IProton sponge as supplement to electrolytes for photocatalytic and electrochemical Co2 reduction

Abstract

The invention relates to a method for converting carbon dioxide and water, wherein the electrolyte comprises a proton sponge which serves to accumulate CO2 in the electrolyte. The invention further relates to a corresponding use of a proton sponge and to an electrolyte comprising at least one proton sponge.

Claims

1. A method comprising: reacting carbon dioxide and water in the presence of an electrolyte to form CO2, and accumulating at least some of the formed CO2 in the electrolyte, the electrolyte comprising a liquid electrolyte or an electrolyte solution including a proton sponge, wherein the proton sponge comprises an aromatic diamine having the general formula: ##STR00050## where: n is =0 or 1; A1 and A2 represent aromatic scaffolds linkable via a further ring A3, and when n is =1, A3 is present and represents a substituted or unsubstituted cyclopentane ring which shares the bonding at positions 1 and 2 with the aromatic scaffold A1 and at positions 3 and 4 with the aromatic scaffold A2, and the carbon at position 5 is present between A1 and A2 at the bottom of the formula with two possible substituents Rd and Rd; Rd and Rd independently represent hydrogen and/or one or more substituted or unsubstituted linear, branched or cyclic alkyl moieties of 1 to 20 carbon atoms and/or substituted or unsubstituted aromatic and/or heteroaromatic moieties of 1 to 40 carbon atoms, wherein when Rd and Rd are present they are combinable to form an aliphatic or aromatic ring or polycycles; when n is =0, the ring A3 is absent and the rings A1 and A2 are fused; Rw, Rx, Ry, and Rz independently represent substituted or unsubstituted linear, branched or cyclic alkyl moieties of 1 to 50 carbon atoms and/or substituted or unsubstituted aromatic and/or heteroaromatic moieties of 1 to 100 carbon atoms and/or substituted or unsubstituted linear or branched sulfonylalkyl moieties of 1 to 50 carbon atoms, where 2 or more of Rx to Rz are combinable to form a ring or polycycles where not only Rw and Rx but also Ry and Rz are each replaceable by a single moiety Rw or Ry to form a double bond on the nitrogen; and Ra and Rb independently represent hydrogen and/or one or more substituted or unsubstituted linear, branched or cyclic alkyl moieties of 1 to 20 carbon atoms and/or substituted or unsubstituted aromatic and/or heteroaromatic moieties of 1 to 40 carbon atoms on a particular ring of a respective naphthalene skeleton, where when 2 or more of Ra and/or Rb are present, they are combinable to form an aliphatic or aromatic ring or polycycles.

2. The method of claim 1, wherein the proton sponge in the liquid electrolyte or the electrolyte solution is present in dissolved or suspended form.

3. The method of claim 1, wherein said reacting comprises photocatalysis.

4. The method of claim 3, wherein the photocatalysis utilizes at least one ceramic photosemiconductor selected from the groups consisting of TiO2, ZnO, GaN, SrTiO3, BaTiO3, GaAs, MoS2, WSe2, MoSe2, and WO3.

5. The method of claim 1, wherein said reacting comprises electrolysis.

6. The method of claim 5, wherein the electrolysis is performed with at least one of: (a) a CO2 reduction catalyst as cathode or (b) an oxidation catalyst as anode.

7. The method of claim 6, wherein the cathode contains at least one element selected from the group consisting of: Cu, Au, Ag, Zn, Pd, Bi, and Ga.

Description

DETAILED DESCRIPTION

(1) The term proton sponge comprehends certain aromatic diamines with unusually high constants of basicity. The aromatic diamines in question are based on aromatics which, in their scaffold structure, include a naphthalene (sub)structure or fluorene (sub)structure where two functional groups derived from amines are present respectively at positions 1 and 8 in the case of naphthalene and at positions 4 and 5 in the case of fluorene, which are shown here.

(2) ##STR00002##

(3) A large diversity of structures derived therefrom are currently known for proton sponges (http://de.wikipedia.org./wiki/Protonenschwamm, as at Nov. 8, 2013; Nuri Cenap Abacilar, New Development in the Chemistry of Superbasic Proton Sponges Based on Guanidine, Iminophosphorane and Sulfoxime Tweezer Ligands for Protons, German-language thesis, Marburg University, 2009).

(4) Even though naphthalene and fluorene are shown here by way of example, the scaffold structure is not limited to these compounds, but comprehends scaffold structures comprising these structures at least. Substitution on the scaffold structures is not foreclosed either.

(5) The basicity constants are high because the closely adjacent amino groups respond to monoprotonation by reducing the destabilizing overlaps between the nitrogen electron pairs and the strong steric stress. The strong NHN hydrogen bond further reduces the steric stress.

(6) The term liquid electrolyte herein comprehends not only electrolytes in liquid form but also in molten form, i.e., for example also a salt melt, and the term electrolyte solution comprehends electrolytes present in one or more solvents in dissolved form, the solvent preferably comprising water.

(7) In the context of the present invention, the proton sponges are not in an immobilized state in the liquid electrolyte or the electrolyte solution and are preferably also not immobilized by further additives, but they are able to freely move in dissolved or suspended form within the liquid electrolyte or the electrolyte solution and are also commixable therein. One particular benefit of proton sponges in this context relies on their action as carbonate traps, i.e., they have a high tendency to form (hydrogen) carbonate salts. Buffering properties and nucleophilicity are less foregrounded. In particular embodiments, the invention does not comprehend polymer-bound proton sponges, since no immobilization is desired in use. The electrolyte and/or electrolyte solution shall be capable of equalizing charge gradients, or the viscosity should be low, preferably <1000 cPs, more preferably <100 cPs, most preferably <10 cPs, for charge transfer.

