EP3481973B1 - Hydrogénation électrochimique sélective d'alkynes en alcènes - Google Patents

Hydrogénation électrochimique sélective d'alkynes en alcènes Download PDF

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EP3481973B1
EP3481973B1 EP17758461.2A EP17758461A EP3481973B1 EP 3481973 B1 EP3481973 B1 EP 3481973B1 EP 17758461 A EP17758461 A EP 17758461A EP 3481973 B1 EP3481973 B1 EP 3481973B1
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Prior art keywords
copper
chemical formula
alkyne
electrode
layer
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German (de)
English (en)
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EP3481973A1 (fr
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Bernhard Schmid
Günter Schmid
Christian Reller
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Siemens AG
Siemens Corp
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Siemens AG
Siemens Corp
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B3/00—Electrolytic production of organic compounds
    • C25B3/20—Processes
    • C25B3/25—Reduction
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/02—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form
    • C25B11/03—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form perforated or foraminous
    • C25B11/031—Porous electrodes

Definitions

  • the present invention relates to a process for the partial electrochemical hydrogenation of alkynes of the chemical formula (I) to alkenes, where R and R 'are selected from inorganic and / or organic radicals, wherein the compound of chemical formula (I) is hydrogenated on a copper-containing electrode, the use of a copper-containing electrode for such a partial electrochemical hydrogenation, and a device for carrying out the process.
  • alkenes such as ethene or propene are mainly produced through the catalytic cleavage of crude oil (naphtha).
  • An alternative approach is the partial hydrogenation of alkynes (e.g. ethyne). These can also be prepared from coal or carbides and are therefore not dependent on crude oil.
  • selectivity problems arise in the classic hydrogenation. Often there is an over-reduction to the alkane.
  • the hydrogen required for hydrogenation is currently also obtained from coal gasification or steam reforming and is therefore also closely linked to oil production.
  • the catalytic hydrogenation of alkynes has previously been achieved using special poisoned noble metal catalysts.
  • An example of this is the Lindlar catalyst, which is a palladium catalyst poisoned with lead and quinoline.
  • Another possibility is the "Birch-analogue reduction", in which a solution of alkali metals in liquid ammonia is used. The latter process is very expensive but selective for E-alkenes.
  • electrification of the chemical industry means electrochemically carrying out processes that were previously carried out using traditional thermal processes or that were previously not possible.
  • electrochemical hydrogenation of ethyne to ethene is also known from X. Song, H. Du, Z. Liang, Z. Zhu, D. Duan, S. Liu, Int. J. Electrochem. Sci., 2013, 8, 6566-6573 .
  • the authors only use electrodes made of the noble metal palladium, and the substrate selection is also limited to ethyne.
  • the JP H 04 290989 A describes a method for synthesizing a hydrogenation product by a diaphragm hydrogenation reaction.
  • the inventors have found that partial reduction of alkynes can be carried out by an electrochemical method using a Cu electrode in water-based electrolytes.
  • the electrode can be designed both as a solid electrode and as a gas diffusion electrode.
  • the better substrate availability for alkynes makes the latter particularly suitable.
  • the process according to the invention shows high selectivity and activity, even in the case of non-activated alkynes and difficult substrates with electron-donating groups and / or steric hindrance.
  • the present invention relates to a process for the partial electrochemical hydrogenation of alkynes of the chemical formula (I) to alkenes, where R and R 'are selected from inorganic and / or organic radicals, wherein the compound of the chemical formula (I) is hydrogenated on a copper-containing electrode, the copper-containing electrode being designed as a gas diffusion electrode.
  • a copper-containing electrode for the partial electrochemical hydrogenation of alkynes of the chemical formula (I) to alkenes is disclosed, where R and R 'are selected from inorganic and / or organic residues, the copper-containing electrode being designed as a gas diffusion electrode.
  • Figure 1 shows a schematic representation of the device according to the invention.
  • a process for the partial electrochemical hydrogenation of alkynes of the chemical formula (I) to alkenes where R and R 'are selected from inorganic and / or organic radicals, wherein the compound of the chemical formula (I) is hydrogenated on a copper-containing electrode, the copper-containing electrode being designed as a gas diffusion electrode.
  • Alkynes are all chemical compounds that have a triple bond between 2 carbon atoms. The process is not limited to ethyne, but can be applied to other alkynes.
  • a general scheme for the electrochemical conversion of alkynes of the chemical formula I is as follows: instead of the H + ions shown, these can also be D + ions, for example.
  • the good selectivity is due to the low reactivity of the resulting alkenes towards electrohydration with Cu electrodes.
  • electronically deactivated internal alkenes such as crotyl alcohol (trans-2-butenol) were found to be inert to overreduction.
  • the copper-containing electrode which is formed as a gas diffusion electrode, is not particularly limited and can include copper among other components, e.g. include other metals and / or ceramics as a substrate, but also consist of copper. It can also be chemically treated, for example to form oxide. It is designed as a gas diffusion electrode. Due to the better substrate availability for alkynes, the gas diffusion electrode is particularly suitable, especially for gaseous alkynes such as ethyne, propyne, 1-butyne or 2-butyne. In contrast to palladium electrodes, the present copper-containing electrodes are much cheaper.
  • a copper-containing electrode can be obtained by depositing a layer comprising a Cu + / Cu-containing catalyst on a non-copper substrate, as in FIG DE 10 2015 203 245 or by depositing the layer on a copper substrate.
  • the Cu + / Cu-containing catalyst is hereinafter also referred to as a copper / copper ion catalyst, copper catalyst or the like or simply as a catalyst, unless the text indicates otherwise, so that these terms are synonymous in the context of the present invention understand are.
