SA518390888B1 - Method for preparing hydrocarbon-selective gas diffusion electrodes based on copper-containing catalysts - Google Patents

Abstract

The present invention relates to a gas diffusion electrode comprising preferably a copper-containing carrier, a first layer containing at least copper and at least one bond, such that the first layer contains hydrophilic and hydrophobic pores and/or channels , additionally comprising a second layer having at least one copper and one bond, so that the second layer rests on the carrier and the first layer falls on the second layer, and so that the bond content of the first layer is less than the second layer. The invention further relates to a method for producing a gas distribution electrode of this type and an electrolysis cell comprising a gas distribution electrode of this type. shape 3

Description

Method for preparing hydrocarbon-selective gas diffusion electrodes based on copper-containing catalysts Full description

Invention background

The present invention relates to a gas diffusion electrode (GDE) comprising preferably

on a carrier containing copper and a first layer comprising at least one copper and at least one bond;

where the (first) layer includes both hydrophilic and hydrophobic pores and/or channels; Include an additional

on a second layer comprising the copper and at least one bond where the second layer is above the carrier

And the first layer is above the second layer, so that the link content in the first layer is less than the layer

the second” and the production process of this gas distribution electrode and the included electrolysis cell

on this gas distribution pole.

Fossil fuel combustion currently covers about 780% of global energy demand. These combustion processes resulted in approximately 7 34 million metric tons of gas

Ladle (CO) carbon dioxide in the atmosphere in 2011. This

Firing is the simplest way to get rid of large amounts of carbon dioxide (lana) coal power

.) The large brown coal power plants exceed 50,000 tons per day

The discussion about the negative greenhouse gas effects of carbon dioxide on climate led to consideration of the (sale) 5 use of carbon dioxide. in thermal terms; carbon dioxide level

das is low and can therefore be reduced back to ALE products for use only with agra

in nature; Carbon dioxide is converted into carbohydrates by photosynthesis

photosynthesis This process; Which is divided into a number of component steps over a period of time

spatially at the molecular level; It can be applied on an industrial scale only with difficulty. Electrochemical 0 reduction of carbon dioxide is the most efficient route at present compared to catalysis

pure photosynthesis. As in photosynthesis; in the process; The carbon dioxide is converted into a high-energy product (such as BL1:©, BL1© CO, C1-C4 alcohols, etc.) with the provision of electrical energy, preferably obtained from renewable energy sources such as wind or sun. 5. The amount of energy required in this reduction corresponds ideally to the combustion energy of the fuel; it should only come from renewable sources or by utilizing electricity that cannot be accepted from the grid at that moment. however; Overproduction of renewable energies is not always available, but for the time being only in periods of strong insulation and/or winds. Nevertheless; The situation will get stronger in the future (Cul).

With the release of renewable energy increasing or will stabilize since the facilities will be in different locations. It was not until the 1970's that there was a high level of systematic studies of the electrochemical reduction of a second

0 carbon dioxide. Despite many efforts; However, until now it has not been possible to develop an electrochemical system in which carbon dioxide can be reduced stably and long-term in a manner that is strongly favorable for competitive energy sources with high current density, Loy, LUSH, and acceptable yield. Because of the scarcity of fossil raw resources and fuel resources; unavailability of volatile renewables; Therefore, research on the reduction of carbon dioxide has become the focus of greater interest

since when. US Patent Document 2006026323211 relates to a process for manufacturing a gas distribution electrode involving preparation of a powder mixture containing at least a catalyst and a hinder, application of the powder mixture to a conducting support to a vessel, and compaction of the powder mixture to the conductive support.

0 US patent document A5873988 relates to a multilayer electrode with a porous core structure produced by sintering and consisting of an electrically conducting material for an electrolysis cell especially with a solid electrolyte electrolyte in which the porous core structure contains at least two layers of spherical bodies made of metal densely packed together; The aforementioned layers are formed by sintering and are joined by clasping

5 with the layer facing the electrolyte constituting the active layer and it is made as a fine layer of 1 for spherical bodies of the same size or almost the same size and the layer that covers

The active layer on the back is made as a coarse layer of spheres that are larger than the spheres in the active layer. US Patent Document 2013022847011 relates to a carbon-based gas conversion process

OS and non-polar organic gases, for example, carbon-based gases, carbon oxides 5 to longer chained organic gases, such as liquid hydrocarbons. longer chained branched-chain liquid cgaseous hydrocarbons “branched-chain gaseous hydrocarbons” gaseous branched-chain hydrocarbons as well as chain or branched-chain organic compounds. in general; Method 0 is for chain modification of hydrocarbons and organic compounds; Loy is the lengthening of the string; The final conversion to liquids includes; but not limited to hydrocarbons » alcohols; and other organic compounds. GENERAL DESCRIPTION OF THE INVENTION The electrochemical reduction of carbon dioxide to hydrocrions is described; especially to chemical raw materials (CoH 61000/0 -) in the literature since 1990. There has been a significant rise in research activities over the past few years because the availability of excess electrical energy from non-fossil generation sources such as solar or wind makes storage The use of this energy seems feasible from an economic point of view. Metals are used as a catalyst for the electrolysis of carbon dioxide” in general; Y. Hori, Electrochemical 002: Some of them are shown for example in Table 1; From reduction on metal electrodes, in: C. Vayenas, et al. (eds.), Modern Aspects of Electrochemistry, Springer, New York, 2008, p. 189-89 Table 1 shows typical Faraday efficiencies (FE) on various metal cathodes for example; Carbon dioxide is practically and exclusively reduced today to CO on Ag, Au, Zn and to some extent on Ga 00, while many 5 hydrocrions have been observed as reduction products on Cu. as well as pure minerals; metal alloys; As well as mixtures of metal oxide and active metal oxide, the co-catalyst, which are bald in place

0 5 — interest” as it can foam the selectivity of a particular hydrocarbon. However, the previous art in this regard has not yet developed. Table 1: Faraday efficiency of carbon dioxide on various metal electrodes

The CHa electrode is wet H> | HCOO | CO | C3H70OH | Total CoHsOH Au |00 )00 ]00 ]00 078710 9800102 Ag ]00 )00 ]00 )00 ]08]815 94.6124 Zn ]00 )00 ]00 ]00 ]61 794 (99 ] 954 [29 ]00 ]00 00 28/283 2262 - Ga |00 )00 ]00 |00 00233 (10201790 F) ]00 ]00 (00 ]00 ]00 ]74 035 1024 He ]00 00) 00 ]00 ]00 ]995 00 ]995 in] 00 0000 00 [21 ]949 33 003 Sn) 00 00 00 00 71 #84 |46 100.1 cd 13 [00] 00 [00] 784139 [94] 1030 TI [00] 00 [00] 00 [00] 951) 62] 1013 8 [00] 01 [00] 00 [00] 14 889 04 - Fe [00 )00 ]00 )00 ]00 ]00 )9481948 Py [00 ]00 ]00 )00 ]00 01 ) 9581957 Ti [00 ]00 ]00 ]00 ]00 ]00 [9971997] Didi's reaction equations for example JE show the reduction reactions at the anode and at the cathode over the copper cathode. Formation of ethylene values is of particular interest here. Reduction on other metals is similar to this. 0 Cathode: 41:0 + © > 12H" + 12 + 00 2 Anode: 12 “ + 1211 * * 02 3 C 611:0 Total equation; Op 3 + pectin — 211:0 + 2 0

The single polar equations show that very complex processes that have not yet been explained in detail are performed here with feedstocks; For example » 0© or format for each of these intermediates; A particularly preferred position at and/or on the copper cathodes should be necessary. This means that the catalytic activity changes according to the crystal orientation of the copper surface; As described in; For example” Y Y. Hori, I. Takahashi, 0. Koga, N. Hoshi, “Electrochemical reduction of carbon dioxide at various series of copper single crystal electrodes”; Journal of Molecular Catalysis A: Chemical 199 (2003) 39-47; or M. Gattrell, N. Gupta, A. Co, “A review of the aqueous electrochemical reduction of 0020 -hydrocarbons at copper”; Journal of Electroanalytical Chemistry 594 (2006) 1-19 For the ability of all these crystal surfaces to provide high ethylene formation efficiency at high current densities; The electrode must not consist of soft paper; But it should be micro to nanostructured. The accessibility of these catalytic activation sites limits ethylene formation to a Faraday efficiency (FE) efficiency of approximately 720 or restricts the achievable current density to +/10 mA

K. I. Kuhl, E. R. Cave, D. N. Abram, and 1. F. Jaramillo, Energy as cited in Zan [15.and Environmental Science 5, 7050-7059 (2012)

H. Yano, T. Tanaka, M. Nakayama, K. Ogura, “Selective electrochemical «21d plus reduction of COxz to ethylene at a three-phase interface on copper(I) halide-confined Cu-mesh electrodes in acidic solutions of potassium halides"; Journal of Electroanalytical ‎«Chemistry 565 (2004) 287293 20 achieved current densities in the region of 100 AL ampere/cm²; Thus the 'intrinsic' Faraday efficiency of the electrode cannot be determined. In short, the current density of methods known from prior art is less HES than the relevant values for economical use. 5 Electrochemical reduction of carbon dioxide to ethylene; it was possible that with the help of copper catalysts deposited on site to achieve a current density of 170 mA/cm2 with a Faraday efficiency of over 755 over an electrolysis time of 60 minutes, as shown in in-house studies. method; the selective electrode can

to decrease over time; which can lead to an increase in hydrogen production The change in selectivity over time can be related to the structural synthesis of the material; Which was noticeable clad (JBI) from microscope images. Dendritic copper nanostructures containing both “n©” and “n©” in the form of C0 as a selective catalyst were identified.

5 Industrially relevant current densities can be achieved using gas diffusion electrodes (GDEs ( electrodes) which is known from prior extant art; eg JE chloralkali electrolyses operated on an industrial scale The use of copper-based gas distribution electrodes in electrolysis cells appears to be useful in the energy-efficient conversion of matter from carbon dioxide to hydrocarbons.

