DE102018201287A1 - Porous electrode for the electrochemical conversion of organic compounds into two immiscible phases in an electrochemical flux reactor - Google Patents

Abstract

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

Description

The present invention relates to a method for the electrochemical conversion 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.

For one thing, organic solvents and lipophilic organic salts are far more expensive than water and inorganic salts.

Second, organic electrolytes typically have much poorer 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 involve protons that must be generated or consumed by the counterreactions. In the case of water, this is typically either the reduction or oxidation of water to hydrogen or oxygen. In organic electrolytes, 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, which in turn massively increase the process costs. At high current density, the proton transport through the electrolyte may even be insufficient for the reaction rate, which may result in protonation or deprotonation and subsequent decomposition of the electrolyte at the electrodes.

Therefore, the use of aqueous electrolytes for electrochemical synthesis seems very desirable. However, the often poor solubility of the reagent molecules in water or even electrolytes with high ionic strength dramatically limit the substrate supply of the electrodes and thus the current densities.

There is currently no general solution to this problem in the application. Suggestions from Beck et al. concern very thin capillary cells, such as in Fritz Beck, reports Bunsen Society 1973, 77 (10/11), pp. 810-817 and F. Beck, H. Guthke, Chemical Engineering Techn. 1969, 41 (17), p. 943-950 discussed.

There is therefore a need for an effective process for the electrochemical conversion of organic compounds, in particular 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.

• - eine poröse erste Elektrode umfassend mindestens eine erste, lipophile Schicht und mindestens eine zweite, hydrophile Schicht, wobei die erste, lipophile Schicht und die zweite, hydrophile Schicht bevorzugt porös sind, und
• - eine zweite Elektrode;

Einbringen der ersten organischen Lösung oder Mischung in die Elektrolysezelle derart, dass die erste organische Lösung oder Mischung die erste, lipophile Schicht der ersten Elektrode kontaktiert;
Einbringen eines ersten polaren Elektrolyten in die Elektrolysezelle derart, dass der erste polare Elektrolyt die zweite, hydrophile Schicht der ersten Elektrode und die zweite Elektrode kontaktiert; und
Elektrochemische Umsetzung des ersten organischen Materials und/oder des ersten unpolaren Lösungsmittels an der ersten Elektrode; oder
Bereitstellen einer Elektrolysezelle umfassend

• - eine poröse erste Elektrode umfassend mindestens eine erste, lipophile Schicht und mindestens eine zweite, hydrophile Schicht, wobei die erste, lipophile Schicht und die zweite, hydrophile Schicht bevorzugt porös sind, und
• - eine zweite Elektrode;

Einbringen des ersten organischen Materials als Flüssigkeit oder Gas in die Elektrolysezelle derart, dass das erste organische Material die erste, lipophile Schicht der ersten Elektrode kontaktiert;
Einbringen eines ersten polaren Elektrolyten in die Elektrolysezelle derart, dass der erste polare Elektrolyt die zweite, hydrophile Schicht der ersten Elektrode und die zweite Elektrode kontaktiert; und
Elektrochemische Umsetzung des ersten organischen Materials an der ersten Elektrode;
wobei

• - das erste unpolare Lösungsmittel und der erste polare Elektrolyt oder
• - das erste organische Material als Flüssigkeit oder Gas und der erste polare Elektrolyt

zueinander eine erste Phasengrenze ausbilden, welche derart ausgebildet wird, dass die erste Phasengrenze bei der elektrochemischen Umsetzung zumindest teilweise innerhalb der ersten Elektrode, bevorzugt an einer Grenzfläche zwischen der ersten, lipophilen Schicht und der zweiten, hydrophilen Schicht, liegt.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 organic 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 electrolytic 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 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 material as a liquid or gas into the electrolytic cell such that the first organic material contacts the first lipophilic layer of the first electrode;
Introducing a first polar electrolyte into the electrolytic cell such that the first polar electrolyte contacts the second hydrophilic layer of the first electrode and the second electrode; and
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 first electrode, preferably at an interface between the first, lipophilic layer and the second, hydrophilic layer.

• - eine poröse erste Elektrode umfassend mindestens eine erste, lipophile Schicht und mindestens eine zweite, hydrophile Schicht, wobei die erste, lipophile Schicht und die zweite, hydrophile Schicht bevorzugt porös sind, und
• - eine zweite Elektrode umfasst;

mindestens eine erste Zuführeinrichtung für die Zufuhr einer ersten Lösung oder Mischung eines ersten organischen Materials, welches in einem ersten unpolaren Lösungsmittel löslich ist oder mit diesem mischbar ist, in oder mit einem ersten unpolaren Lösungsmittel, oder für die Zufuhr eines ersten organischen Materials, welches in einem ersten unpolaren Lösungsmittel löslich ist oder mit diesem mischbar ist, die dazu ausgebildet ist, die erste Lösung oder Mischung des ersten organischen Materials in oder mit dem ersten unpolaren Lösungsmittel, oder das erste organische Material, zur Elektrolysezelle derart zuzuführen, dass die erste organische Lösung oder Mischung oder das erste organische Material die erste, lipophile Schicht der ersten Elektrode kontaktiert; und mindestens eine erste Abführeinrichtung für das Abführen der verbleibenden ersten Lösung oder Mischung und ggf. mindestens eines ersten Produkts der elektrochemischen Umsetzung des ersten organischen Materials und ggf. des ersten unpolaren Lösungsmittels, oder des verbleibenden ersten organischen Materials und ggf. mindestens eines ersten Produkts, oder des verbleibenden ersten unpolaren Lösungsmittels und ggf. mindestens eines ersten Produkts, oder mindestens eines ersten Produkts, die dazu ausgebildet ist, die verbleibende erste Lösung oder Mischung und ggf. mindestens das erste Produkt der elektrochemischen Umsetzung des ersten organischen Materials und ggf. des ersten unpolaren Lösungsmittels, oder das verbleibende erste organische Material und ggf. mindestens das erste Produkt, oder das verbleibende erste unpolare Lösungsmittel und ggf. mindestens das erste Produkt, oder mindestens das erste Produkt aus der Elektrolysezelle abzuführen.In another aspect, the invention relates to a device for electrochemically reacting a first organic material which is soluble in or miscible with a first non-polar solvent comprising an electrolytic cell, the electrolytic cell

