Hydrogen peroxide (H2O2) is one of the world's most important bulk inorganic chemicals with current global production in excess of 2 million tonnes per annum.

The chemistry associated with the anthraquinone auto- oxidation process (AOP) by which H2O2 is predominantly manufactured is shown in Scheme 1 below. catalyst

Scheme 1

The process involves dissolving a substituted anthraquinone (AQ-R, R = hydrocarbon group) in a water-immiscible solvent (or solvent mixture) such as tetramethylbenzene. R-substitution of the anthraquinone ensures maximum solubility in the organic phase while maintaining minimum solubility in the extraction aqueous phase. The anthraquinone is subsequently catalytically reduced to the anthrahydroquinone (AH2Q) using H2<g) under pressure in the presence of a hydrogenation catalyst such as supported Pd or Pt. The supported catalyst is then removed by filtration. Passing O2(g) (usually in air or as pure O2) through the resultant solution results in the highly selective 2 electron/2 proton reduction (otherwise known as hydrogenation) of O2 to H2O2 accompanied by the 2 electron/2 proton oxidation (otherwise known as dehydrogenation) of AH2Q back to AQ. The hydrogen peroxide is then recovered from the organic solvent media phase by extraction into an immiscible water phase. Addition of water is generally concomitant with the addition of oxygen. After extraction, the AQ solution is reused within the process while the aqueous H2O2 is concentrated via H2O evaporation. Typical production facilities have capacities of 40,000 to 60,000 tonnes per annum; such facilities are usually located in regions of high peroxide consumption.

The AOP approach is used because of its selectivity, and therefore, its high atom efficiency and also because of the relative ease with which pure aqueous solutions of peroxide can be obtained. Notwithstanding, considerable effort exists to find alternative routes to peroxide.

One alternative route is based on the direct heterogeneous catalytic reaction of hydrogen and oxygen in aqueous solution. In such a process, the reaction medium is an acidic solution containing halide ions. Inevitably, the use of such a corrosive liquid has a detrimental effect both on the catalyst stability and the reactor, and results in a complex aqueous mixture from which the H2O2 must be isolated and the catalyst recovered. One approach to addressing these problems has been to incorporate both the halide ions and acid functions into the solid catalyst. The halide, which promotes the Pt- group metal catalyst, is provided as an insoluble organo-silane precursor; and the acid function is provided by using acidic or super acid solids as the catalyst support.

A homogeneous alternative to the above route is disclosed in US 4336240 wherein the reaction medium comprises an immiscible (biphasic) mixture of water and an organic fluorocarbon solvent in which an organometallic Pd-catalyst is dissolved. On formation, the hydrogen peroxide dissolved in the aqueous phase, preventing further catalytic reaction (to H2O) . A similar approach is disclosed in US 4347232, except that in this case the catalyst (a dibenzylidene acetone complex of palladium) is dissolved in chlorobenzene. This type of homogeneous/bi-phasic reaction has the drawback of producing H2O2 in low concentrations.

In order for direct routes to compete with the AOP approach, they should advantageously have comparable H2O2-formation efficiency and preferably lower capital, separation and catalyst-recycling costs. However, existing processes (both heterogeneous and homogeneous) show a recurrence of one or more of the following limitations:

• low rate of H2O2 formation;

• finite solubility of (heterogeneous) catalyst in the reaction medium,-

• difficult separation of H2O2 from reaction medium;

• poor performance of homogeneous catalyst; • frequently reaction can only be carried out in batch mode;

• organic solvents must be used;

• high pressure required (leading to widening of flammability window and high capital cost of compression) .

Accordingly there remains a need to develop a H2O2 generation process which addresses these limitations.

Furthermore, for a variety of reasons, including the explosive nature of H2O2 and its frequent use in remote locations, there is considerable interest in developing technology for on-site on-demand peroxide generation so as to avoid transport/storage hazards and associated costs.

The electrolytic production of hydrogen peroxide has been known since the nineteenth century. For many years the primary method of manufacturing hydrogen peroxide was by electrolysis using a route where persulfate is formed at an anode and then hydrolysed (Kirk-Othmer Encyclopaedia of Chemical Technologies, 3rd Edition, Volume 13, (1981)) . An approach based on the direct electrochemical reduction of O2 to H2O2 at gas diffusion electrodes has been developed. Typically, reduction occurs at gold gas diffusion electrodes in alkaline electrolytes with H2O oxidation occurring at a Pt anode. In this arrangement, O2 generated at the anode from H2O oxidation, as well as atmospheric O2, is fed to the cathode to be reduced to peroxide. This approach generates an alkaline solution of hydrogen peroxide that can be used directly in many applications e.g. pulping/bleaching.