0 selectivity (Faraday efficiency in 7) and material conversion (current density in mA/cm2) are a characteristic of the specific electrode of interest. Gas distribution electrodes based on Silver/silver oxide/_PTFE were used (PTFE) polytetrafluoroethylene was recently used on an industrial scale to produce a sodium hydroxide solution in existing chlora-alkali electrolysis processes (oxygen-depolarized electrodes). It was possible to increase the efficiency of the chlora electrolysis process. Alkali at a ratio of 30-740 compared to conventional electrodes The methodology for embedding the catalyst with PTFE is known from many publications and patterns The known embedding methods are divided into three different process paths: 0 1. Wet methods using a micro-emulsion of PTE stabilized with a masticating agent .microemulsion 2. Wet methods using an emulsion (38) of Nafion® surfactant stabilized. 3. Dry methods by rectification of the pre-mixed catalyst / PTFE mixture Yen. in this context; The aforementioned wet method 1 can have the aforementioned disadvantages of ns 5 apart from the fact that examples of gas distribution electrodes known from the literature contain only the catalyst as a material

Additives consisting mainly of conductive coal bound (the loading of high catalyst shunts must be high): Suspensions or pastes that are usually applied by spraying or tape coatings usually have a long drying period; Which means that continuous production with relatively large electrode areas (industrial related) is not economically feasible. excessive drying quickly leads to cracking; is termed "mud cracking" within the applied layers rendering the electrode unusable. The porosity of the applied (generated) layer is determined almost exclusively by evaporation of the solvent. This process is solvent-dependent or The boiling point is in the form of Je and can lead to a high rate of rejection of the electrodes produced, as it is not possible to guarantee evaporation in a homogeneous manner 0 in the whole area.Another pivotal disadvantage is the use of surfactants (surfactants) or thickeners; plastic materials; which Used to stabilize particle suspensions because they cannot be removed without residue by the corresponding drying stages or thermal crosslinking process Embedding Process 2 where Nafion® (perfluorosulfonic acid (PESA) acid) is used as a binder instead of polytetrafluoroethylene. It has identical drawbacks as a 5 wet chemical method with an appropriate surfactant is used here as well.Nafion® itself is a hydrophilic ionomer having groups and 1150-18 that are highly acidic which can lead to acidic corrosion Unwanted or partial decomposition of the metal in the case of some catalysts. Nafion® bonded films also have a much lower porosity than PTFE bonded films. The purely hydrophilic properties of Nafion® can also be undesirable because Nafion® 0 (due to its hydrophilic properties) is not suitable for the formation of useful hydrophobic channels for gas transport within the gas distribution electrode. Therefore, interchangeable electrodes must be formed Nafion®-based coating processes may require multiple coatings to be able to implement the essential properties of a gas distribution electrode.However, multi-layer coating processes are not very attractive for economic reasons.Nafion®-based coating processes can lead to uneven formation 5 Drying method 3 is based on a cylindrical grinding process, eg on PTFE powder/catalyst The corresponding technology can be attributed to EP No. 210297377

According to which electrodes were produced based on :00020 for batteries. German Patent No. 13,710,168 is the first reference to employ the drying process in connection with the preparation of electrocatalyst electrodes This technique was further used in patents related to the production of silver (I) or silver (II) oxide (©5117)11 Gas distribution electrodes (oxygen-dpolarized electrodes). European patent No. 212444526 and German patent No. 023612 2005 1110 mentioned mixtures with a linker content of 0.5-77. The carrier used was Ag or Crosslinked nickel the wire diameter is 0.3-0.1 mm and the mesh size is 0.2-1.2 mm The powder is applied directly to the mesh before being fed to the roller burnish Described German Patent No. 10148599 A1 or 0 European Patent No. 0115845 B1 A similar process in which the powder mixture is first extruded to give paper or film which is then pressed onto a mesh in a further step. Due to the lower mechanical stability, the latter method is less suitable than the single shall process mentioned above. Describes European Patent No. 2410079A2 A single-stage process for the production of an oxygen-dpolarized electrode based on silver with the addition of 5 Jie metal oxide supplements. MnsOs, WO3, ,11102, Jie spinels +20) adapted bridle and reversed spinels ((Co,Ni,Zn)(Ti,ADOs Jie) LaNiOs, ie perovskites B0201. It was also found that the supplementation of silicon nitride with boron nitride TIN, AIN, SiC, TiC, CrC, WC, Cr3Ca, 1107 is suitable; Oxides of type 7102 and 170 were found to be particularly suitable. The material is expressly declared to be a filler with no stimulating effect. The goal here is explicitly to reduce the hydrophobic characteristic of the electrode. German Patent No. 10335184A1 discloses catalysts that can be used as substitutes for depolarized oxygen-electrodes: precious metals; For example Pt, Rh, Ir, Re, Pd are precious metal alloys; For example. :04; ddl metal compounds, for example, 5 metal sulfides (dial metal sulfides and oxides) and Chevrel phases, for example, and 11048025 or: 1108256, as it may also contain Re, Pd, etc.

Copper-based gas distribution electrodes known to generate hydrocriones based on carbon dioxide “for example” are mentioned in papers R.2,2.

Cook [J.

electrochem.

Soc., vol. 137, no. [2.1990 1990]. This stated a wet chemical method based on a mixture of PTFE 30B305 (suspension) Vulkan XC 72 [Cu(OAc): The method describes how to apply a hydrophobic gas transfer layer using three coating cycles” and a catalyst containing three layers extra. Each step follows a drying phase (325°C) with a subsequent static pressure process (5000-1000 psi). for the electrode obtained; Faraday efficiency > 760 and current density > 400 Ampere / Pan are recorded however; Cloning experiments cited hereafter as comparative examples demonstrate that the described static pressure method does not lead to stable electrodes. The added Vulkan 0 2072 was also found to have a negative effect; Thus it was not possible for Lad to obtain any hydrocriones. German Patent No. 441 30 101 a1 discloses a biporous pore system in a “Sl” distribution electrode but without a two-layer structure. For this Jie single layer structure, electrode flux has been observed in preliminary tests at the commission. 5 single-layer structure (Sarg also found; for example” in German Patent No. 571 031 2010 10 1. According to German Patent No. 441 30 11101) a metal support structure is rolled in a catalyst film produced herein. Disclosure US Patent No. 2013/0280625 | Describes a two-layer structure of a gas distribution electrode but does not reveal any hydrophobic pores; only the pores in the distribution layer 0 are disclosed as hydrophobic layer. A resinous material is used in a binding manner in it and is coated to form the pores. That »Initial preliminary internal tests showed that this is not suitable for the purpose.Therefore a cathode for the electrolysis of carbon dioxide is needed, since the carbon dioxide can be converted in serious form to hydrocarbons.In addition, the object of the invention is to provide a concept for a catalyst that does not depend on 5 Deposition of copper in situ but provides a copper gas distribution electrode which can be processed to give the electrode.Furthermore, the object of the present invention is to develop an electric chain

electrocatalysts 48 are long-term stable and embedded in gas distribution electrodes that can be connected to electrical contacts. The inventors found that the electrodes for distributing a particularly reactive and selective CoH gas must meet several parameters required for ethylene formation. The following is a discussion of the electrode-specific characteristics of the invention. Furthermore; The inventors found that there were ,dala to specific demands on the catalyst in order for it to form the electrode for ethylene. These criteria are not clear from prior art and form the basis for the development of hydrocarbon-selective electrodes of this type. It was found that the important specific factors and requirements for a gas-selective hydrocarbon distribution electrode are as follows: 0 Good wettability of the electrode surface in order for the aqueous electrolyte to be 0 or *11 ions in catalytic contact. *11 is required for ethylene, alcohol, Jie ethanol, propanol, or glycol 0 High electrical conductivity of the electrode or catalyst and homogeneous potential distribution across the entire electrode area (product-dependent selectivity). 0 High chemical and mechanical stability in the electrolytic process (suppression of cracking and corrosion) 0 5 Porosity defined by an appropriate ratio between hydrophilic or hydrophobic channels or pores (ensuring simultaneous availability of CO2 with presence of HF ions) This may or may be accomplished according to the invention.In the first cls the present invention relates to a gas distribution electrode comprising preferably a copper-containing carrier preferably in the form of a foil-like structure and a first layer comprising at least 0 of copper and at least one bond where The first layer includes hydrophilic and/or hydrophobic pores and/or channels; further includes a second layer comprising copper and at least one binder; where the second layer is over the carrier and the first layer is over the second layer where the binder content in the first layer is less than second class . In another aspect the present invention relates to a process for producing a gas distribution electrode comprising 5- production of a first mixture comprising at least copper and optionally at least one binder; - production of a second mixture that includes at least copper and at least one linker;

- apply the second mixture containing at least copper and at least one binder to the copper-containing carrier preferably”; preferably in the form of a wafer-like structure; - application of the first mixture containing at least copper and optionally at least one bond to the second mixture; - optionally applying more mixture to the first mixture and - circulating dry the first and second mixtures and optional additional mixtures on the stand to form a second layer, first layer and optionally further layers; So that the ratio of the binder in the second mixture is 730-3 “Calls, preferably 730-10 by weight,” and more preferably 720-10 by weight; depending on the second mixture; such that the binder ratio in the first mixture is 0 2110-0 by weight; preferably 710-0.1 wt; 1-710 by weight is more preferred; rather, 1 to 77 by weight is preferred; Thanks even more by 77-3 by weight; Depending on the first mixture;» such that the content of the binder in the first mixture is smaller than in the second mixture; or comprising - the production of the first mixture comprising at least copper and at least one binder; 5 - Apply the first mixture comprising at least an alkaline and at least one binder preferably to the copper-containing carrier; preferably in the form of a plate-like structure; - dry rolling of the first mixture on the conveyor to form the first layer; so that the ratio of the binder in the mixture is 730-3 by weight; diag 720-3 wt.; It is also preferred 3-0 by weight” depending on the first mixture. 0 as the present invention relates; in another aspect of the electrolytic cell incorporating the gas distribution electrode of the invention. Other aspects of the present invention may be taken from the dependent claims and detailed description. BRIEF EXPLANATION OF DRAWINGS The appended drawings are intended to clarify and give greater understanding to embodiments of the present invention. 5 In conjunction with the description, they serve to clarify the concepts and principles of the invention. Other renderings and many of the features mentioned are shown in connection with the graphics.

Items in graphics are not necessarily shown to be scaled relative to each other. Identical attributes and components have the same function and effect for every single reference number in graphics forms unless otherwise indicated. Figure 1 shows a schematic diagram of the gas distribution electrode of the invention with hydrophobic and hydrophilic regions or channels. Figure 2 shows a schematic diagram of the production of the gas distribution electrode of the invention based on the illustrative polytetrafluoroethylene-linked catalyst. Figure 3 shows a schematic diagram of the DAT embodiment of the gas distribution electrode of the invention in the form of a layered preparation. 0 Figures 4 to 6 appear; in schematic form; Illustrative diagrams of a possible electrolysis cell construction in an embodiment of the present invention. Figures 7 and 8 show illustrative characterization models of the gas distribution chamber downstream of the gas distribution electrode of the invention in the electrolytic cell of the invention. Figure 9 shows the Faraday efficiency results for the electrolytic cell from comparative example 3. 5 Figures 10 and 11 show the Faraday efficiency results for the electrolytic cell from comparative example A Detailed description: Definitions “hydrophobic” is understood in the context of the present invention as water repellent . according to the invention; Hydrophobic pores and/or channels are those that repel water. on dag in particular; The hydrophobic properties according to the invention are associated with substances or molecules having non-polar groups. In contrast; 'Eld moheb) is understood to mean the ability to interact with water and other polar substances. in demand; Figures are indicated by 7 by weight; Unless otherwise specified or clear from the description. 5 In aspect (J) the present invention relates to a gas distribution electrode comprising

Preferably copper-containing carrier; Preferably in the form of a structure (GEL and

And

the first layer containing at least copper and at least one bond; So that the class includes

(First) on the pores and/or hydrophobic and hydrophilic channels [coll] comprising a second layer comprising

Copper eg at least one bond” with the second layer above the conductor and the first layer above

layer cdl) so that the link content in the first layer is lower than in the second layer.

the second layer; Just like the first class; They may include hydrophobic and/or hydrophilic pores and ducts

waterproof.

