WO2019145112A1

WO2019145112A1 - Porous electrode for the electrochemical reaction of organic compounds in two immiscible phases in an electrochemical flow reactor

Info

Publication number: WO2019145112A1
Application number: PCT/EP2018/097087
Authority: WO
Inventors: Bernhard Schmid; Christian Reller; Günter Schmid
Original assignee: Siemens Aktiengesellschaft
Priority date: 2018-01-29
Filing date: 2018-12-28
Publication date: 2019-08-01
Also published as: US20200385875A1; DE102018201287A1; CN111655904A; EP3704287A1

Abstract

The present invention relates to a method for the electrochemical reaction of an organic material, and to a device in which a corresponding method can be carried out.

Description

description

Porous electrode for the electrochemical conversion of organic compounds into two immiscible phases in an electrochemical flow reactor

The present invention relates to a method for the electrochemical reaction of an organic material and to a device in which a corresponding method can be carried out.

The use of electrochemical methods in the synthesis of bulk and fine chemicals has always been a major challenge. Many organic substrate molecules are very poorly soluble in water, but much better in non-polar solvents, ie organic solvents.

However, the use of organic solvent-based electrolytes involves some significant disadvantages for electrochemistry.

On the one hand, organic solvents and lipophilic organic salts are much more expensive than water and inorganic salts.

Second, organic electrolytes typically have much worse conductivity than aqueous electrolytes, resulting in high cell voltages and high ohmic losses.

Third, in electrochemical processes, the electrolyte is often a consumable material. Although the overall reaction does not involve water, it can be consumed locally and then regenerated in the bulk electrolyte. Each electrochemical process requires a backlash reaction at the counter electrode. Many, especially organic, electrochemical transformations also include protons that he witnessed by the counter-reactions or consumed must be. In the case of water, this is typically either the reduction or oxidation of water to hydrogen or oxygen. In organic Elekt rolyten the organic solvent takes over the role of water and is decomposed at the counter electrode. This can be avoided by the use of sacrificial materials or sacrificial materials ver, however, in turn, the process costs massively increase. At high current density, the proton transport through the electrolyte may even be insufficient for the reaction rate, resulting in protonation or

Deprotonation and subsequent decomposition of the electrolyte can lead to the electrodes.

Therefore, the use of aqueous electrolytes for electrochemical synthesis seems very desirable. The often

poor solubility of the reagent molecules in water or even electrolytes with high ionic strength, however, limit the sub stratversorgung the electrodes and thus the current densities dramatically.

There is currently no general solution to this problem in the application. Proposals by Beck et al. pertain to very thin capillary cells, as for example in Fritz Beck, reports of the Bunsen Society 1973, 77 (10/11), p. 810-817 and F.

Beck, H. Guthke, Chemical-Ing. -Techn. 1969, 41 (17), pp. 943-950.

There is therefore a need for an effective process for the electrochemical conversion of organic compounds, in particular special organic compounds which are not or poorly soluble in water. The inventors have found that an electrochemical reaction of organic compounds can be effectively performed at a phase boundary when it is within a multilayer porous electrode comprising a hydrophilic and a lipophilic layer.

In a first aspect, the present invention relates to a process for electrochemically reacting a first organic material which is soluble in or miscible with a first nonpolar solvent, comprising introducing the first organic material into the first nonpolar solvent to produce a first organi solution or mixture;

Providing an electrolytic cell comprising

a porous first electrode comprising at least a first, lipophilic layer and at least one second hydrophilic layer, wherein the first, lipophilic layer and the second, hydrophilic layer are preferably porous, and

a second electrode;

Introducing the first organic solution or mixture into the electrolytic cell such that the first organic solution or mixture contacts the first lipophilic layer of the first electrode;

Introducing a first polar electrolyte into the electrolysis cell such that the first polar electrolyte contacts the second, hydrophilic layer of the first electrode and the second electrode; and

Electrochemically reacting the first organic material and / or the first nonpolar solvent on the first electrode; or

Providing an electrolytic cell comprising

a porous first electrode comprising at least one first lipophilic layer and at least one second, hydrophobic layer phile layer, wherein the first, lipophilic layer and the second, hydrophilic layer are preferably porous, and

a second electrode;

Introducing the first organic material as a liquid or gas in the electrolytic cell such that the first orga African material, the first, lipophilic layer of the first

Electrode contacted;

Electrochemical conversion of the first organic material at the first electrode; in which

the first nonpolar solvent and the first polar electrolyte or

the first organic material as a liquid or gas and the first polar electrolyte

form a first phase boundary to each other, which is formed such that the first phase boundary in the electrochemical reaction at least partially within the ers th electrode, preferably at an interface between the first, lipophilic layer and the second, hydrophilic

Layer, lies.

In another aspect, the invention relates to a device for the electrochemical conversion of a first organic material which is soluble in or miscible with a first nonpolar solvent

an electrolysis cell, wherein the electrolysis cell

a porous first electrode comprising at least a first, lipophilic layer and at least a second, hydrophilic layer, wherein the first, lipophilic Layer and the second hydrophilic layer are preferably porous, and

a second electrode

includes;

at least one first feed device for the supply of a first solution or mixture of a first organic material which is soluble in or miscible with a first non-polar solvent, in or with a first non-polar solvent, or for the supply of a first organic material, which is soluble in, or miscible with, a first non-polar solvent which is designed to supply the first solution or mixture of the first organic material into or with the first non-polar solvent, or the first organic material, to the electrolytic cell in that the first organic solution or mixture or the first organic material contacts the first lipophilic layer of the first electrode; and at least one first discharge device for discharging the remaining first solution or mixture and optionally at least one first product of the electrochemical conversion of the first organic material and optionally the first nonpolar solvent, or the remaining first organic material and optionally at least one first product , or the remaining first nonpolar solvent and optionally at least one first product, or at least one first product, which is formed, the remaining first solution or mixture and optionally at least the first product of the electrochemical reaction of the first organic mate rials and, if necessary of the first nonpolar solvent, or the remaining first organic material and optionally at least the first product, or the remaining first non-polar solvent and optionally at least the first product, or at least the first product to be removed from the electrolysis cell. Further aspects of the present invention are the dependent claims and the detailed description to entneh men.

Description of the figures

The accompanying drawings are intended to illustrate embodiments of the present invention and to provide further understanding thereof. In the context of the description, they serve to explain concepts and principles of the invention. Other embodiments and many of the genann th advantages will become apparent with regard to the drawings.

The elements of the drawings are not necessarily to measure scale shown to each other. The same, functionally identical and same-acting elements, features and components are provided in the figures of the drawings, unless otherwise stated, each provided with the same reference numerals.

Figures 1 to 6 show schematically exemplary embodiments of a device according to the invention, with which he inventive method can be performed.

Figures 7 and 8 represent results obtained in an example of the method according to the invention.

Detailed description of the invention

definitions

Thus, unless otherwise defined, technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. Quantities in the context of the present invention are based on wt. %, unless otherwise stated or obvious from the context. In the gas diffusion electrode according to the invention, the weights complement each other. % Shares to 100 wt. %.

In the context of the present invention, what is meant to be hydrophobic is water-repellent. Hydrophobic pores and / or channels according to the invention are therefore those which repel water. In particular, hydrophobic properties are associated according to the invention with substances or molecules with nonpolar groups.

In contrast, the ability to interact with water and other polar substances is understood to be hydrophilic.

A lipophilic property is understood to mean that a substance dissolves well in fats and oils, or that the substance dissolves fats and oils well. In particular, lipophilic substances are to be understood as those which do not mix with a first polar solvent of the first polar electrolyte and / or dissolve in it and / or have it off, and which in particular are hydrophobic, that is, pointing water-repellent.

Gas diffusion electrodes (GDE) in general are electrodes in which liquid, solid and gaseous phases are present, and where, in particular, a conductive catalyst catalyzes an electrochemical reaction between the liquid and the gaseous phase ka.

The design can be of different nature, for example, as a porous "solid catalyst" with possibly auxiliary layers for adjusting the hydrophobicity, in which case, for example, a membrane-GDE composite, eg AEM-GDE composite, can be produced; as a conductive porous support on which a catalyst can be applied in a thin layer, in which case again a membrane-GDE composite, for example AEM-GDE composite, can be produced; or as composite catalyst porous, which can optionally be applied with additive directly on a membrane, for example an AEM, and then in the composite can form a catalyst coated membrane (CCM).