An alternative indirect electrolytic strategy, that combines the heterogeneous nature of electrochemistry with the selectivity/efficiency of the hydroquinone approach, has been demonstrated (see for example Hoang et al, J. Electrochem Soc. 1985 Vol. 132 pp 2129-2133 and DeGrand et al, J. Electroanalytical Chem. 1984 Vol. 169 pp 259-268, 1981, ibid Vol. 117 pp.267-281) . In this approach, polymeric materials possessing pendant anthraquinone functional groups are attached to electrode surfaces . In the presence of a proton (H+) source, the anthraquinone can be electrolytically converted into anthrahydroquinone by direct electron transfer from the electrode accompanied by protonation from the electrolyte. There has also been disclosure of an indirect electrochemical means for generating hydrogen peroxide where an electrochemical cell is used to reduce quinone species anchored to high surface area support particles suspended in electrolyte solution (see for example US 4,533,443, US 4,533,443 and US 4,572,774) . The suspended particles are removed from the cell and reacted with oxygen to produce hydrogen peroxide. The oxidized anchored quinone is subsequently returned to the electrolytic cell for re-reduction.

Although the concept of small-scale on-site electrolytic generation of peroxide is attractive, such technology is unable to supply the volume demands for the majority of peroxide users. For this reason, this approach is viewed as only potentially useful for particular niche markets rather than an alternative to the large-scale production and therefore, the AOP process continues to be the main global source of bulk peroxide.

While the AOP is the predominant manufacturing technology for peroxide generation it is widely considered to be unsustainable because it requires vast quantities of volatile toxic solvents, produces associated toxic emissions and is notoriously hazardous (explosive risk of H2O2 combined with volatile organic solvents) . In order to render it less hazardous, total elimination of organic solvents from the process would be desirable. It is an object of the present invention to provide a process for generating H2O2 which represents an alternative to the processes described above.

It is therefore an object of the present invention to provide an alternative to the solvent based and electolytic processes for the preparation of hydrogen peroxide which address limitations of the prior art processes discussed above.

It is a further object of the invention to provide a class of molten salts which may be used as catalysts, and in particular as homogeneous catalysts of reactions such as the redox production of hydrogen peroxide. Accordingly, the present invention provides, in general terms, a class of molten salts, useful as catalysts, a process for the production of said molten salts and a process for the preparation of hydrogen peroxide which uses ionic hydroquinones (or hydroquinone derivatives) as homogeneous O2 reduction catalysts preferably in the absence of molecular solvents .

According to a first aspect of the present invention there is provided a molten salt (Cat+An~) comprising a quinone or quinone derivative as anion or cation said quinone or quinone derivative having the structure of Formula I, II or III.

Formula I

Formula II

Formula II I

wherein : • one or more of any ring atom of any one of Formulae I-III may be a heteroatom, such as N, S, O or P, that may suitably be quaternised to from a cationic species; • the position of the carbonyl species of any one of Formulae I to III (C=O) may be anywhere on any of the rings; • R1 to R7 may independently be A; hydrogen; Ci-io linear, branched chain or cyclic alkyl groups; aryl; heterocycles; CN; OH; or NO2 wherein said alkyl and aryl substituents may themselves be substituted or unsubstituted; • if the quinone or quinone derivative is anionic A represents SO3" or COO"; and • if the quinone or quinone derivative is cationic either: A and optionally one or more of R1 - R7 independently represent imidazolium, piperidinium, pyridinium, phosphonium, pyrazinium, quaternary amine, ammonium species or derivatives thereof; or one or more of the ring atoms is a quaternised heteroatom and each quaternised heteroatom may independently represent an imidazolium, piperidinium, pyridinium, phosphonium, pyrazinium, quaternary amine, ammonium species or derivatives thereof and A represents hydrogen,- a Ci_io linear, branched chain or cyclic alkyl group; an aryl group; a heterocycle group; CN; OH or NO2 wherein said alkyl and aryl substituents may themselves be substituted or unsubstituted.

The term aryl includes for example phenyl, polyphenyl, benzyl and similar moieties.

The term quinone derivative includes quinone, naphthoquinone, hydroquinone and anthroquinone derivatives .

In one embodiment the molten salt consists of cations and anions only.