(8) As noted above, the proton sponges of Equation 1 have a high tendency to bind protons that the hygroscopy of the aqueous or nonaqueous electrolyte is enhanced to such an extent that water is even attracted from the air (PS=proton sponge)
PS+H.sub.2O.fwdarw.PS.H.sup.++OH.sup.Equation 1:

(9) Highly active OH.sup. ions are then present in nonaqueous electrolytes in particular, and are neutralized by CO.sub.2 from the air to form (hydrogen)carbonates (Equation 2). At the same time, therefore, the CO.sub.2 accumulates on the catalyst particle.
OH+CO.sub.2.fwdarw.HCO.sup.3Equation 2:

(10) Since, in the process, CO.sub.2 passes from the air and/or from physical solution into a chemically dissolved state, the proton sponge serves as carbonate trap.

(11) The invention in one aspect provides a method of reacting carbon dioxide and water that utilizes a liquid electrolyte or an electrolyte solution comprising one or more than one proton sponge used to accumulate CO.sub.2 in the electrolyte. In preferred embodiments, the proton sponge in the liquid electrolyte or the electrolyte solution may be present therein in dissolved or suspended form. Preferably, however, the proton sponge is in dissolved form, so that it may also serve to bring the carbon dioxide into solution. This also facilitates the transfer to a reaction surface at which the carbon dioxide reacts, for example the surface of a photocatalyst or of an electrode of an electrolytic cell, and the surface is more readily accessible to the proton sponge.

(12) In preferred embodiments, the present method of reaction comprises those wherein the reaction is a photocatalysis. Nor is this photocatalysis restricted in any way, and it may take any form that in principle allows a photocatalysis of carbon dioxide. A photocatalysis may take place on surfaces which corresponds to a solar collector for example. In preferred embodiments, the photocatalysis takes place by using a ceramic photosemiconductor, preferably TiO.sub.2, ZnO, GaN, SrTiO.sub.3, BaTiO.sub.3, GaAs, MoS.sub.2, WSe.sub.2, MoSe.sub.2 and/or WO.sub.3. Photosemiconductors herein are materials that enable a conversion of light into electrical energy within a cell having two electrodes. In photocatalysis, this electrical energy is then used to drive a chemical reaction, for example an electrolysis of water, wherein the photosemiconductor preferably also acts as a catalyst. Suitable photosemiconductors thus preferably evince as well as good absorption of light, good efficiency of conversion into electrical energy (depending for example on the bandgap of the material) and also some catalytic activity in the chemical conversion of an input material such as water.

(13) In further preferred embodiments, an electrolysis is concerned in the reaction method of the present invention. No particular limitation applies to the cathode space and the anode space in this electrolysis. In the electrolysis, the carbon dioxide may be present in the electrolyte in a dissolved and/or gaseous form, in which case the proton sponge by acting as a carbonate trap then contributes to the increasing rate at which carbon dioxide is converted into carbonate/hydrogencarbonate and thus dissolves. However, the possibility that gaseous carbon dioxide continues to remain in the electrolyte is not ruled out.

(14) There are certain embodiments where it is environmentally preferable for the electrolyte to be further present dissolved in water. The electrolyte herein is not particularly limited as long as it permits a (possibly physical) dissolving of the carbon dioxide. The electrolyte may for example comprise KCl, K.sub.2SO.sub.4, KHCO.sub.3 or mixtures thereof. In principle, any combinations of cations and anions can serve as conducting salts provided they allow the current densities required.

(15) The electrolysis in certain embodiments may be carried out using a CO.sub.2 reduction catalyst as cathode and/or an oxidation catalyst as anode. The cathode-side reaction herein depends on the cathode material and is not limited. Useful cathode materials include, for example, copper, gold, silver, zinc, palladium, gallium, bismuth and also mixtures or alloys thereof. A preferred cathode material comprises copper, for example in an amount of 10 to 100 wt %, based on the cathode material, and preferably the cathode consists essentially of copper or a copper alloy, preferably at more than 90 wt %, more preferably at more than 99 wt % of copper. In principle, conductive doped/undoped oxides such as TiO.sub.2, ZnO, ITO (indium tin oxide), AZO (aluminum-doped zinc oxide), etc. are also suitable. The anode material is not subject to any special restrictions and includes any anode materials capable of being used in an electrolysis of water, for example anodes based on platinum, ruthenium or graphite.

(16) In certain embodiments, the cathode-side electrolyte and the anode-side electrolyte may be identical. In such embodiments, an electrolytic cell for the electrolysis of the present invention does not require a membrane. However, it is not ruled out that the electrolytic cell in such embodiments has a membrane, yet this is associated with additional cost and inconvenience regarding the membrane and also the applied voltage.

(17) In certain embodiments, the electrolytic cell has a membrane which separates the cathode space and the anode space of the electrolytic cell to prevent any mixing of the electrolytes. The membrane herein is not subject to any special restrictions provided it separates the cathode space and the anode space. In particular, it prevents essentially any crossover of carbon dioxide and/or its dissolved form to the anode. A preferred membrane is an ion exchange membrane, for example a polymer-based ion exchange membrane. A preferred material for an ion exchange membrane is a sulfonated tetrafluoroethylene polymer such as Nafion, for example Nafion 115. Ceramic membranes, for example those mentioned in EP 1685892 A1, are useful as well as polymer membranes.

(18) The present invention further provides the method of using a proton sponge in a liquid electrolyte or an electrolyte solution in the reaction of carbon dioxide and water to accumulate CO.sub.2 in the electrolyte. In this method of use, the proton sponge in the electrolyte may preferably be present therein in a dissolved or suspended form and more preferably is present in a dissolved form.

(19) The present invention further includes an electrolyte or electrolyte solution comprising one or more than one proton sponge. The proton sponge in the electrolyte may preferably be present therein in a dissolved or suspended form and is more preferably in a dissolved form.

(20) The electrolyte herein is not particularly limited as long as it permits a (possibly physical) dissolving of the carbon dioxide. The electrolyte may for example comprise KCl, K.sub.2SO.sub.4, KHCO.sub.3 or mixtures thereof. More than one compound may accordingly be present in the electrolyte or electrolyte solution. In principle, any combinations of cations and anions can serve as conducting salts provided they allow the current densities required. In certain embodiments, the electrolyte may comprise organic cations such as guanidium ions and/or organosubstituted phosphonium ions, organosubstituted sulfonium, pyridinium, pyrrolidinium or morpholinium ions and/or the most commonly used imidazolium ions. These may be used in the anode space, but also in the cathode space, since they are capable of catalyzing the reduction of CO.sub.2.

