The peak appearing at 0.2 V is assigned to the oxidation of either S2O42- or S2O4-center dot. The activation energy for the reduction of SO2 in [C(4)mim][NO3] was measured to be 10 (+/-2) kJ mol(-1) using chronoamperometric data at different temperatures. The stabilizing interaction of the solvent with the reduced species SO2-center dot leads to a different mechanism than that observed in conventional aprotic solvents. The high sensitivity of the system to SO2 also suggests that [C(4)mim][NO3] may be a viable solvent in gas sensing applications.

Voltammetric characterization of the ferrocene vertical bar ferrocenium and cobaltocenium vertical bar cobaltocene redox couples in RTILs

Ferrocene, Fc, and cobaltocenium hexafluorophosphate, CcPF(6), have been recommended for use as internal reference redox couples in room-temperature ionic liquids (RTILs), as well as in more conventional aprotic solvents. In this study, the electrochemical behavior of Fc and CcPF(6) is reported in eight commonly used RTILs; [C(2)mim][NTf2], [C(4)mim][NTf2], [C(4)mim][BF4], [C(4)mim][PF6], [C(4)mim][OTf], [C(4)mim][NO3], [C(4)mpyrr][NTf2], and [P-14,P-6.6,P-6][FAP], where [C(n)mim](+) = 1-butyl-3-methylimidazolium, [NTf2](-) = bis(trifluoromethylsulfonyl)imide, [BF4](-) = tetrafluoroborate, [PF6](-) = hexafluorophosphate, [OTf](-) = trifluoromethylsulfonate, [NO3](-) = nitrate, [C(4)mpyrr](+) = N-butyl-N-methylpyrrolidinium, [P-14,P-6,P-6,P-6](+) = tris(ri-hexyl)-tetradecylphosphonium and [FAP](-) = trifluorotris(pentafluoroethyl)phosphate, over a range of concentrations and temperatures. Solubilities and diffusion coefficients, D, of both the charged and neutral species were determined using double potential-step chronoamperometry, and CcPF(6) (36.5-450.0 mM) was found to be Much more Soluble than Fc (27.5-101.8 mM). It was observed that classical Stokes-Einstein diffusional behavior applies for Fc and CcPF(6) in all eight RTILs. Diffusion coefficients of Fc and CcPF(6) were calculated at a range of temperatures, and activation energies calculated. It was also determined that D for Fc and CcPF(6) does not change significantly with concentration. This supports the use of both Fe and CcPF(6) to provide a well-characterized and model redox couple for use as a voltammetric internal potential reference in RTILs contrary to previous literature reports in the former case.

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.

Mechanistic studies of the electro-oxidation pathway of ammonia in several room-temperature ionic liquids

A mechanistic study of the direct oxidation of ammonia has been reported in several room-temperature ionic liquids (RTILs), namely, [C(4)mim][BF4], [C(4)mim][OTf], [C(2)mim][NTf2], [C(4)mim][NTf2], and [C(4)mim][PF6], on a 10 mu m 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(-)). In contrast, NH4+ is formed first in [C(4)mim][PF6], followed by the protonated anion(s), HA. In all five RTILs, both HA and NH4+ are reduced at the electrode surface, forming hydrogen gas, which is then oxidized. The effect of changing the RTIL anion is discussed, and this may have implications in the defining of pK(a) in RTIL media. This work also has implications in the possible amperometric sensing of ammonia gas.

Voltammetric studies of gold, protons, and [HCl2](-) in ionic liquids

The comparative study of the voltammetry of H[NTf2], HCl and H[AuCl4] in [C(4)mim][NTf2] has provided an insight into the influence of protons on the reduction of [AuCl4](-) at Au, Pt or glassy carbon (GC) electrodes, and has allowed the identification of an unprecedented proton-induced electroless deposition of Au on relatively inert GC surfaces. For the first time, clear evidence of the quantitative formation of [HCl2](-) has been obtained in HCl/[C(4)mim][NTf2] mixtures, and the electrochemical behavior of these mixtures analyzed. In particular, a significant shift of the dissociation equilibrium toward the formation of chloride and the solvated proton (H-IL(+)), following electrochemical reduction of H-IL(+) has been observed in the time-scale of the experiments.

An electrochemical study of the oxidation of hydrogen at platinum electrodes in several room temperature ionic liquids

The electrochemical oxidation of dissolved hydrogen gas has been studied in a range of room-temperature ionic liquids (RTILs), namely [C(2)mim][NTf2], [C(4)mim][NTf2], [N-6,N-2,N-2,N-2][NTf2], [P-14,P-6,P-6,P-6][NTf2], [C(4)mpyrr][NTf2], [C(4)mim][BF4], [C(4)mim][PF6], [C(4)mim][OTf], and [C(6)mim]Cl on a platinum microdisk electrode of diameter 10 mu m. In all cases, except [C(6)mim]Cl, a broad quasi-electrochemically reversible oxidation peak between 0.3 to 1.3 V vs Ag was seen prior to electrode activation ([C(6)mim]Cl showed an almost irreversible wave). When the electrode was pre-anodized (

Using XPS to determine solute solubility in room temperature ionic liquids

X-Ray Photoelectron Spectroscopy (XPS) was used to quantify the amount of bromide ions present in two samples of [C(4)mpyrr]Br dissolved in the room temperature ionic liquid (RTIL) [C(4)mpyrr][N(Tf)(2)]. One sample was of a known concentration (0.436 Br atom%); the other was a saturated solution. The results obtained from quantitative XPS analysis indicated that the saturated sample had a concentration, or solubility, of 0.90 Br atom% (746 mM) at 298 K, which was then independently confirmed by potential-step chronoamperometry of the same solution.