For the purposes of describing the invention anions of Formulae I, II and III are referred to collectively as An".

If the quinone or quinone derivative is anionic it typically has a hydroquinone structure:

In one embodiment the quinone derivative has the following structure

Alternatively the anionic quinone or quinone derivative has the structure:

If the quinone or quinone derivative is anionic the cation (Cat+) of the molten salt is suitably an aliphatic or aromatic hydrocarbon species typically possessing a hetero-atom, such as N, S, P and O. The aliphatic or aromatic hydrocarbon species may be substituted or unsubstituted, typically with one or more of any substituted or unsubstituted alkane, alkene, alkyne or aromatic hydrocarbon or any halogen group such as a fluorocarbon group. The cation may comprise one or more amine, amide, nitrile, halogen, ether, alcohol, thiol, acid, ester, aldehyde, ketone or phosphine group. Suitably the cation comprises a branched alkyl chain such as a fluorinated branched alkyl chain. In one embodiment the cation is tetraalkylphosphonium. Alternatively the cation may be selected from the group consisting of imidazolium, piperidinium, pyridinium, phosphonium, pyrrolidinium, pyrazinium, quaternary amine, ammonium species and derivatives thereof. Suitably the cation is selected from the group consisting of imidazolium, piperidinium, phosphonium quaternary amine and ammonium species . When Cat+ is an imidazolium cation it is preferably a cation of Formula IV:

Formula IV In one embodiment the cation is:

When Cat+ is a piperidinium cation it is preferably a cation of Formula V:

Formula V In one embodiment the cation is Alternatively the cation is:

When Cat+ is a pyridinium cation it is preferably a cation of Formula VI:

Formula VI When Cat+ is a phosphonium cation it is preferably a cation of Formula VII: R '2 R3 \ / P+ \ R R4

Formula VII

In one embodiment the cation is

tetradecyltrihexylphosphonium and has the structure:

'13

Where they appear in Formulae IV to VII R.'1 to R'7 may

independently be hydrogen, a substituted or

unsubstituted C1-Io linear or branched alkyl chain a

substituted or unsubstituted cyclic alkyl group, an

aryl group, CN, OH, NO2, SO3 or COO.

When Cat+ is a quaternary amine it is preferably of

the form NR4+ where each R is independently a

substituted or unsubstituted Ci-20 linear or branched

alkyl chain or a substituted or unsubstituted cyclic

alkyl group. Suitably the alkyl groups may be

substituted with one or more alkane, alkyne or

aromatic hydrocarbon or any halogen group such as a

fluorocarbon group.

If the quinone or quinone derivative is cationic it

typically has the structure:

If the quinone or quinone derivative is cationic the anion of the molten salt is any suitable anionic species such as PFζ, tetrafluoroborate, bistriflimide, triflate, nitrate, a phosphate such as hexafluorophosphate, carboxylic acid, dicyanamide or thiocyanate.

In one embodiment the molten salt has a melting point of less than 1000C preferably less than 00C. Suitably the molten salt consist entirely of anions and cations. The preferred molten salt is preferably as hydrophobic as possible.

In one embodiment the molten salt is N-butyl-N-methyl piperidinium hydroquinone sulfonate. Alternatively the molten salt may be N-octyl-N-methyl piperidinium hydroquinone sulfonate or l-octyl-4-methyl imidazolium hydroquinone sulfonate. In a further embodiment the molten salt may be tetradecyltrihexylphosphonium hydroquinone sulfonate, butylmethylimidazolium hydroquinonesulfonate, butylmethylpyrrolidinium hydroquinonesulfonate or butylmethylimidazolium anthraquinone-2-carboxylate.

In one embodiment the molten salt is an ionic liquid. According to a further aspect of the present invention there is provided a mixture of two or more of the abovementioned molten salts, or combination of ions thereof.

The present invention further provides a method of preparing a molten salt (Cat+An~) as described above comprising the steps of: (a) dissolving a first salt nCat+Xπ~, where X = Cl", Br" or I" in which case n = 1, or X = SO42" in which case n = 2, in an organic solvent; (b) dissolving a second salt xM+Anx~, where M = K+, Na+, Li+ or Ag+ and x = 1 to 8, in an organic solvent; (c) precipitating the inorganic salt (nMXn~) by mixing the solutions formed according to steps (a) and (b) ; and (d) removing the organic solvent to recover the molten salt (Cat+An") .

Optionally the inorganic salt (nMXn~) is removed from the solution through filtration.