• 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 comprises;

at least one first supply means for supplying 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 in soluble or miscible with a first non-polar solvent adapted to supply the first solution or mixture of the first organic material in or with the first non-polar solvent, or the first organic material, to the electrolytic cell 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 material and optionally the first nonpolar solvent, or the remaining first organic material and optionally at least the first product, or the remaining first nonpolar solvent and optionally at least the first product, or at least to remove the first product from the electrolysis cell.

Further aspects of the present invention can be found in the dependent claims and the detailed description.

list of figures

• 1 bis 6 zeigen schematisch beispielhafte Ausführungsformen einer erfindungsgemäßen Vorrichtung, mit denen das erfindungsgemäße Verfahren durchgeführt werden kann.
• 7 und 8 stellen Ergebnisse dar, welche in einem Beispiel des erfindungsgemäßen Verfahrens erzielt wurden.

The accompanying drawings are intended to illustrate embodiments of the present invention and to provide a 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 stated advantages will become apparent with reference to the drawings. The elements of the drawings are not necessarily to scale. Identical, functionally identical and identically acting elements, features and components are in the figures of the drawings, unless otherwise stated, each provided with the same reference numerals.

• 1 to 6 schematically show exemplary embodiments of a device according to the invention, with which the inventive method can be performed.
• 7 and 8th represent results obtained in an example of the method according to the invention.

Detailed description of the invention

definitions

Unless defined otherwise, 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 relate to wt.%, Unless otherwise specified or apparent from the context. In the invention Gas diffusion electrode complement the wt.% - Shares to 100 wt.%.

In the context of the present invention, hydrophobic is understood as meaning 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, hydrophilic is understood as the ability to interact with water and other polar substances.

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 those which do not mix with and / or dissolve in a first polar solvent of the first polar electrolyte and / or repel it, and which are hydrophobic in particular, ie 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 catalyses an electrochemical reaction between the liquid and the gaseous phase.

The design may be of a different nature, for example, as a porous "bulk catalyst" with optional adjuvants to adjust the hydrophobicity, then, for example, a membrane-GDE composite, e.g. AEM-GDE composite, can be produced; as a conductive porous support to which a catalyst can be applied in a thin layer, in which case again a membrane-GDE composite, e.g. AEM-GDE composite, can be produced; or as a composite porous catalyst, optionally with additive directly on a membrane, e.g. AEM, can be applied and then in combination 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. If a galvanic current flows, a stream of the particles with a positive zeta potential also flows to the cathode, irrespective of whether the species participates in the reaction 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 designed to separate electrodes and / or electrolytes or the reaction spaces or half-cells in an electrolysis cell from each other. It is electrically insulating for the electrodes of an electrolytic cell itself and, in particular, according to certain embodiments, at least partially prevent, preferably substantially prevent, the mixing of two electrolytes and / or possibly product gases and / or reaction gases of an electrochemical reaction in half cells separated by the separator. In particular, a separator can prevent the mixing of product gases and / or reaction gases of half-cells separated thereby. However, a separator allows sufficient material and, above all, charge carrier exchange with an electrolyte medium to allow ionic 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 isolate electrodes from each other but has no intrinsic ion conductivity or transport selectivity. In particular, a diaphragm according to certain embodiments may also prevent the mixing of reaction gases in electrolyte streams. It is a sheet-like component, for example a paper-like or porous composite material. The ionic conductivity is achieved in a diaphragm via the absorbency of the diaphragm to 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 to substantially prevent the mixing of two electrolytes and gas bubbles contained therein, in particular to prevent the mixing of at least gas bubbles contained therein. However, the membrane may have an active ion transport function through appropriate chemical groups. If this ion transport is ion selective for One or more ions, for example cations and / or protons or anions, are also called an ion-selective membrane. An ion-selective membrane is accordingly an electrically insulating polymer film for the electrodes of the electrolysis cell, which is designed to electrically insulate electrodes against each other and in particular to substantially prevent the mixing of two electrolytes and gas bubbles contained therein, in particular to prevent the mixing of at least gas bubbles contained therein. The polymer carries functional groups charged with mobile counterions in such an ion-selective membrane and therefore represents a macromolecular salt, an acid and / or a base. In a pure solvent such as water swollen, these membranes have intrinsic ionic conductivity. In electrolyte solutions you usually have 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 ion transport in the membrane.