(21) Examples of organic cations are thus guanidinium, pyridinium, pyrrolidinium, morpholinium, organosubstituted phosphonium or sulfonium and also imidazolium ions, which are most commonly used.

(22) Examples of suitable guanidinium cations include those of the following general formula (1):

(23) ##STR00003##

(24) where the substituents R.sub.1-R.sub.6 may in principle be selected independently of each other from the group of linear, branched or cyclic C1-C25 alkyl, C6-C25 aryl, C7-C25 alkylaryl, C7-C25 arylalkyl, C1-C25 heteroalkyl or C1-C25 heteroaryl, C2-C25 alkylheteroaryl, C2-C25 heteroarylalkyl moieties or hydrogen and may also be asymmetrical. It is further possible for two or more of the substituents to be also bridged with one another via cyclic or heterocyclic compounds. The substituents R.sub.1-R.sub.6 on the guanidinium cations may be selected for example from the group of linear, branched or cyclic C1-C25 alkyl, C6-C25 aryl, C7-C25 alkylaryl, C7-C25 arylalkyl, C1-C25 heteroalkyl, or C2-C25 heteroaryl, C3-C25 alkylheteroaryl, C3-C25 heteroarylalkyl, C7-C25 heteroalkylaryl, C7-C25 arylheteroalkyl, C3-C25 heteroalkylheteroaryl, C3-C25 heteroarylheteroalkyl moieties, oligoether moieties (e.g., [CH.sub.2CH.sub.2O-].sub.n) where n may be an integer from 1-12, oligoesters (e.g., [CH.sub.2COO-].sub.n), where n may be an integer from 1-12, or oligoamides (e.g., [CONR-].sub.n) or oligoacrylamides (e.g., [CH.sub.2CHCONH.sub.2-].sub.n), where n may be an integer from 1-12, or hydrogen.

(25) Heteroalkyl and heteroaryl moieties and also the corresponding constituents in alkylheteroaryl and heteroarylalkyl moieties here correspond to moieties/constituents in which one carbon atom of the alkyl chain and of the aryl group, respectively, is replaced by a heteroatom, for example N, S or O.

(26) Exemplary guanidinium cations have for example the following formula (2):

(27) ##STR00004##

(28) where R.sub.p may be = branched, unbranched or cyclic C1-C20 alkyl, C6-C20 aryl, C7-C20 alkylaryl, C7-C20 arylalkyl, C1-C20 heteroalkyl, or C1-C20 heteroaryl, C2-C20 alkylheteroaryl, C2-C20 heteroarylalkyl moieties and R.sub.1-R.sub.4 may be independently selected from the group of branched or unbranched C1-C20 alkyl, C6-C20 aryl, C7-C20 alkylaryl, C7-C20 arylalkyl, C1-C20 heteroalkyl, or C2-C20 heteroaryl, C3-C20 alkylheteroaryl, C3-C20 heteroarylalkyl, C7-C20 heteroalkylaryl, C7-C20 arylheteroalkyl, C3-C20 heteroalkylheteroaryl, C3-C20 heteroarylheteroalkyl moieties, oligoether moieties (e.g., [CH.sub.2CH.sub.2O-].sub.n) where n may be an integer from 1-12, oligoesters (e.g., [CH.sub.2COO-].sub.n), where n may be an integer from 1-12, or oligoamides (e.g., [CONR-].sub.n) or oligoacrylamides (e.g., [CH.sub.2CHCONH.sub.2-].sub.n), where n may be an integer from 1-12, or hydrogen.

(29) Further examples of suitable organic cations are bisguanidinium cations of general formula (3)

(30) ##STR00005##

(31) The substituents R.sub.1-R.sub.11 may independently be linear, branched or cyclic C1-C25 alkyl, C6-C25 aryl, C7-C25 alkylaryl, C7-C25 arylalkyl, C1-C20 heteroalkyl or C2-C25 heteroaryl, C3-C25 alkylheteroaryl, C3-C25 heteroarylalkyl, C7-C25 heteroalkylaryl, C7-C25 arylheteroalkyl, C3-C25 heteroalkylheteroaryl, C3-C25 heteroarylheteroalkyl moieties or hydrogen and also form asymmetrical or symmetrical bisguanidinium cations. It is further possible for two or more of the substituents to be also bridged with one another via cyclic or heterocyclic compounds.

(32) Examples of organosubstituted phosphonium ions are compounds of the general formula [R.sub.fR.sub.gR.sub.hR.sub.jP].sup.+, where R.sub.f, R.sub.g, R.sub.h and R.sub.j may be independently selected from the group of linear, branched or cyclic C1-C25 alkyl, C6-C25 aryl, C7-C25 alkylaryl, C7-C25 arylalkyl, C1-C20 heteroalkyl or C2-C25 heteroaryl, C3-C25 alkylheteroaryl, C3-C25 heteroarylalkyl, C7-C25 heteroalkylaryl, C7-C25 arylheteroalkyl, C3-C25 heteroalkylheteroaryl, C3-C25 heteroarylheteroalkyl moieties or hydrogen where at least one of R.sub.f, R.sub.g, R.sub.h and R.sub.j is not hydrogen. These, like the other cations mentioned also, may likewise also be employed with preference in electrolytes in the cathode space.

(33) Examples of organosubstituted sulfonium ions are compounds of the general formula [R.sub.fR.sub.gR.sub.hS].sup.+ where R.sub.f, R.sub.g and R.sub.h may be independently selected from the group of linear, branched or cyclic C1-C25 alkyl, C6-C25 aryl, C7-C25 alkylaryl, C7-C25 arylalkyl, C1-C20 heteroalkyl or C2-C25 heteroaryl, C3-C25 alkylheteroaryl, C3-C25 heteroarylalkyl, C7-C25 heteroalkylaryl, C7-C25 arylheteroalkyl, C3-C25 heteroalkylheteroaryl, C3-C25 heteroarylheteroalkyl moieties or hydrogen where at least one of R.sub.f, R.sub.g and R.sub.h is not hydrogen. These, like the other cations mentioned also, may likewise also be employed with preference in electrolytes in the cathode space.