Preferably the solvent used in either or both of steps (a) and (b) is selected from the group consisting of acetonitrile, acetone, dimethylformamide, tetrahydrofuran, dimethylsulfoxide and mixtures thereof.

The molten salt thus produced may be purified by redissolving in an organic solvent, such as those listed above, filtration and removal of the solvent. According to a further aspect of the present invention there is provided an alternative method of preparing a molten salt (Cat+An~) as described above comprising the step of: (A) heating, in the solid state, a mixture of a carboxylic or sulfonic acid (bH+Anb~) where b= 1 to 8 and a salt (nCat+Xn~) (as defined above) liberating nH+Xn~; and (B) recovering the molten salt (Cat+An~) .

Suitably a solvent is added to the mixture, dissolving the molten salt (Cat+An~) . The solvent is then suitably removed from the molten salt under vacuum. The solvent may be organic. Preferably the solvent is acetonitrite, acetone, dimethylformamide, tetrahydrofuran, dimethylsulfoxide or mixtures thereof.

The present invention provides a catalyst comprising the molten salt (Cat+An~) as described above suitable, for example, in the production of hydrogen peroxide.

The present invention also provides a process for the production of hydrogen peroxide comprising the step of: oxidising a molten salt comprising a hydroquinone or hydroquinone derivative as anion (An") or cation (Cat+) to form the corresponding quinone or quinone derivative and produce hydrogen peroxide. In one embodiment the process comprises the step of reducing a molten salt comprising a quinone or quinone derivative as anion (An") or cation (Cat+) to produce the hydroquinone or hydroquinone derivative.

Preferably the process is carried out substantially in the absence of any molecular solvent.

The reduction step may be effected by any suitable means such as, for example, catalytic hydrogenation or electrolysis. Suitably the reduction step involves contacting the molten salt with E2 suitably with a supported or unsupported metal hydrogenation catalyst such as palladium, platinum and nickel under a pressure of up to 60 bar.

In one embodiment of the invention, the process may optionally comprise the step of adding an ionic liquid to the molten salt comprising a hydroquinone or hydroquinone derivative. Suitably the ionic liquid comprises imidazolium, pyridinium, piperidinium, phosphonium or quaternary ammonium salts of triflate, bistriflimide, nitrate, hexafluorophosphate and tetrafluoroborate.

In one embodiment the reduction step takes place in the presence of one or more organic solvents such as alcohols, alkanes, nitriles etc. The presence of organic solvents may enhance the reduction step or may facilitate further processing.

The oxidation step may be effected by any suitable means such as contacting the hydroquinone or hydroquinone derivative with oxygen, or with air and water. Suitably the hydroquinone or hydroquinone derivative is contacted with air and water to produce biphasic products wherein H2O2 is in the water phase.

Preferably the molten salt is as described above.

The invention also provides for the use of the molten salt as described above in a process for the preparation of hydrogen peroxide using a homogeneous O2 reduction catalyst which is itself in the form of a molten salt.

Various molten salts or combinations of salts composed entirely of cations and anions, are known which may be useful as alternatives to conventional reaction media. The process of the invention disclosed herein employs hydroquinones or hydroquinone derivatives as homogenous O2 reduction catalysts, preferably in the absence of molecular solvents . This is effected by synthesising the molten salts described above. Any combination of the aforementioned anions and cations may be used in the synthesis of a mixed molten salt suitable for use in the process of the invention (ie the molten salt used in the invention may comprise more than one anion and/or cation) .

In effect the present invention provides for an immobilised hydroquinone redox catalyst in liquid molten salt form in a medium which may be substantially free of molecular solvents. This contrasts with the conventional auto-oxidation process where the catalytic hydroquinone species is dissolved in an organic solvent or solvent mixture. Therefore, the catalytic process of the invention is capable of generating peroxide substantially in the absence of organic solvent. Furthermore, since the hydroquinone/quinone catalyst comprises up to 50 mole % of the molten salt, extremely high catalyst loading can be obtained. Further advantages of the process for the production of hydrogen peroxide of the invention include: • the redox catalyst is in the form of a processable liquid; • the redox catalyst is the highly selective/efficient quinone moiety; • the process may be carried out in the absence of any, or any substantial amount, of conventional solvents; • non-volatile, non-flammable, non-explosive catalytic medium; • high catalyst loading; • amenable to both small-scale electrolytic generation and catalytic H2 generation of peroxide. • the process of the present may have through-puts significantly exceeding the AOP approach; • the process may have greater space-time yields than the AOP reaction.