What is also shown is the gas distribution electrode preferably comprising the 0 Cu-containing carrier by virtue of being in the form of a foil-like structure; And

The first layer contains copper at least eg one bond on (JW) so that it includes

Hydrophobic and hydrophilic pores and/or channels.

Figure 1 shows the relationships between the hydrophobic and hydrophilic regions of a gas distribution electrode

Achieves a good triangular liquid/solid/gas relationship. In this case; at the pole; There shall be 5 hydrophobic channels or regions 1 and hydrophilic channels or regions 2 on the electrolyte side

With 3 catalytic sites of low activity are present in the 2 hydrophilic regions. In addition;

There are 5 catalytically inactive sites on the gas side.

The 4 particularly active catalytic sites are located in the three-phase liquid/solid/gas region.

The ideal gas distribution electrode thus has the maximum penetration of the bulk material by the hydrophobic and hydrophilic 0 channels in order to obtain the maximum number of three-phase regions of the catalyst sites

active. In this caval) according to the invention it is necessary to ensure that the first layer includes pores and/or

Hydrophobic and hydrophobic channels. Through the appropriate adjustment of the first layer; effect can be achieved

It has the maximum number of active catalytic sites in the Gl distribution electrode which is further explained in

other preferred models; and/or affiliate protections.

For Hydrocarbon Selective Gas Distribution Electrodes for Carbon Dioxide Reduction; More core features are required than conventional systems can provide. Thus, the electrocatalyst and the electrode are closely related. The stand here is not particularly restricted; A ribbon that is suitable for a gas distribution pole, and it is preferable that it contain copper. For example; Parallel wires can also form the rack in the extreme case. J specific embodiments; The carrier shall have a “FEL”-like structure, preferably a net; Preferably a copper mesh, this can ensure sufficient mechanical stability and efficiency as a GL distribution electrode, for example, Led, with regard to high electrical conductivity. and in certain embodiments; The carrier may be suitable for Lad with regard to the electrical conductivity of the first layer. By using 0 copper in the holder; It is possible to provide proper conductivity and reduce the risk of drawing in unwanted foreign metals. and in favorite personifications; The stand is made of brass. Preferred carrier contains copper; In the pals embodiment it is a copper mesh with mesh size “ 0.3 mm > » > 2.0 mm; 0.5 mm > » < 1.4 mm; wire diameter x is 5 mm > X < 0.5 mm In addition, by virtue of the fact that the first layer includes copper, it is also possible to ensure high electrical conductivity of the catalyst, especially in combination with the copper grid, and homogeneous voltage distribution across the entire electrode area (selective voltage-dependent product). In order to achieve good conductivity and stability.In certain embodiments, the binder includes eg ads, hydrophobic and/or hydrophilic, eg hydrophobic coll, especially polytetrafluoroethylene.This can achieve proper organization of pores or channels More specifically, the first layer is produced using polytetrafluoroethylene particles having a particle diameter between 5 and 95 micrometers; preferably between 8 and 70 µm. Suitable PTFE powders include; Jha on Dyneon® TF 5 and 1750 Dyneon TF. Suitable binder particles; For example particles

polytetrafluoroethylene; may be; For example; are nearly spherical ie spherical; can produce; For example, through emulsion polymerization. in certain embodiments; The binder particles are free of active surfactants. The particle pas can be specified here for example; In accordance with ISO 13321 13321 or 50 108-4894 (D4894-982) and may correspond, for example, to manufacturer data (eg TF 9205 117: Average Particle Size 8 µm ISO 13321; 1750 (TF) Average Particle Size 25 µm ASTM J American Society for Testing and Material (D4894-98a 198-4894) Plus However, the first layer comprises at least copper which may be, for example, in the form of metallic copper and/or copper oxide serving as a catalyst site. In certain embodiments the first layer comprises metallic copper in the (0) oxidation state. In embodiments Certain; the first layer includes copper oxide and in particular 00120. The oxide here may contribute to the stabilization of the +1 oxidation state of copper, thus to maintain selectivity for ethylene with a long-term stability of 5. Under electrolytic conditions, it can be reduced to copper. Certain embodiments; the first layer includes at least 40 by 7 (ns maize (maize) preferably at least 50 at 7# and preferably at least 60 at brass; depending on the class. This can ensure adequate mechanical stability and suitable catalytic activity of this first layer acting as the catalyst layer (CL) in certain embodiments; Analgesia to produce the gas distribution electrode 0 of the invention is provided as particles; which is further defined later here. in addition to; The first layer Lad may include additional enhancers that improve the catalytic activity of the gas distribution electrode in combination with copper. in certain embodiments; The first layer includes at least one metal oxide that preferably has a lower reduction potential than the evolution of ethylene; By virtue of being CeO, ©»:0:, 7200:, MgO,:0DaH, 7:02 and/or at least one phase of 5 Cu-rich minerals; Preferably, the Cu-rich phase should be at least a unit selected from the combination of Cu-Al Cu-Zr, Cu-Y, Cu-Hf, CuCe, Cu-Mg and Cu-Y- dE systems.

Al, Cu-Hf-Al, Cu-Zr-Al, Cu-Al-Mg, Cu-Al-Ce with copper contents > 60 at#; and/or copper-containing perovskite and/or impurity perovskite and/or related perovskite compounds; Cus YBaxCusOr5 1< 6 > is preferred. (corresponding YBaxCu3075Xsd ( ¢ Lai 85S10.15Cu03.930Clo.053, (La,S1)2CuO4 , 114012 02003). The preferred enhancers here are metal oxides in certain embodiments; the metal oxide used is insoluble in water, so that the electrolytes can be used in electrolysis using the gas distribution electrode of the invention. Furthermore, by virtue of the fact that the oxidation-reduction potential of the metal oxide is lower aie for the evolution of ethylene" it is possible to ensure that ethylene can be prepared from carbon dioxide by means of the gas distribution electrode of the invention In certain embodiments the oxides are not reduced in the reduction of carbon dioxide Nickel and iron, for example, are unsuitable as hydrogen is formed here Furthermore the metal oxides are preferably not inert but preferably form the hydrophilic reaction sites which 5 can be provided to provide protons, especially metal oxide, which are able to enhance the function and production of electrocatalysts that are stable in the long term, as they stabilize the active catalytic nanostructures. (Kar of the structural enhancers here can reduce the elevated surface motion The strength of copper nanostructures and thus reduces their tendency to sinter. This concept originates from a heterogeneous catalyst and will be successfully used in high temperature processes. The promoters used for the electrochemical reduction of carbon dioxide can be in particular the following non-reducible metal oxides within the electrochemical window: (B= 7:02 ZrO; (E = -2.3 7), ALOs (E = 7). -2.4 V), CeO; (E = -2.3 V), MgO (E = -2.5) It should be noted here that the mentioned oxides are not added as additives but gga from the catalyst itself. canny) as well as function as a promoter” it also achieves the advantage of stabilizing copper in the oxidation state 1 and in addition to that it is also an intermediate in the reduction of carbon dioxide; CO, CH ie (or (OH 5) There are many Cu(l) complexes of CO and B13:©, suggesting the stability of these putative feedstocks (see, for example, H. 1935, 57).

Tropsch, W.

J.

Mattox, J.

Am.

Chem Soc

-p. 18- ‎Ogura, Inorg.

Chem., 1976, 15 (9), 2301-2303; J.

S.

Thompson, R.

L. 1 ;1102-1103 Harlow, J.

F.

Whitney, J.

Am.

Chem.

Soc., 1983, 105 3522-3527; and V.

A.

K.

Adiraju, J.

A.

Flores, M.

Yousufuddin, H.

V.

Rasika Dias, Organometallics, 2012, 31, 7926- 7932) In certain embodiments the catalyst has the following inventive properties: In industry; in an embodiment of (ald) very galvanic-rich catalysts having a molar ratio > 60 at /Ja electrochemical sensitization of carbon dioxide are preferably used because of the required electrical conductivity. Particularly preferred in the gas distribution electrodes of the invention are the catalyst structures of Metal oxide/0 Cu produced as follows: to produce metal oxides precipitation does not occur; in certain embodiments; as frequently shown in the pH regime between pH = 6.5-5.5; but can occur in the range of -68.5 0, so that the constituent precursors are not hydroxide carbonates similar to malachite ([2])011(2]605n0©) » azurite ((0:(:)011den) or oycalcite aurichalcite [(2(d0(:])011(”))0N20,0)”; but hydrotalcites ¢(CusALCO3(OH) 16 4(H20)) can be obtained Here's a bigger output. likewise; It is appropriate that layered double hydroxides (LDHs) have the composition -. yH20 where M!'* = Li*, Na*, K*, M?* = ALY, Ti, Hf, Ga ; the corresponding CAD can be precipitated under pH control by 0 co-dose of metal salt solution and basic crionate solution 0. The special feature of these materials is the presence of special copper microcrystals having a size of 4-10 nm which are structurally stabilized by the oxide present.It is possible to achieve the following effects: Ol oxide due to its high surface area can lead to better distribution of catalyst metals; highly dispersed metal sites can be stabilized by metal oxide; chemisorption of carbon dioxide can be improved by metal oxide; and copper oxide can be stabilized.

0 1 9 0 that Lad Drying can occur after precipitation by post calcination in a gas stream :0:/8. can

Ho/Ar The oxide precursor produced is reduced; according to this method; Subsequently directly into a gas stream and keep the oxide booster. The step of Cu to CuO or CuO reduction only 'activation by electrochemical means can also occur at a later time. In order to improve the electrical conductivity of the layer applied before electrochemical activation; It is also possible for the oxide precursor and the activator precursor 5 710-0 to be partially mixed. to be able to increase the base conductivity; It is also possible to mix in and it is not excluded according to the invention that the registered-ready electrode is subjected to subsequent calcination/heat-treatment prior to electrochemical activation. Among copper-rich metals for example CusiZris 77 and 01 «CusZr, which can be prepared from fusion 0 The alloy can then be made as a base and calcined LIS or partly in an argon gas stream 02 and convert it to oxide form. Cu-rich phases of binary systems Cu-Al, Cu-Zr, Cu-Y, CuCe, Cu-Mg 0-112 and the corresponding ternary systems have Cu contents >60 at 7: CuYAL CuHfAL CuZrAl, CuAIMg, CuAlCe 5 is of particular interest. Copper-rich phases are known; For example; from E. Kneller, Y. Khan, U. Gorres, The Alloy System Copper-Zirconium, Part I. Phase Diagram and Structural Relations, for Cu-Zr phases, from Braunovic, M.; 1986, 43-48. ,(1) 77 Zeitschrift fiir Metallkunde Konchits, V.V.; Myshkin, N.K.: Electrical contacts, fundamentals, applications and technology; CRC Press 2007 for Cu-Al phases, from Petzoldt, F.; Bergmann, J.P.; 20 2 (See, for example, Table 507 Schirer, R.; Schneider, 2013, 67 Metall, 504-507

Landolt-Bernstein - Group IV Physical Chemistry Volume 5d, from Cu-Al daly from 1994, p. 1-8 for Cu-Ga phases, and from P. R. Subramanian, D. E. Laughlin, Bulletin of . For Copper-0-11n0 Alloy Phase Diagrams, 1988, 9,1, 51-56 Petzoldt, F.; (taken from Copper-aluminum phases Table 2: Copper-aluminum phases 5) (Bergmann, J. P.; Schirer, R.; Schneider, 2013, 67 Metall, 504-507).