  • the non-copper substrate is also simply referred to as the substrate, unless the text indicates otherwise.
  • the non-copper substrate contains copper as long as it does not essentially consist of copper.
  • the substrate can also consist of brass or comprise brass.
  • the non-copper substrate comprises less than 60% by weight of copper, based on the total weight of the substrate, preferably less than 50% by weight, more preferably less than 40% by weight and particularly preferably less than 20% by weight of copper, for example no copper.
  • the substrate comprises at least one metal such as silver, gold, platinum, nickel, lead, titanium, nickel, iron, manganese, or chromium or their alloys such as stainless steels, and / or at least one non-metal such as carbon, Si, boron nitride (BN ), Boron-doped diamond, etc., and / or at least one conductive oxide such as indium tin oxide (ITO), aluminum zinc oxide (AZO) or fluorinated tin oxide (FTO), for example for the production of photoelectrodes, and / or at least one polymer based on polyacetylene, Polyethoxythiophene, polyaniline or polypyrrole for the production of polymer-based electrodes.
  • the substrate comprises at least one metal such as silver, gold, platinum, nickel, lead, titanium, nickel, iron, manganese, or chromium or their alloys such as stainless steels, and / or at least one non-metal such as carbon, Si, boron nit
  • the production of the Cu + / Cu-containing catalyst can take place in various ways and is not particularly restricted, the various production methods of the Cu + / Cu-containing catalyst also being able to take place on copper substrates.
  • electro-reduction catalysts can be obtained if the catalyst is deposited in situ on the electrode substrate.
  • An ex-situ deposition is not excluded according to the invention.
  • the substrate does not necessarily have to comprise copper or be copper, but can contain any conductive material, in particular also conductive oxides.
  • the porous configurations of such an electrode are particularly preferred in order to obtain gas diffusion electrodes.
  • Charge compensation in the Cu + / Cu-containing catalyst can be carried out by incorporating anions in solution during production, for example hydroxide ions (OH - ), O 2 - , halide ions (halogen - ), for example fluoride, chloride, Bromide, iodide, sulfate, hydrogen carbonate, carbonate or phosphates etc.
  • anions in solution during production for example hydroxide ions (OH - ), O 2 - , halide ions (halogen - ), for example fluoride, chloride, Bromide, iodide, sulfate, hydrogen carbonate, carbonate or phosphates etc.
  • the layer comprising copper can also be deposited on the surface of the electrode from a solution comprising copper ions.
  • dendritic structures can be applied from solution, in which case it is not necessary to achieve a complete coating of the substrate, i.e. parts of the substrate can also still be visible.
  • the coating of the substrate, as well as the structures of the catalyst, can be analyzed, for example, by means of scanning electron microscopy (SEM) or transmission electron microscopy (TEM).
  • the substrate is not necessarily completely covered by the coating.
  • the area covered by the coating can be, for example, 10 to 99.9%, based on the area of the substrate, preferably 50 to 95%, more preferably 70 to 90%.
  • the substrate is only covered in such a way that the catalyst grows dendritically.
  • the Cu + / Cu-containing catalyst can have pores in a size from 10 nm to 100 ⁇ m, preferably from 50 nm to 50 ⁇ m, more preferably from 100 nm to 10 ⁇ m.
  • the Cu + / Cu-containing catalyst can also have dendritic structures with a fine structure, for example the distance between two dendrites, with a size of 1 to 100 nm, preferably 2 to 20 nm, more preferably 3 to 10 nm porous.
  • the Cu + / Cu-containing catalyst can be at least 40% by weight crystalline, based on the catalyst, more preferably at least 70% by weight, particularly preferably at least 80% by weight, it being possible for the Cu + / Cu-containing catalyst and / or the coating to be crystalline.
  • the substrate can be porous in order to be able to produce gas diffusion electrodes.
  • the substrate can have pores in a size from 10 nm to 100 ⁇ m, preferably from 50 nm to 50 ⁇ m, more preferably from 100 nm to 10 ⁇ m.
  • the porous design of the non-copper substrate or a copper substrate, such as a gas diffusion electrode ensures good transport of a gaseous alkyne to the Cu + / Cu-containing catalyst and further improves the efficiency of the electrolysis.
  • a suitable pore size can be used to ensure targeted feeding to specific sections of the catalyst.
  • the concentration of Cu + in the porous copper catalyst layer / the coating comprising the Cu + / Cu-containing catalyst is, for example, greater than 1 mol%, preferably greater than 5 mol%, more preferably more than 10 mol%, particularly preferably greater than 20 mol %, and for example up to 99.9 mol%, based on the coating.
  • the substrate can be porous.
  • the substrate can have pores in a size from 10 nm to 100 ⁇ m, preferably from 50 nm to 50 ⁇ m, more preferably from 100 nm to 10 ⁇ m. This is the case, for example, for preferred embodiments.
  • the substrate in the copper-containing electrode includes, for example, at least one metal such as silver, platinum, nickel, lead, titanium, nickel, iron, manganese or chromium or their alloys such as stainless steels, and / or at least one non-metal such as carbon, Si, boron nitride ( BN), boron-doped diamond, etc., and / or at least one conductive oxide such as indium tin oxide (ITO), aluminum zinc oxide (AZO) or fluorinated tin oxide (FTO) - for example for the production of photoelectrodes, and / or at least one polymer based on polyacetylene, polyethoxythiophene, polyaniline or polypyrrole, such as in polymer-based electrodes. Copper alloys or mixtures of the materials mentioned with copper as well as substrates made of copper or copper oxide are also possible.