Electrochemical studies of gold and chloride in ionic liquids

For the first time, the electrochemistry of gold has been studied in detail in a 'second-generation', non-haloaluminate, ionic liquid. In particular, the electrochemical behaviour of Na[AuCl4] has been investigated in 1-butyl-3-methylimidazolium bis{(tifluoromethyl)sulfonyl} imide, [C(4)mim][NTf2], over gold, platinum and glassy carbon working electrodes. The reduction of [AuCl4](-) initially forms [AuCl2](-) before deposition on the electrode as Au(0). To enable stripping of deposited gold or electrodissolution of bulk gold, the presence of chloride, trichloride or chlorine is required. Specifically trichloride and chlorine have been identified as the active species which preferentially form Au(I) and Au(III), respectively.

Electrochemistry of phenol in bis{(trifluoromethyl)sulfonyl}amide ([NTf2](-)) based ionic liquids

The electrochemistry of phenol and 4-tert-butyl-phenol is described in [C(2)mim][NTf2] and [C(4)mpyrr][NTf2] ionic liquids. Oxidation of phenol and phenolate is observed at E-p(a) = +1.64 and +0.24 V vs. Ag in both ionic liquids. On the cathodic sweep at a potential of -2.05 P 02 V vs. Ag under an oxygen atmosphere, the production of O-2(2-) dianions triggers the formation of phenolate anions which undergo chemical oxidation to the phenoxyl radical. The phenoxyl radical then reacts with the [NTf2](-) anion of the ionic liquid to form the corresponding phenyl triflate molecule. (c) 2005 Elsevier B.V. All rights reserved.

A mechanistic study of the electro-oxidation of bromide in acetonitrile and the room temperature ionic liquid, 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide at platinum electrodes

The oxidation of bromide has been investigated by linear sweep and cyclic voltammetry at platinum electrodes in the room temperature ionic liquid, 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl) imide, ([C(4)mim][NTf2]), and the conventional aprotic solvent. acetonitrile, (MeCN). Similar voltammetry was observed in both solvents, despite their viscosities differing by more than an order of magnitude. DigiSim(R) was employed to simulate the voltammetric response. The mechanism is believed to involve the direct oxidation of bromide to bromine in a heterogeneous step, followed by a homogenous reaction to form the tribromide anion: 2Br(-) --> Br-2 + 2e(-)

Electroanalytical determination of trace chloride in room-temperature ionic liquids

The electroanalytical quantification of chloride in [C(4)mim][BF4], [C(4)mim][NTf2] and [C(4)mim][PF6] ionic liquids has been explored using linear sweep and square wave voltammetry. Cathodic stripping voltammetry at a silver disk electrode is found to be the most sensitive. The methodology is based on first holding the potential of the electrode at +2.0 V (vs Ag wire), to accumulate silver chloride at the electrode. On applying a cathodic scan, a stripping wave is observed corresponding to the reduction of the silver chloride. This stripping protocol was found to detect ppb levels of chloride in [C(4)mim][BF4], [C(4)mim][NTf2], and [C(4)mim][PF6]. Although other methods for chloride have been reported for [BF4](-)- and [PF6](-)-based ionic liquids, no methods have been reported for [NTf2](-) ionic liquids.

Stereochemical and mechanistic aspects of dioxygenase-catalysed benzylic hydroxylation of indene and chromane substrates

Toluene dioxygenase (TDO)-catalysed benzylic hydroxylation of indene substrates (8, 16 and 17), using whole cell cultures of Pseudomonas putida UV4, was found to yield inden-1-ol (14 and 22) and indan-1-one bioproducts (15 and 23). The formation of these bioproducts is consistent with the involvement of carbon-centred radical intermediates. TDO-catalysed oxidation of indenes 8 and 16 also gave cis-diols 13 and 18 respectively. TDO and naphthalene dioxygenase (NDO), used as both whole-cell preparations and as purified enzymes, were found to catalyse the benzylic hydroxylation of chromane 30, deuteriated (+/-)-chromane 30(D) and enantiomers (4S)-30(D) and (4R)-30(D) to yield (4R)- and (4S)-chroman-4-ols 31/31(D) respectively. The mechanism of benzylic hydroxylation of chromane 30/30(D) involves the stereoselective abstraction of a pro-R (with TDO) or a pro-S (with NDO) hydrogen atom at C-4 and a marked preference for retention of configuration.

Hydroisomerisation of n-alkanes over partially reduced MoO3: Promotion by CoAlPO-11 and relations to reaction mechanism and rate-determining step

The reaction mechanism and the rate-determining step (RDS) of the isomerisation of n-alkanes (C-4-C-6) over partially reduced MoO3 catalysts were studied through the effects of the addition of an alkene isomerisation catalyst (i.e. CoAlPO- 11). When an acidic CoAlPO- 11 sample was mechanically mixed with the MoO3, a decrease of the induction period and an increase of the steady-state conversion of n-butane to isobutane were observed. These data support previous assumptions that a bifunctional mechanism occurred over the partially reduced MoO3 (a complex nanoscale mixture of oxide-based phases) during n-butane isomerisation and that the RDS was the skeletal isomerisation of the linear butene intermediates. The only promotional effect of CoAlPO-11 on the activity of partially reduced MoO3 for C-5-C-6 alkane hydroisomerisation was a reduction of the induction period, as the RDS at steady-state conditions appeared to be dehydrogenation of the alkane in this case. However, lower yields of branched isomers were observed in this case, the reason of which is yet unclear. (c) 2005 Elsevier B.V. All rights reserved.