• - eine poröse erste Elektrode umfassend mindestens eine erste, lipophile Schicht und mindestens eine zweite, hydrophile Schicht, wobei die erste, lipophile Schicht und die zweite, hydrophile Schicht bevorzugt porös sind, und
• - eine zweite Elektrode;

Einbringen der ersten organischen Lösung oder Mischung in die Elektrolysezelle derart, dass die erste organische Lösung oder Mischung die erste, lipophile Schicht der ersten Elektrode kontaktiert;
Einbringen eines ersten polaren Elektrolyten in die Elektrolysezelle derart, dass der erste polare Elektrolyt die zweite, hydrophile Schicht der ersten Elektrode und die zweite Elektrode kontaktiert; und
Elektrochemische Umsetzung des ersten organischen Materials und/oder des ersten unpolaren Lösungsmittels an der ersten Elektrode; oderAccording to a first aspect, the present invention relates to a process for the electrochemical conversion of a first organic material which is soluble in or miscible with a first nonpolar solvent
Introducing the first organic material into the first nonpolar solvent to produce a first organic 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 electrolytic 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

• - eine poröse erste Elektrode umfassend mindestens eine erste, lipophile Schicht und mindestens eine zweite, hydrophile Schicht, wobei die erste, lipophile Schicht und die zweite, hydrophile Schicht bevorzugt porös sind, und
• - eine zweite Elektrode;

Einbringen des ersten organischen Materials als Flüssigkeit oder Gas in die Elektrolysezelle derart, dass das erste organische Material die erste, lipophile Schicht der ersten Elektrode kontaktiert;
Einbringen eines ersten polaren Elektrolyten in die Elektrolysezelle derart, dass der erste polare Elektrolyt die zweite, hydrophile Schicht der ersten Elektrode und die zweite Elektrode kontaktiert; und
Elektrochemische Umsetzung des ersten organischen Materials an der ersten Elektrode;
wobei

• - das erste unpolare Lösungsmittel und der erste polare Elektrolyt oder
• - das erste organische Material als Flüssigkeit oder Gas und der erste polare Elektrolyt

zueinander eine erste Phasengrenze ausbilden, welche derart ausgebildet wird, dass die erste Phasengrenze bei der elektrochemischen Umsetzung zumindest teilweise innerhalb der ersten Elektrode, bevorzugt an einer Grenzfläche zwischen der ersten, lipophilen Schicht und der zweiten, hydrophilen Schicht, liegt.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 material as a liquid or gas into the electrolytic cell such that the first organic material contacts the first lipophilic layer of the first electrode;
Introducing a first polar electrolyte into the electrolytic cell such that the first polar electrolyte contacts the second hydrophilic layer of the first electrode and the second electrode; and
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 first electrode, preferably at an interface between the first, lipophilic layer and the second, hydrophilic layer.

In the method of the present invention, the first organic material is not particularly limited so long as it is soluble in or miscible with a first nonpolar solvent. Here, as in the second embodiment of the process according to the invention, not even the first non-polar solvent must be used in the process 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 nonpolar 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 or dissolved with the first organic material and the first polar electrolyte. In this regard, it should be noted that in this first embodiment of the method according to the invention, the first organic material can be present as a solid, liquid or gas, which can then be dissolved in the first non-polar solvent or 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, this can better get to the first electrode and preferably can penetrate into this, in particular for the case that the first electrode is formed as a gas diffusion electrode, can more easily get to the 3-phase interface in the first electrode. In addition, by mixing with the first nonpolar solvent or dissolving in the first nonpolar solvent, the concentration of the first organic material can be more easily adjusted by the dilution, whereby the reaction at the electrode can be better controlled and in particular an overreduction can be reduced or avoided.

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

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, wherein the substituents are not particularly limited, as long as the first organic material is soluble in or miscible with a first non-polar solvent. For example, polar substituents can also be used if the first organic material itself is still soluble in or miscible with a first non-polar 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 part. For example, the first organic material for reduction may be selected from unsaturated hydrocarbons, aldehydes, ketones, nitro compounds, nitroso compounds, nitriles, etc .; and be selected for oxidation from alcohols, unsaturated hydrocarbons, amines, mercaptans, etc.

In particular, according to certain embodiments, the first organic material is not miscible with water and / or is 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 compound such as optionally substituted alkanes such as pentane, hexane, heptane, octane, etc., partially or fully 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 in water or in water as the solvent in the first polar electrolyte, in particular therefore is hydrophobic.

The first non-polar solvent need not be electrically conductive, but it is not excluded that conductive nonpolar solvents such as ionic liquids (IL) are used, provided they are stable and immiscible with the first polar electrolyte, especially an aqueous phase. In particular, since hydrophobic organic salt melts such as 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 solvent. The hydrophobic ionic liquids are not particularly limited.

A first nonpolar solvent is used, for example, in the embodiments set forth above for the first organic compound. In addition, a non-polar solvent may be required if in the electrochemical reaction at the porous first electrode at the reaction temperature of the electrochemical Conversion solid, first organic product is formed that does not dissolve in the first polar electrolyte and should be correspondingly removed again with the first polar solvent from the first electrode.

The term "miscible with a first non-polar solvent" means that when mixed with the nonpolar solvent, no two phases are formed, i. 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. However, a homogeneous solution is preferably produced when introducing the first organic material into the first non-polar 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 comprises at least one first polar solvent, such as 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 SO 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 electrolytic 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 metals and / or alkaline earth metals, for example, lithium, sodium, potassium, magnesium, calcium, etc., such as halides, sulfates, etc. In addition, the first polar electrolyte may still contain substances commonly contained in electrolytes, 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 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 ethylmethylimidazolium hydrogensulfate and / or triethanolmethylammonium methylsulfate can also be used here, provided that they are polar. In particular, such further, preferably protic, solvents can be used in reactions in the electrolysis cell which neither consume nor produce water - for example with respect to the second electrode, as long as the reaction takes place within its 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 those indicated above. According to certain embodiments, the first polar electrolyte - hereinafter also referred to optionally as the first phase - is 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 discharge device the electrolysis cell can be removed.