  • metal such as silver, platinum, nickel, lead, titanium, nickel, iron, manganese or chromium or their alloys such
  • the coating is at least partially crystalline.
  • the Cu + / Cu-containing catalyst is at least 40% by weight crystalline, based on the catalyst, more preferably at least 70% by weight, particularly preferably at least 80% by weight.
  • the Cu + / Cu-containing catalyst and / or the coating is crystalline.
  • the coating of the copper-containing electrode is micro- to nanoporous and / or has a particularly high surface area of, for example, more than 500 m 2 / g, preferably equal to or more than 800 m 2 / g, more preferably equal to or more than 1000 m 2 / g.
  • the coating is thus porous.
  • the Cu + / Cu-containing catalyst can have pores in a size from 10 nm to 100 ⁇ m, preferably from 50 nm to 50 ⁇ m, more preferably from 100 nm to 10 ⁇ m.
  • the Cu + / Cu-containing catalyst can also have dendritic structures with a fine structure, for example the distance between two dendrites, with a size of 1 to 100 nm, preferably 2 to 20 nm, more preferably 3 to 10 nm.
  • the concentration of Cu + in the porous copper catalyst layer is, for example, greater than 1 mol%, preferably greater than 5 mol%, more preferably more than 10 mol%, particularly preferably greater than 20 mol%, and up to 99.9 mol%, based on on the coating.
  • the coverage of the coating as an area in the copper-containing electrode can be, for example, 10 to 99.9%, based on on the area of the substrate, preferably 50 to 95%, more preferably 70 to 90%.
  • the substrate is covered in such a way that the catalyst grows dendritically.
  • the copper-containing electrode is designed as a gas diffusion electrode (GDE)
  • GDE gas diffusion electrode
  • a gas diffusion electrode as a copper-containing electrode comprises, for example, a, preferably copper-containing, carrier, preferably in the form of a flat structure, and a first layer comprising at least copper and at least one binder, the (first) layer comprising hydrophilic and hydrophobic pores and / or channels, further comprising a second layer comprising copper and at least one binder, the second layer being on the carrier and the first layer being on the second layer, the content of binder in the first layer being smaller than in the second layer.
  • hydrophobic is understood to be water-repellent. Hydrophobic pores and / or channels are therefore those which repel water.
  • hydrophobic properties are associated with substances or molecules with non-polar groups.
  • hydrophilic is understood to mean the ability to interact with water and other polar substances.
  • the second layer can comprise hydrophilic and / or hydrophobic pores and / or channels.
  • a gas diffusion electrode comprising a carrier, preferably containing copper, preferably in the form of a sheet-like structure, and a first layer comprising at least copper and at least one binder, the layer comprising hydrophilic and hydrophobic pores and / or channels.
  • the hydrophilic and hydrophobic areas of the GDE can achieve a good three-phase relationship liquid, solid, gaseous.
  • Particularly active catalyst centers in the three-phase region are liquid, solid, gaseous.
  • An ideal GDE thus has a maximum penetration of the bulk material with hydrophilic and hydrophobic channels in order to obtain as many three-phase regions as possible for active catalyst centers.
  • the first layer comprises hydrophilic and hydrophobic pores and / or channels. By suitably setting the first layer, it can be achieved that as many active catalyst centers as possible are present in the gas diffusion electrode.
  • the carrier is not particularly limited insofar as it is suitable for a gas diffusion electrode and preferably contains copper.
  • parallel wires can also form a carrier in extreme cases.
  • the carrier is a flat structure, more preferably a mesh, very preferably a copper mesh. This makes it possible to ensure both sufficient mechanical stability and functionality as a gas diffusion electrode, for example with regard to high electrical conductivity.
  • the use of copper in the carrier can provide suitable conductivity and reduce the risk of the introduction of undesired foreign metals. According to preferred embodiments, the carrier is therefore made of copper.
  • a preferred copper-containing carrier is a copper mesh with a mesh size w of 0.3 mm ⁇ w ⁇ 2.0 mm, preferably 0.5 mm ⁇ w ⁇ 1.4 mm and one Wire diameter x of 0.05 mm ⁇ x ⁇ 0.5 mm, preferably 0.1 mm x 0.25 mm.
  • the first layer comprises copper
  • a high electrical conductivity of the catalyst and, in particular in connection with a copper mesh a homogeneous potential distribution over the entire electrode surface (potential-dependent product selectivity) can be ensured.
  • the binder comprises a polymer, for example a hydrophilic and / or hydrophobic polymer, for example a hydrophobic polymer, in particular PTFE.
  • a suitable setting of the hydrophobic pores or channels can hereby be achieved.
  • PTFE particles with a particle diameter between 5 and 95 ⁇ m, preferably between 8 and 70 ⁇ m, are used to produce the first layer.
  • Suitable PTFE powders include, for example, Dyneon® TF 9205 and Dyneon TF 1750.
  • Suitable binder particles, for example PTFE particles can for example be approximately spherical, for example spherical, and can for example be produced by emulsion polymerization.
  • the binder particles are free of surfactants.
  • the particle size can for example be determined according to ISO 13321 or D4894-98a and can for example correspond to the manufacturer's instructions (e.g. TF 9205: mean particle size 8 ⁇ m according to ISO 13321; TF 1750: mean particle size 25 ⁇ m according to ASTM D4894-98a).
  • the first layer comprises at least copper, which can be in the form of metallic copper and / or copper oxide, for example, and which functions as a catalyst center.
  • the first layer here preferably contains metallic copper in the 0 oxidation state.
  • the first layer can also contain, for example, copper oxide, in particular Cu 2 O.
  • the oxide can contribute to to stabilize the oxidation states +1 of the copper and thus to maintain the selectivity for ethylene with long-term stability. Under electrolysis conditions it can be reduced to copper.