(34) Examples of pyridinium ions are compounds of general formula [4],

(35) ##STR00006##

(36) where R and R.sup.1-R.sup.5 may be independently selected from the group of linear, branched or cyclic C1-C25 alkyl, C6-C25 aryl, C7-C25 alkylaryl, C7-C25 arylalkyl, C1-C20 heteroalkyl or C2-C25 heteroaryl, C3-C25 alkylheteroaryl, C3-C25 heteroarylalkyl, C7-C25 heteroalkylaryl, C7-C25 arylheteroalkyl, C3-C25 heteroalkylheteroaryl, C3-C25 heteroarylheteroalkyl moieties or hydrogen. These, like the other cations mentioned also, may likewise also be employed with preference in electrolytes in the cathode space.

(37) Examples of morpholinium ions are compounds of general formula [5]

(38) ##STR00007##

(39) where R, R and R.sup.1-R.sup.8 may be independently selected from the group of linear, branched or cyclic C1-C25 alkyl, C6-C25 aryl, C7-C25 alkylaryl, C7-C25 arylalkyl, C1-C20 heteroalkyl or C2-C25 heteroaryl, C3-C25 alkylheteroaryl, C3-C25 heteroarylalkyl, C7-C25 heteroalkylaryl, C7-C25 arylheteroalkyl, C3-C25 heteroalkylheteroaryl, C3-C25 heteroarylheteroalkyl moieties or hydrogen.

(40) These, like the other cations mentioned also, may likewise also be employed with preference in electrolytes in the cathode space.

(41) Examples of pyrrolidinium ions are compounds of general formula [6],

(42) ##STR00008##

(43) where R, R and R.sup.1-R.sup.8 may be independently selected from the group of linear, branched or cyclic C1-C25 alkyl, C6-C25 aryl, C7-C25 alkylaryl, C7-C25 arylalkyl, C1-C20 heteroalkyl or C2-C25 heteroaryl, C3-C25 alkylheteroaryl, C3-C25 heteroarylalkyl, C7-C25 heteroalkylaryl, C7-C25 arylheteroalkyl, C3-C25 heteroalkylheteroaryl, C3-C25 heteroarylheteroalkyl moieties or hydrogen. These, like the other cations mentioned also, may likewise also be employed with preference in electrolytes in the cathode space.

(44) Examples of imidazolium ions are compounds of general formula [7],

(45) ##STR00009##

(46) where R and R.sup.1-R.sup.4 may be independently selected from the group of linear, branched or cyclic C1-C25 alkyl, C6-C25 aryl, C7-C25 alkylaryl, C7-C25 arylalkyl, C1-C20 heteroalkyl or C2-C25 heteroaryl, C3-C25 alkylheteroaryl, C3-C25 heteroarylalkyl, C7-C25 heteroalkylaryl, C7-C25 arylheteroalkyl, C3-C25 heteroalkylheteroaryl, C3-C25 heteroarylheteroalkyl moieties or hydrogen. These, like the other cations mentioned also, may likewise also be employed with preference in electrolytes in the cathode space.

(47) In certain embodiments, the proton sponge is of general formula (I):

(48) ##STR00010##

(49) where n is =0 or 1;

(50) A1 and A2 represent aromatic scaffolds, for example a benzene or naphthalene scaffold, which may be linked through a further ring A3, wherein when n is =1, A3 is present and represents a substituted or unsubstituted cyclopentane ring or five-membered ring which shares the bonding at positions 1 and 2 with the aromatic scaffold A1 and at positions 3 and 4 with the aromatic scaffold A2, and the carbon at position 5 is present in the formula at the bottom between A1 and A2 and may have two substituents R.sup.d and R.sup.d;

(51) where R.sup.d and R.sup.d independently represent hydrogen and/or one or more substituted or unsubstituted linear, branched or cyclic alkyl moieties of 1 to 20 carbon atoms and/or substituted or unsubstituted aromatic and/or heteroaromatic moieties of 1 to 40 carbon atoms, wherein when R.sup.d and R.sup.d are present they may combine to form an aliphatic or aromatic ring or polycycles; when n is =0, the ring A3 is absent and the rings A1 and A2 are fused; where R.sup.w, R.sup.x, R.sup.y and R.sup.z independently represent substituted or unsubstituted linear, branched or cyclic alkyl moieties of 1 to 50 carbon atoms and/or substituted or unsubstituted aromatic and/or heteroaromatic moieties of 1 to 100 carbon atoms and/or substituted or unsubstituted linear or branched sulfonylalkyl moieties of 1 to 50 carbon atoms, where 2 or more of R.sup.x to R.sup.z may combine to form a ring or polycycles where not only R.sup.w and R.sup.x but also R.sup.y and R.sup.z may each be replaced by a single moiety R.sup.w or, respectively, R.sup.y to form a double bond on the nitrogen; and where R.sup.a and R.sup.b independently represent hydrogen and/or one or more substituted or unsubstituted linear, branched or cyclic alkyl moieties of 1 to 20 carbon atoms and/or substituted or unsubstituted aromatic and/or heteroaromatic moieties of 1 to 40 carbon atoms on the particular ring of the aromatics skeleton, where when 2 or more of R.sup.a and/or R.sup.b are present, these may combine to form an aliphatic or aromatic ring or polycycles. Preferably, however, R.sup.a and R.sup.b in formula (I) each represent hydrogen.