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 comprising 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 is not particularly limited. Apart from the two electrodes, wherein the second electrode is not particularly limited, the electrolytic cell is also not particularly limited in its material and configuration. Exemplary embodiments of the electrolysis cell will be described below.

The first electrode is porous, ie has pores, and comprises at least a first, lipophilic layer and at least one second, hydrophilic layer. But it is not excluded that the first electrode also comprises regions which are not designed to be porous, such as a grid for electrical contacting, but here, if appropriate, a layer can be pressed into the grid, in order to form a porous structure again. 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 ^- using water in the polar electrolyte, can be reduced or prevented.

The pore size is not particularly limited, but according to certain embodiments is in the range of 0.1 to 500 μm, for example in the range of 0.2 to 100 μm, e.g. 0.5 to 10 μm. The pore size can be suitably determined, for example, by means of 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 adjoin one another. In accordance with certain embodiments, at least one first electrocatalyst or catalyst for the electrochemical conversion of the first organic material is also found in this area, which is not particularly limited. The first electrocatalyst may, for example, metals and / or compounds thereof, such as, for example, 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, and suitably adapted to a desired electrochemical reaction. 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 as a whole can also consist only of materials which comprise pores, ie in accordance with certain embodiments only comprises porous layers. With porous layers in particular a good separation of the two phases in the process, ie the non-polar phase of the nonpolar solution or mixture or the nonpolar solvent, and the polar phase of the polar electrolyte is possible. This also makes it possible 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 non-polar solution or mixture, or the first organic solvent as liquid or gas, in bulk, and / or on the hydrophilic layer on the side which is in contact with the first polar electrolyte in bulk.

Within the present concept, ie in relation to the present method as well as to the present device, the first electrode forms a "three-phase half cell" within the electrolysis cell. Thus, 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, one of which is non-polar and contains the substrate, and the other a polar current carrying the ionic current Electrolyte is that may possibly serve as a consumable. The electrolyte phase is in this case the one which is directed towards the counter electrode.

The porous first electrode has an amphiphilic character and comprises at least two layers, one of which is more hydrophilic and the other more lipophilic. Both layers are preferably electrically conductive and porous. Since electrodes 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. In this way, the transport of the first organic material, optionally dissolved in the first non-polar solvent or mixed with it, can be controlled so that, if appropriate, there is no overreaction. 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, be lipophilic layer electrochemically inactive as a catalyst, especially when it is introduced into the first polar electrolyte, for example an aqueous electrolyte. In particular, this ensures 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, knitted, spongy, etc. constructed. According to certain embodiments, the first lipophilic layer is realized by using particles which are in particular 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 bonded. The production of the first, lipophilic layer can take place simultaneously with the production of the second hydrophilic layer and optionally further layers, for example by co-rolling, coextrusion, etc., or separately therefrom, wherein the layers can then be suitably connected subsequently ,

According to certain embodiments, the first lipophilic layer has substantially no catalytic activity for the first polar electrolyte, thus having a high overpotential for the competition reaction with the first polar electrolyte, for example a high overpotential for hydrogen evolution or oxygen evolution, as 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 also be formed as a gas diffusion electrode so that the first lipophilic layer may be formed accordingly.

Also, the second hydrophilic layer is not particularly limited and is wettable particularly 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, porous and / or electrically conductive.

In principle, the second, hydrophilic layer can also be realized with bound particles, optionally with at least one binder. In contrast, however, these particles are at least partially electrochemically active catalyst particles. This layer preferably consists to a large extent of the first electrocatalyst. But it is also an embedding of the first electrocatalyst in an inert, conductive matrix possible. As a binder may also be e.g. PTFE or PTFCE are used. However, to further increase the hydrophilic character of this layer, these polymers may also be partially filled by hydrophilic binder polymers such as polyarylsulfones, e.g. PPSU (polyphenylene sulfone), to be replaced.

Also hydrophilic additives, eg. B. metal oxides such. B. Al ₂ O ₃ , TiO ₂ , 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 hydrophilic layer may also include an inherently ion-conducting additive such as a cation or anion exchanger. In order to achieve an inherent ionic conductivity, ion conductivity additives such as ion exchange resins or other solid electrolytes may be incorporated 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 similar can 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 can be a first pantograph For example, be realized as eg incomplete metal coating of the first, lipophilic layer. Preferably, a metal braid is used because it can also provide additional mechanical support. For example, the first current collector may lie on or be embedded in the first lipophilic layer, 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. 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 to protect the layer. The hydrophilic membrane may optionally be soaked and passed through the electrolyte. The main function of this layer is to protect the electrode from erosion. This layer may also form an additional flow barrier to avoid migration of the liquid-liquid boundary. Such a membrane on the second hydrophilic layer is porous according to certain embodiments.

Also or alternatively, for example, a protective layer may be used as a "backing layer" on the first, lipophilic, e.g. hydrophobic layer, for example in the form of a hydrophobic membrane for the first lipophilic layer, e.g. for better wetting with the non-polar phases, e.g. based on polyamide, etc., to prevent erosion and / or to avoid flow through the electrode. However, since this side is on the opposite side of the counter electrode, it is preferably used for electrical contacting, which accordingly makes such a hydrophobic membrane less practicable. In such a case, then preferably the layer should not be continuous, and for example, wires of the pantograph, if any, 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 overall charge transport between the first electrode and the first polar electrolyte. Thus, e.g. Anion-exchange membranes can be used to limit the charge transport in cathodes to anions that leave the first electrode in the polar electrolyte and protons that penetrate through the Grotthuß mechansim. Accordingly, for example, cation exchange membranes can be used on the anode. 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 realized, for example, as anion exchange membrane (AEM), cation exchange membrane (CEM), or bipolar membrane in both directions.