— 0 2 — copper phase | Aluminum | hardness | Resistance [7 wt] |71 wt] A I Specific Electricity [uQcm] RIN m CwAl T [80 ]20 1050 6 l |55 45 so an] 8 1 © A in the case of these phases Which are also among the minerals rich in copper, it is preferable that the ratio of sensitization be greater than 40 at and with a ratio of more than 50 at 7; Thanks to over 60 Jodie though; It is not excluded here that the phases between minerals also contain the non-metallic elements Jie 5 oxygen, nitrogen, sulfur, selenium, and | Or phosphorus, i.e., for example, cooxides, sulfides, selenides, nitrides, and/or phosphides are present. in certain embodiments; The inter-metallic phases Aja were additionally oxidized; The following copper-containing perovskite structures, 0 1 impurity perovskites, and/or perovskite-related compounds can be used for electrocatalysts; Especially for the formation of hydrocrions: 732001076 such that 0 = 1 < 6 CaCusTisOr2, (La,Sr)2CuOs4 ,53m0l18: .45970.15,0003900. in addition to; It does not rule out the use of mixtures of these materials to prepare the electrode of as required »; For subsequent calcination or to perform activation steps. in certain embodiments; The catalyst particles comprise or consist of copper; eg copper particles; which is used to produce z the gas distribution electrode of the invention “having a homogeneous particle size between 5 and 0 µm” and thanks to being 10 to 50 µm; Thanks to between 30 and 50 micrometers. In addition, the catalyst particles in certain embodiments; It has high purity without traces of foreign metals.

through the appropriate structure; Optionally with the help of enhancers, high selectivity and long-term stability can be achieved. It is also possible for reinforcers; for example metal oxides; particle size vs. in production. The above promoters can additionally achieve or improve the following properties: 0 Good wettability of the electrode surface so that it is possible for the aqueous electrolyte or ions *11 to become in contact with the catalyst. (HY is required for ethylene or an alcohol such as ethanol, propanol, or glycol). 0 High chemical and mechanical stability in the electrolytic process (inhibition of cracking and corrosion). 0 0 Determine the porosity in the appropriate ratio between the hydrophilic or hydrophobic channels or pores (ensure that CO2 is available with the presence of *11 ions at the same time). In order to further adjust the porosity of the electrode; in certain embodiments; Copper powder which has a particle diameter of 50 to 600 μm can be supplemented; 100 to 450 jing Kae ¢ is preferred and 100-200 µm is preferred. particle diameter of these supplements; in certain embodiments; It is 1/1-3/5 10 of the total layer thickness of the layer. instead of copper; The supplement may also be an inert mineral oxide jie. This can achieve improved formation of pores or channels. The gas distribution electrode of the invention can be specially produced by the production process of the invention as described below. in certain embodiments; The first class includes less than 75 “calle and preferably less than 71 0 by weight” but also preferably no coal-based, black creon or semi-fillers eg conductive fillers; Class based. It should be noted here that methods known from the literature to produce a gas distribution electrode generally refer to both dry or wet application; To add activated carbon; and conductive black (such as Vulkan XC72), acetylene black, or other charcoal. However, according to the invention it has been found that even traces of charcoal and/or creon black can significantly reduce the selectivity of the catalyst Lad related to hydrocriones and enhance the formation of hydrogen unwanted.

It was found through experiments in the institution with electrodes produced by wet chemical methods that this residue irreversibly poisons the copper-based catalyst (cd) and therefore the produced electrodes do not show any reduction of carbon dioxide to hydrocriones. Therefore, the use of surfactants or surfactants should be avoided. For example Triton 76; in certain embodiments; The wet chemical procedure for embedding copper-based catalysts is therefore not suitable. If only one (first) layer is present at the gas distributing electrode the content or ratio of the binder eg polytetrafluoroethylene; in certain embodiments; It may be 730-3 by weight, preferably 720-3 by weight, and also 10-3 7 by weight, and more preferred by 77-3 by weight; depending on

One (first) layer.

0 The gas distribution electrode of the invention Lad comprises a second layer containing copper and one bonder on (JY) such that the second layer is on top of the carrier and the first layer on top of the (Ald) layer and such that the bond content of the first layer is lower than that of the In addition, the second layer can include coarse copper particles or inert material particles, eg particle diameters range from 50 to 700 μm; preferably 100-450 “sing Sue” to provide structure.

5 channel or breathable fit. in preferred forms; In this (Bland) the second layer consists of 3-730 by weight of the binder »preferably 10-730 by weight of dahl and by virtue of 10-720 Ug of dahil and preferably <710 by weight of the binder by more than 710 by weight and 720 by weight of the binder» based on the second layer; The first layer preferably includes 710-0 by weight of the binder, for example 710-0.1 by weight of the ¢ bond.

0 7110-1 by weight of the link » Thanks also 77-1 by weight of the link; Even preferred also 3 77 weight of the link; Based on the first layer. The link here may be the same link as the first layer; For example polytetrafluoroethylene. In addition; Layer production particles (All) can be in certain embodiments; identical to the molecules in the first layer; But it may also be different. The second layer here is the metal particle layer (MPL) under the catalyst layer. through layers of this sill

5 can specifically create highly hydrophobic regions in the metal particle layer and generate a catalyst layer that has hydrophilic properties. By virtue of the strongly hydrophobic character of the mineral particle layer; He is

Lad can prevent unwanted penetration of electrolyte into Glad transport channels ie flooding

Of which. Furthermore it; The second layer forms contact with carbon dioxide; And therefore should also

be hydrophobic.

in certain embodiments; The second layer partially penetrates the first layer. This can be achieved; For example, Jad

By virtue of the process of the invention a good transition between layers with respect to diffusion is possible.

In addition to the second layer; The gas distribution pole of the invention Lad may have other layers; on

For example above the first layer and/or on the other side of the stand.

to produce a multilayer gas distribution electrode; For example Gul can first be applied through an application

(Jal) admixture for mineral particle layer based on Cu mixture Je conductivity of Cu 0 dendritic having particle sizes between 5-100 jing Sie ¢ with a thickness of less than 50 μm »

Coarse copper or particles of inert materials have particle sizes of 100-450 μm.

Thanks to be 100-200 μm; It has a PTFE content of 730-3 by weight;

preferably 720 by weight; with a layer thickness of 0.5 mm for example; to a copper mesh of mesh size 1

mm for example (thickness; for example » 0.6-0.2 mm; for example 0.4 mm); And to pull it off 5 by taping the frame or paint. Corresponding dendritic Cu may be present Lad in the layer

The first. This can be followed by further application of the catalyst/PTFE mixture (catalyst bed);

For example with a polytetrafluoroethylene content of 0.1-710 by weight; smoothing or clouding;

For example, by means of a frame with a thickness of 1 can, in order to obtain the total thickness of the layer

(HI) layer thickness of 1 mm. The layer previously prepared in this way may then be fed with polish having a gap width Hp = 0.7-0.4 mm; preferably 0.5-0.46mm; come out; to get

The multilayer gas distribution electrode as shown Lily in Fig. 3; copper mesh 6;

metal particle layer 9 and catalyst layer 10. Mechanical stability can be better achieved;

further reduction in electrolyte penetration and better conductivity; Especially when using the network as a carrier.

Gradual production of gas distribution electrode by applying sieving and rolling each layer 5 apart can reduce adhesion between layers; Hence it is less preferred.

on the other hand; The present invention relates to a process for producing a GA distribution electrode comprising:

– production of a first mixture comprising at least copper and optionally at least one binder; - production of a second mixture that includes at least copper and at least one linker; - application of the second mixture comprising at least copper and at least one bond to the carrier preferably containing copper”; preferably in the form of a wafer-like structure; Gadi - 5 The first mixture comprising at least copper and optionally at least one linker to the mixture

the second; - optionally apply more mixtures to the first mixture; (f) dry rolling of the first, second and optional additive mixtures on the stand to form a second layer, first layer and optionally further layers;

0 wherein the binder ratio in the second mixture is 30 710 by weight; Preferably 720-10 by weight» on a second mixture basis; Whereas the binder ratio in the first mixture is 710-0 by weight; preferably 0.1 = 0 wt; 710-1 wt is preferred; It is preferred more than that 77-1 by weight, but also by 7 7-3 by weight; Based on the first mixture where the content of the binder in the first mixture is lower than in the second mixture.

Lad is described for a process for producing a gas distribution electrode comprising – production of a mixture of Jl comprising at least copper and at least one binder; - apply the first mixture comprising at least copper and optionally at least one bond to the preferably copper-containing carrier; preferably in the form of a wafer-like structure;

0 - dry rolling of the first mixture on the stand to form the first layer; where the ratio of the binder in the mixture is 730-3 by weight; preferably 720-3 wt. li 710-3 wt.; It is also preferred at a ratio of 77-3 by weight; based on the first mixture. The production of first and second mixtures or first mixtures is not particularly restricted here and may be carried out in an appropriate manner; For example by moving; distraction etc.

5 when applying the second mixture; The first mixture can also include 70 by weight of dahl) that is, there is no OF daly the binder from the second mixture (Sa) to diffuse into the first layer that forms from the mixture

the first is in a trending context» hence it can also be the content of the link in the first layer; For example; not less than 70.1 wt.; eg 70.5 wt.; As shown in preliminary experiments. in certain embodiments; however; The first mixture if 2 or more mixtures are applied includes a binder.

in certain embodiments; The binder contains a polymer; For example a hydrophilic and/or hydrophobic polymer; For example, hydrophobic polymers, especially polytetrafluoroethylene. This can achieve proper adjustment of hydrophobic pores or channels. more specifically; to produce the first layer; Polytetrafluoroethylene particles having a particle diameter between 5 and 95 µm are used; Preferably between 8 and 70 µm. Suitable PTFE powders include; For example; on Dyneon®

0 179205 and 1750 .Dyneon TF in certain embodiments; The copper for the production of the mixture is in the form of particles or catalyst particles; For example; including dendritic copper having a homogeneous particle size between 5 and 80 “ag Kae and preferably 10 to 50 µm; Preferably between 30 and 50 µm. in addition to; the catalyst particles in certain embodiments; High purity without

BT 5 is an exotic metal. through the appropriate structure; optionally with the help of reinforcers; as described above; It is possible to achieve high selectivity and long-term stability. by proper adjustment of the copper particle sizes, the binder and any other additives such as enhancers; Pores and/or ducts can be controlled; i.e. hydrophobic and hydrophilic pores or channels; from the gas distribution electrode to the passage of the gas and/or electrolyte; Hence the catalytic reaction.

0 in private embodiments; The first and/or second mixture does not contain any sacrificial cmaterial e.g. sale bitumen having a firing temperature of about 275 °C; For example, less than 300°C or less than 350°C; Particularly the formed pores that can usually remain at least partially in the electrode in Alla production of electrodes using Jie this material.

5 in certain embodiments; The first and/or second mixture shall not be in a paste form; for example in the form of toners or pastes; But it is in the form of powder mixtures.

The application of first, second and additional mixtures is not particularly restrictive; it can be implemented; for example

(JU) by applying dispersion; palm application; paint banding; and so on.