The normal pressure is 101325 Pa = 1.01325 bar.

Electro-osmosis:

Electro-osmosis is an electrodynamic phenomenon in which a force towards the cathode acts on particles in solution with a positive zeta potential and a force acts on the anode on all particles with a negative zeta potential. If conversion takes place at the electrodes, i. flows a galvanic current, so it comes also to a stream of particles with positive zeta potential for Ka method, regardless of whether the species is involved in the implementation or not. The same applies to a negative zeta potential and the anode. If the cathode is porous, the medium is also pumped through the electrode. It is also known as an electro-osmotic pump.

The material flows caused by electro-osmosis can also flow in opposite directions to concentration gradients. Diffusion-related currents that balance the concentration gradients can thereby be overcompensated.

A separator is a planar structure that is ausgebil det, electrodes and / or electrolytes or the reaction spaces or half-cells in an electrolysis cell to separate from each other. It is electrically insulating for the electrodes ei ner electrolysis cell itself and in particular according to certain embodiments Be the mixing of two electrolytes th and / or optionally of product gases and / or reaction gases of an electrochemical reaction in GE by the separator separated half cells at least partially prevent, preferably in Substantially prevent. In particular, a separator can prevent the mixing of product gases and / or reaction gases of half-cells separated thereby. However, a separator he leaves a sufficient material and, above all, charge carrier exchange with an electrolyte medium to allow ioni's flow. As separators, for example, frits, membranes, diaphragms, etc. generally allow a diffusive mass transport of liquids and solutes.

A diaphragm is a special separator designed to electrically insulate electrodes against each other but has no intrinsic ion conductivity or transport selectivity. In particular, according to certain embodiments, a slide may also prevent the mixing of reaction gases in electrolyte streams. It is a sheet-like component, for example a papierarti ges or porous composite material. The ionic conductivity is achieved in a diaphragm on the absorbency of the Dia phragmas against the electrolyte. Diaphragms therefore often have a very sharp pore size distribution.

A membrane is an electrically insulating polymer film which is designed to electrically insulate electrodes against each other and preferably prevents the mixing of two electrolytes and gas bubbles contained therein substantially. in particular to prevent the mixing of at least ent contained gas bubbles in it. However, the membrane may have an active ion transport function by corresponding chemical groups. When this ion transport ion is selective for one or more ions, eg cations

and / or protons or anions is also referred to as an ion-selective membrane. An ion-selective membrane is accordingly an electrically insulating polymer film for the electrodes of the electrolysis cell, which is adapted to electrically isolate electrodes against each other and in particular special mixture of two electrolytes and tener gas bubbles contained therein substantially to prevent, in particular the mixing of at least contained therein gas bubbles to prevent. The polymer carries functional groups with mobile counterions charged in such an ion-selective membrane and therefore constitutes a macromolecular salt, an acid and / or a base. In a pure solvent such as e.g. Water swollen, these membranes have an intrinsic ionic conductivity. In electrolyte solutions you also have i.d.R. a selectivity towards the nature of the transported charge carrier. The ionic functionalization can also lead, under potential, to the formation of new charge carriers in the membrane, which are then responsible for the transport of ions in the membrane.

According to a first aspect, the present invention relates to a method for the electrochemical reaction of a first organic material which is soluble in or soluble in a first nonpolar solvent

Introducing the first organic material into the first non-polar solvent to produce a first organic solution or mixture; Providing an electrolytic cell comprising

a second electrode;

Providing an electrolytic cell comprising

a second electrode;

Electrode contacted;

the first nonpolar solvent and the first polar electrolyte or

the first organic material as a liquid or gas and the first polar electrolyte

form a first phase boundary to each other, which is formed such that the first phase boundary in the elekt rochemical implementation at least partially within the ers th electrode, preferably at an interface between the first, lipophilic layer and the second, hydrophilic layer is located.

In the process of the present invention, the first organic material is not particularly limited, as long as it is soluble in or miscible with a first nonpolar solvent. In this case, as in the second embodiment of the method according to the invention clearly, not even the first non-polar solvent in the process find application, when the first organic material is liquid or gaseous. It is only important that a phase boundary is formed within the first electrode. For this purpose, it is also logical that the first organic material and the first polar electrolyte form a phase boundary, ie two separate phases. For this purpose, it is sufficient, for example, if the first organic material is non-polar according to certain embodiments.

In the first embodiment of the present method, this phase boundary is formed between the first solution or mixture in which the nonpolar solvent is mixed with or dissolved the first organic material and the first polar electrolyte. In this regard, it should be noted that in this first implementation In the form of the method according to the invention, the first organic material may be present as a solid, liquid or gas, which may then be dissolved in the first nonpolar solvent or may be mixed with it. In this case, the first organic material does not necessarily have to be nonpolar when it dissolves or mixes with the first nonpolar solvent.

The introduction of the first organic material as a liquid or gas, in particular liquid, in a non-polar solvent can be carried out, for example, to adjust the viscosity of the first organic material so that it can better get to the first electrode and preferably penetrate into it in particular, in the case that the first electrode is ausgebil Det as a gas diffusion electrode, can easily get to the 3-phase interface in the first electrode. In addition, by mixing with the first non-polar solvent or dissolving in the first non-polar solvent, the concentration of the first organic material can be more easily adjusted by dilution, whereby the reaction at the electrode can be better controlled and, in particular, over-reduction or avoided can be.

In the method according to the invention, there are thus two variants of electrochemically reacting the first organic material, depending on whether it is present as a fluid, ie liquid or gas, or not. If the first organic material is present as fluid, it can also be introduced as such directly into the electrolytic cell, since it can form a first phase boundary with the first polar electrolyte. If the first organic material is in the form of a solid, it must be dissolved in a first non-polar solvent so that it can be introduced into the electrolysis cell and there first non-polar solvent forms the first phase boundary with the first polar electrolyte. In addition, of course, the first organic material may be mixed as a fluid with a first nonpolar solvent or dissolved in this, for example, to be able to form a better first phase boundary to the first polar electrolyte can.

The first organic material which is soluble in or miscible with a first non-polar solvent is not further limited apart from this.

Also, regarding possible classes of compounds, the first organic material is not particularly limited. It may be a saturated, unsaturated and / or aromatic hydrocarbon which is substituted or unsubstituted, the substituents being not particularly limited so long as the first organic material is soluble in or miscible with a first nonpolar solvent. For example, polar substituents can also be used if the first organic material itself is still soluble in or miscible with a first nonpolar solvent. For this reason, the kind of the substituents is not particularly limited, nor is the number of carbons in the first organic material. According to certain embodiments, the first organic material is aromatic or at least in the structure comprises an aromatic moiety. For example, the first organic material may be selected for reduction from unsaturated hydrocarbons, aldehydes, ketones,

Nitro compounds, nitroso compounds, nitriles, etc .; and be selected for an oxidation of alcohols, unsaturated hydrocarbons, amines, mercaptans, etc. In particular embodiments, the first organic material is, in particular, immiscible with water and / or soluble in water as a solvent in the first polar electrolyte. According to certain embodiments, the first organic material is hydrophobic, especially when present as a liquid or gas.

Likewise, the first nonpolar solvent is not particularly limited so long as it forms a phase boundary with the first polar electrolyte. This may be a pure Ver bond, such as, for example, optionally substituted alkanes such as pentane, hexane, heptane, octane, etc., partially or fully dig dig halogenated alkanes such as dichloromethane, etc .; substituted or unsubstituted aromatics such as benzene, toluene, etc .; alkenes; alkynes; esters; Ethers, such as diethyl ether,

Tetrahydrofuran, etc. act. Also, mixtures of nonpolar solvents can be used. In particular, the first non-polar solvent is not soluble with water or in water as a solvent in the first polar electrolyte, in particular therefore hydrophobic.

The first non-polar solvent need not be electrically conductive, but it is not excluded that conductive non-polar solvents such as ionic liquids (IL) are used, provided they are stable and immiscible with the first polar electrolyte, especially an aqueous phase , Since, in particular, hydrophobic organic salt melts, such as, for example, Bu ₃ MeP ⁺ ((CF ₃₎ SO ₂₎ N as ionic liquids, often have very desirable dissolution properties, they can also be used instead of the first nonpolar solution. The hydrophobic ionic liquids are not particularly limited. A first non-polar solvent is used, for example, in the embodiments described above for the first organic compound. In addition, a non-polar solvent may also be required if, during the electrochemical reaction on the porous first electrode, a first organic product which is solid at the reaction temperature of the electrochemical reaction is formed which does not dissolve in the first polar electrolyte and correspondingly reacts with the first polar solvent from the first electrode leads abge.