  • the first layer comprises at least 40 at.% (Atomic percent), preferably at least 50 at.%, More preferably at least 60 at.% Copper, based on the layer.
  • the first layer can also contain further promoters which, in cooperation with the copper, improve the catalytic activity of the GDE.
  • the first layer contains at least one metal oxide, preferably ZrO 2 , Al 2 O 3 , CeO 2 , Ce 2 O 3 , ZnO 2 , MgO; and / or at least one copper-rich intermetallic phase, preferably at least one Cu-rich phase, which is selected from the group of binary systems Cu-Al, Cu-Zr, Cu-Y, Cu-Hf, CuCe, Cu-Mg and the ternary Systems Cu-Y-Al, Cu-Hf-Al, Cu-Zr-Al, Cu-Al-Mg, Cu-Al-Ce with Cu contents> 60 at .-%; and / or copper-containing perovskites and / or defect perovskites and / or perovskite-related compounds, preferably YBa 2 Cu 3 O 7- ⁇ , where 0 1 (corresponding to YBa
  • the metal oxide used is preferably water-insoluble so that aqueous electrolytes can be used in an electrolysis using the gas diffusion electrode according to the invention.
  • the metal oxides are preferably not inert, but rather should represent hydrophilic reaction centers which can serve to provide protons.
  • the promoters in particular the metal oxide, can promote the function and production of electrocatalysts with long-term stability by stabilizing catalytically active Cu nanostructures.
  • the structural promoters can reduce the high surface mobility of the Cu nanostructures and thus their tendency to sinter.
  • the concept comes from heterogeneous catalysis and is used successfully within high temperature processes.
  • Metal oxide-copper catalyst structures which are produced as follows are particularly preferred for such gas diffusion electrodes.
  • Similar hydroxide carbonates are formed, but hydrotalcites (Cu 6 Al 2 CO 3 (OH) 16 ⁇ 4 (H 2 O)), which can be obtained in greater yield.
  • the corresponding precursors can be added by co-metering a metal salt solution and a basic carbonate solution pH controlled precipitated.
  • a special feature of these materials is the presence of particularly fine copper crystallites with a size of 4-10 nm, which are structurally stabilized by the oxide present.
  • oxide precursors generated can then also be poured directly into an H 2 / Ar Gas flow are reduced, only the Cu 2 O or CuO is reduced to Cu and the oxide promoter is retained.
  • the activation step can also be carried out electrochemically afterwards.
  • oxide precursors and activated precursors can also be mixed in some cases.
  • 0-10% by weight of copper powder with a similar particle size can also be added.
  • the finished calendered gas diffusion electrode is subjected to a subsequent calcination / thermal treatment before the electrochemical activation is carried out.
  • Cu-rich intermetallic phases such as Cu 5 Zr, Cu 10 Zr 7 , Cu 51 Zr 14 , which can be produced from the melt.
  • Corresponding ingots can subsequently be ground and completely or partially calcined in an O 2 / argon gas stream and converted into the oxide form.
  • Cu-rich phases of the binary systems Cu-Al, Cu-Zr, Cu-Y, Cu-Hf, CuCe, Cu-Mg as well as the corresponding ternary systems with Cu contents> 60at%: CuYAl, CuHfAl, CuZrAl, CuAlMg, CuAlCe.
  • the proportion of copper is preferably greater than 40 at.%, More preferably greater than 50 at.%, Particularly preferably greater than 60 at.%.
  • the intermetallic phases also contain non-metal elements such as oxygen, nitrogen, sulfur, selenium and / or phosphorus, that is to say, for example, oxides, sulfides, selenides, nirides and / or phosphides are contained.
  • the intermetallic phases are partially oxidized.
  • the following copper-containing perovskite structures and / or defect perovskites and / or perovskite-related compounds can be used for electrocatalysts: YBa 2 Cu 3 O 7- ⁇ , where 0 ⁇ 1, CaCu 3 Ti 4 O 12 , La 1, 85 Sr 0.15 , CuO 3.930 Cl 0.053 , (La, Sr) 2 CuO 4 . Furthermore, it is not ruled out that mixtures of these materials can be used for electrode preparation or as required subsequent calcination or activation steps can be carried out.
  • the catalyst particles comprising or consisting of copper, for example copper particles, which are used to produce the GDE, have a uniform particle size between 5 and 80 ⁇ m, preferably 10 to 50 ⁇ m, more preferably between 30 and 50 ⁇ m. Furthermore, the catalyst particles preferably have a high purity without traces of foreign metal. A high level of selectivity and long-term stability can be achieved through suitable structuring, if necessary with the aid of the promoters.
  • the promoters for example the metal oxides, can also have a corresponding particle size during production.
  • Cu powder aggregates with a particle diameter of 50 to 600 ⁇ m, preferably 100 to 450 ⁇ m, preferably 100-200 ⁇ m, can be added.
  • the particle diameter of these additives is, for example, 1 / 3-1 / 10 of the total thickness of the layer.
  • the aggregate can also be an inert material such as a metal oxide. In this way, an improved formation of pores or channels can be achieved.
  • the first layer comprises less than 5% by weight, more preferably less than 1% by weight and even more preferably no carbon- and / or carbon-black-based or -like, for example conductive, filler, based on the layer.
  • the first layer does not contain any surface-active substances.
  • the first and / or second layer also contain no sacrificial material, for example a sacrificial material with a release temperature of approximately below 275 ° C, for example below 300 ° C or below 350 ° C, in particular no pore former, which or which is usually at Manufacture of electrodes using a such material can remain at least partially in the electrode.