The rolling application is also not particularly restrictive” and can be implemented in an appropriate way. Rotate the mixture or

the mass (particles) in the carrier structure; For example a network structure; Clearly desirable in

5 specific embodiments in order to ensure the high mechanical stability of the electrode.

Under the above two-stage process with film forming; This is not the case; The movie falls

The outlet is previously only on the net and has less adhesion; And also mechanical stability.

The result of cll in Alla is the application of multiple layers (lad). Layer mixtures are preferably applied uniformly

individually on the stand and then collectively rotated; To achieve better adhesion between layers. in this way 0; Layers may penetrate each other on (BY for example) in thicknesses of 1-20

micrometer

mechanical stress on the linker” e.g. of the polymer linia; by the trading process

to entanglement of the powder by forming binder channels eg polytetrafluoroethylene fibres.

Achieving this condition is particularly important to ensure proper porosity or mechanical stability of the electrode. The oS of water can be modified by polymer content or by Goh physical properties

for the catalyst. if two (or more) layers are applied; Found the appropriate link content

in the second mixture it is 730-10 by weight; 720-10 wt is preferred; Depending on the second mixture;

The appropriate ratio for the binder in the first mixture is 710-0 by weight, 710-0.1 by weight, preferably 1710-1.

by weight” but also preferably 77-1 by weight; Rather prefers Wad with a 77-3 weight ratio. In dlls only one patch 0 application” found to be particularly suitable for linker content; For example polytetrafluoro content

Ethylene is 730-3 ella, preferably 720-3 by weight, preferably 710-3 by weight, but preferably

Lad 77-3 by weight of polytetrafluoroethylene; Depending on the first mixture.

degree of fibrosis of the link” eg polytetrafluoroethylene (structure parameter

); directly related to the applied shear rate; As the bond, for example, the polymer, behaves as a liquid (semi-elastic) in the application of circulation. after exclusion; layer obtained; by virtue of fibrosis;

It has flexible qualities. This change in structure is irreversible; Thus, this effect cannot be enhanced

Later by way of more trading. Instead of that; class; By virtue of the elastic properties; Shattered by more shear forces. Particularly fibrosis can lead to defects in electrode circulation on the layer side; Hence excessively high contents of the link should be avoided. for dry handling application; It is better that the water content in the circulation process corresponds; For example; with ambient humidity at most. For example; The content of water and solvents in the circulation application is less than 75 wt. Thanks to less than 71 wt.; For example » up to 70 wt. in special forms; The copper-containing carrier shall be a copper mesh with a mesh size of 3 mm < » > 0.2 mm; Thanks to be 0.5 mm > » > 1.4 mm; and wire diameter ox is 5m > x > 0.5mm; 0.1 mm > x > 0.25 mm is preferred. Rotation is allowed within the grid; For example, the copper mesh; by installing links in the network; For example, the copper mesh; It is effectively bridged by the overlying layer (eg highly conductive) and enables full three-dimensional contact with the electrode. as a result; The oxide contents shall be as high as possible. in certain embodiments; The production of the gas distribution electrode of the invention is also based on the exclusion of coal-based and/or Creon black fillers or semi-fillers; For example; Conductive padding. The catalyst itself or the dendritic copper (component; eg JB by activation of the catalyst) or mixtures of the two are considered here as an alternative to charcoal. In addition, the method of invention; particularly in embodiments; No need for any surfactants/surfactants or thickeners and additives (Jie) flow improvers that are defined as stimulating toxins. 0.3 mm <> 0.3 mm; preferably 0.5 mm <y> 0.1 mm. In the case of multiple layers, each layer may have a corresponding jp height (; however, it is preferable that the bed heights of all layers not be more than 2.0 mm; Thanks to greater than 1.5 mm; preferably more than 1 mm.In certain embodiments the width of the gap in circulation application Ho is the height of the rack + 740 to 7 5 50 of the total bed height HE of mixtures of different layers; ie the height of the bed y of the first mixture if it is the only one used.

in certain embodiments; Trading application is implemented by refinement. in certain embodiments; The copper content of the mixture shall be at least 40 JA and preferably at least 50 in 7 and preferably at least 60 in JA; They are used to the mixture. in certain embodiments; Other additions to the mixture include: at least one metal oxide having a lower reduction potential than ethylene evolution” preferably ALOs, 7102 , 2:02 MgO , 700 Mada D00 . and/or at least one phase among the copper-rich minerals; Preferably at least one of the Cu-rich phases selected from the combination of Cu-AL Cu-Zr, Cu-Y, Cu- Hf, CuCe, Cu-Mg and/or Cu-Y ternary systems -Al, Cu-Hf-Al, Cu-Zr-Al, Cu-Al-Mg, Cu-Al-Ce 0 with copper contents >60 in ¢ and/or at least one metal to form an inter-metal rich phase with copper; AL preferably Zr, Y, HI, Ce, Mg or at least two metals to form ADEN phases and preferably Y-Al, Zr-Al, Al-Mg, Al-Ce ,11-1; so that the copper content is >60 in 7; and/or copper-containing perovskites and/or denatured perovskites and/or 5-perovskites - cdlall ald preferably YBaxCu3075Xs, ~~ CaCusTisOra, -Lai1.85510.15Cu03.930Clo.0s3, (La,Sr)2CuO4 adding metal to form a phase between copper-rich minerals; AL preferably Zr, Y, Hf, Ce, Mg or at least two metals to form ADEN phases and preferably Hf-Al, Zr-Al, Al- but Mg, Al-Ce ; so that the copper content is more than 60 in 7; It can be implemented. for example 0; which way; In the production of a gas distribution electrode, phases are formed between metals; for example through co-dissolution and thermal oxidation; It can then be reduced selectively, for example by electrochemical means. however; Co-dissolving in the mixture is performed here and prior to the addition of the binder. In this case; There is the sequence in which the metal is added first and fused with the copper before the binder and any other materials are added to the mixture. 5 in certain embodiments; The process of the invention can thus be carried out by means of a sanding process as shown schematically in Figure 2. In this case; Catalyst particles 6 and linker particles 7 are circulated on

eg “polytetrafluoroethylene” particles on holder 8; Here in copper mesh form; assisted refinement 11. in certain embodiments; The rolling or polishing process takes place at a roller speed between 0.3 and 3 rpm in dasa, preferably 0.5-2 rpm. in certain embodiments; The flow rate or rate of advance (from the gas distribution electrode in a length per unit length; eg in the case of polishing) is in the range 0.004 to 0:4 m/min; 0:07 to 0:3 m/min is preferred. In order to further adjust the porosity of the electrode; in certain embodiments; Copper powder supplements may have a particle diameter of 50 to 600 µm »preferably 100 to 450 µm » and more preferably 100 to 200 µm; Especially to the second mixture if applying multiple layers. 0 particle diameter of these supplements; in certain embodiments; It is 1/1-3/10 of the total layer thickness of the layer. instead of copper; The complement may also be an inert substance such as a metal oxide. In this way; An improved formation of pores or channels can be achieved. An illustrative process for producing a Gl distributing electrode (Jaa) can thus be illustrated as follows: The gas distributing electrode can be produced using the dry polishing method in which a mixture of cold-flowing polymer 5 (preferably polytetrafluoroethylene) and a catalyst powder Previously calcined comprising copper and optionally augmented Produced in an intensive mixing apparatus or on a laboratory scale with a knife mill (HCL).The mixing procedure for example may follow the following procedure, but without limitation: Milling/Mixing for 30 sec on and 15 sec off for 6 min These formats are based eg on a knife mill with a total load of 50g After mixing the mixed powder gives a viscous 0 consistency SLB with fibrosis eg of binder eg Example Polytetrafluoroethylene.According to the amount of powder or polymer/chain length chosen there may also be a variation in the mixing time before this condition is achieved.The powder mixture obtained later has to be scattered or sieved on the copper grating having a mesh size of >0.5mm and <1.0 mm wire diameter of 0.25-0.1 mm in a bed thickness of 1 mm. love the powder mixture that was applied; For example» with paint tape. This process can be repeated more than once until a homogeneous layer is obtained. Instead of that; Powder mixture can be pelleted

during or after the mixing process in order to obtain the pourable material; For example it has a block diameter of 0.05 to 0.2 mm. so that the powder does not flow through the mesh; The reverse side of the copper mesh can be sealed with a film that is not subject to further restrictions. The prepared layer is compacted with the help of two-roll circulation (polishing) devices. The trading process itself is characterized as a reservoir of upstream material form of circulation. Winding speed is between 0.5-2 rpm and the gap width is adjusted to the height of the stand + 740 to 750 of the bed height “HF of powder” or roughly corresponds to the mesh thickness + 0.1- 0.2 mm already. in addition to; Lad can be hot burnished. Preference is given to temperatures in the range of 20-200 ° C; Preferably 20 - 50 ° Agia 10 The catalyst itself can be processed before application in the calcined state for example also as precursors of metal oxides; or already in the reduced state. The mixtures can be in two forms. This is also true in the case of phases between metallic or lined surfaces; It can also be used in the oxide form or in the metallic state. Furthermore it; It is not excluded that the electrode can be calcined as a polish at a later time; eg at 360-300°C for 5 to 15 minutes. 5. It is advantageous for the gas distribution electrode of the invention, particularly in the case of the hydrocorion selective copper catalyst electrodes, to apply the copper-PTFE base layer as a second layer for better contact with the nanomaterials; while maintaining high porosity. The base layer can have a high conductivity clas for example 7 mOhm/cm or more; preferably with high porosity; For example 770-50 has hydrophobic property. 0 link content can be selected» for example polytetrafluoroethylene» for example; between 730-3 wt; For example 730-10 wt. The intermediate copper layer as the second active layer can be catalyst in the overlapping region with the catalyst layer as the first layer; In particular, it represents a better electrode contact area for electrocatalysts and can improve the availability of PUY due to its high porosity. With the help of this method; The required amount of catalyst can be reduced by a factor of 20-30. maybe; In step 5 first; The electrocatalyst/binder mixture (eg polytetrazoroethylene) is deflected to the reverse side of the current distributor and polished. In addition it is also possible to apply a layer-2 variant which

It has been described as a double layer. The binder used must be specially treated with polytetrafluoroethylene; in private embodiments; in a knife mill to form fibres. It was found that the special suitable polytetrafluoroethylene powders are; For example » 9205 Dyneon® TF and 1750 -Dyneon® TF In order to enhance this effect; Solid abrasives may be mixed in the range between 0-750 wt. The following are examples of suitable materials: SiC, BoC, ALO (high quality corundum); 5:02 (crushed glass); Preferably in a grain size of 50-150 μm. The production of a gas distribution electrode with a linker-dependent diffusion bond (eg based on polytetrafluoroethylene) is based on multiple layers that cannot be considered in isolation “andl” but preferably have an overlapping region of maximum amplitude in the boundary regions; Example 1-20 µm.

0 The two-layer construction method also includes the option to dispense the binder as a first layer within the Gia layer) which means that better electrical conductivity can be achieved. It can also process very brittle or ductile powder particles. This is not possible in a single class building. In the case of mechanical sensitive stimuli; The knife mill process step can be dispensed with; This means that the catalyst remains unchanged as the mechanical stress caused by the mixing process can be avoided.