The term "miscible with a first nonpolar solvent" herein means that when mixed with the non-polar solvent, no two phases are formed, that is, no phase boundary.

The introduction of the first organic material into the first nonpolar solvent for producing a first organic solution or mixture is not particularly limited. For example, it may be mixed, dripped, stirred, etc. Preferably, however, a homogeneous solution is prepared when introducing the first organic material into the first nonpolar solvent.

The first polar electrolyte is also not particularly limited. According to certain embodiments, the first polar electrolyte is liquid. According to certain embodiments, the first polar electrolyte is protic. In particular embodiments, the first polar electrolyte, in particular, comprises at least one first polar solvent, such as, for example, water; Alcohols such as methanol, ethanol, propanol, butanol, phenol, etc .; Carboxylic acids such as formic acid, acetic acid, propionic acid, etc .; Aldehydes such as acetaldehyde, etc., ketones such as acetone; Acids such as H ₂ S0 ₄ , HCl, HBr, etc .; sulfone; amines; nitrites; amides; lactones; sulfoxides; etc., as well as mixtures; and especially water as a polar solvent. In addition, it comprises compounds such as conductive salts which are soluble in the at least one first polar solvent and allow ionic contacting of the electrodes, ie the first and second electrodes of the electrolysis cell, so that a charge carrier transport, for example an ion transport, can take place. The conductive salt is not particularly limited, and includes, for example, salts of alkali metal and / or alkaline earth metals, for example, lithium, sodium, potassium, magnesium, calcium, etc., such as halides, sulfates, etc. In addition, the first polar

Electrolyte still contain substances that are usually contained in Elek rolyten, such as pH regulators, buffers, etc.

In addition to the first polar solvents mentioned, it is also possible to use other, in particular protic, solvents in the first polar electrolyte, either alone or as a solvent, or in combination with the abovementioned polar solvents. For example, HF can also be used at low temperatures <15 ° C. Likewise, salt melts or ionic liquids such as

Ethylmethylimidazoliumhydrogensulfat and / or

Triethanolmethylammoniummethylsulfat be used so far as they are polar. In particular, such further, preferably protic, solvents in reactions in the

Electrolysis cell can be used, which neither use water nor produce water - for example, with respect to the second electrode, as long as the reaction takes place within their stability window. Accordingly, the polar solvent can be suitably selected. According to certain embodiments, the first polar electrolyte contains water and optionally at least one salt, for example one of the abovementioned ones. According to certain embodiments, the first polar electrolyte - hereinafter also referred to as first phase if appropriate - forms an aqueous solution of salts which can serve as electrolyte and possibly consumables, that is to say optionally supplied via a feed device to the electrolysis cell and via a Laxative device can be removed from the electrolysis cell.

On the other hand, the first organic solution or mixture, or the first organic material as a liquid or gas, forms a second phase which is a non-polar phase containing the first organic material as a substrate. This nonpolar phase is not or only with difficulty miscible with the polar electrolyte as the first phase, for example the aqueous electrolyte, so that a phase boundary is formed.

As stated above, the first organic material must be soluble or miscible as a substrate in a nonpolar solvent, but may be solid, liquid or gaseous. Also, the first organic material may be the non-polar phase as a pure substrate. The non-polar phase does not have to be electrically conductive. According to certain embodiments in the first variant, this is a substrate solution in a nonpolar organic solvent.

Also, providing an electrolytic cell comprises a porous first electrode comprising at least a first lipophilic layer and at least one second hydrophilic layer, the first lipophilic layer and the second hydrophilic layer being preferably porous, and a second electrode not being particularly limited. Apart from the two electrodes, wherein the second electrode is not particularly limited, the electrolysis cell is in its Mate- and its design are not particularly limited. Exemplary embodiments of the electrolysis cell will be described below.

The first electrode is porous, i. has pores, and at least includes a first, lipophilic layer and at least a second, hydrophilic layer. However, it is not excluded that the first electrode also includes areas that are not porous, such as a grid for electrical contacting, but here, if necessary, a layer may be pressed into the grid, in turn, to form a porous structure , According to certain embodiments, the first lipophilic layer is porous. According to certain embodiments, the second hydrophilic layer is porous. According to certain preferred embodiments, both the first lipophilic layer and the second hydrophilic layer are porous. In particular, the first lipophilic layer and the second hydrophilic layer are in contact with each other. When both layers contact and both

Layers are porous, the formation of by-products, which must be removed, such as OH when using water in the polar electrolyte, can be reduced or prevented.

The pore size is not particularly limited in this case, however, according to certain embodiments, in the range of 0.1 to 500 ym, for example in the range of 0.2 to 100 ym, for example 0.5 to 10 ym. The pore size can be determined, for example, appro priate by porosimetry. The first electrode thus has at least one region with pores, in particular pores being present in the region in which the electrochemical conversion of the first organic material takes place, ie in particular in the region in which the first, lipophilic layer and the second, hydrophilic layer aneinan- the adjoin. In this area, accordingly, according to certain embodiments, there is at least one ers ter electrocatalyst or catalyst for the electrochemical reaction of the first organic material, which is not particularly limited. The first electrocatalyst may, for example, metals and / or compounds thereof, such as Cu, Ag, Au, Pd, Zr, Zn, Cd, Pb, Ir, Sn, Zn, Pb, Ti, Fe, Ni, Co, Rh, Ru , W, Mo, and the compounds, such as oxides or suitable modifications of the carbon, etc., as well as mixtures and / or alloys thereof, to summarize and be adapted to a desired electrochemical imple mentation. For example, it may be incorporated into the second, hydrophilic layer. However, the first electrocatalyst is preferably not found in the first, lipophilic layer.

However, the first electrode can also consist entirely of mate rialia materials that comprise pores, so according to certain embodiments comprises only porous layers. With porous layers in particular a good separation of the two Pha sen in the process, ie the non-polar phase of the nonpolar solu tion or mixture or the nonpolar solvent, and the polar phase of the polar electrolyte is possible. It is also possible hereby to increase the area-related current density within the electrode, in particular if the first, lipophilic layer and / or the second, hydrophilic layer are conductive. In addition, the electrochemically catalyzed reaction to the desired product is improved by the pore structure. According to certain embodiments, the first electrode consists of the first, lipophilic layer and the second, hydrophilic layer and optionally a material for electrical contacting. Possibly. In some embodiments, the first electrode may also be coated, for example on the lipophilic layer on the side which is in contact with the first nonpolar solution or mixture, or the first organic solvent as a liquid or gas, in bulk in contact, and / or on the hydrophilic layer on the side, which che with the first polar electrolyte in bulk in contact.

Within the present concept, that is to say with regard to the present method as well as to the present device, the first electrode forms a "three-phase half-cell" within the electrolysis cell. Within the concept, at least one electrochemical half-cell now comprises three phases, namely, the solid but porous electrode which lies between two immiscible fluid phases of which one is nonpolar and contains the substrate, and the other is a polar electrolyte carrying the ionic current which may possibly serve as a consumable material Electrolyte phase here is the one that is directed towards the counter electrode ge.

The porous first electrode has an amphiphilic character and comprises at least two layers, one hydrophilic and the other more lipophilic. Both layers are preferably electrically conductive and porous. Since electrochemical as a rule become more hydrophilic due to electrochemical stress, it is possible to introduce the electrical contact or the electrical contact also in the hydrophilic layer or in the layer boundary.

The first lipophilic layer is not particularly limited as long as it is lipophilic. In certain embodiments, it is hydrophobic. According to certain embodiments, the first, lipophilic layer is porous, thus having pores. Here by the transport of the first organic material, optionally dissolved in the first non-polar solvent or with This mixed, controlled so that, if necessary, no Überre action takes place. The first lipophilic layer may also be constructed, for example, as a lattice or the like, but this is not preferred.

According to certain embodiments, the first lipophilic layer is electrically conductive. According to certain embodiments, the first lipophilic layer is to be electrochemically inactive as a catalyst, especially when it is introduced into the first polar electrolyte, for example an aqueous electrolyte. In this way, it can be ensured in particular that no electrochemical reactions take place when a part of this layer comes into contact with the electrolyte. Otherwise, the electroosmotic pressure in the porous electrode may draw the electrolyte into the lipophilic layer and force the liquid-liquid interface out of the first electrode, thereby cutting off its substrate supply.