  • the content or proportion of binder for example PTFE, for example 3-30% by weight, preferably 3-20% by weight, more preferably 3-10% by weight, even more preferably 3 to 7% by weight, based on the one (first) layer.
  • the GDE described above further comprises a second layer comprising copper and at least one binder, the second layer being on the carrier and the first layer on the second layer, the content of binder in the first layer being smaller than in the second layer .
  • the second layer can comprise coarser copper or inert material particles, for example with particle diameters of 50 to 700 ⁇ m, preferably 100-450 ⁇ m, in order to provide a suitable channel or pore structure.
  • the second layer here has 3 to 30% by weight of binder, preferably 10 to 30% by weight of binder, more preferably 10 to 20% by weight of binder, preferably> 10% by weight of binder, more preferably> 10% by weight and up to 20% by weight of binder, based on the second layer, and 0-10% by weight of binder for the first layer, for example 0.1-10% by weight of binder, preferably 1-10% by weight of binder, more preferably 1 - 7% by weight, even more preferably 3 - 7% by weight of binder, based on the first layer.
  • the binder can be the same as in the first layer, for example PTFE.
  • the particles for producing the second layer can correspond to those of the first, but can also be different from them.
  • the second layer is a metal particle layer (MPL), which is below the catalyst layer (CL).
  • MPL metal particle layer
  • CL catalyst layer
  • Such a layering can specifically create strongly hydrophobic areas in the MPL and generate a catalyst layer with hydrophilic properties. Due to the strongly hydrophobic character of the MPL, an undesirable Penetration of the electrolyte into the gas transport channels, i.e. flooding thereof, can be prevented.
  • the second layer partially penetrates the first layer. This enables a good transition between the layers in terms of diffusion.
  • the GDE according to the invention can also have further layers, for example on the first layer and / or on the other side of the carrier.
  • a mixture for an MPL based on a highly conductive Cu mixture of dendritic Cu with particle sizes between 5-100 ⁇ m, preferably smaller than 50 ⁇ m and coarser copper or inert material particles with particle sizes of 100-450 ⁇ m can be used , preferably 100-200 ⁇ m, with a PTFE content of 3-30% by weight, preferably 20% by weight, in a layer thickness of, for example, 0.5 mm on a Cu mesh with a mesh size of, for example, 1 mm (thickness, for example, 0.2- 0.6mm, e.g. 0.4 mm) and pulled off using a frame or squeegee.
  • Corresponding dendritic copper can also be present in the first layer.
  • the catalyst / PTFE mixture (CL) can then be sieved again, for example with a PTFE content of 0.1-10% by weight, and smoothed or peeled off, for example over a 1 mm thick frame, so that a total layer thickness (Hf) of 1 mm can be obtained.
  • the MPL can achieve better mechanical stability, a further reduction in the penetration of electrolyte and better conductivity, in particular when nets are used as carriers.
  • a step-by-step production of the GDE by sifting and rolling each individual layer can lead to less adhesion between the layers and is therefore less preferred.
  • the degree of fibrillation of the binder correlates directly with the applied shear rate, since the binder, for example a polymer, behaves as a shear-thinning (pseudoplastic) fluid when it is rolled out. After extrusion, the layer obtained has an elastic character due to the fibrillation. This structural change is irreversible, so that this effect can no longer be subsequently increased by further rolling, but the layer is damaged by the elastic behavior when further shear forces are applied. Particularly strong fibrillation can disadvantageously lead to the electrode curling up on the layer side, so that excessively high binder contents should be avoided.
  • the base layer can be characterized by a very high conductivity, for example 7 mOhm / cm or more, and preferably has a high porosity, for example of 50-70%, and a hydrophobic character.
  • the binder content, for example PTFE can for example be selected between 3-30% by weight, for example 10-30% by weight.
  • the intermediate copper layer as the second layer can itself be catalytically active as the first layer in the area of the overlap zone with the catalyst layer, and is used in particular to improve the electrical connection of the electrocatalyst over a large area. With the help of this method, the required amount of catalyst can be reduced by a factor of 20-30.
  • the method of the two-layer structure also offers the possibility of dispensing with binder materials as the first layer within the catalyst layer, as a result of which better electrical conductivity can be achieved. Very ductile or brittle powder particles can also be processed.
  • a subsequent electrochemical activation of the electrode obtained can optionally be carried out, for example by chemical or electrochemical activation, and is not particularly restricted.
  • An electrochemical activation procedure can lead to cations of the conductive salt of the electrolyte (eg KHCO 3 , K 2 SO 4 NaHCO 3 , KBr, NaBr) penetrating the hydrophobic GDE channels and thereby creating hydrophilic areas.
  • the conductive salt of the electrolyte eg KHCO 3 , K 2 SO 4 NaHCO 3 , KBr, NaBr
  • the process according to the invention is suitable for the partial electrochemical hydrogenation of alkynes of the chemical formula (I) to alkenes, where R and R 'are selected from inorganic and / or organic radicals.
  • the inorganic and / or organic radicals are not particularly restricted here, and the inorganic radicals can also include organic substructures, for example in adducts or complexes.
  • organic radicals comprise 1 to 100 C atoms, for example 1 to 40 C atoms, preferably 1 to 20 C atoms, for example 1 to 10, 1 to 6, 1 to 4, 1 to 2 C atoms or else also only 1 carbon atom. All inorganic radicals are suitable as inorganic radicals. Derivatives of inorganic radicals and / or substituted organic radicals are also suitable.