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, are incorporated.

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

Besides, the electrolytic cell includes a second electrode, which is not particularly limited. It may be similar or different in structure to that of the first electrode, depending on the desired half-cell reaction. Thus, the second electrode as a full electrode or solid electrode, as a gas diffusion electrode, as a porous bound catalyst structure, as a particulate catalyst on a support, as a coating of a particulate catalyst on a membrane, as a porous conductive support in which a catalyst is impregnated, and / or be formed as a non-closed sheet. For example, in the case of an aqueous first polar electrolyte, water electrolysis to H ₂ or O ₂ can also take place at the second electrode.

The second electrode can also be carried out as a direct catalyst coating on a membrane or in direct contact with a membrane, especially if it is an open-planar construct such. B. network is. 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 at the second electrode, preferably a reaction of the first polar electrolyte or a component thereof, for example water, takes place.

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

• - eines zweiten organischen Materials als Flüssigkeit oder Gas, oder
• - einer zweiten organischen Lösung oder Mischung umfassend ein zweites organisches Material, welches in einem zweiten unpolaren Lösungsmittel löslich ist oder mit diesem mischbar ist, und ein zweites unpolares Lösungsmittel,

in die Elektrolysezelle derart, dass das erste organische Material oder die zweite organische Lösung oder Mischung die dritte, lipophile Schicht der zweiten Elektrode kontaktiert, wobei

• - das zweite organische Material und/oder das zweite unpolare Lösungsmittel, oder
• - das zweite organische Material

an der zweiten Elektrode elektrochemisch umgesetzt werden. Hierbei können beispielsweise zwei organische Substrate im Sinne einer Tandem-Elektrolyse gleichzeitig umgesetzt werden.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. If, for example, the first electrode is the cathode, then the second electrode in the layer structure could be mirrored as an anode towards the center of the electrolysis cell (between the two electrodes).

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 fourth, hydrophilic layer may be constructed of the same material as the second, lipophilic layer, or of another 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, but also preferably selected from the materials mentioned above for the first electrocatalyst. Any combinations are possible here, as well as the presence of further layers in the second electrode, such as a second current collector, which may be the same as or different from the first current collector but which may be one of the materials mentioned for the first current collector , 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. In accordance with the first electrode, membranes may also be applied to the layers of the second electrode in such embodiments, 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 support structure, for example also for all layers, can 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 reactions will proceed at the anode other than at the cathode, the first organic material and the second organic material will be different, for example also with respect to the aggregate form and whether or not they are in solution or mixture. Similarly, the second nonpolar solvent used in the process may be the same or different than the first non-polar solvent used.

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 electrode and the second electrode at least one separator, for example a diaphragm and / or a membrane - which are not particularly limited, so that the space between the two electrodes is divided into two subspaces wherein a first polar electrolyte can be introduced into the one subspace, for example adjacent to the second hydrophilic layer of the first electrode, and another subspace - for example adjacent to the fourth hydrophilic layer of the second electrode or generally the second electrode - a second polar electrolyte which may be the same as or different from the first polar electrolyte, but the materials for this second polar electrolyte may be the same which are called for the first polar electrolyte. However, this is not preferred. According to certain embodiments, the second, hydrophilic layer of the first electrode at least partially contacts a first separator.

Alternatively or additionally, further separators and optionally further polar electrolytes may be used with which product removal from the first, polar electrolyte is possible, for example if in the electrochemical reaction at the first and optionally second electrode a soluble in the first polar electrolyte organic product is produced. 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, that is not consumed, or simply can be tracked.

In addition to separators, the electrolysis cell may also comprise other constituents which are usually used for electrolysis cells, such as corresponding supply and discharge means for the first polar electrolyte, the first non-polar solution or mixture or the first organic material as a liquid or gas, and optionally for the second non-polar solution or mixture or the second organic material as a liquid or gas, heating and / or cooling means, 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 such 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 take place at the same time or at different times.

After introducing the first organic solution or mixture, or the first organic material as a liquid or gas, as a nonpolar phase, and after the introduction of the first polar electrolyte as a polar phase, form the non-polar phase and the polar phase, a first phase boundary is formed such that the first phase boundary in the electrochemical reaction is at least partially within the first electrode, preferably at an interface between the first, lipophilic layer and the second, hydrophilic layer. By using the first hydrophilic layer and the first lipophilic layer, it can be ensured in this case that the first phase boundary forms at least partially and preferably completely in the first electrode in the electrochemical conversion, so that the first organic material can reach the latter for electrochemical conversion However, a suitable cell voltage can be adjusted by the first polar electrolyte. 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 an electrocatalyst of the first electrode, for example the first catalyst, simultaneously has access to electrical contact, ion contact, possibly protons from the first polar electrolyte and the first organic material as substrate. In order to achieve high current densities, the total area 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 at or in the electrode, it is necessary for the electrode to have an amphiphilic character as achieved by the lipophilic layer and the hydrophilic layer, the side facing the counterelectrode being defined by the polar, for 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 order to bring the phases into contact, 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 forming a second phase boundary between the first polar electrolyte (or another, eg second, polar electrolyte) and the second nonpolar solution or mixture or the second organic material as a liquid or gas.