The structure of the first lipophilic layer is not particularly limited, and it may be net-like, as a scrim, knit, Ge effect, spongy, etc. constructed. According to certain embodiments, the first lipophilic layer is realized by forming particles which are particularly inert, conductive and / or hydrophobic, e.g. hydrophobic carbon

and / or glassy carbon, with a hydrophobic binder material such as PTFE (polytetrafluoroethylene), PCTFE

(Polychlorotrifluoroethylene), PFA (perfluoroalkoxy) and / or FEP (fluoroethylene-propylene) are bound. The preparation of the first, lipophilic layer can take place at the same time as the preparation of the second, hydrophilic layer and optionally further layers, for example by common Auswal zen, coextrusion, etc., or separately from this, the layers then connected appropriately can be. According to certain embodiments, the first lipophilic layer has substantially no catalytic activity for the first polar electrolyte, thus has a high overvoltage for the competing reaction with the first polar electrolyte, for example high overpotential for hydrogen evolution or oxygen evolution, as the case may be how the electrode is switched. According to certain embodiments, the first, lipophilic layer comprises hydrophobic, preferably conductive, first particles and / or at least one first hydrophobic binder. When the first lipophilic layer of the first electrode is in contact with a gas as the first organic material, the first electrode may be formed as a gas diffusion electrode so that the first lipophilic layer may be formed accordingly.

The second hydrophilic layer is also not particularly limited and is particularly wettable with the first polar electrolyte, especially water. According to certain embodiments, the second, hydrophilic layer comprises a first electrocatalyst and optionally at least one second binder. Thus, according to certain embodiments, the hydrophilic layer is the electrochemically active layer. It contains or even consists essentially of the first electrocatalyst. It is also preferably hydrophilic, po rosy and / or electrically conductive.

In principle, the second, hydrophilic layer can also be realized with bonded particles, if appropriate with at least one binder. In contrast, however, these particles are at least partially electrochemically active catalyst part chen. This layer preferably consists to a large extent of the first electrocatalyst. However, it is also an imbedding of the first electrocatalyst into an inert, conductive possible matrix. As a binder, for example, PTFE or PTFCE can be used. However, in order to further increase the hydrophilic character of this layer, these polymers may also be partially supported by hydrophilic binder polymers such as

Polyarlysulfones, e.g. PPSU (polyphenylene sulfone), replaced who the.

Also hydrophilic additives, eg. B. metal oxides such. As Al ₂ O ₃ , TiCg, ZnO, Y ₂ O ₃ , etc. may be incorporated into the second, hydrophilic layer. According to certain embodiments, the second hydrophilic layer thus comprises first hydrophilic additives, in particular metal oxides.

According to certain embodiments, the second layer may also comprise an inherently ion-conductive additive such as a cation or anion exchanger. In order to achieve an inherent ionic conductivity, therefore, it is possible to introduce ion-conducting additives such as ion-exchange resins or other solid electrolytes into this layer, which are not particularly limited. According to certain embodiments, the second, hydrophilic layer comprises a first ion-conducting additive, in particular a cation or anion exchanger.

In addition to the first, lipophilic layer and the second hydrophilic layer, the first electrode may comprise further "layers".

For a better current distribution in large electrodes, for example, a first current collector may be added, which is not particularly limited in terms of material and shape and may comprise, for example, a metal, a conductive oxide, a ceramic, a conductive polymer, etc., which may be used, for example, as a lattice, Braid, knitted fabric, or crocheted similar may be formed. Since the first current collector should not come into contact with the first polar electrolyte, in particular an aqueous electrolyte, it is preferably connected to the first lipophilic layer. Thus, according to certain embodiments, the first electrode comprises a first current collector, which preferably is not in contact with the second, hydrophilic layer. Also, a first current collector can be realized, for example, as eg incomplete metal coating of the first, lipophilic layer. Preferably, a metal braid is used because it can also provide additional mechanical support. The first current collector may for example lie on the first lipophilic layer or be embedded therein, for example by being rolled out with this layer.

In addition to the first, lipophilic layer and the second, hydrophilic layer and optionally the first current collector, the first electrode may also comprise additional additional layers. Thus, for example, a protective layer may be provided as a "top layer" on the second, hydrophilic layer, for example in the form of a hydrophilic membrane for the second, hydrophilic layer for protecting the layer The hydrophilic membrane may optionally be soaked through and through the electrolyte The main function of this layer is to protect the electrode from erosion, and this layer may also form an additional flow barrier to avoid migration of the liquid-liquid interface, such a membrane being on the second, hydrophilic layer Porous according to certain embodiments.

Also or alternatively, for example, a protective layer as a "backing layer" on the first, lipophilic, eg hydrophobic ben, layer may be provided, for example in the form of a hydrophobic membrane for the first, lipophilic layer, eg for better wetting with the non-polar phases, eg based on polyamide, etc., in order to prevent erosion and / or to avoid flow through the electrode. However, since this side is on the counter electrode gegenüberlie ing side, it is preferably used for elec- cal contacting, which makes correspondingly such a hydrophobic membrane less practicable. In a sol chen case, then preferably the layer should not be common, and for example, wires of Stromabneh mer, if available, stand out.

The second, hydrophilic layer can also be fused with an ion-conductive membrane. In this case, an inherent ionic conductivity of the second, hydrophilic layer is particularly preferred, which corresponds in particular to that of the ion-conducting membrane. Like the top layer layer discussed above, this layer also offers erosion protection and flow resistance. However, it can also be used to increase the total charge transport between the first electrode and the first polar electrolyte. Thus, for example, anion exchange membranes can be used to limit charge transport in cathodes to anions that leave the first electrode in the polar electrolyte and to protons that penetrate through the Grotthuss mechansim. Accordingly, cation exchange membranes can be used on the anode, for example become. This can be used to control the electroosmotic pressure and / or protect the electrode from electrolyte cations and / or anions. Like cathodes, anodes can therefore be shielded from electrolyte anions. Also, the anion and / or cation exchange membranes are not particularly limited like top layer and back layer. The anion and / or cation exchange membranes can be used, for example, as anion exchange membrane (AEM), cation exchange membrane ran (CEM), or bipolar membrane in both directions reali Siert.

Furthermore, in the first electrode as a mechanical support at least one support structure, for example in the form of Isolierpolymermatten, etc., for example, in each

Layer of the electrode to be incorporated.

In the electrolytic cell, the first electrode can be connected as a cathode or anode, depending on the desired electrochemical mixing reaction, ie reduction or oxidation.

Besides, the electrolytic cell includes a second electrode, which is not particularly limited. It may be similar in design to that of the first electrode or may differ therefrom, depending on the desired half-cell reaction. So the second one

Electrode as a solid electrode or solid electrode, as a gas diffusion electrode, as a porous bound catalyst structure, as a particulate catalyst on a support, as coating of a particulate catalyst on a membrane, as a porous conductive support into which a catalyst is impregnated, and / or be designed as a non-closed Flächengebil de. At the second electrode may, for example, in an aqueous first polar electrolyte and a water electrolysis to H ₂ or Cg done.

The second electrode can also be designed as a direct catalyst coating on a membrane or in direct contact with a membrane, in particular if it is a non-closed planar construct such. B. Network han delt. Also, the second electrode may be isolated by a separator to protect the first electrode from gases generated at the second electrode. In the above cases, according to certain embodiments, a first organic material is reacted on the first electrode, while preferably a reaction of the first polar electrolyte or a component thereof, for example water, takes place at the second electrode.

The arrangement of the electrodes is not particularly limited. For example, they can be arranged substantially parallel, so that corresponding electrode stacks can be formed, or they can also be arranged concentrically, etc.

According to certain embodiments, the second electrode comprises at least a third, lipophilic layer and at least a fourth, hydrophilic layer,

wherein the third lipophilic layer and the fourth, hydrophilic layer are preferably porous,

wherein the first polar electrolyte contacts the fourth, hydrophilic layer of the second electrode,

further comprising an introduction

a second organic material as a liquid or gas, or

a second organic solution or mixture comprising a second organic material which is soluble in or miscible with a second non-polar solvent and a second nonpolar solvent,

into the electrolysis cell such that the first organic material or the second organic solution or mixture contacts the third, lipophilic layer of the second electrode, wherein

the second organic material and / or the second non-polar solvent, or

the second organic material be implemented electrochemically at the second electrode. Here, for example, two organic substrates in the sense of a tandem electrolysis can be implemented simultaneously.