(52) Preferred moieties R.sup.w, R.sup.x, R.sup.y and R.sup.z are independently substituted or unsubstituted linear, branched or cyclic alkyl moieties of 3 to 50 carbon atoms and/or substituted or unsubstituted aromatic and/or heteroaromatic moieties of 1 to 100 carbon atoms and/or substituted or unsubstituted linear or branched sulfonylalkyl moieties of 1 to 50 carbon atoms, where 2 or more of R.sup.x to R.sup.z may combine to form a ring or polycycles where not only R.sup.w and R.sup.x but also R.sup.y and R.sup.z may each be replaced by a single moiety R.sup.w or, respectively, R.sup.y to form a double bond on the nitrogen.

(53) Suitable substituents for the moieties R.sup.w, R.sup.x, R.sup.y, R.sup.z, R.sup.a and R.sup.b include not only heteroatoms such as N, P, O, S in the alkyl chain but also substituents for the hydrogen atoms of the alkyl chain, for example halogen atoms such as F, Cl, Br, I, preferably F, CF.sub.3 or CN. It is also possible here for two or more heteroatoms to be linked in the alkyl chain, for example P and N or S and O. Suitable heteroatoms for the heteroaromatics are for example N, P, O, S.

(54) Suitable moieties R.sup.w, R.sup.x, R.sup.y, R.sup.z, R.sup.a and R.sup.b may thus be for example independently methyl, ethyl, generally unbranched, branched, fused (decahydronaphthyl), ring-shaped (cyclohexyl) or fully or partially substituted C1-C20 alkyl moieties, as well as ether groups (ethoxy, methoxy, etc.), ester, amide, carbonate groups, CN, etc., and also be as well as contain ether groups (ethoxy, methoxy, etc.), ester, amide, carbonate groups and contain for example halogens, in particular F, CF.sub.3 or CN as substituents. Substituted or unsubstituted aliphatic rings and/or ring systems, such as cyclohexyl, are also within the meaning of the invention.

(55) R.sup.w, R.sup.x, R.sup.y, R.sup.z, R.sup.a and R.sup.b are not restricted to saturated systems, but also comprise for example substituted/unsubstituted aromatics such as phenyl, biphenyl, naphthyl, phenanthryl, etc., and/or benzyl etc.

(56) An exemplary compilation of suitable heterocycles for the moieties R.sup.w, R.sup.x, R.sup.y, R.sup.z, R.sup.a and R.sup.b is depicted in the following view where for simplicity only the skeleton of the aromatics is depicted, which skeletons may in principle be substituted with further substituted linear, branched or cyclic alkyl moieties and/or substituted or unsubstituted aromatic and/or heteroaromatic moieties, in which case the definition of suitable substituents and heteroatoms follows by analogy to the definition for the moieties R.sup.w, R.sup.x, R.sup.y, R.sup.z, R.sup.a and R.sup.b. In the bypyridine system, X.sub.1 to X.sub.12 may each represent N as well as C. The bonding to the aromatic scaffold A1 and/or A2 and/or to alkyl or substituted alkyl moieties on the aromatic scaffold may be effected at any bonding-capable place on the skeleton.

(57) ##STR00011## ##STR00012##

(58) Formula (I) above may be considered to subsume two formulae (Ia) and (Ib), which represent the formula for n=0 and n=1 respectively, and are shown hereinbelow:

(59) ##STR00013##

(60) Formula (Ia) herein represents those cases where the two aromatics A1 and A2 are fused, whereas formula (Ib) represents those cases where the two aromatics A1 and A2 are linked via a five-membered ring. In the formulae (Ia) and (Ib), R.sup.w, R.sup.x, R.sup.y and R.sup.z and also R.sup.a and R.sup.b are each as defined above in general formula (I). The compound of formula (Ia) is preferred.

(61) Preference for use as proton sponge of the present invention, for example as compound of formula (I), is given to a compound of the following formulae (II), (III), (IVa); (IVb), (Va) or (Vb):

(62) ##STR00014##

(63) where R.sup.1 to R.sup.4 independently represent substituted or unsubstituted linear, branched or cyclic alkyl moieties of 1 to 20 carbon atoms and/or substituted or unsubstituted aromatic and/or heteroaromatic moieties of 1 to 40 carbon atoms and/or substituted or unsubstituted linear or branched sulfonylalkyl moieties of 1 to 20 carbon atoms, where 2 or more of R.sup.1 to R.sup.4 may combine to form an aliphatic or aromatic ring or polycycles; and

(64) where R.sup.a and R.sup.b independently represent hydrogen and/or one or more substituted or unsubstituted linear, branched or cyclic alkyl moieties of 1 to 20 carbon atoms and/or substituted or unsubstituted aromatic and/or heteroaromatic moieties of 1 to 40 carbon atoms on the particular ring of the naphthalene skeleton, where when 2 or more of R.sup.a and/or R.sup.b are present, these may combine to form an aliphatic or aromatic ring or polycycles;

(65) ##STR00015##

(66) where R.sup.5 to R.sup.8 independently represent substituted or unsubstituted linear, branched or cyclic alkyl moieties of 1 to 20 carbon atoms and/or substituted or unsubstituted aromatic and/or heteroaromatic moieties of 1 to 40 carbon atoms and/or substituted or unsubstituted linear or branched sulfonylalkyl moieties of 1 to 20 carbon atoms, where 2 or more of R.sup.5 to R.sup.8 may combine to form an aliphatic or aromatic ring or polycycles; and

(67) where R.sup.a and R.sup.b independently represent hydrogen and/or one or more substituted or unsubstituted linear, branched or cyclic alkyl moieties of 1 to 20 carbon atoms and/or substituted or unsubstituted aromatic and/or heteroaromatic moieties of 1 to carbon atoms on the particular ring of the fluorene skeleton, where when 2 or more of R.sup.a and/or R.sup.b are present, these may combine to form an aliphatic or aromatic ring or polycycles; and

(68) where R.sup.d and R.sup.d independently represent hydrogen and/or one or more substituted or unsubstituted linear, branched or cyclic alkyl moieties of 1 to 20 carbon atoms and/or substituted or unsubstituted aromatic and/or heteroaromatic moieties of 1 to 40 carbon atoms, wherein when R.sup.d and R.sup.d are present they may combine to form an aliphatic or aromatic ring or polycycles;