5 It is optionally possible to perform post-electrochemical activation of the obtained electrode; in certain embodiments; for example by chemical or electrochemical activation; This is not particularly restrictive. The electrochemical activation procedure may result in cations of the conductive salt penetrating into the electrolyte (e.g. (KHCO3, K2SOs, 11011005, KBr, NaBr) in the hydrophobic gas distribution electrode channels; thus creating hydrophobic regions. This effect is particularly beneficial and is not Complete

0 described so far in the literature. In another aspect the present invention relates to the electrolytic cell comprising the gas distribution electrode of the invention; which is preferred as a cathode in certain embodiments; The gas distribution electrodes of the invention can be operated specifically dag in plate electrolyzers. The other components of the electrolytic cell; For example, the anode is optionally a single film

5 or more entrance(s) and exit(s); voltage source etc.; and more optional devices such as cooling or heating units; are not particularly restrictive according to the invention; nor do they contain

Anolite 05 and | or the catholytes used in such an electrolytic cell; And used

The electrolytic cell in certain embodiments is on the cathode side for the reduction of carbon dioxide.

In the context of pla) the shape of the anode area and the cathode area also is not particularly restricted.

Figures 4 to 6 show schematic configurations of the JE construction of a typical electrolytic cell and the possible anode and cathode spaces.

The electrochemical reduction of carbon dioxide, for example, occurs; in the electrolytic cell

Typically consisting of an anode and cathode space. The following Figures 4 through 6 show examples

on the potential arrangement of the cell. For each of these cellular arrangements; It is possible to use a distribution pole

Gas of the invention» eg cathode.

0 for example; The cathode space 17 in Figure 4 is configured such that the catholyte is supplied from below and then the cathode space [1] is left on top. Instead of that; The catholyte can also be supplied from above; As is the case in; For example; Falling film electrodes. at the anode A which is electrically connected to the cathode K by means of a power source to provide voltage for electrolysis; oxidation of the material supplied from below; For example; With anolite occurring in the space of the anode and the anolite along with

5 The oxidation product then leaves the anode space. In the 3-room construction shown in Figure 4; In addition, it is possible that celal Sle, for example, carbon dioxide, is transported through the gas distribution electrode in the cathode space 17 for reduction. Although it is not shown; Porous anode embodiments can be visualized alternatively. in Figure 4; Spaces 1 and 11 are separated by the eM membrane in contrast; In the construction of Fig. 5 the proton exchange membrane (PEM).

0 or the ion exchange membrane 1; the gas distribution electrode 1 and the porous anode A are directly adjacent to the membrane 84 through which the anode space I is separated from the cathode space LIT The construction in Fig. 6 is identical to the mixed form of the construct of Fig. 4 and construct of Fig. 5 where the construction is provided with the gas distribution electrode as shown in Fig. 4 on the “Gila catholyte” while the construction in Fig. 5 is provided on the anolite side placement will

5 Estimate that mixed shapes or other configurations of electrode spaces as shown by example are conceivable. Solidifications can also be visualized without a membrane. in certain embodiments; may be

The electrolyte on the cathode side and the electrolyte on the anode side are identical; The electrolysis cell/electrolysis unit may not require a membrane. however; It is not excluded that the Jie electrolytic cell in these embodiments would have celia although this would be associated with additional cost and inconvenience in respect of the membrane as well as the applied voltage. Optionally the catholyte and anolyte can also be mixed again outside the electrolysis cell. Figures 4 to 6 are schematics. The electrolysis cells of Figures 4 to 6 can also be combined to form mixed variants. For example; The LIAS anode space may be composed of a half proton exchange membrane; As in Figure 5; While the cathode area consists of half of the cell containing a certain volume of electrolyte between the membrane and the electrode; As shown in Figure 4. In 0 particular embodiments; The distance between the electrode and the membrane is very small or 0 when the membrane is porous and includes a feed electrolyte. The membrane may also have a multilayered configuration; So that separate feeding for anolite and catholyte is enabled. The separation effects are achieved in the electrolytes (Alla calla) for example” through the hydrophobic interlayer. However, connectivity can be ensured if conductive groups are integrated into separation layers of this type. The membrane may be a “conducting membrane 5-100” or a separator that performs only mechanical separation and is permeable to cations and anions. The use of a gas distribution electrode of the invention makes it possible to construct a three-phase electrode. For example; The gas can be directed from the back towards the electroactive front side of the electrode in order to carry out the electrochemical reaction there. in certain embodiments; There may also be a flow of 0 along the posterior gall of the Gla distribution electrode This means that the gas Jie CO is directed along the back side of the gas distribution electrode relative to the electrolyte; Ag In this case the gas can penetrate through the pores of the gas distributing electrode (Sang) product removal at the rear. In the reverse flow case the gas flow is preferably opposite to the electrolyte flow so that any liquid passing through can be forcibly pushed away. In this case Also, the presence of a gap between the gas distribution electrode and the membrane as an electrolyte reservoir 5 is useful.

With sufficient porosity of the distribution electrode ll two modes can be operated: Single cell variable(s) allowing direct active flow of gas such as CO2 through the gas distribution electrode. The formed products are removed from the electrolysis cell through the catholyte outlet and separated from the liquid electrolyte in the downstream stage separator. This method has the disadvantage of high mechanical stress on the gas distribution electrode and severe partial or total pushing of the electrolyte out of the pores. It was also found that the high presence of gas in the electrolyte space and the displacement of the electrolyte were among the defects. For the method of operation; in addition to; An excess of carbon dioxide is needed. in private embodiments; The electrodes have a gas-only distribution, porosity >770 and high mechanical stability is suitable for this mode of operation. The second variant of the cell describes the mode of operation in which 0 carbon dioxide flows into the back region of the gas distribution electrode by virtue of the modified gas pressure. The gas pressure here should be chosen to equal the hydrostatic pressure of the electrolyte in the cell; So that no electrolyte penetrates through it by force. The high conversion of the reaction gas used is a primary spe of the lal variable eg carbon dioxide; compared to the flow variable. In order to prevent the passage of the electrolyte through the gas distribution electrode it is possible to apply ald to the Gils 5 gas distribution electrode away from the electrolyte; that is, on the pregnant woman; For example JB network; In order to prevent the electrolyte from passing into the gas. The film can be provided here in a suitable and non-hydrophobic form eg. in certain embodiments; The electrolysis cell has a membrane separating the cathode space and the anode space of the electrolysis cells in order to prevent mixing of the electrolytes. The membrane is not constrained in the form of pals 0 provided it separates the cathode space and the anode space. More specifically; it essentially prevents the passage of gases that form at the cathode and/or anode through the anode space or cathode space. The preferred membrane is the ion exchange membrane; Example in a polymer-based form. Preferred materials for 1-ion exchange membranes are ol) sulfonated tetrafluoroethylene polymer “Nafion® Jie” eg Nafion® 115 as well as polymer membranes. polymer cmembranes 5 It is also possible to use ceramic membranes, for example

Polymers mentioned in EP No. 1,685,892 A1 and/or loaded with zirconia; on

eg Polysulfones Likewise, materials for the anode are not specifically limited and depend primarily on the reaction required. Illustrative anode materials include platinum or platinum calloys 5, palladium or palladium alloys, and glassy carbon. Additional anode materials are also oxides. Conductive TiO, Jie treated and untreated, indium tin oxide, fluorine- (FTO) doped tin oxide, AZO aluminum-doped zinc oxide iridium oxide, etc. Only catalyst active compounds may also be applied

0 superficially in the daa membrane methodology) eg on a titanium carrier The electrolytic cells of Figures 4 to 6 can also be combined to form mixed variants. For example; The anode space can be configured as a half-cell proton exchange membrane; Whereas the cathode space consists of one half of the cell which contains a certain volume of electrolyte between the membrane and the electrode. in the ideal case; The distance between the electrode and the membrane is very small or 0 when it is

The membrane is porous and contains an electrolyte feed. The membrane may also be a multilayered configuration; So that separate feeding of anolyte and catholyte is enabled. Separation effects are achieved in the case of All electrolyte) eg; By hydrophobic interlayer. However, connectivity can be ensured if conductive groups are integrated into separation layers of this type. The membrane may be the ion conduction membrane; or a separator leading to mechanical separation only.

0 reaction gas distribution; For example, the carbon dioxide “behind the gas distribution electrode of the invention”, that is, on the JU side, different gas distribution chambers can be provided, in which there are two gas distribution chambers shown in Figures 7 and 8. They can be provided in order to increase the residence time of the reaction gas Gas distributors, especially in the Alla gas distribution electrode with back flow, can contribute to enhanced mass transfer across the entire electrode area.

Other aspects of the present invention relate to the electrolysis system comprising the electrode of the invention or the electrolysis cell of the invention” and the use of the gas distribution electrode of the invention in the electrolysis cell or electrolysis system. Additional components of the electrolysis system are not limited to this and can be provided appropriately. The above incarnations, achievements and developments may be combined; if possible; with each other as required. Further variations, developments and applications of the invention also include combinations not expressly stated of the features of the invention described above or described hereinafter in connection with working examples. In particular; The person skilled in the art will also add individual aspects as improvements or supplements to the basic form of the present invention. The invention Led is described below with some illustrative embodiments; without limitation of the invention. Examples All experiments as well as comparison examples and examples were performed at room temperature of approximately 20°C-25°C; Unless otherwise specified. 5 Likewise the pressure in the comparison and examples was not varied but left at room pressure (about .3 bar). Additional detailed data were recorded for relevant comparative examples or examples. Comparative examples (negative experiences) Comparative Jd 1 0 In comparative example 1; The multilayer gas distribution electrode was produced according to the instructions of R R.

Cook.

electrochem.

Soc. 1990, 137, 2) A hydrophobic gas transfer layer was produced according to the publication: 5 g of Vulkan XC 72 and 2.8 g of Teflon 308 (DuPont) were dispersed in 25 mL of water and applied to the dense copper grid ( 100 mesh). The applied layer was dried under 5 air and pressurized at 344 bar for 2 minutes. This procedure was used to produce a total of three layers. This is followed by applying pressure to three more layers containing the catalyst with the following mixing ratio: 2.5

g of Vulkan XC 72; 2.61 g of Cu(OAC)*H20; 0.83 g of 303 “Teflon volatile in 25 mL of 11:0. Each applied layer was dried under air and then pressurized at 69 bar. The final gas distribution electrode was activated at 324 °C in 710 volume of HyAr gas mixture s.d. 4-3 hours and finally pressurized again at 69 bar for 30 seconds.

Result: No mechanically stable gas distribution electrode was obtained over an area of 3.3 cm 2 . The drying procedure resulted in an unwanted 'crack-paste' layer. The electrochemical characterization was accomplished using a test setup that basically corresponds to the electrolysis system described above in Figure 6. With WIA flow electrolysis In the flow cell the cathode used was a special gas distribution electrode with an active area of 3.3 cm

0© and the rate of carbon dioxide gas feed on the cathode side was 50 mL/min; And the electrolyte flow rate on both sides was 130 mL/min. The anode was iridium oxide on titanium dala with an active area of 10 cm. The catholyte was a solution of 11410100 with KHCO at a concentration of 1 mol; The anolite was JSKHCO; Jsel in deionized water (18 MQ each) in a quantity of 100 cde and a temperature of 25 °C. In addition, 0.50.5 was tested.