The second electrode in such embodiments is similar or even similar to the first electrode. Thus, if, for example, the first electrode is the cathode, then the second electrode could be layered up to the center of the electrolysis cell (between the two electrodes) as an anode.

In such a second electrode, the third, lipophilic layer may be constructed of the same material as the first, lipophilic layer, or of another material, that of the first, lipophilic layer. Likewise, the four te, hydrophilic layer may be constructed of the same material as the second, lipophilic layer, or from another Ma material. In particular, the fourth hydrophilic layer may comprise the same electrocatalyst as the second electrocatalyst, such as the second hydrophilic layer, or a different one, but is also preferably selected from the materials mentioned above for the first electrocatalyst. Any combinations are possible, as well as the presence of further layers in the second electrode, such as a second pantograph, which may correspond to the ers th pantograph or may be different from this, but from one of the customers for the first stream Materials can be. Also in terms of shape, the individual layers may be the same or different. Preferably, however, the third, lipophilic layer and / or the fourth, hydrophilic layer are porous. Preferably, the third lipophilic layer and the fourth hydrophilic layer are in contact with each other. Also, appropriate In such embodiments, membranes may be applied to the first electrode on the layers of the second electrode, for example a hydrophobic membrane on the third, lipophilic layer and / or a hydrophilic membrane or an ion exchange membrane on the fourth, hydrophilic layer. Again, the materials that can be used may correspond to those of the above analogous layers, the layers being the same or different. Also, at least one Stützkonstruk tion, for example, for all layers may be provided in the second electrode.

In addition, the second organic material may be the same as or different from the first organic material. However, since other reactions take place at the anode than at the cathode, the first organic material and the second organic material are different, for example in terms of the aggregate form and in terms of sen, whether or not they are in solution or mixture. Accordingly, the second non-polar solvent, as it is used in the process, the first non-polar solvent, if this is used, correspond or be different from ver.

In the embodiments having the second electrode comprising the fourth hydrophilic layer, it is usually in contact with the first polar electrolyte. However, it is also conceivable that the electrolytic cell between the first elec- tion and the second electrode at least one separator, such as a diaphragm and / or a membrane - which are not particularly limited, so that the space between the two electrodes divided into two subspaces is, wherein in the one subspace - for example, adjacent to the second hydrophilic layer of the first electrode - a first polar electrolyte can be introduced and another subspace - for example adjacent to the fourth layer of the second electrode or second electrode in general - a second polar electrolyte, which may correspond to the first polar electrolyte or may be different from the sem, however, the materials for this second polar electrolyte may be the same as those named for the first polar electrolyte. However, this is not preferred. According to certain embodiments, the second, hydrophilic layer of the first electrode contacts a first separator at least partially.

Alternatively or additionally, if necessary, further separators and, if appropriate, further polar electrolytes may be used with which a product removal from the first, polar

Electrolytes possible, for example, when in the electrochemical mixing reaction at the first and possibly the second electrode, a soluble in the first polar electrolyte organic Pro product is shown. Here then the organic product can be easily cleaned.

According to certain embodiments, the second hydrophilic layer of the first electrode and the fourth hydrophilic layer of the second electrode contact a first separator at least partially on opposite sides of the first separator. According to certain embodiments, the first polar electrolyte is at least partially contained in the first separator. According to certain embodiments, the first separator is swollen by the first polar electrolyte. As a result, good contact between the two electrodes can be made possible with a small volume of electrolyte. In particular, this is advantageous if the first polar electrolyte is not reacted, so it is not consumed, or can be tracked a fold. In addition to separators, the electrolysis cell may also comprise other constituents Be, which are usually used for Elektrolysezel sources, such as appropriate supply and Abführein directions for the first polar electrolyte, the first non-polar solution or mixture or the first organic mate rial as liquid or gas, and optionally for the second non-polar solution or mixture or the second organic material Ma as liquid or gas, heating and / or Kühleinrich lines, pumps, valves, housings, etc. However, the electrolytic cell comprises at least one power source.

In the method according to the invention, introducing the first organic solution or mixture, or the first organic material as liquid or gas, into the electrolysis cell such that the first organic solution or mixture or the first organic material contacts the first, lipophilic layer of the first electrode, the introduction of a first polar electrolyte into the electrolysis cell in such a way that the first polar electrolyte contacts the second, hydrophilic layer of the first electrode and the second electrode, and possibly introducing the second organic solution or mixture comprising a second organic material or the second organic material as a liquid or gas such that the second organic solution or mixture or the second organic material contacts the third, lipophilic layer of the second electrode, not particularly limited, and the introduction can be carried out simultaneously or at different times.

After introduction of the first organic solution or mixture, or the first organic material as a liquid or gas, as a nonpolar phase, and after introduction of the first polar electrolyte as a polar phase, the form Nonpolar phase and the polar phase of a first phase boundary, which is formed such that the first phase boundary in the electrochemical reaction at least teilwei se within the first electrode, preferably at an interface between the first, lipophilic layer and the two th, hydrophilic Layer, lies. By using the first hydrophilic layer and the first lipophilic layer, it is possible to ensure that the first phase boundary forms at least partially and preferably completely in the first electrode during the electrochemical conversion, so that the first organic material reaches the latter for the electrochemical reaction however, a suitable cell voltage can be set by the first polar electrolyte as well. The first phase boundary as a liquid-liquid phase boundary must therefore be at least partially in contact with the electrode surface. As a result, it is also possible to form a three-phase interface at which a

Electrocatalyst of the first electrode, for example, the first catalyst, simultaneously access to electrical con tact, ion contact, possibly protons from the first polar electrolyte and the first organic material as a substrate has. In order to achieve high current densities, the Gesamtflä surface of these three phase interfaces should be as large as possible. For this purpose, it is possible to place the liquid-liquid interface within a porous electrode.

In order for the liquid-liquid boundary to remain on or in the electrode, it is necessary for the electrode to have a

amphiphilic character has, as it is achieved by the lipophilic layer and the hydrophilic layer, wherein the Ge gene electrode towards lying side by the polar, example, aqueous, wettable phase, while the other side is wetted by the non-polar phase. The electrode thus has at least two layers. However, in contact with the phases to bring, the second, hydrophilic layer preferably also has a certain amount of lipophilic pores, for example, <30%, preferably <25%, more preferably <20%, based on the pores of the hydrophilic layer.

Corresponding considerations apply to the second electrode when it has the third lipophilic layer and the fourth hydrophilic layer and has a second phase boundary between the first polar electrolyte (or another, eg, second, polar electrolyte) and the second non-polar one Form solution or mixture or the second organic material as a liquid or gas.

The electrochemical conversion of the first organic Materi as and / or the first non-polar solvent or the first organic material as a liquid or gas at the first electrode, and optionally the electrochemical reaction of the second organic material and / or the second non-polar solvent, or the second Organic material as a liquid or gas, are not particularly limited and can be suitably adapted to a starting material and a desired product.

In the electrochemical reaction of the first organic material and / or the first non-polar solvent ent is at least a first organic product, which depending on the solubility and polarity on the first non-polar phase, ie first nonpolar solution or mixture or first organi cal material, or the first polar electrolyte as po lar phase from the first electrode can be dissipated. It can either be discharged from the electrolytic cell via the appropriate phase and then optionally separated / extracted and possibly purified outside, or in further phases in the electrolytic cell, for example by means of suitable separation. parators, and thus possibly separated from by-products.

It should be noted that in addition to the electrochemical im plementation at the first electrode - in which at least one ers tes organic product is formed - also an electrochemical reaction takes place at the second electrode, wherein at least a second inorganic product such as chlorine, oxygen, etc ., Or at least a second organi cal product, for example, with the second electrode to summarize the third, lipophilic layer and the fourth, hydrophilic layer can arise. Of course, in the inventions to the invention process then the first organic product with the second inorganic or organic product, preferably after a previous separation and purification, be further reacted so that not only an organic synthesis step can be carried out electrochemically with the inventive method, but also at the same time a wide res reactant can be obtained for a subsequent step, for example, waste heat from the electrochemical imple mentation can be used for this further implementation in the subsequent step.