The electrochemical conversion of the first organic material and / or the first nonpolar solvent or the first organic material as liquid or gas at the first electrode, and optionally the electrochemical reaction of the second organic material and / or the second nonpolar solvent, or the second organic Materials as 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 nonpolar solvent, at least one first organic product is formed which, depending on solubility and polarity, over the first nonpolar phase, ie first nonpolar solution or mixture or first organic material, or the first polar electrolyte can be removed as a polar phase from the first electrode. It can either be discharged from the electrolytic cell via the corresponding phase and then optionally separated / extracted outside and if necessary cleaned, or in the electrolysis cell into further phases, e.g. by suitable separators, extracted and thus optionally separated from by-products.

It should be noted that in addition to the electrochemical conversion at the first electrode - in which at least a first 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 organic product may be formed, for example with the second electrode comprising the third lipophilic layer and the fourth, hydrophilic layer. Of course, in the process according to the invention, the first organic product can then be reacted further with the second inorganic or organic product, preferably after a previous separation and purification, so that not only an organic synthesis step can be carried out electrochemically using the process according to the invention, but also simultaneously Further starting material can be obtained for a subsequent step, wherein, for example, waste heat from the electrochemical reaction for this further reaction can be used 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, the electrolyte, after leaving the cell according to certain embodiments, will pass through a pure organic solvent extraction vessel 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 . 8th . 9 . 10 or more separators, as stated above, be equipped to simplify the extraction.

• - eine poröse erste Elektrode umfassend mindestens eine erste, lipophile Schicht und mindestens eine zweite, hydrophile Schicht, wobei die erste, lipophile Schicht und die zweite, hydrophile Schicht bevorzugt porös sind, und
• - eine zweite Elektrode umfasst;

mindestens eine erste Zuführeinrichtung für die Zufuhr einer ersten Lösung oder Mischung eines ersten organischen Materials, welches in einem ersten unpolaren Lösungsmittel löslich ist oder mit diesem mischbar ist, in oder mit einem ersten unpolaren Lösungsmittel, oder für die Zufuhr eines ersten organischen Materials, welches in einem ersten unpolaren Lösungsmittel löslich ist oder mit diesem mischbar ist, die dazu ausgebildet ist, die erste Lösung oder Mischung des ersten organischen Materials in oder mit dem ersten unpolaren Lösungsmittel, oder das erste organische Material, zur Elektrolysezelle derart zuzuführen, dass die erste organische Lösung oder Mischung oder das erste organische Material die erste, lipophile Schicht der ersten Elektrode kontaktiert; und mindestens eine erste Abführeinrichtung für das Abführen der verbleibenden ersten Lösung oder Mischung und ggf. mindestens eines ersten Produkts der elektrochemischen Umsetzung des ersten organischen Materials und ggf. des ersten unpolaren Lösungsmittels (je nachdem, ob dieses polar ist oder nicht und entsprechend in den ersten polaren Elektrolyten übergehen kann), oder des verbleibenden ersten organischen Materials und ggf. mindestens eines ersten Produkts, oder des verbleibenden ersten unpolaren Lösungsmittels und ggf. mindestens eines ersten Produkts, oder mindestens eines ersten Produkts, die dazu ausgebildet ist, die verbleibende erste Lösung oder Mischung und ggf. mindestens das erste Produkt der elektrochemischen Umsetzung des ersten organischen Materials und ggf. des ersten unpolaren Lösungsmittels, oder das verbleibende erste organische Material und ggf. mindestens das erste Produkt, oder das verbleibende erste unpolare Lösungsmittel und ggf. mindestens das erste Produkt, oder mindestens das erste Produkt aus der Elektrolysezelle abzuführen.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 one second, hydrophilic layer, wherein the first, lipophilic layer and the second, hydrophilic layer are preferably porous, and
• a second electrode comprises;

at least one first supply means for supplying 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 in soluble or miscible with a first non-polar solvent adapted to supply the first solution or mixture of the first organic material in or with the first non-polar solvent, or the first organic material, to the electrolytic cell 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 (depending on whether this is polar or not and correspondingly in the first can pass over polar electrolyte), or the remaining first organic material and optionally at least a first product, or the remaining first nonpolar solvent and optionally at least a first product, or at least a first product, which is formed, the remaining first solution or Mixture and if necessary at least that first product of the electrochemical reaction of the first organic material and optionally the first nonpolar solvent, or the remaining first organic material and optionally at least the first product, or the remaining first nonpolar solvent and optionally at least the first product, or at least the first product remove from the electrolysis cell.

In addition, the device according to the invention may also comprise at least one second supply means for the first polar electrolyte, which is adapted to supply the first polar electrolyte of the electrolytic cell such that the first polar electrolyte, the second, hydrophilic layer of the first electrode and the second electrode, if necessary the fourth, hydrophilic layer of the second electrode, contacted, and / or a second discharge means 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 is formed remove the first polar electrolyte and optionally 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. However, if the first polar electrolyte is not reacted or changed overall in the electrochemical conversion in the electrolysis cell and also no product of the electrochemical conversion of the first organic material and possibly the first nonpolar solvent passes into this, it is also conceivable that the second Feed device and / or the second discharge device 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 design of the second electrode) is formed during the electrochemical conversion and this passes into the first (and / or second) polar electrolyte, an extraction (possibly via a Separator or a plurality of separators) into further polar electrolytes within the first electrolysis cell, so that correspondingly also further supply and discharge devices for further polar electrolytes can be provided.