KaSOs 5 4 as a catholyte” and M KOH 2.5 as an anatolyte. In the electrochemical characterization of the gas distributing electrode no ethylene could be detected but exclusively hydrogen along with small percentages of 00. Comparative example 2

0 in other pas; The aqueous dispersion was exchanged for ethylene glycol”; Otherwise, Comparative Example 2 corresponds to Comparative Example 1 unless otherwise stated. the use of high-boiling dispersions prevent cracking; But again no selectivity to ethylene could be detected. The following method was used for this purpose: 1.440 g of “sll 749.5 (72 Vulkan XC 3.2 mg/cm*) was vigorously mixed with 15 mL of

5 ethylene glycol with dispersant over 1 hour. 2.44 g of polytetrafluoroethylene suspension “Teflon 30B (750.41 by weight” 3.25 mg/cm2) was added with stirring. The mixture was applied

on a copper grid corresponding to that used in Comparative Example 1 with a coating bar of 100 µm thickness and dried under air for at least 24 hours. Then three additional catalyst layers were applied as in Comparative Example 1. Subsequently, the solvent was removed in a drying cabinet at 270 °C with a slope of 10 K/min and isothermal conditions for 1 hour. After coll) a layer corresponding to the first layer (thickness 100 µm) was applied and the solvent was removed again as above and left to dry under air for 24 hours. The electrode was then calcined in an oven at 0 °C with a slope of 10 16/min and isothermal conditions for 2 h and pressure at

5 bar and 160°C for 2 minutes.

aid 0 Comparison 3.5-3.1 The substrate used in comparative example 3.1 was a commercially available creon cloth for gas distribution electrodes (Elat® LT1400W, NuVant) in the form of a microporous layer. A 0521 Nafion® dispersion was applied to this gas distribution bed as an electrocatalyst which was produced as follows:

5" 087 g of 0802-11:0:© was dissolved in approximately 1 mL of 11:0. In addition, 6 g of 72 Vulkan XC was mixed with 15 mL of ethylene glycol and Cu( OAc), dissolved and dispersed for 1 hour. After ell) 1.5 g of 0521 Nafion® suspension was added and stirred with a glass rod. Thereafter; the mixture was applied to the hydrophobic gas distribution layer; dried under air and prepared in a drying tank at 120 °C for 2 hours, followed by calcination in an oven

0 at 250 °Lge with a slope of 10 K/min in an atmosphere of 710 of .11 in argon; The calcination was continued under isothermal conditions for a total time of 240 minutes. The obtained electrode was then described in terms of its electrochemical properties with a test setup ¢ apart from which gas distribution electrode ¢ corresponds to one from Comparative Example 1. In this case; The copper catalyst was provided by the reduction of .Cu(OAC)HO

— 9 3 — in the electrochemical characterization; The results shown in Figure 9 were achieved; which shows the Faraday efficiency as a function of current density. He found that the Faraday efficiency is 710 for ethylene, but it is not stable for a long time. According to Comparative Example 1-3 the results shown in Table 3 were achieved by varying the carrier (copper mesh with mesh size of 0625 and wire diameter of 0:14 mm) and the mixture that was applied. In comparative example 2 in addition; Polytetrafluoroethylene was used instead of Nafion® Table 3: Amounts and Results in Comparative Examples 3.5-3.2 Nafion® Precursor Catalyst Amount FE 2 : Al Maximum Carbon Catalyst Catalyst | [7 by weight] for Lu 7 . [mg / | wt] CoH wt] cm [ ]17 70.8 8.94 ] 500 mesh Cu (poly)Cu(OAc) 2 | 8.7 | 46.56 | mM 1 - 0.14 tetrafluoro i ethylene 1 mM/cm] 76 [400 mesh Cu Cu(OAc) 16.8 442 | 14.2 39 m - 0.14 sal [cm] 73.8 Elat® Cu(OAc) 233 2 LT1400W | 14.2 | 39] 400 m

— 0 4 — Ambi [ 2 cm ] 70.2 ] 300 Elat® 1 38.6 | 17.2] Cu(OAc) 17.4 44 mA [ 2 cm ] LT1400W Comparative Examples 4-1-4 The multilayer gas distribution electrode was produced as in Comparative Example 3.1; using the :2:0/n catalyst obtained from CugZis as a catalyst. In Examples 4.2 and 4.4; The gas distribution electrode is further shorted before the plug; 4.3 in relation to the electrochemically activated electrode and 4.4 in relation to the hydrogen-activated electrode The quantities used and the results obtained in the comparative examples 4.4-1-4 are given in Table 4; The results are also shown in figures 10 and 11 for comparative example 4.3. in this context; Figure 10 shows the current Series 0; Figure 11 is the measurement at DC. Table 4 Amounts and Results in Comparative Examples 4-1-4 Binding Carrier Nafion® Sulfate Catalyst Amount FE [7 wt] a) Carbon 1 | a catalyst | [7 to a maximum of] 7 [m<wt] can | |wt] cm [ II 5 7 Elat® CuO/ZrO; L8| 295 lu00w | 68.7|355| ] 300 ms

— 1 4 — Amp/ [on 702 ]400 Elat® She | 355] 6837 | CuO/ZrO, 1.8 29.5 LT1400W A/Pom 713 [300 Elat® She | 355] 97.6 | CuO/ZrO, 2.4 LT1400W A/ [on 33%] 300 Elat® She | 355] 97.6 | CuO/ZrO, 2.4 LT1400W Amp/Pom in dls using Cu/ZrOr as catalyst; The spectrum of the stable product was obtained over an electrolysis period of 150 minutes. in general; The coal-based gas distribution electrodes in Comparative Examples 4-1 showed the higher Faraday efficiency of hydrogen. It was concluded from this that the creon in the form of conductive black or the active creons are less suitable for the production of ethylene gas-selective distribution electrodes. Comparative Example 5 at a later date. Thus » A gas distribution electrode was produced based on a dispersion of liquid polytetrafluoroethylene with pure copper powder having a grain size of <45 µm according to the method in Chemical -Engineering and Processing 52 (2012) 125-131 0 In this method, there was no use of carbon on J release in the form of conductive blacks or active craions.The materials used were the following:

Polytetrafluoroethylene suspension: TF5035R « 758 wt. » (Dyneon™) Surfactant: (Fluka Chemie AG) 100- Triton Thickener: WalocelMKX ( hydroxyethyl methylcellulose PP 01, Wolff Cellulosics GmbH & Co.

70000 KG). As a starting mixture, a solution containing 797 wt. of copper and 73 wt. of PTFE was produced as follows: 0 g of thickener for consistency (71 wt. of methylcellulose in 0:11); g of copper powder; 53.7 g of 1170 and 1.5 g of surfactant were dispersed with a 125 Ultra-Turrax separator at 13,500 rpm for 5 minutes (waiting 2 minutes after 0 dispersing for 1 minute). Stirring 4.8 g of polytetrafluoroethylene suspension in a glass rod and the obtained suspension was applied to a copper grid as shown in comparative example 3.2 at 100 °C.Another gas distribution electrode was produced based on 70.5 weight of polytetrafluoroethylene Ethylene by the same procedure.5 The gas distribution electrodes produced had weak hygroscopicity, and in Ala the content of polytetrafluoroethylene is 70.5, the porosity is poor, as determined visually and microscopically.In addition, it was found that the gas distribution electrodes contain It contains large proportions of the surfactant used, which has been identified as an inducing poison in the mediation experiment t on it. Nor was it possible to eject the corresponding 100 p-tert-octyl-(phenoxy)polyethoxyethanol (P-tert-octyl-phenoxy) Triton X without residue at temperatures > 340 degrees. percentage; As confirmed by electron microscopy, hydrogen was obtained exclusively with the electrodes produced by this process. Experiments showed that the use of a surfactant has disadvantage in the formation of ethylene. Also, the method did not lead to homogeneous porosity; and in the case of 73 by weight of polytetrafluoroethylene; It resulted in a very poor wetting ability.

Reference example 1

Production of a mixed metal oxide catalyst by precipitation: illustrative method for l and 0dl/e Hydrotalcite precursors suitable for the composition 010-011([0:(4)/mL] are prepared (water content is unknown for freshly precipitated hydrotalcite ) by sedimentation. At the same time 0.41 mol of mineral brine (A) consisting of Cu(NOz)2-3H20 (0.246 mol) and AINO3)3-9H20 (0.164 mol) and carbonate hydroxide solution (B) was added which consists of 0.3 mol of “(pn 12)NaOH 0.045 mol :000:00 (4.32 g); So that the pH is between pH 8 and 8.5. The rate of mineral saline addition was chosen at 120 mL/hr. Oswalt ripening was performed for 0 30 min. after that; The solids were filtered and washed until neutral. after that; The precursor was dried at 80 °C for 12 hours; crushing and calcining it. The calcination step is achieved in a tubular furnace having a temperature slope of K = 2 B/min up to 300°C with isothermal conditions for 4 hours in an argon/oxygen mixture: 720 by 0/7 volume with flow rate from 200 to 600?. Jass the precursor prepared before use.

Examples: Production of Comparative Metal Powder-Based Gas Distribution Electrodes 6 The catalyst powder is prepared by co-precipitation of Cu(NO3)2-3H20 and ZrO(NO3)2:xH20 according to reference example 1 with molar amounts of them ( mall). The previously calcined catalyst powder (weight 45 µm particle size < 75 µm by sieve analysis) is mixed on a laboratory scale with a knife mill (IKA) (large scale; eg with an intensive mixing device). (mixing apparatus with PTFE particles (weight 5 TF 1750 fan ©1101600; particle size (150) = 8 μm according to manufacturer) Mixing procedure follows the following procedure: grinding/mixing for 30 seconds and waiting for 15 seconds of a total duration of 6 minutes.This statement is based on a 5 knife mill with a total load of 50g.The mixed powder will have a slightly viscous consistency after the mixing process.The mixing time before this condition is achieved may also vary according to the amount of powder or polymer chosen

or the length of the string. The powder mixture thus obtained is applied later by means of

Dispersion or sieving to copper mesh with mesh size greater than 0.5mm and <1.0mm and wire diameter

From 0.25-0.1 mm in a bed thickness of 1 mm.

so that the powder does not flow through the net; The reverse side of the copper mesh can be closed with the film which is not subject to further restrictions. The preparation layer is compacted with the help of the circulation device

Double-rolled (refinement). The trading process itself is characterized by the fact that the material reservoir is the source of the circulation. Trading speed

between 0.5-2 rpm and the gap width is adjusted to the rack height +740 to 750 from

Bed height HE of powder or approximately corresponds to mesh thickness +0.1-0.2mm already.