As stated above, an extraction can also follow in the process according to the invention. In some cases, such as As the cathodic reduction of nitro compounds or the anodization of aldehydes, the hydrophilicity of the product is increased, resulting in a partial extraction in the electrolyte. In this case, after leaving the cell, in accordance with certain embodiments, the electrolyte will pass through an extraction vessel with pure organic solvent to recover the product. For these applications, the electrolyte gap can also be used with a non-limited number of separators, eg 2, 3, 4, 5, 6,

7, 8, 9, 10 or more separators, as stated above, be equipped to simplify the extraction.

Another aspect of the present invention is directed to an apparatus for electrochemically reacting a first organic material which is soluble in or miscible with a first nonpolar solvent

an electrolysis cell, wherein the electrolysis cell

a porous first electrode comprising at least a first, lipophilic layer and at least a second, hydrophilic layer, wherein the first, lipophilic

Layer and the second hydrophilic layer are preferably porous, and

a second electrode

includes;

at least one first feed device for the supply of a first solution or mixture of a first organic material which is soluble in or miscible with a first non-polar solvent, in or with a first non-polar solvent, or for the supply of a first organic material, which is soluble in, or miscible with, a first non-polar solvent which is designed to supply the first solution or mixture of the first organic material into or with the first non-polar solvent, or the first organic material, to the electrolytic cell in that the first organic solution or mixture or the first organic material contacts the first lipophilic layer of the first electrode; and at least one first discharge device for discharging the remaining first solution or mixture and optionally at least one first product of the electrochemical conversion of the first organic material and optionally the first non-polar solvent (depending on whether it is polar or not and can pass into the first polar electrolyte accordingly), or of the remaining first organic material and optionally at least one first product, or of the remaining first nonpolar solvent and optionally at least one first product, or at least one first product, which is formed, the remaining first solution or mixture and optionally at least the first product of the electrochemical reaction of the first organic material and optionally the first nonpolar solvent, or the remaining first non-polar solvent and optionally at least the first product, or at least the first product, to be removed from the electrolysis cell.

In addition, the device according to the invention may also comprise at least one second feed device for the first polar electrolyte, which is designed to supply the first polar electrolyte to the electrolysis cell such that the first polar electrolyte comprises the second, hydrophilic layer of the first electrode and the second electrode, optionally, the fourth, hydrophilic layer of the second electrode, contacted, and / or a second discharge device for the first polar electrolyte and optionally at least a first product of the electrochemical reaction of the first organic material and optionally the first non-polar solvent, which forms out is to dissipate the first polar electrolyte and possibly at least a first product of the electrochemical reaction of the first organic material and optionally the first nonpolar solvent from the electrolysis cell. These are also not particularly limited, as long as they are suitable for the corresponding materials, and may also be designed as pipes, pipes, etc. If the first polar However, electrolyte is not reacted or changed in the electrochemical reaction in the overall electrolytic cell and also not a product of the electrochemical reaction of the first organic material and optionally the first

Nonpolar solvent passes into these, it is also conceivable that the second feeder and / or the two te discharge means omitted, for example, when in an aqueous first polar electrolyte no water is consumed in the electrolysis. For reasons of thermal engineering, however, the first polar electrolyte is usually added and removed even in such cases, so that the corresponding supply and discharge devices are present.

If at least one first polar product (and / or second polar product with a corresponding configuration of the second electrode) is formed during the electrochemical conversion and this goes into the first (and / or second) polar electrolyte, an extraction (possibly via a separator or several separators) in further polar

Electrolytes take place within the first electrolysis cell, so that accordingly further supply and discharge devices can be provided for further polar electrolytes.

In particular, the inventive method can be carried out with the device according to the invention. Accordingly, the above remarks on the method according to the invention, in particular those which relate to constituents of the device such as an electrolytic cell and its components, also apply to the device according to the invention, and reference is thus made to this reference. In particular the special embodiments of the first and second electrodes correspond to those of the device according to the invention as discussed above for the method according to the invention. Furthermore, the electrolysis cell in the invention comprises Device according to the invention at least one power source, and may also include the components that were called for which he inventive method, such as separators, pumps, valves, heating and / or cooling equipment, etc.

According to certain embodiments, the first electrode and / or possibly the second electrode (in particular if it comprises the third, lipophilic layer and the fourth, hydrophilic layer) comprises a current collector which does not interact with the second, hydrophilic layer or optionally with the second electrode fourth, hydrophilic layer is in contact. This type of electrode is advantageous if the solubility of a substrate, ie the corresponding organic material, is too low in aqueous electrolytes to achieve suitable current densities or the separation of the product from the electrolytes is very expensive.

The first and / or second electrodes can also be formed as vapor diffusion electrodes / gas diffusion electrodes. In this electrolyte concept, the first and / or second organic material may be supported as a substrate by a non-polar phase flowing through or through the backside of the electrode. In principle, this phase can also be a substrate vapor, a vapor carrier gas mixture or even a clean gaseous substrate. In this last special case, the amphiphilic electrode would become a gas diffusion electrode. It is not excluded that the organic material undergoes a phase transition during the electrochemical process. A liquid substrate can also lead to a gaseous product. A gaseous substrate may also give a product with a higher boiling point which condenses after conversion. According to certain embodiments, the first lipophilic layer comprises hydrophobic, preferably conductive, first particles and / or at least one first hydrophobic binder.

According to certain embodiments, the second hydrophilic layer comprises a first electrocatalyst and optionally at least one second binder. According to certain embodiments, the second, hydrophilic layer comprises a first ion-conducting additive, in particular a cation or anion exchanger, and / or first hydrophilic additives, in particular metal oxides.

According to certain embodiments, the second, hydrophilic layer of the first electrode at least partially contacts a first separator. It has already been discovered that the electrodes may contain a fused membrane. This membrane can also be shared by both electrodes according to bestimm th embodiments. In this case, the membrane swollen with the first polar electrolyte, e.g. a water-swollen membrane, to the polar, e.g. aqueous phase, and a membrane-electrode assembly (MEA) can be formed. However, in particular in the case of non-water-releasing reactions, it may be necessary to saturate the organic phase with water. The membrane is not limited in its ionic conductivity. The functionalization of the membrane polymers can be adapted to the requirements of the specific reaction. Therefore, this membrane can be realized as a cation exchange, an anion exchange or a bipolar membrane in both directions.

The first feeding device and the first discharging device are not particularly limited, as far as they are suitable for the supply and discharge of the corresponding material, and For example, they may be formed as pipes, pipes, etc.

wherein the second, hydrophilic layer and the fourth, hydrophilic layer in the electrolysis cell are opposite, but preferably not contact, further comprising at least one further supply means for supplying ei ner second solution or mixture of a second organic material, which in a second non-polar solvent is soluble or miscible with it, in or with a second non-polar solvent, or for the supply of a second organic material which is soluble in or miscible with a second non-polar solvent adapted to effect the second solution or mixture the second organic material in or with the second nonpolar solvent, or the second organic material, to be supplied to the electrolytic cell such that the second organic solution or mixture or the second organic material contacts the third, lipophilic layer of the second electrode; and

at least one further discharge device for discharging the remaining second solution or, if appropriate, at least one second product of the electrochemical conversion of the second organic material and optionally the second nonpolar solvent, or the remaining second organic material and optionally at least one second product, or the remaining second nonpolar solvent and optionally at least one second product, or at least one second product, which is the remaining one second solution or mixture and optionally at least the second product of the electrochemical reaction of the second organi's material and optionally the second nonpolar Lösungsmit means, or the remaining second organic material and optionally at least the second product, or the remaining second non-polar solvent and optionally at least the second product, or at least the second product from the electrolysis cell dissipate.

In such embodiments, if at least a first polar (organic) product is formed on the first electrode and at least one second polar (organic) product is formed on the second electrode, then it can not be ruled out that both will transition to the first polar electrolyte. Preferably, however, a separator is provided between the two electrodes, so that the at least one first pola re product merges into the first polar electrolyte and the at least one second polar product in another (eg second) polar electrolyte, different from the first polar electrolyte can be or correspond to this. However, if the at least one first polar product and the at least one second polar product transfer to the first polar electrolyte, it is not excluded that the two be allowed to react thereafter.