In particular, the inventive method can be carried out with the device according to the invention. Accordingly, the above statements on the method according to the invention, in particular those relating to components of the device such as an electrolytic cell and its components, also apply to the device according to the invention, and it is thus also hereby incorporated by reference. In particular, the embodiments of the first and second electrodes in the device according to the invention correspond to those discussed above for the method according to the invention. Furthermore, the electrolysis cell in the device according to the invention comprises at least one power source, and may also include the components which have been mentioned for the inventive method, such as separators, pumps, valves, heating and / or cooling devices, 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 fourth , hydrophilic layer is in contact. This type of electrode is advantageous if the solubility of a substrate, ie of the corresponding organic material, in aqueous electrolytes is too low 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 designed 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 one 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 may also be shared by both electrodes according to certain 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 may be formed, for example, as pipes, conduits, 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 second, hydrophilic layer and the fourth, hydrophilic layer in the electrolytic cell are opposed, but preferably not contact, further comprising at least one further supply means for supplying a second solution or mixture of a second organic material which is soluble in a second nonpolar solvent or is miscible with, 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 be the second solution or mixture of 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 remaining second non-polar solvent and optionally at least one second product, or at least one second product, which is formed, the remaining second solution or mixture and optionally at least the second product of the electrochemical reaction of the second organic material and optionally the second non-polar solvent , 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 to be removed from the electrolysis cell.

In such embodiments, if at least one 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 is not excluded that both transition into the first polar electrolyte. Preferably, however, a separator is provided between the two electrodes, so that the at least one first polar product passes into the first polar electrolyte and the at least one second polar product passes into another (eg second) polar electrolyte which is different from the first polar electrolyte may or may correspond to this. However, if the at least one first polar product and the at least one second polar product pass into the first polar electrolyte, it is not excluded that the two may thereafter be reacted.

In these embodiments, the second hydrophilic layer and the fourth hydrophilic layer oppose each other 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 preferred.

The at least one further feed device for the supply of a second solution or mixture of a second organic material which is soluble in or miscible with a second nonpolar solvent, 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 nonpolar solvent, and
the at least one further discharge device for discharging the remaining second solution or mixture and optionally at least one second Products of the electrochemical reaction 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, are not particularly limited, as long as they are suitable for the supply and removal of the corresponding material, and may be formed, for example, as pipes, pipes, etc.

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

According to certain embodiments, the fourth, hydrophilic layer comprises a second electrocatalyst, which may be the same as or different from the first electrocatalyst, and optionally at least a fourth binder, 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 be different 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 hydrophilic additives may correspond or may be different.

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 exemplified electrolysis cell.

According to certain embodiments, the device according to the invention further comprises at least one recycling device, for the first nonpolar solvent and / or the first organic material, the first polar electrolyte, optionally further polar electrolytes and / or optionally the second non-polar solvent and / or the second organic Material, if appropriate, also comprising corresponding separating devices and / or cleaning devices 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 constituents 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, some of which are set forth by way of example 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 bond cleavages 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 dialkyl sebacates has been extensively studied in the past, but could not be realized because of the high cell voltages provided 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, in this case, by avoiding catalysts present 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 is clear from the above variations, various 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 electrolytic cell with an amphiphilic electrode is shown in FIG 1 shown schematically

This includes a working electrode 1 a first lipophilic layer 2 , which is preferably hydrophobic and with a nonpolar phase 5 in contact, and a second, hydrophilic layer, which with a first polar electrolyte 6 is in contact. The first polar electrolyte is also with the counter electrode 4 in contact.

Further embodiments based on this embodiment are in 2 to 4 and in these embodiments a basic operation for these amphiphilic electrodes is shown in combination with a water-consuming counter electrode that develops H ₂ or O ₂ .

In 2 In this case, the nonpolar phase is passed through the first cell space I, wherein a nonpolar product P is formed from an organic material as the reagent R, while the first polar electrolyte E is formed by the second cell space II is pumped. The construction in 3 corresponds to a large part of the 2 , wherein the second electrode 4 at the first electrode 1 is located, in this case according to an insulation between the two electrodes is present. The second electrode 4 is porous, so that the first polar electrolyte E, the first electrode 1 can contact. In 4 is the cell space II in two cell spaces II II ⁺ split, creating the second electrode 4 is washed around. To protect the first electrode 1 lies the second electrode 4 at a separator S on.

It makes more sense, however, to carry out both electrodes in the cell by means of amphiphilic electrodes, as in 5 and 6 shown by way of example. In this case, both electrodes can be used for electrochemical transformations of nonpolar reagents R1 . R2 to non-polar products P1 . P2 be used on the amphiphilic cells as the cathode K and anode A with additional benefits, in 6 the two electrodes have a common separator S , here exemplified as a common membrane with contained polar electrolyte share. 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. (Hereinafter: 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 electrolyte.
eg: aldehyde reduction + Kolbe coupling of adipic acid RED: R-CHO + 2e ^- + 2H ₂ O → R-CH ₂ -OH + 2OH ^-
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 O + 2OH ^- + 2H ⁺ = 0
REDOX: R-COH + 2 EtO ₂ C- (CH ₂ ) ₄ -CO ₂ H → R-CH ₂ -OH + 2 CO 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 + 2OH ^- | x2
OX: R-CH ₂ -OH + H ₂ O → R-COOH + 4e ^- + 4H ⁺
Electrolyte: - 2H ₂ O + 2OH ^- -H ₂ O + 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.
z. For example: nitro reduction + oxidative alkyne coupling
RED: R-NO ₂ + 6e ^- + 4H ₂ O → R-NH ₂ + 6OH ^-
OX: 2R-CCH → R-CC-CC-R + 2e ^- + 2H ⁺ | x3
Electrolyte: - 4H ₂ O + 6OH ^- + 6H ⁺ = + 2H ₂ O
REDOX: R-NO 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 US Pat Fritz Beck, reports of 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 ,

Here, the present invention is characterized in the use of special electrodes for performing electro-organic redox processes at a phase boundary.