The gas distribution electrode obtained in the electrolysis bath is activated in solution 114

SKHCO; 0 current density of 15 Me ampere cm add 6 hours. Comparative Example 7 Dendritic copper powder (45 g; particle size <45 µm; determined by sieving with an appropriate mesh size (45 µm)) is mixed with 5 g poly

5 Tetrafluoroethylene in a knife mill M168 by the procedure in Comparative Example 6; gig is cured under the same conditions to give a gas distribution electrode. After activation, the described gas distribution electrode gave a Faraday efficiency of 716 at 170 mA/cm©; which remained constant over the measurement time of about 90 minutes. Comparative metallurgy 8

0:0:2 is calcined in a tubular kiln with janie at 8 = 2 16/min up to 600°C with isothermal conditions for 4 hours in an argon/oxygen mixture (720 by 0/8 volume with a flow rate of 200 6600). The oxide precursor is positioned; before using it; in a planetary ball mill (pulverisette) for 3 minutes and then sieved ana (particles >75 μm). 45 g of the obtained catalyst is mixed with 5 g polytetrafluoroethylene

5 in an IKA knife mill by the procedure shown in comparative example 6 and processed under the same conditions to give a gas distribution electrode.

The gas distribution electrodes from Comparative Examples 6 to 8 can be used in an electrolytic cell as shown above or in eg cans as a cathode in which carbon dioxide can be reduced. Example 1 Produce a 2-layer electrode

Copper powder with a particle diameter of 100-200 μm was mixed and PTFE Dyneon 1750 17 was mixed in an IKA 10m knife mill for 6 minutes (grinding 15 seconds; waiting 30 seconds). Then the powder layer was separated and sieved by a 0.5 mm thick die to form the base layer. This is followed by exclusion with 2-roll polishing with a roll separation of 0.5 mm. after that; Done

0 catalyst layer by applying Jail) for example in each case similarly to comparison examples 6 to 8; With a frame of 0.2 cae the extrusion was again carried out with 2-roll polishing with a roll separation of 0.35 mm. The result was a highly porous base layer with a porosity >770; It has good mechanical stability and very good conductivity at 5 mOhm/cm. It was possible to use catalysts having a copper content of 740 by weight.

5 The catalysts should preferably have higher purity than commercially available materials or quality standards; Like in the example too. This has been detected by Gob XPS (Surface Sensitivity). Lad SEM/EDX mapping analysis indicated no impurities whatsoever in the hydrophobic base layer. It was also found that the copper content of SST of 770 is beneficial in order to enable low electrical resistance.

0 from the catalyst. The effect of the (polytetrafluoroethylene) binder content with respect to the carrier oxide is much smaller in terms of the effect on conductivity. Illustrative polytetrafluoroethylene construction from a typical electrolysis cell: electrochemical reduction of carbon dioxide occurs for example; In a typical electrolytic cell it usually consists of an anode and cathode space. Figures 4 through 6 show examples of

5 Possible arrangement of the cell. The concept presented later applies to all arrangements of these cells.

The electrolysis cells of Figures 4 through 6 can also be combined to form mixed variants. For example; The anode space can be configured as a half-cell proton exchange membrane; Whereas the cathode space consists of one half of the cell which contains a certain volume of electrolyte between the membrane and the electrode. in the ideal case; The distance between the electrode and the membrane is very small or 0 when the membrane is porous and includes a feed electrolyte. The membrane may also be a multilayered configuration; So that separate feeding of anolyte and catholyte is enabled. Separation effects are achieved in the case of the liquid electrolyte; For example » through the hydrophobicity of the interlayer. However, connectivity can be ensured if conductive groups are integrated into separation layers of this type. The membrane may be the ion conduction membrane; or a separator leading to mechanical separation only. 0 The present invention provides the possibility to produce Sle ethylene selective dispensing electrodes; Dimensionally stable based on the catalyst powder. This technique forms the basis for producing electrodes on a larger scale; lly can achieve current densities > 170 Me ampere/cm2 depending on mode of operation. All methods known to date for the production of copper AE ethylene electrodes are unsuitable for scaling or are not dimensionally stable. maybe; In contrast; Obtaining the gas distribution electrodes of the invention according to Gob 5. Appropriate adjustment of the circulation process, especially the calendering process. According to the invention, it is possible to obtain a high electrical conductivity; particularly stable metal oxide copper catalysts with copper nanostructures that enable oxidation between Cu(I)/Cu(0) in certain embodiments; The production of the gas distribution electrode of the invention as well as the exclusion of conductive 0 gaskets is based on coal or carbon black. The coal substitute used here is the catalyst itself, copper ferrites, or a mixture of the two. Moreover, the method of invention; particularly in embodiments; You do not need surfactants/surfactants or thickeners and additives (eg flow enhancers) that have been identified as catalytic toxins. relay list co, '" 5

H 'b'

CH: ja bla SSFE- "a fof wal Gl) (48) "g" time 5

FE-H, 'Z'

FE-CO'L

FE-CH: '&

FE-CoH, Co0

Claims (1)

protection elements 1. Gas diffusion electrode including Jala containing a copper ccopper-containing carrier in the form of a sheetlike ¢structure and a first layer containing copper and a Cua chinder including The first layer has 5 pores and/or channels hydrophilic and/or hydrophobic additionally includes a second layer which includes a copper and a Cus chinder The second layer is located on top of the carrier carrier and the first layer above the ASB layer where the content of the binder in the first layer is less than in the second layer.” Gus The second layer includes 730-3 wt of binder on a second layer basis; The first layer includes Zero-710 wt. of binder on the basis of the first layer Gua The first layer includes 60 by 7 copper Copper on the basis of the layer; Whereas the first layer includes a metal oxide selected from Wuerach; «Ce02:0e»©; : 200 MgO and/or where the first layer includes one phase between the copper-rich intermetallic phase selected from the set of binary systems Cu-Mg «CuCe «Cu-Hf «Cu-Y » Cu-Zr “Cu-Al 5” and gravitational systems “Cu-Y-Al ternary systems” Cu-Al-Ce “Cu-Al-Mg” Cu-Zr-Al “Cu-Hf-Al with copper contents copper > 60 at /¢ lf where the first layer includes copper-containing perovskites and/or defect perovskites and/or Lay 85510.15Cu03.930Clo.053 and/or “(La,S1)2Cu04 where zero > § > 1 Lai 5S10.15Cu03.030Clo0ss “CaCusTisOp f/r (La,S1)2Cu0s 20 2. gas diffusion electrode as specified in claim 1; The first layer does not contain any fillers based on charcoal and/or carbon black (gS). black 3. The gas diffusion electrode as specified in claim 1 or 2 where the first layer does not contain any surface-active substances 4. The gas diffusion electrode as specified in claim 1 ; Where the carrier 5 containing copper is copper mesh. 5. The gas diffusion electrode, as specified in Clause 1, where the second layer partially penetrates the first layer. 0 6. Process for producing a combined diffusion electrode including - Production of a first mixture including copper and a binder - Production of a second mixture including copper and a binder - Application of the second mixture included on copper and binder on carrier dels containing copper 5 - apply the first mixture comprising copper and binder to the second mixture; - optionally application of additional mixtures to the first mixture and - dry rolling of the first and second mixture and optionally additional mixtures to the carrier to form a second layer, first layer and optionally additional layers; Cua The binder ratio in the second mixture is 730-3 by weight of the binder based on the second mixture 0; and WHEREAS, the binder ratio in the first mixture is 710-0 by weight on the basis of the first mixture; Where the content of the binder in the first mixture is less than it is in the second mixture where the content of copper in the mixture is 60 times that of copper on the basis of the mixture; Whereas, the first mixture includes the following additional additions: one metal oxide having a reduction potential less than that of ethylene 5 and/or one stage between copper-rich intermetallic phases to be selected from a group of Cu-Mg «CuCe» Cu-Hf «Cu-Y »Cu-Zr »Cu-Al binary systems and/or Cu-Al-Ce «Cu-Al-Mg»Cu-Zr-Al «Cu-Hf-Al «Cu-Y-Al ternary systems with copper contents >60 at /; and/or metal to form a copper-rich metallic phase so that the copper content is > 60 at ./¢ perovskites containing copper and/or defect roasted perovskites and/or Lai 85S10.15Cu03.930Clo.0s3 and/or B5020(0,A1)”; Cus 0 > 68 > 1 Lai 85510.15Cu03.930Clo.os3 “CaCusTisO12 and/or (La,Sr)2Cu04. 7. The process is as specified in claim 6) wherein the copper welded carrier is a copper mesh having a mesh size w of 0.3 mm > » > 2 mm. 8. operation on sail) specified in claim 6; Where the bed height of the first mixture 5 on the application carrier is within 0.3 mm (> 2 mm). 9. the process as defined in claim 6; where the gap width in a ho rolling application is the height of the carrier + 740 to 750 of the total height of the HF bed of the first mixture and any additional mixtures. 0. The process as defined in claim 6 where the circulation takes place by means of a “calendar”. 1. An electrolysis cell comprising a gas diffusion electrode as specified in claim 1. — 5 1 — 7) Ne a Ds. La. “INF or ; / JS Sy 7p 1a27)2,@ MF AN an A DA B 7 ov, Nn + oN : Zr RN Ny, QE ONS NN 8 NN SER A : Chess Sade 4 Ben B Ny 1 Azan Mei Shape ARE 4] Lamjam M Correct Sh a Ee EERE C= = seitseio Null EEO yy 1 = Rio = JE Oy 7 1k — form? 0 5 2 — 'Wamem M Noum M 000000 000.0 Ona 0400 ay Hades Ton ROAD Aba NAT 10 Remy Hamam Haramat Wan wa Al 0 Rise SORA) Sogn pes Pal REE 0 Hajj for Me 0 0 WAY mah So meaning = 0 oR 0 60 c 2 b wa la 000 m RN ew ie ee ee wo Ig 5 BD A PB 0 1 i Al a a m d form “1 form o form; Pain or VA NAAN L for 226 RUB [ARS — Z 2 Z | (Samastanta: AA EN NA ie nin B Shakka A Shirk V 8 d 0 sat ya fasr: a 0 a asm 5 sah b OL % ab oath sah fig mso sa a PIE Bt he * ae kay l hra 5 a? And Osa: 'I corrected the situation WR Ajim ty i foes, Joan ho [IY ke £5 aaa ald 0 I. 12 3: ] } 8 3 Youn 1 y 1 NEN vy + no y « 8: aj lar + a v 1#: % 4 b 4 ab a 1 and ta } 2 anem in 0 siq 1 oe ¥ Li SH fe 1 sah wa 0 a and Ee LL ME b ay mdb m sine l TR Ree th l sa EER jaa RR * ¥ or 1% fig. 01 0 5 6 — Lee Oye dan AA pel and Mia Dossy Ra 7 | 8% Da © NEE Name Semel -1-0-1-0/ Aw ol En 8 A Tro WA b 1 & ?? ss ys ys ys ys ys ys ys ys ys ys ys ys ys ys ys ys ys ys ys ys ys ys ys ys a. 1 + % left * d fig. 11 Sued Authority for Intellectual Property RE .¥ + \ A 0 § 8 Ss o + < M SNE A J > E K J TE I UN BE Ca a a a ww > Ld Ed H Ed - 2 Ld, provided that the annual financial consideration is paid for the patent and that it is not null and void for violating any of the provisions of the patent system, layout designs of integrated circuits, plant varieties and industrial designs, or its implementing regulations. Ad Issued by + bb 0.b The Saudi Authority for Intellectual Property > > > This is PO Box 1011 .| for ria 1*1 v= ; Kingdom | Arabic | For Saudi Arabia, SAIP@SAIP.GOV.SA