In these embodiments, the second hydrophilic layer and the fourth hydrophilic layer are opposed in the electrolytic cell, but preferably do not contact each other, especially if they are both conductive. However, they may partially contact each other if they are not conductive as long as it can be ensured that the first electrode and the second electrode come into contact with the first polar electrolyte. However, this is not preferable. Also, the at least one further feeding device for the supply of a second solution or mixture of a second orgasmic African material which is soluble in a second non-polar solvent or is miscible with this, in or with a second non-polar solvent, or for the drive to a second organic material which is soluble in or miscible with a second nonpolar solvent, and

the at least one further discharge device for Abfüh ren of the remaining second solution or mixture and optionally at least a second product of the electrochemical imple mentation of the second organic material and optionally the two th nonpolar solvent, or the remaining second organic material and optionally at least one second product, or the remaining second non-polar solvent and optionally at least one second product, or at least one second product, are not particularly limited, as far as they are suitable for the supply and removal of the corresponding Mate rials, and can, for example as Tubes, pipes, etc. may be formed.

According to certain embodiments, the third, lipophilic layer comprises hydrophobic, preferably conductive, third particles, which may correspond to or be different from the first particles, and / or at least one second hydrophobic binder, which may correspond to or from the second hydrophobic binder can be different.

According to certain embodiments, the fourth, hydrophilic layer comprises a second electrocatalyst, which may correspond to the first electrocatalyst or may be different from it, and optionally at least one fourth binder. tel, which may be the same as or different from the second binder. According to certain embodiments, the fourth, hydrophilic layer comprises a second ion-conducting additive which may correspond to or differ from the first ion-conducting additive, in particular a cation or anion exchanger, and / or second hydrophilic additives, in particular metal oxides, which are the first Kgs may correspond or may be different from hydrophilic additives.

According to certain embodiments, the second hydrophilic layer of the first electrode and the fourth hydrophilic layer of the second electrode contact a first separator at least partially on opposite sides of the first separator. According to certain embodiments, a first polar electrolyte is at least partially contained in the first separator. According to certain embodiments, the first separator is swollen by the first polar electrolyte.

According to certain embodiments, the device according to the invention is an electrolysis system. According to certain embodiments, an electrolysis plant according to the invention comprises a multiplicity of electrolysis cells which can be constructed in accordance with the electrolytic cell exemplified.

According to certain embodiments, the device according to the invention further comprises at least one recycling device, for the first non-polar solvent and / or the first organic material, the first polar electrolyte, optionally further polar electrolytes and / or possibly the second nonpolar solvent and / or or the second organic material, if necessary, including appropriate separation devices and / or cleaning supply facilities for providing the same. According to certain embodiments, the device according to the invention further comprises an external device for the electrolyte treatment of at least the first polar electrolyte, optionally with a supply for lost electrolyte or components thereof.

With the method according to the invention and the device according to the invention, a large number of electrochemical reactions of organic compounds can be carried out, of which some are exemplified below.

Examples of cathodic transformations:

Many organic transformations can be carried out electrochemically. These may include various hydrogenation reactions of polar and non-polar multiple bonds. Reductive binding splits are also possible.

Examples of anodic transformations:

Also oxidations of alcohols or oxidative compounds are possible. The Kolbe coupling of adipic acid half ester to dialky sebacates has been extensively studied in the past, but could not be realized because of the high cell tensions imposed by the acetonitrile based solvent. Alkynes can also be coupled oxidatively.

The process according to the invention is also of interest for pharmaceutical syntheses since, by avoiding catalysts in solution or suspension in the synthesis, these too can be avoided in the product, for example in the case of heavy metal catalysts.

As can be seen from the above variations, different cell concepts are possible for the device according to the invention. some of which are described below by way of example.

A first exemplary embodiment of an electrolysis cell with an amphiphilic electrode is shown schematically in Fig. 1

In this case, a working electrode 1 comprises a first lipophilic layer 2, which is preferably hydrophobic and in contact with a non-polar phase 5, and a second, hydrophilic layer, which is in contact with a first polar electrolyte 6. The first polar electrolyte is also in contact with the counter electrode 4.

Further embodiments based on this embodiment are shown in Figures 2 to 4, wherein in this embodiment, a basic operation for these amphiphilic electrodes in combination with a water-consuming Ge gene electrode is shown, the H ₂ or O ₂ developed.

In FIG. 2, the non-polar phase is passed through the first cell space I, wherein a non-polar product P is formed from an organic material as reagent R, while the first polar electrolyte E is pumped through the second cell space II. The structure in Fig. 3 corresponds to a large extent to that of Fig. 2, wherein the second electrode 4 is located on the first electrode 1, wherein there is correspondingly an insulation between the two electrodes. In this case, the second electrode 4 is porous so that the first polar electrolyte E can contact the first electrode 1. In Fig. 4 is the

Cell space II divided into two cell spaces II, II ⁺ , whereby the second electrode 4 is washed around. To protect the first Elektode 1, the second electrode 4 is applied to a separator S. It makes more sense, however, to carry out both electrodes in the cell with means of amphiphilic electrodes, as shown by way of example in FIGS. 5 and 6. In this case, both electrodes for electrochemical conversions of non-polar reagents RI, R2 to nonpolar products PI, P2 can be used on the amphiphilic cells as the cathode K and anode A with added benefit, in Fig. 6, the two electrodes a common separator S, here exemplified as a common membrane with contained polar electrolyte. The maximum Faraday efficiency is then 200%. Since all electro-organic transformations are proton transfers, the transformations in this cell type can be divided into three categories. (In the following: RED: reduction, OX: oxidation, REDOX: redox reaction, R: organic radical, Et: ethyl)

Non-water-consuming or water-producing processes: In these processes, water is locally converted to OH or H ⁺ , but the water is regenerated in the bulk electrolyte. These systems (theoretically) do not require an electro lyt. eg aldehyde reduction + Kolbe coupling of adipic acid

RED: R-CHO + 2e + 2H ₂ O - R-CH ₂ -OH + 20H

OX: 2 EtO ₂ C- (CH ₂ ) ₄ -CO ₂ H-EtO ₂ C- (CH ₂ ) ₈ -CO ₂ Et + 2e + 2H ⁺ + 2CO ₂ Electrolyte: - 2H ₂ 0 + 20H + 2H ⁺ = 0

REDOX: R-COH + 2EtO ₂ C- (CH ₂ ) ₄ -CO ₂ H -

R-CH ₂ -OH + 2C0 ₂ + EtO ₂ C- (CH ₂ ) ₈ -CO ₂ Et

Water-consuming processes: In these processes, water is consumed overall. The electrolyte must therefore be continuously supplemented with water,

z. For example: aldehyde reduction + alcohol oxidation

RED: R-CHO + 2e + 2H ₂ O - R-CH ₂ -OH + 20H | x2 OX: R-CH ₂ -OH + H ₂ O-R-COOH + 4 e + 4 H ⁺

Electrolyte: - 2H ₂ 0 + 20H -H ₂ 0 + 2H ⁺ = - H ₂ O

REDOX: 2 R-COH + R-CH ₂ -OH + H ₂ O-2 R-CH ₂ -OH + R-COOH

Water-producing processes: In these processes, water is released overall. The electrolyte must therefore be concentrated continuously Lich.

z. For example: nitro reduction + oxidative alkyne coupling

RED: R-N0 ₂ + 6e + 4H ₂ 0 -R-NH ₂ + 60H

OX: 2R-CCH - R-CC-CC-R + 2e + 2H ⁺ | x3

Electrolyte: - 4H ₂ 0 + 60H + 6H ⁺ = + 2H ₂ 0

REDOX: R-N0 ₂ + 6 R-CCH-R-NH ₂ + 3 R-CC-CC-R + 2 H ₂ O

Further possible applications of the method according to the invention as well as the device according to the invention can be found for example in Fritz Beck, reports the Bunsen Society 1973,77 (10/11), 810-817; F. Beck, H. Guthke Chemical-Ing. -

Technology. 1969, 41 (17), 943-950; DE1643693A1; DE2023080A1;

DE2336288A1; DE2345461A1; and DE3615472A1.

In this case, the present invention is characterized in the use of special electrodes for carrying out electro-organic redox processes at a phase boundary.

The above embodiments, embodiments and Weitererbil applications can, if appropriate, combine with each other. Further possible refinements, developments and implementations of the invention also include combinations of features of the invention which have not been explicitly mentioned above or described below with regard to the exemplary embodiments. In particular, the person skilled in the art will also add individual aspects as improvements or additions to the respective basic form of the present invention. The invention will be further explained in detail with reference to various examples thereof. However, the invention is not limited to these examples.