The above embodiments, refinements and developments can, if appropriate, be combined with one another as desired. 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 made according to 1 realized.

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 counterelectrode, a Ti sheet coated with IrO ₂ , as second electrode, consumed water in a 2.5M KOH and was passed through a CEM, Nafion N11 , separated to avoid reoxidation of the partially water-soluble product aniline. The non-polar 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 along on both 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 nonpolar phase) and a dendritic copper catalyst bound to anion exchange resin as a hydrophilic layer (in contact with the first polar electrolyte). The dendritic copper catalyst bound to anion exchange resin has been described in: "Selective Electroruction of CO2 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

In 7 is the working electrode potential E _WE versus 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. Also, the decrease in gas evolution at the working electrode was 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.

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

QUOTES INCLUDE IN THE DESCRIPTION

This list of the documents listed by the applicant has been generated automatically and is included solely for the better information of the reader. The list is not part of the German patent or utility model application. The DPMA assumes no liability for any errors or omissions.

Cited patent literature

• DE 1643693 A1 [0122]
• DE 2023080 A1 [0122]
• DE 2336288 A1 [0122]
• DE 2345461 A1 [0122]
• DE 3615472 A1 [0122]

Cited non-patent literature

• Beck et al. concern very thin capillary cells, as for example in Fritz Beck, reports of Bunsen Society 1973, 77 (10/11), pp. 810-817 [0009]
• F. Beck, H. Guthke, Chemical Engineering Techn. 1969, 41 (17), p. 943-950 [0009]
• Fritz Beck, Reports of the Bunsen Society 1973, 77 (10/11), 810-817 [0122]
• F. Beck, H. Guthke Chemical-Ing. - Technology. 1969, 41 (17), 943-950 [0122]

Claims (15)

A method of 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 nonpolar solvent to produce a first organic 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 electrolytic 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 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 material as a liquid or gas into the electrolytic cell such that the first organic material contacts the first lipophilic layer of the first electrode; Introducing a first polar electrolyte into the electrolytic cell such that the first polar electrolyte contacts the second hydrophilic layer of the first electrode and the second electrode; and 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 first electrode, preferably at an interface between the first, lipophilic layer and the second, hydrophilic layer. Method according to Claim 1 , wherein the first polar electrolyte is liquid and in particular contains water and optionally at least one salt. Method according to Claim 1 or 2 wherein the first electrode comprises a first current collector which is not in contact with the second hydrophilic layer. Method according to one of Claims 1 to 3 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 conductive, first particles and / or at least one first hydrophobic binder. Method according to one of Claims 1 to 4 wherein the second, hydrophilic layer comprises a first electrocatalyst and optionally at least one second binder, and / or wherein 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, includes. Method according to one of Claims 1 to 5 wherein the second, hydrophilic layer of the first electrode at least partially contacts a first separator. Method according to 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, hydrophilic layer are preferably porous, wherein the first polar electrolyte contacts the fourth, hydrophilic layer of the second electrode further comprising introducing 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 nonpolar solvent, and a second nonpolar solvent 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 nonpolar solvent, or - the second organic material at the second electrode electrochemically umgese be protected. Method according to 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 separator, preferably wherein the first polar electrolyte is at least partially contained in the first separator; more preferably wherein the first separator is swollen by the first polar electrolyte. Apparatus for electrochemically reacting a first organic material which is soluble in or miscible with a first non-polar solvent comprising an electrolytic cell, the electrolytic cell 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 comprises; at least one first supply means for supplying 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 in soluble or miscible with a first non-polar solvent adapted to supply the first solution or mixture of the first organic material in or with the first non-polar solvent, or the first organic material, to the electrolytic cell 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 material and optionally the first nonpolar solvent, or the remaining first organic material and optionally at least the first product, or the remaining first nonpolar solvent and optionally at least the first product, or at least to remove the first product from the electrolysis cell. Device after Claim 9 wherein the first electrode comprises a first current collector which is not in contact with the second hydrophilic layer. Device after Claim 9 or 10 wherein the first lipophilic layer comprises hydrophobic, preferably conductive, first particles and / or at least one first hydrophobic binder. Device according to one of Claims 9 to 11 wherein the second, hydrophilic layer comprises a first electrocatalyst and optionally at least one second binder, and / or wherein 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, includes. 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. 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, hydrophilic layer are preferably porous, wherein the second, hydrophilic layer and the fourth, hydrophilic layer in opposite to the electrolysis cell, but preferably does not contact, further comprising at least one further feed device for supplying a second solution or mixture of a second organic 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 supply of a second organic material, which is soluble in or miscible with a second non-polar solvent, which is adapted to the second solution or mixture of the second organic material in or with the second non-polar solvent, or the second organic Mat erial supply 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 reaction 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 non-polar solvent and optionally at least one second product, or at least one second product formed, the remaining second solution or mixture and optionally at least the second product of the electrochemical reaction of the second organic material and optionally the second nonpolar solvent, 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 to be removed from the electrolysis cell. Device after 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 contained in the first separator, more preferably wherein the first first separator is swollen by the first polar electrolyte.

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