  • inorganic and / or organic radicals are -H, -D, -OH, -OR *, -SH, -SR *, -NH 2 , -NR * R ⁇ , -COOH, -COOR *, -CHO, -COR *, -PH 2 , -PR * R ⁇ , -F, -Cl, -Br, -I, -NO, -NO 2 , as well as substituted or unsubstituted alkyl, alkenyl, alkynyl and aryl groups are conceivable, where R * and R ⁇ are also any organic, for example with 1 to 100 carbon atoms, for example 1 to 40 carbon atoms, preferably 1 to 20 carbon atoms, for example 1 to 10, 1 to 6, 1 to 4, 1 to 2 carbon atoms or even just 1 carbon atoms -Atom, or inorganic side chains, such as -H, -D, -OH, -SH,
  • Partial hydrogenation is understood here to mean the hydrogenation of alkyne, that is to say triple bond, to alkene, that is to say double bond. Electrochemically, the reaction takes place using electricity, for example in an electrolysis cell.
  • the inorganic and / or organic radicals R and R ' are selected from substituted or unsubstituted alkyl, alkenyl, alkynyl and / or aryl radicals, preferably alkyl and / or aryl radicals, preferably with 1 to 40 carbon atoms, preferably 1 to 20 carbon atoms, for example 1 - 10, 1 to 6, 1 to 4, 1 to 2 carbon atoms or only 1 carbon atom, -H, -D, -OH, -OR *, - SH, -SR *, -NH 2 , -NR * R ⁇ , -COOH, -COOR *, -CHO, -COR *, -PH 2 , -PR * R ⁇ , -F, -Cl, -Br, - I, - NO, and -NO 2 , where R * and R ⁇ represent organic and / or inorganic radicals, which are preferably selected from - H,
  • Substituents for the substituted or unsubstituted alkyl, alkenyl, alkynyl and aryl groups or radicals are, for example, -D, -OH, -SH, -NH 2 , -COOH, -CHO, -PH 2 , -F, - Cl, -Br, -I, -NO, -NO 2 are possible.
  • Functionalized side chains such as —CH 2 —OH or fluorinated alkyl and / or aryl radicals such as —CF 3 can thus result.
  • R and R 'are each -H or -D the special case ethyne results as a compound of the chemical formula (I). If either R or R ', but not both, is -H or -D, the alkyne is referred to as the terminal alkyne. For internal alkynes, neither R nor R 'is -H or -D. In the case of terminal alkenes, the amount of charge used is preferably precisely controlled, since overhydration, albeit with poor efficiency, is possible. According to certain embodiments, because of this necessary control, neither R nor R 'are -H or -D, so internal alkynes are hydrogenated.
  • alkynes which do not carry any electron-withdrawing radicals such as, for example, -COOH, -COOR *, -CF 3 (where R * is as defined above), are preferred according to the invention.
  • the alkyne of the chemical formula (I) thus has no electron-withdrawing radicals.
  • the electron-withdrawing radicals are selected from -COOH, -COOR *, and fluorinated alkyl and / or aryl radicals, preferably perfluorinated alkyl and / or aryl radicals such as -CF 3 .
  • alkynes which do not carry any functional groups which in turn can be converted by electro-reduction are alkynes which do not carry any functional groups which in turn can be converted by electro-reduction.
  • Simultaneous electroreduction of a reducible side chain or a reducible radical is possible, however.
  • alkynes with a reducible side chain or a reducible radical are alkynes which carry functional groups such as -CHO, -COR *, -NO, or -NO 2 or whose side chains contain these radicals.
  • the reduction of aldehydes (-CHO), ketones (-COR *) and nitro compounds (-NO 2 ) could be confirmed experimentally.
  • Aldehydes (-CHO) and ketones (-COR *) gave alcohols (-CH 2 -OH) or (-CHR * -OH) and nitro compounds (-NO 2 ) amines (-NH 2 ).
  • the alkyne of the chemical formula (I) thus has no further reducible functional groups apart from the triple bond.
  • gaseous or water-soluble / water-miscible alkynes for example gaseous alkynes, as alkyne of the chemical formula (I).
  • Examples of such suitable compounds are ethyne, propyne, 1-butyne or 2-butyne, propargyl alcohol (2-propyn-1-ol) and 2-butyn-1-ol.
  • the copper-containing electrode is therefore designed as a gas diffusion electrode, the alkyne of the chemical formula (I) being in gaseous form.
  • the hydrogenation is carried out with a proton donor selected from water and alcohols having 1 to 20 carbon atoms, preferably water and alcohols having 1 to 12, for example 1 to 6 or 1 to 4 carbon atoms, particularly preferred Water.
  • a proton donor selected from water and alcohols having 1 to 20 carbon atoms, preferably water and alcohols having 1 to 12, for example 1 to 6 or 1 to 4 carbon atoms, particularly preferred Water.
  • the water can do this too be partially or completely deuterated, that is to say include HDO or D 2 O, or also tritium, for example in the production of radioactive markers.
  • an electrolyte that can be used in the method of the present invention is not particularly limited, an aqueous electrolyte is advantageously used.
  • any conductive salts and / or ionic liquids can be used.
  • Mixtures of water with inert organic solvents such as e.g. 1,4-Dioxane can be used to improve substrate solubility.
  • the present invention relates to the use of a copper-containing electrode for the partial electrochemical hydrogenation of alkynes of the chemical formula (I) to alkenes, where R and R 'are selected from inorganic and / or organic residues, the copper-containing electrode being designed as a gas diffusion electrode.
  • the copper-containing electrode corresponds to that which was described in connection with the method according to the invention.
  • the electrolysis cell is not particularly restricted here, provided it has the copper-containing electrode, which is designed as a gas diffusion electrode and which can correspond to that in the method according to the invention.