Examples

example 1

An exemplary cell construction was realized according to FIG.

Here, the electro-reduction of nitrobenzene to aniline was demonstrated. The first polar electrolyte was realized by an aqueous 0.5M K ₂ SO ₄ solution. The counter electrode, a TiC sheet coated with IrCg, as the second electrode consumed water in a 2.5M KOH and was separated by a CEM, Nafion Nil, to avoid reoxidation of the partially water-soluble product aniline. The nonpolar organic phase was a 5M solution of nitrobenzene in

Diethyl ether (50-fold concentration compared to the maximum solubility in pure water). The phases were pumped up at the sides of the working electrode as a first electrode. This consisted of a carbon GDL (Freudenberg H23 C2) as a hydrophobic layer (in contact with the non-polar phase) and a bound to anion exchange resin dendritic copper catalyst as a hydrophilic layer (in contact with the first polar electrolyte). The on

An dendritic copper catalyst bound to anion exchange resin has been described in: "Selective Electroreduction of C02 toward Ethylene on Nano-Dendritic Copper Catalysts at High Current Density"; Christian Reller, * Ralf Krause, Elena Volkova, Bernhard Schmid, Sebastian Neubauer, Andreas Rucki, Manfred Schuster , and Günter Schmid, Adv. Energy Mater., 2017, 1602114 FIG. 7 shows the working electrode potential E _{WE in} relation to a silver-silver chloride electrode in nitrobenzene bulk electrolysis.

The supply of organic phase was switched on 3 min after the current. A spontaneous increase in working electrode potential is observed, indicating that the electrode has switched from hydrogen production to nitro reduction. The decrease in gas evolution at the work electrode was also observed.

After 38 minutes, the organic phase was stopped, resulting in irreversible impregnation of the entire electrode in the aqueous phase. After switching on, the supply could not be continued, which shows that the substrate is actually supplied directly from the organic phase and not by extraction of the substrate into the aqueous phase.

1 H NMR analysis of the aqueous and organic phases showed that the only product of this transformation was aniline. Fig. 8 shows the NMR spectrum of the organic phase after electrolysis. No aniline products are observed.

Claims

claims

A process for electrochemically reacting a first organic material which is soluble in or miscible with a first nonpolar solvent

Introducing the first organic material into the first non-polar solvent to produce a first organic solution or mixture;

Providing an electrolytic cell comprising

a second electrode;

Providing an electrolytic cell comprising

a second electrode; Introducing the first organic material as a liquid or gas in the electrolytic cell such that the first orga African material, the first, lipophilic layer of the first

Electrode contacted;

the first nonpolar solvent and the first polar electrolyte or

the first organic material as a liquid or gas and the first polar electrolyte

Layer, lies.

2. The method of claim 1, wherein the first polar Elekt rolyt is liquid and in particular contains water and optionally at least one salt.

3. The method of claim 1 or 2, wherein the first electrode comprises a first current collector which is not in contact with the second hydrophilic layer.

4. The method of claim 1, wherein the first lipophilic layer has substantially no catalytic activity for the first polar electrolyte, and / or wherein the first lipophilic layer comprises hydrophobic, preferably preferably conductive, first particles and / or at least one first hydrophobic binder.

5. The method according to any one of claims 1 to 4, wherein the second, hydrophilic layer comprises a first electrocatalyst and optionally at least a second binder, and / or wherein the second, hydrophilic layer a first ionenlei border additive, in particular a cation or

Anion exchanger, and / or first hydrophilic additives, in particular metal oxides, comprises.

6. The method according to any one of claims 1 to 5, wherein the second, hydrophilic layer of the first electrode at least partially contacts a first separator.

7. The method according to any one of claims 1 to 6, wherein the second electrode comprises at least a third, lipophilic layer and at least a fourth, hydrophilic layer, wherein the third, lipophilic layer and the fourth, the hydrophilic layer are preferably porous,

further comprising an introduction

a second organic material as a liquid or gas, or

into the electrolysis cell such that the first organic material or the second organic solution or mixture contacts the third, lipophilic layer of the second electrode, wherein the second organic material and / or the second non-polar solvent, or

the second organic material

be implemented electrochemically at the second electrode.

8. The method of claim 7, wherein the second, hydrophilic layer of the first electrode and the fourth, hydrophilic

Layer of the second electrode contact a first separator at least partially on opposite sides of the first Sepa rators, preferably wherein the first polar Elekt electrolyte is at least partially contained in the first separator, more preferably wherein the first separator is swollen by the first polar electrolyte.

9. An apparatus for the electrochemical conversion of a first organic material which is soluble in a first non-polar solvent or is miscible with it, comprising send

an electrolysis cell, wherein the electrolysis cell

Layer and the second hydrophilic layer are preferably porous, and

a second electrode

includes;

at least one first feed device for the supply of a first solution or mixture of a first organic material which is soluble in or miscible with a first non-polar solvent, in or with a first non-polar solvent, or for the supply of a first organic material, which is soluble or miscible with a first non-polar solvent which is to be formed therefrom, the first solution or mixture of the first organic material in or with the first nonpolar solvent, or the first organic material, to the electrolytic cell supply such that the first organic solution or mixture or the first organic material contacts the first, lipophilic layer of the first electrode; and at least one first discharge device for discharging the remaining first solution or mixture and optionally at least one first product of the electrochemical conversion of the first organic material and optionally the first nonpolar solvent, or the remaining first organic material and optionally at least one first product , or the remaining first nonpolar solvent and optionally at least one first product, or at least one first product, which is formed, the remaining first solution or mixture and optionally at least the first product of the electrochemical reaction of the first organic mate rials and, if necessary of the first non-polar solvent, or the remaining first organic material and optionally at least the first product, or the remaining first non-polar solvent and optionally at least the first product, or at least the first product from the electrolytic cell.

10. The device of claim 9, wherein the first electrode comprises a first current collector which is not in contact with the second hydrophilic layer.

11. The device according to claim 9 or 10, wherein the first, lipophilic layer comprises hydrophobic, preferably conductive, first particles and / or at least one first hydrophobic Bindemit tel.

12. Device according to one of claims 9 to 11, wherein the second, hydrophilic layer comprises a first electrocatalyst and optionally at least a second binder, and / or wherein the second, hydrophilic layer a first ionenlei border additive, in particular a cation or

13. Device according to one of claims 9 to 12, wherein the second, hydrophilic layer of the first electrode at least partially contacts a first separator.

14. Device according to one of claims 9 to 13, wherein the second electrode comprises at least a third, lipophilic layer and at least a fourth, hydrophilic layer, wherein the third, lipophilic layer and the fourth, the hydrophilic layer are preferably porous,

wherein the second, hydrophilic layer and the fourth, hydrophilic layer in the electrolysis cell are opposite, but preferably not contact, further comprising at least one further supply means for supplying ei ner second solution or mixture of a second organic material, which in a second non-polar solvent is soluble or miscible with it, in or with a second non-polar solvent, or for the supply of a second organic material which is soluble in or miscible with a second non-polar solvent adapted to effect the second solution or mixture the second organic material in or with the second nonpolar solvent, or the second organic material, to be supplied to the electrolytic cell such that the second organic solution or mixture or the second organic material contacts the third, lipophilic layer of the second electrode; and at least one further removal device for discharging the remaining second solution or mixture and optionally at least one second product of the electrochemical imple tion of the second organic material and optionally the second nonpolar solvent, or the remaining second or ganic material and optionally at least a second Pro dukts, or the remaining second nonpolar Lösungsmit means and optionally at least one second product, or at least a second product which is adapted to the remaining second solution or mixture and optionally at least the second product of the electrochemical reaction of the two th organic Material and optionally the second non-polar Lö sungsmittels, or the remaining second organic materi al and optionally at least the second product, or the remaining second non-polar solvent remaining solvent and possibly at least the second product, or at least the second product from the electrolysis cell dissipate.

15. The apparatus of claim 14, wherein the second hydrophilic layer of the first electrode and the fourth hydrophilic layer of the second electrode contact a first separator at least partially on opposite sides of the first separator, preferably wherein a first polar electrolyte is at least partially in first separator is included, more preferably wherein the first separator is swelled by the first polar electrolyte.