The invention is described in further detail below with reference to the accompanying drawings in which:

Figure 1 shows the infrared (IR) spectra of butylmethylpyrrolidinium hydroquinonesulfonate; Figure 2 shows the IR spectra of butylmethylimidazoium hydroquinonesulfonate;

Figure 3 shows the IR spectra of butylmethylpyrrolidinium anthraquinone-2-sulfonate;

Figure 4 shows the IR spectra of butylmethylimidazolium anthraquinone-2-sulfonate;

Figure 5 shows the IR spectra of tetraphenylphosphonium hydroquinone sulfonate;

Figure 6 shows the IR spectra of butylmethylpyrrolidinium anthraquinone-2-carboxylate;

Figure 7 shows the IR spectra of N-butyl-N-methyl piperidinium hydroquinone sulfonate;

Figure 8 shows the IR spectra of N-octyl-N-methyl piperidinium hydroquinone sulfonate;

Figure 10 shows the IR spectra of tetradecyltrihexyl- phosphonium hydroquinone sulfonate;

Figure 11 is a current-voltage profile for butylmethylimidazolium anthraquinone-2-carboxylate;

Figure 12 is a series of current-voltage profiles for 1.0 X 10~3 mol dm"3 butylmethylimidazolium anthraquinone-2-carboxylate in acetonitrile with 1.0 X 10"3 mol dm"3 tetrabutylammonium tetrafluoroborate and 0.1 mol dm"3 benzoic acid; and Figure 13 is a series of cyclic voltammograms for the detection of hydrogen peroxide.

Examples

Example 1: Synthesis of quinoαe-containing- molten salts

Synthesis of the aforementioned catalytic molten salts may be effected as follows;

1) ion metathesis reaction of a halide salt (X") of the aforementioned cations (or combination thereof) with a metal salt (Mn+) of the carboxylate and/or sulfonate substituted quinones. Typically, this may be carried out in any suitable organic solvent (or solvent mixture) such as for example dimethylformamide (DMF) , acetone, acetonitrile, ethanol or methanol (and mixtures thereof) . In such solvents the insoluble inorganic salt Mn+nX" precipitates and may be removed by filtration. The solvent may be removed from the filtrate by evaporation and the resultant product (molten salt) recovered. The product may then be purified by repeated dissolution in organic solvent with any residual insoluble Mn+nX" removed by filtration.

The molten salts (1.1 - 2.2) listed below were made by preparing and mixing separate solutions of the anion and cation in volumes appropriate to give stoichiometric quantities of each. The concentration of anion and cation solutions used were typically in the order of 10 % wt/vol in the solvent in question. All quinone anion salts were dissolved in DMF, while acetonitrile was used to dissolve all iπiidazolium and pyrrolidinium cation salts . Tetraphenylphosphonium salts were dissolved in DMF, although ethanol was found to be a useful alternative for phosphonium salts . The reactions were carried out at room temperature under stirring conditions for 24 hours . The molten salt product was recovered as outlined above. Yields were quantitative and determined to be approximately 100 % in each case.

2) Reaction of the carboxylic or sulfonic acid derivatives of the quinone or hydroquinone with the halide (X") salt of the aforementioned cations. This reaction may be carried out in the solid-state with gentle heating to initiate the reaction which results in HX(9) evolution which may be removed by vacuum.

The following salts were synthesised according to the above procedure (melting points shown in brackets) :

1.1 [Bmpyr] [HQS]" (105-107 0C) 1.2 [Bmim]+[HQS]" (< -20 0C) 1.3 [Bmpyr]+[AQS]" (108-1150C) 1.4 [Bmim]+[AQS]" (1530C) 1.5 [Bmim]+[AQCOO]" (97 0C) 1.6 [TPP]+[HQS]" (2400C) 1.7 [BTFAP]+[AQS]" 1.8 [Bmpyr]+[AQCOO]" (>200 0C) 1.9 N-butyl-N-methyl piperidinium hydroquinone sulfonate; 2.0 N-octyl-N-methyl piperidinium hydroquinone sulfonate; 2.1 l-octyl-4-methyl imidazolium hydroquinone sulfonate; 2.2 tetradecyltrihexylphosphonium hydroquinone sulfonate.