  • the method according to the invention can be carried out with the device according to the invention.
  • the copper-containing electrode can function as a cathode.
  • the other components of the electrolysis cell such as anode, possibly membrane, power source, etc. are not particularly restricted, nor are their arrangement.
  • a cathode compartment II can be designed in such a way that a catholyte is supplied from below and then exits the cathode compartment II upwards.
  • the catholyte can also be fed in from above, as is the case with falling film electrodes, for example.
  • the anode A which is electrically connected to the cathode K by means of a current source to provide the voltage for the electrolysis, the oxidation of a substance takes place in an anode compartment I, which is supplied from below, for example with an anolyte, the anolyte then leaves the anode compartment with the product of the oxidation.
  • Anode compartment and cathode compartment can be through a membrane M be separated.
  • a reaction gas such as an alkyne of the chemical formula (I) can be conveyed through a gas diffusion electrode as cathode into the cathode space II for reduction.
  • a porous anode are also conceivable. Rooms I and II can be separated by a membrane M as described.
  • cathode K e.g. a gas diffusion electrode
  • an anode A directly on the membrane M, whereby the anode compartment I is separated from the cathode compartment II.
  • a structure with a gas diffusion electrode can be provided on the catholyte side, which is not on the membrane, whereas on the anolyte side the anode can be on the membrane.
  • a structure with a gas diffusion electrode can be provided on the catholyte side, which is not on the membrane, whereas on the anolyte side the anode can be on the membrane.
  • other mixed forms or other configurations of the electrode spaces shown by way of example are also conceivable.
  • the cathode-side electrolyte and the anode-side electrolyte can thus be identical, and the electrolysis cell / electrolysis unit can do without a membrane.
  • the electrolysis cell has a membrane in such embodiments, but this is associated with additional expenditure with regard to the membrane and the applied voltage.
  • the catholyte and anolyte can optionally be mixed again outside of the electrolysis cell.
  • the membrane if present, can also have a multilayer design so that separate feeds of anolyte and catholyte are made possible. With aqueous electrolytes, separation effects are achieved, for example, through the hydrophobicity of intermediate layers. Conductivity can still be guaranteed if conductive groups are in such separating layers are integrated.
  • the membrane can be an ion-conducting membrane or a separator which only effects mechanical separation and is permeable to cations and anions.
  • a gas diffusion electrode By using a gas diffusion electrode, it is possible to build a three-phase electrode.
  • a gas can be fed from behind to the electrically active front side of the electrode in order to carry out an electro-chemical reaction there.
  • the gas diffusion electrode can only flow behind, i.e. a gas such as the alkyne of the chemical formula (I) is led past the rear of the gas diffusion electrode in relation to the electrolyte, the gas then being able to penetrate through the pores of the gas diffusion electrode and the product being discharged at the rear.
  • the gas flow is the reverse of the flow of the electrolyte when flowing behind, so that any liquid that may have been forced through can be transported away.
  • a cell variant enables a gas to flow directly through the GDE.
  • the resulting products are removed from the electrolysis cell through the catholyte outlet and can be separated from the liquid electrolyte in a subsequent phase separator.
  • the second cell variant describes a mode of operation in which the gas flows through an adapted gas pressure in the rear area of the GDE.
  • the gas pressure should be chosen so that it is equal to the hydrostatic pressure of the electrolyte in the cell so that no electrolyte is pushed through.
  • a foil can be applied to the side of the gas diffusion electrode facing away from the electrolyte in order to prevent the electrolyte from passing over to the gas.
  • the film can be provided in a suitable manner and is, for example, hydrophobic.
  • the electrolytic cell has a membrane which separates the cathode compartment and the anode compartment of the electrolytic cell in order to prevent the electrolytes from mixing.
  • the membrane is not particularly limited here, provided it separates the cathode compartment and the anode compartment. In particular, it essentially prevents the gases generated at the cathode and / or anode from passing to the anode or cathode compartment.
  • a preferred membrane is an ion exchange membrane, for example based on polymers. In addition to polymer membranes, ceramic membranes can also be used.
  • the material of the anode is not particularly limited and depends primarily on the desired reaction.
  • exemplary anode materials include platinum or platinum alloys, palladium or palladium alloys, and vitreous carbon.
  • Other anode materials are also conductive oxides such as doped or undoped TiO 2 , indium tin oxide (ITO), fluorine-doped tin oxide (FTO), aluminum-doped zinc oxide (AZO), iridium oxide, etc.
  • ITO indium tin oxide
  • FTO fluorine-doped tin oxide
  • AZO aluminum-doped zinc oxide
  • iridium oxide etc.
  • the source of the alkyne of the chemical formula (I) and a first feed device (2) for the alkyne of the chemical formula (I) are not particularly limited.
  • the alkyne of the chemical formula (I) can originate, for example, from a storage container or other container as well as from a separate reactor, etc. as a source.
  • pipes, hoses, etc. can serve as the first feed device.
  • the source for the alkyne of the chemical formula (I) and the first feed device (2) for the alkyne of the chemical formula (I) are adapted to the respective alkyne with regard to the materials used, so that they are not affected by the alkyne of the chemical formula ( I) be attacked.
  • the first supply device (2) for the alkyne of the chemical formula (I) supplies the alkyne of the chemical formula (I) to the gas diffusion electrode.
  • Example 1 Reduction of ethyne:
  • the cell was flushed with argon throughout the experiment. After a 10 minute break-in period of fumaric acid was (58.7 mg, 0:51 m mol) and KOH (200 ⁇ l 5M, 1 m mol) was added. The conversion to potassium succinate after an equivalent charge of 4.1 F / mol was complete. The initial current efficiency was over 90%.