(69) ##STR00016##

(70) where R.sup.11 to R.sup.14 independently represent substituted or unsubstituted linear, branched or cyclic alkyl moieties of 1 to 20 carbon atoms and/or substituted or unsubstituted aromatic and/or heteroaromatic moieties of 1 to 40 carbon atoms and/or substituted or unsubstituted linear or branched sulfonylalkyl moieties of 1 to 20 carbon atoms, where 2 or more of R.sup.11 to R.sup.14 may combine to form an aliphatic ring or polycycles; and

(71) where R.sup.a and R.sup.b independently represent hydrogen and/or one or more substituted or unsubstituted linear, branched or cyclic alkyl moieties of 1 to 20 carbon atoms and/or substituted or unsubstituted aromatic and/or heteroaromatic moieties of 1 to 40 carbon atoms on the particular ring of the naphthalene skeleton, where when 2 or more of R.sup.a and/or R.sup.b are present, these may combine to form an aliphatic or aromatic ring or polycycles;

(72) ##STR00017##

(73) where R.sup.21 to R.sup.28 independently represent hydrogen and/or substituted or unsubstituted linear, branched or cyclic alkyl moieties of 1 to 20 carbon atoms and/or substituted or unsubstituted aromatic and/or heteroaromatic moieties of 1 to 40 carbon atoms, where 2 or more of R.sup.21 to R.sup.28 may combine to form an aliphatic or aromatic ring or polycycles; and

(74) where R.sup.a and R.sup.b independently represent hydrogen and/or one or more substituted or unsubstituted linear, branched or cyclic alkyl moieties of 1 to 20 carbon atoms and/or substituted or unsubstituted aromatic and/or heteroaromatic moieties of 1 to carbon atoms on the particular ring of the naphthalene skeleton, where when 2 or more of R.sup.a and/or R.sup.b are present, these may combine to form an aliphatic or aromatic ring or polycycles;

(75) ##STR00018##

(76) where R.sup.31 to R.sup.36 and R.sup.31 to R.sup.36 independently represent hydrogen and/or substituted or unsubstituted linear, branched or cyclic alkyl moieties of 1 to 20 carbon atoms and/or substituted or unsubstituted aromatic and/or heteroaromatic moieties of 1 to 40 carbon atoms and/or one or more of the pairs R.sup.31 and R.sup.31, R.sup.32 and R.sup.32, R.sup.33 and R.sup.33, R.sup.34 and R.sup.34, R.sup.35 and R.sup.35, R.sup.36 and R.sup.36, preferably R.sup.32 and R.sup.32 and also R.sup.35 and R.sup.35, by forming a double bond instead of the two substituents, represent a phosphazene derivative P(NR.sup.c.sub.2).sub.3, where two or more of R.sup.31 to R.sup.36 and R.sup.31 to R.sup.36 and/or R.sup.c may combine to form an aliphatic or aromatic ring or polycycles;

(77) where the R.sup.cs independently represent one or more substituted or unsubstituted linear, branched or cyclic alkyl moieties of 1 to 20 carbon atoms and/or substituted or unsubstituted aromatic and/or heteroaromatic moieties of 1 to 40 carbon atoms; and where R.sup.a and R.sup.b independently represent hydrogen and/or one or more substituted or unsubstituted linear, branched or cyclic alkyl moieties of 1 to 20 carbon atoms and/or substituted or unsubstituted aromatic and/or heteroaromatic moieties of 1 to carbon atoms on the particular ring of the naphthalene skeleton, where when 2 or more of R.sup.a and/or R.sup.b are present, these may combine to form an aliphatic or aromatic ring or polycycles.

(78) Preferred moieties R.sup.1 to R.sup.4 in formula (II) are independently substituted or unsubstituted linear, branched or cyclic alkyl moieties of 3 to 20 carbon atoms and/or substituted or unsubstituted aromatic and/or heteroaromatic moieties of 1 to 40 carbon atoms and/or substituted or unsubstituted linear or branched sulfonylalkyl moieties of 1 to 20 carbon atoms, where or more of R.sup.1 to R.sup.4 may combine to form an aliphatic or aromatic ring or polycycles.

(79) Preferably, however, R.sup.a and R.sup.b in formulae (II), (III), (IVa), (IVb), (Va) and (Vb) each represent hydrogen, and/or R.sup.d and R.sup.d in formula (III) each preferably represent hydrogen.

(80) Suitable substituents for the moieties R.sup.1 to R.sup.8, R.sup.11 to R.sup.14, R.sup.21 to R.sup.28, R.sup.31 to R.sup.36, R.sup.31 to R.sup.36, R.sup.a and R.sup.b and R.sup.c and R.sup.d in formulae (II), (III), (IVa), (IVb), (Va) and (Vb) include not only heteroatoms such as N, P, O, S in the alkyl chain but also substituents for the hydrogen atoms of the alkyl chain, for example halogen atoms such as F, Cl, Br, I, preferably F, CF.sub.3 or CN. It is also possible here for two or more heteroatoms to be linked in the alkyl chain, for example P and N or S and O. Suitable heteroatoms for the heteroaromatics are for example N, P, O, S.

(81) Suitable moieties R.sup.1 to R.sup.8, R.sup.11 to R.sup.14, R.sup.21 to R.sup.28, R.sup.31 to R.sup.36, R.sup.31 to R.sup.36, R.sup.a and R.sup.b and R.sup.c and R.sup.d in formulae (II), (III), (IVa), (IVb), (Va) and (Vb) may thus be for example independently methyl, ethyl, generally unbranched, branched, fused (decahydronaphthyl), ring-shaped (cyclohexyl) or fully or partially substituted C1-C20 alkyl moieties, as well as ether groups (ethoxy, methoxy, etc.), ester, amide, carbonate groups, CN, etc., and also be as well as contain ether groups (ethoxy, methoxy, etc.), ester, amide, carbonate groups and contain for example halogens, in particular F, or CN as substituents. Substituted or unsubstituted aliphatic rings and/or ring systems, such as cyclohexyl, are also within the meaning of the invention. R.sup.1 to R.sup.4 in formula (II), however, are preferably not methyl and ethyl moieties.