Where [Bmim]+ = butylmethylimidazolium, [Bmpyr]+ = butylmethylpyrrolidiniuπi, [TPP]+ = tetraphenylphosphoniuna, [BTFAP]+ = 2- [N,N- bis (trifluoromethanesulfonyl) amino pyridinium, [HQS]" = hydroquinonesulfonate, [AQS]" = anthraquinone-2- sulfonate and [AQCOO]" = anthraquinone-2-carboxylate.

Figures 1 to 10 show infrared spectra for compounds 1.1, 1.2, 1.3, 1.4, 1.6 and 1.8 to 2.2 respectively. IR spectra were recorded using a Perkin-Elmer 'Spectrum RX/FT-IR' spectrometer with a resolution of 4 cm"1. Samples which were solid at room temperature were prepared as KBr disks, while samples which were liquid at room temperature were prepared as pure liquid films between NaCl plates .

Example 2s Assessment of catalytic activity of molten salts for O2 reduction

Activation of the quinone (or quinone derivative) species to the catalytically active hydroquinone (or anthrahydroquinone) may be effected by catalytic H2(g> reduction or by reductive electrolysis at an electrode in the presence of a proton source. At catalytic electrodes such as Pd or Pt, the reaction is identical to the H2<g) approach.

Example 2.1: Electrolytic reduction of the molten salt [Bmim+] [AQ-COO""] (where [Bmim+] is l-butyl-3- methylimidazolium and [AQ-COO"] is 9,10- anthraquinone-2-carboxylate) in the pure state and dissolved in an organic solvent (acetonitrile with tetrabutylammonium borate electrolyte) :

Figure 11 shows the current (i) versus electrode potential for the pure molten salt. It can be seen that the current (negative cathodic current) begins to increase monotonically from -0.5 V. The cathodic current response is due to the reduction of the anthraquinone species which clearly indicates the retention of anthraquinone/hydroquinone electrochemical activity in the molten salt. In order to assess the electrochemical activity of the [Bmim+] [AQ-COO"] in the absence and presence of O2, the salt was dissolved in acetonitrile to give a 1.0 X 10"2 mol dm"3 solution of [Bmim+] [AQ-COO"] along with 1.0 X 10~2 mol dm"3 tetrabutylammonium tetrafluoroborate electrolyte and 0.1 mol dm"3 benzoic acid acting as the proton source.

Figure 12a shows the cyclic voltammogram for the [Bmim+] [AQ-COO"] under 02-free conditions where a broad reduction process occurs at -0.85 V vs. Ag/Ag+ due to the two electron/two proton reduction of the anthraquinone to the anthrahydroquinone. On the reverse voltage sweep, a reoxidation process is observed which is due to the oxidation of the anthrahydroquinone back to the anthraquinone.

Figures 12b and 12c show voltammograms recorded as O2 is emitted to the electrochemical cell . Time open to the atmosphere is the variable, curve a) is at time = 0, curve b) is after 10 minutes and curve c) is after 20 minutes. Curve d) is after O∑ has been removed by N2 sparging-. These curves show that; 1) the cathodic reduction current is increased and 2) that the anodic reoxidation current disappears . The acceleration of the cathodic current is due to the chemical reaction of O2 with the anthrahydroquinone (which returns anthraquinone which is re-reduced and hence an accelerated current) while the absence of the reoxidation process indicates that the anthrahydroquinone is consumed in the O2 reduction reaction. This behaviour is identical to that for anthraquinone electrochemistry in protic media in the absence/presence of O2. Figure 12d shows the cyclic voItammogram after O2 has been remover (via N2 sparging of the solution) , it can be seen that the electrochemical behaviour returns to its original behaviour after removal of O2.

Example 3: Detection of generated peroxide

Although the reaction is kinetically slow, peroxide can be oxidised at voltages >0.25 V at carbon electrodes. In this way peroxide generated due to the reaction of O2 with electrogenerated anthrahydroquinone can be detected. Figure 13a shows a current-voltage profile for [Bmim+] [AQ-COO"] in the presence of O2, while Figure 13b shows a current- voltage profile also in the presence of O2 but at less negative voltage limits. In Figure 13a, the anthrahydroquinone is formed at the negative voltages (cathodic current) whereas in Figure 13b, anthrahydroquinone is not formed. Comparing Figures 13a and 13b, it can be seen that there is an enhanced anodic current in the peroxide oxidation region. Subtracting Figure 13b from 13a yields Figure 13c which is the response due to peroxide oxidation (the first peak in Figure 13c) . This demonstrates that peroxide is generated as anthrahydroquinone is generated.