  • the good selectivity comes from the low reactivity towards electrohydration with Cu electrodes conditions.
  • Electronically deactivated internal alkenes such as crotyl alcohol were found to be inert to overreduction.
  • Ethyne, propargyl alcohol and 2-butyn-1-ol were evaluated as substrates. None of the 3 substrates can be regarded as activated, which underlines the high activity of the catalytic process. Propargyl alcohol and 2-butyn-1-ol are difficult substrates to consider, since both have electron-donating substituents. 2-Butyn-1-ol is also an internal alkyne that is sterically hindered.
  • alkyne hydrogenation described here can, in addition to the high-volume compounds, also be used for the electro-organic synthesis of specialty chemicals such as active ingredients or feed additives.

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Claims (9)

  1. Procédé d'hydrogénation électrochimique partielle d'alcynes de formule chimique (I) en alcène,
    Figure imgb0019
     dans laquelle R et R' sont choisis parmi des radicaux minéraux et/ou organiques,
    dans lequel on hydrogène le composé de la formule chimique (I) à une électrode contenant du cuivre, l'électrode contenant du cuivre étant constituée sous la forme d'une électrode à diffusion de gaz.
  2. Procédé suivant la revendication 1, dans lequel le radical minéral et/ou organique est choisi parmi -H, -D, des radicaux alcoyle, alcényle, alcinyle et/ou aryle, substitués ou non substitués, -OH, -OR*, -SH, -SR*, -NH2, -NR*R‡, -COOH, -COOR*, -CHO, -COR*, -PH2, -PR*R‡, -F, -Cl, -Br, -I, -NO, et -NO2, R* et R‡ représentant des radicaux organiques et/ou minéraux.
  3. Procédé suivant la revendication 1 ou 2, dans lequel, ni R, ni R' ne sont -H ou -D.
  4. Procédé suivant l'une des revendications précédentes, dans lequel l'alcyne de formule chimique (I) n'a pas de radicaux attirant les électrons,
    dans lequel les radicaux attirant les électrons sont choisis parmi -COOH, -COOR*, et des radicaux alcoyle et/ou aryle fluorés, R* représentant un radical organique et/ou minéral.
  5. Procédé suivant l'une des revendications précédentes, dans lequel on effectue l'hydrogénation par un donneur de protons, choisi parmi l'eau et les alcools ayant de 1 à 20 atomes de carbone.
  6. Procédé suivant l'une des revendications précédentes, dans lequel l'alcyne de formule chimique (I) se présente sous forme gazeuse.
  7. Utilisation d'une électrode contenant du cuivre pour l'hydrogénation électrochimique partielle d'alcynes de formule chimique (I) en alcène,
    Figure imgb0020
     dans laquelle R et R' sont choisis parmi des radicaux minéraux et/ou organiques, l'électrode contenant du cuivre étant constituée sous la forme d'une électrode à diffusion de gaz.
  8. Installation d'hydrogénation électrochimique partielle d'alcynes de formule chimique (I) en alcènes
    Figure imgb0021
     dans laquelle R et R' sont choisis parmi des radicaux minéraux et/ou organiques, comprenant
    une cellule (1) d'électrolyse, comprenant une électrode contenant du cuivre, qui est constituée pour réduire l'alcyne de formule chimique (I) en alcène ;
    une source de l'alcyne de formule chimique (I) (3), qui est constituée pour mettre à disposition l'alcyne de formule chimique (I) ; et
    un premier dispositif (2) d'envoi de l'alcyne de formule chimique (I), qui est constitué pour envoyer l'alcyne de formule chimique (I) de la source d'alcyne de formule chimique (I) à la cellule d'électrolyse, l'électrode contenant du cuivre étant constituée sous la forme d'une électrode à diffusion de gaz.
  9. Installation suivant la revendication 8, dans laquelle le premier dispositif (2) d'envoi de l'alcyne de formule chimique (I) envoie l'alcyne de formule chimique (I) à l'électrode à diffusion de gaz.
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US11746426B2 (en) 2019-07-10 2023-09-05 California Institute Of Technology Stabilization of a co-bound intermediate via molecular tuning promotes CO2-to-ethylene conversion
CN110438523B (zh) * 2019-09-05 2021-12-03 南京大学 一种以重水为氘源的无催化剂电化学氘代方法
CN112342562B (zh) * 2020-10-24 2023-03-07 西北工业大学 一种电催化乙炔偶联制1,3－丁二烯的方法
CN112301373A (zh) * 2020-10-24 2021-02-02 西北工业大学 一种电催化选择性还原烯烃中炔烃杂质的方法
CN112301369A (zh) * 2020-10-24 2021-02-02 西北工业大学 一种电催化半氢化气相炔烃合成烯烃的方法
CN113388853B (zh) * 2021-05-27 2022-05-17 杭州师范大学 一种对碳碳叁键高选择性加氢的电化学催化方法
DE102021119761A1 (de) 2021-07-29 2023-02-02 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung eingetragener Verein Verfahren zur selektiven katalytischen Hydrierung organischer Verbindungen sowie Elektrode und elektrochemische Zelle für dieses Verfahren
CN114411179B (zh) * 2021-12-31 2024-09-06 西北工业大学 一种电催化1，4-丁炔二醇加氢制备1，4-丁二醇的方法
CN114411177A (zh) * 2021-12-31 2022-04-29 西北工业大学 一种用于合成氘代烯烃的电催化方法
CN114196984B (zh) * 2022-01-20 2023-12-08 辽宁大学 一种碳纸上恒电流电沉积铜基催化剂及其制备方法和在电催化4-乙炔基苯胺中的应用
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