(82) R.sup.1 to R.sup.8, R.sup.11 to R.sup.14, R.sup.21 to R.sup.28, R.sup.31 to R.sup.36, R.sup.31 to R.sup.36, R.sup.a and R.sup.b and R.sup.c and R.sup.d in formulae (II), (III), (IVa), (IVb), (Va) and (Vb) are not restricted to saturated systems, but also comprise for example substituted/unsubstituted aromatics such as phenyl, biphenyl, naphthyl, phenanthryl, etc., and/or benzyl etc.

(83) An exemplary compilation of suitable heterocycles for the moieties R.sup.1 to R.sup.8, R.sup.11 to R.sup.14, R.sup.21 to R.sup.28, R.sup.31 to R.sup.36, R.sup.31 to R.sup.36, R.sup.a and R.sup.b and R.sup.c and R.sup.d in formulae (II), (III), (IVa), (IVb), (Va) and (Vb) is depicted in the following view regarding R.sup.w, R.sup.x, R.sup.y, R.sup.z, R.sup.a and R.sup.b where for simplicity only the skeleton of the aromatics is depicted, which skeletons may in principle be substituted with further substituted linear, branched or cyclic alkyl moieties and/or substituted or unsubstituted aromatic and/or heteroaromatic moieties, in which case the definition of suitable substituents and heteroatoms follows by analogy to the definition for the moieties R.sup.w, R.sup.x, R.sup.y, R.sup.z, R.sup.a and R.sup.b. In the bypyridine system, X.sub.1 to X.sub.12 may each represent N as well as C. The bonding to the aromatic scaffold A1 and/or A2 and/or to alkyl or substituted alkyl moieties on the aromatic scaffold may be effected at any bonding-capable place on the skeleton.

(84) Preference is further given to proton sponges of formulae (III), (IVa), (IVb), (Va) and (Vb).

(85) Examples of proton sponges for the purposes of the invention are the following compounds:

(86) Substituted and unsubstituted compounds based on 1,8-diamino-naphthalene derivatives:

(87) For example: N,N,N,N-tetraalkyl- or aryl-1,8-naphthalene-diamines of formula (II)

(88) Particularly high basicities are possessed by the guanidine- substituted 1,8-naphthalene derivatives, of formula (Va).

(89) One exemplary compound is the compound having the formula 5*.

(90) ##STR00019##

(91) The sulfonamide derivatives of formula (IVa) are also within the meaning of the invention.

(92) In particular, all compounds and references are within the meaning of this invention notification that in the doctoral thesis New Development in the Chemistry of Superbasic Proton Sponges Based on Guanidine, Iminophosphorane and Sulfoxime Tweezer Ligands for Protons by Nuri Cenap Abacilar from Hanau, Marburg/Lahn 2009, in the chemistry department of the Philipps University (Aug. 19, 2009). Also described therein are in particular phosphazene derivatives such as those of general formula (Vb), of which exemplary compounds of formulae 3, 8# and 7* are depicted hereinbelow.

(93) ##STR00020##

(94) The use of the proton sponges in an electrolyte in the manner of the present invention also encompasses the electrolyte itself. The electrolyte, in addition to the proton sponge, may contain further, commonplace additives, for example of the type used in photocatalysis or electrolysis, which are not subject to special restrictions in the context of the invention.

(95) In certain embodiments, the electrolyte solution comprises water and one or more than one conducting salt. The electrolyte herein is otherwise not particularly limited as long as it permits a (possibly physical) dissolving of the carbon dioxide. The electrolyte may for example comprise KCl, K.sub.2SO.sub.4, KHCO.sub.3 or mixtures thereof as conducting salt. In principle, any combinations of cations and anions can serve as conducting salts provided they allow the current densities required, also including for example those specified above.

(96) The liquid electrolyte or the electrolyte solution of the present invention may further comprise one or more than one ionic liquid.

(97) Exemplary and preferred ionic liquids are based on: imidazolium, pyridinium, pyrrolidinium, piperidinium and guanidinium cations, with corresponding anions. These may be halides, or complex halides such as BF.sub.4.sup. or PF.sub.6.sup., carboxylates, sulfates, triflates, bistrifluoromethanesulfonimidates, carbonate or hydrogencarbonate, etc., more preferably carbonate or hydrogencarbonate.

(98) Ionic liquids are organic salts having a melting point below 300 C., preferably below 100 C., more preferably below 50 C.

(99) Possible examples of suitable ionic liquids are listed in table 3 and the list hereinbelow.

(100) TABLE-US-00003 TABLE 3 Exemplary ionic liquids 1-benzyl-3-methylimidazolium hexafluorophosphate 1-butyl-2,3-dimethylimidazolium hexafluorophosphate 1-butyl-3-methylimidazolium hexafluorophosphate 1-ethyl-3-methylimidazolium hexafluorophosphate 1-hexyl-3-methylimidazolium hexafluorophosphate 1-butyl-3-(3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl) imidazolium hexafluorophosphate 1-methyl-3-(3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl) imidazolium hexafluorophosphate 1-methyl-3-octylimidazolium hexafluorophosphate 1-benzyl-3-methylimidazolium tetrafluoroborate 1-butyl-2,3-dimethylimidazolium tertrafluoroborate 0 1-butyl-3-methylimidazolium tetrafluoroborate 1-ethyl-3-methylimidazolium tetrafluoroborate 1-hexyl-3-methylimidazolium tetrafluoroborate 1-methyl-3-octylimidazolium tetrafluoroborate 1-butyl-3-methylimidazolium trifluoromethanesulfonate 1-ethyl-3-methylimidazolium trifluoromethanesulfonate 1,2,3-trimethylimidazolium trifluoromethane sulfonate 1-ethyl-3-methylimidazolium bis(pentafluoroethylsulfonyl)imide 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide 1-butyl-3-methylimidazolium methanesulfonate 0 Tetrabutylammonium bistrifluoromethanesulfonimidate Tetrabutylammonium methanesulfonate Tetrabutylammonium nonafluorobutanesulfonate Tetrabutylammonium heptadecafluorooctanesulfonate Tetrahexylammonium tetrafluoroborate Tetrabutylammonium trifluoromethanesulfonate Tetrabutylammonium benzoate Tetrabutylammonium chloride Tetrabutylammonium bromide 1-benzyl-3-methylimidazolium hexafluorophosphate 1-butyl-2,3-dimethylimidazolium hexafluorophosphate 1-butyl-3-methylimidazolium hexafluorophosphate 1-ethyl-3-methylimidazolium hexafluorophosphate 1-hexyl-3-methylimidazolium hexafluorophosphate 1-butyl-1-(3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl)- imidazolium hexafluorophosphate 1-methyl-3-(3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl)- imidazolium hexafluorophosphate 1-methyl-3-octylimidazolium hexafluorophosphate 1-butyl-2,3-dimethylimidazolium tetrafluoroborate 1-butyl-3-methylimidazolium tetrafluoroborate 1-hexyl-3-methylimidazolium tetrafluoroborate 1-methyl-3-octylimidazolium tetrafluoroborate 1-butyl-3-methylimidazolium trifluoromethanesulfonate 1-ethyl-3-methylimidazolium trifluoromethanesulfonate 1,2,3-trimethylimidazolium trifluromethanesulfonate 1-ethyl-3-methylimidazolium bis(pentafluoroethylsulfonyl)imide 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide 1-butyl-3-methylimidazolium methanesulfonate tetrabutylammonium bistrifluoromethanesulfonimidate tetrabutylammonium methanesulfonate tetrabutylammonium nonafluorobutanesulfonate tetrabutylammonium heptadecafluorooctanesulfonate tetrahexylammonium tetrafluoroborate tetrahexylammonium trifluoromethanesulfonate tetrabutylammonium benzoate tetrabutylammonium chloride tetrabutylammonium bromide 1-benzyl-3-methylimidazolium tetrafluoroborate trihexyltetradecylphosphonium hexafluorophosphate tetrabutylphosphonium methanesulfonate tetrabutylphosphonium tetrafluoroborate tetrabutylphosphonium bromide 1-butyl-3-methylpyridinium bis(trifluoromethylsulfonyl)imide 1-butyl-4-methylpyridinium hexafluorophosphate 1-butyl-4-methylpyridinium tetrafluoroborate tetrabutylammonium tetraphenylborate sodium tetraphenylborate sodium tetrakis(1-imidazolyl)borate cesium tetraphenylborate

(101) The electrolyte may further also comprise supercritical CO.sub.2 itself. However, it is then necessary to supply water at the rate of consumption.

(102) In certain embodiments, the liquid electrolyte of the present invention or the electrolyte solution of the present invention comprises one or more than one polar or apolar organic solvent, in particular an alcohol having more than 5 carbon atoms, a high-boiling ether having a boiling point of more than 80 C., preferably 150 C., a high-boiling amine having a boiling point of more than 80 C., preferably 150 C., or a polyamide liquid under electrolysis conditions.

(103) In particular, the liquid electrolyte or the electrolyte solution may consist mainly or partly of water. In particular, high-boiling additives are of advantage (high-boiling alcohols from six carbon atoms, ethers (polyethylene glycol), or amines and liquid polyamides) in order that the electrolyte may not evaporate even in prolonged operation. The defined admixture of water may alter the product spectrum in an electrochemical reduction in particular. This is because a mixture of various hydrocarbon-type compounds such as CH.sub.4, C.sub.2H.sub.4, CO, etc. are formed at a copper cathode according to the potential and the available CO.sub.2 concentration (controllable via the pressure and the temperature in the case of aqueous systems). The mixture can then be shifted to favor a desired hydrocarbon such as, for example, CH.sub.4 by precisely adjusting the proton sponge-to-water ratio. When, by contrast, a reduction of CO.sub.2 to CO is intended, the omission of water may be used to ensure that no undesired additional evolution of hydrogen shall be observed, but all electrons are employed for the reduction of CO.sub.2 (Faraday efficiency of approximately 100% of CO). comprise polar or apolar organic solvents, such as high-boiling alcohols from six carbon atoms, ethers (polyethylene glycol), or amines (pyridine, quinoline, etc.) and polyamides. ionic liquids have by their very nature but a very low and/or virtually no vapor pressure at all and therefore are also very highly suitable for use as solvents for the organic proton sponges.

(104) In principle, the compositions thus constructed are employable in methods of reacting CO.sub.2 and water, for example photocatalysis or electrolysis, of CO.sub.2 or carbonate-containing electrolyte at a comparatively low temperature, in particular room temperature, i.e. 15-30 C., preferably about 20 to 25 C.

(105) Particular preference is given to the employment in a panel for photocatalytic reduction of CO.sub.2 in the presence of water. The panel is for example provided means for separating off the products such as methanol or methane. The electrolyte encloses for example the catalytically active particle and thus ensures that matter and electron cycles are closed-loop.

(106) The photocatalytic reduction of CO.sub.2 to methanol, methane or other energy carriers or foundation chemicals is so far only delivering very poor yields in the region of mol/h per gram of catalyst used. One optimization variable is the enhancement in the concentration of protons and CO.sub.2 on the catalyst particle in order to increase the probability that the reaction may take place. This is achievable according to the present invention.

(107) In an electrochemical reduction, the use of the proton sponges discussed herein makes it possible to improve efficiencies, for example by reducing the overvoltage at the cathode in the electrolysis. The efficiency for any commercial deployment is at present still not good enough with the systems hitherto discussed in the literature. As well as an improved efficiency, it is possible to improve the selectivity (reduction to one desired hydrocarbon, suppressed formation of other reduction products), specifically in the electrolysis at high current densities in particular. This is achievable by specifically providing to the cathode sufficient CO.sub.2 and H.sub.2O to form one particular hydrocarbon.

(108) What is claimed is: