In-situ electrocatalytic electrode, catalytic reaction device and method thereof

Abstract

The present invention provides an in-situ electrocatalytic electrode, and a catalytic reaction device and method thereof. The in-situ electrocatalytic electrode comprises a carrier with a pore structure, and at least one side surface of the carrier is sequentially stacked with a porous hydrophobic membrane, a conductive layer and a catalyst layer. The catalytic reaction device comprises a first reaction module and a second reaction module that are interconnected, wherein the first reaction module is provided with an in-situ electrocatalytic electrode, and the second reaction module is provided with a counter electrode, and the in-situ electrocatalytic electrode and the counter electrode are connected by a wire. The method comprises: an electrolyte is electrolyzed on the surface of the in-situ electrocatalytic electrode to produce active reactants, and the raw materials introduced react with the active reactants under the action of the catalyst layer and the power supply to produce products. The present invention generates active reactants in situ on the surface of the catalyst layer, optimizes the steps of adsorption of reactants on the catalyst surface and conversion into active reactants during the catalytic reaction, and effectively improves the efficiency of the catalytic reaction.

Description

Technical Field

[0001] The present invention belongs to the technical field of electrocatalysis, and relates to a catalytic electrode, and in particular to an in-situ electrocatalytic electrode, and a catalytic reaction device and method thereof. Background Art

[0002] Catalytic reactions are widely used in modern chemical industry, petroleum processing industry, energy, environmental protection and other fields. According to the "phase" of the catalyst and reactants in the reaction system, catalytic reactions can be divided into homogeneous catalytic reactions and heterogeneous catalytic reactions. Among them, heterogeneous catalytic reactions in which the catalyst and reactants are in different "phases" are more common in industry, such as the synthesis of ammonia, the epoxidation of ethylene to synthesize ethylene oxide, and the cracking of petroleum.

[0003] In the heterogeneous catalytic process, the key step is the adsorption of reactants on the catalyst surface and the transformation into reactive species (such as the dissociation of molecules into corresponding atoms). In order to achieve this step, higher temperature conditions are often required. Taking the ethylene epoxidation process as an example, the reaction temperature of the direct oxidation of ethylene to synthesize ethylene oxide currently used in industry is 200-300°C. One of the main reasons for using a higher reaction temperature is that high temperature conditions are conducive to the dissociation and adsorption of reactant oxygen molecules on the surface of the silver catalyst to generate the key species of the reaction - atomic oxygen. However, the equipment used to maintain temperature is generally driven by fossil fuels, which will consume a large amount of non-renewable energy in the production process, which is not conducive to the sustainable development of energy. At the same time, more stringent reaction conditions will also increase the risk of catalyst deactivation, thereby increasing the production and use costs of the catalyst.

[0004] To solve the above-mentioned temperature condition problems and energy consumption problems, a feasible way is to introduce electrochemical technology into the catalytic reaction and construct an electrocatalytic system. On the one hand, the driving force of the reaction is electrical energy, which can be supplemented by renewable energy (such as solar energy, wind energy, tidal energy, etc.) to reduce the consumption of fossil fuels; on the other hand, by using suitable electrocatalysts, the target product can be synthesized under mild conditions, which can reduce the negative impact caused by harsh temperature conditions to a certain extent. However, current research on electrocatalytic methods mainly focuses on the design and preparation of electrocatalysts in order to obtain better catalytic performance; while there are relatively few studies on optimizing the catalytic reaction process, especially the step of adsorption of reactants on the catalyst surface and conversion into active species to improve catalytic efficiency.

[0005] CN111505083A discloses a novel ceramic catalytic electrode and a preparation method thereof, wherein the novel ceramic catalytic electrode comprises a ceramic substrate, a precious metal disposed inside and on the surface of the ceramic substrate, the ceramic substrate being a porous ceramic having tiny three-dimensional pores inside and on the surface, and the precious metal being distributed in a three-dimensional network in the ceramic substrate. The structure of the invention greatly increases the number of three-phase interfaces between the precious metal, the porous solid electrolyte ceramic and oxygen, and reduces the production cost when a small amount of precious metal is used. However, its structure is complex and the preparation conditions are difficult.

[0006] CN106474923A discloses an electrocatalytic electrode, a preparation method and use thereof, wherein the electrocatalytic electrode comprises a metal Ti substrate and an active material layer located on the surface of the Ti substrate, wherein the active material layer is a dense layer formed by stacking nanoparticles, wherein the nanoparticles are made of doped SnO2, and the doping elements include F and Sb. The active component layer of the electrocatalytic electrode is dense and crack-free, and is stacked by nanoparticles, thereby increasing the contact area between the active component layer and the pollutants to be eliminated. In addition, the preparation method of the electrocatalytic electrode is simple and easy to prepare.

[0007] CN107768688A discloses a gas diffusion catalytic electrode and a preparation method thereof, wherein the gas diffusion catalytic electrode comprises a porous metal substrate of foamed nickel or nickel mesh, nickel-plated copper mesh, and oxidized exfoliated graphite microsheets attached to the substrate, wherein the graphite microsheets are in an upright state and an active catalyst is attached to the surface. The electrode is used as an electrode of a rechargeable zinc-air battery, and has the advantages of high activity, low cost, simple preparation process, good use effect, etc.

[0008] Existing catalytic electrodes are rarely designed around the idea of ​​improving the step of reactants adsorbing on the catalyst surface and converting them into active species during the chemical synthesis process. It is necessary to further study the catalytic electrode structure to optimize the step of reactants adsorbing on the catalyst surface and converting them into active reactants during the catalytic reaction, so as to improve the catalytic efficiency. Summary of the invention

[0009] In view of the deficiencies in the prior art, the present invention aims to provide an in-situ electrocatalytic electrode, a catalytic reaction device and a method thereof, wherein an electrolyte is electrolyzed on a catalyst layer to produce active reactants, and raw materials diffuse to the catalyst layer through the in-situ electrocatalytic electrode to directly undergo an electrocatalytic reaction with the active reactants, or raw materials soluble in the electrolyte directly undergo an electrocatalytic reaction with the active reactants, thereby optimizing the steps of adsorption of reactants on the catalyst surface and conversion into active reactants during the catalytic reaction. For example, in the catalytic preparation of ethylene oxide from ethylene, the temperature required for the reaction in the prior art is 200-300°C, while by using the catalytic reaction device described in the present invention, the reaction temperature only needs to be 30°C, thereby effectively improving the catalytic efficiency, and can be used for a variety of catalytic reactions, with the characteristics of simple structure and strong adaptability.

[0010] To achieve this object, the present invention adopts the following technical solutions:

[0011] In a first aspect, the present invention provides an in-situ electrocatalytic electrode, which comprises a carrier with a pore structure, wherein a porous hydrophobic membrane, a conductive layer and a catalyst layer are sequentially stacked on at least one side surface of the carrier, and a raw material enters the carrier and diffuses through the pores to the porous hydrophobic membrane, the conductive layer and the catalyst layer.

[0012] The present invention passes the raw materials into the carrier, and utilizes the pore structure to diffuse the raw materials to the porous hydrophobic membrane, the conductive layer and the catalyst layer, wherein the porous hydrophobic membrane draws the raw materials out of the pores and prevents the external electrolyte from penetrating into the interior of the carrier; the conductive layer is used to transmit electrons participating in the electrochemical reaction process, and the present invention diffuses the raw materials to the catalyst layer through the pores, thereby achieving full contact between the raw materials and the active reactants generated by electrolysis on the catalyst surface, and the reaction catalytic efficiency is improved.

[0013] It should be noted that the present invention does not impose any specific requirements or restrictions on the material of the conductive layer. Any material with a stable conductive effect can be used in the present invention. For example, the material of the conductive layer includes copper or platinum.

[0014] As a preferred technical solution of the present invention, the carrier is a cavity structure, and at least one through hole is opened on the surface of the carrier close to the porous hydrophobic membrane.

[0015] The present invention designs the carrier to have a cavity structure and a through-hole structure so that the raw material can be buffered in the cavity, thereby avoiding the problem of excessive raw material pressure during the reaction causing turbulence on the carrier surface fluid, thereby reducing the contact area between the reactant and the catalyst layer.

[0016] The material of the carrier is any one of ceramic, polytetrafluoroethylene, polymethyl methacrylate or glass, or a combination of at least two of them.

[0017] Preferably, the wall thickness of the carrier is ≥1 cm, for example, the wall thickness is 1.0 cm, 1.5 cm, 2.0 cm, 2.5 cm, 3.0 cm, 3.5 cm, 4.0 cm, 4.5 cm, 5.0 cm, 5.5 cm, 6.0 cm, 6.5 cm, 7.0 cm, 7.5 cm, 8.0 cm, 8.5 cm, 9.0 cm, 9.5 cm or 10.0 cm.

[0018] Preferably, the shape of the carrier includes a cuboid, a cube, a cylinder or a trapezoid.

[0019] Preferably, when the shape of the carrier is a rectangular parallelepiped, the specifications of the carrier are: length ≥ 2.5 cm, for example, the length of the carrier is 2.5 cm, 3.0 cm, 3.5 cm, 4.0 cm, 4.5 cm, 5.0 cm, 5.5 cm, 6.0 cm, 6.5 cm, 7.0 cm, 7.5 cm, 8.0 cm, 8.5 cm, 9.0 cm, 9.5 cm or 10.0 cm; the width of the carrier is ≥ 2.5 cm; ... The width is 2.5cm, 3.0cm, 3.5cm, 4.0cm, 4.5cm, 5.0cm, 5.5cm, 6.0cm, 6.5cm, 7.0cm, 7.5cm, 8.0cm, 8.5cm, 9.0cm, 9.5cm or 10.0cm; the height of the carrier is 1 to 1.5cm; for example, the height of the carrier is 1.0cm, 1.1cm, 1.2cm, 1.3cm, 1.4cm or 1.5cm.

[0020] Preferably, the shape of the cavity includes a cuboid, a cube, a cylinder or a trapezoid.

[0021] Preferably, when the shape of the cavity is a rectangular parallelepiped, the specifications of the cavity are: length ≥ 1.5 cm, for example, the length of the cavity is 1.5 cm, 2.0 cm, 2.5 cm, 3.0 cm, 3.5 cm, 4.0 cm, 4.5 cm, 5.0 cm, 5.5 cm, 6.0 cm, 6.5 cm, 7.0 cm, 7.5 cm, 8.0 cm, 8.5 cm, 9.0 cm, 9.5 cm or 10.0 cm; width of the cavity ≥ 1.5 cm, for example, the width of the cavity is 1.5 cm m, 2.0cm, 2.5cm, 3.0cm, 3.5cm, 4.0cm, 4.5cm, 5.0cm, 5.5cm, 6.0cm, 6.5cm, 7.0cm, 7.5cm, 8.0cm, 8.5cm, 9.0cm, 9.5cm or 10.0cm; the height of the cavity is 0.5 to 0.8cm, for example, the height of the cavity is 0.50cm, 0.55cm, 0.60cm, 0.65cm, 0.70cm, 0.75cm or 0.80cm.

[0022] Preferably, the through holes are evenly distributed on the surface of the carrier.

[0023] Preferably, the through hole has a diameter of 0.1-0.15 cm, for example, a diameter of 0.10 cm, 0.11 cm, 0.12 cm, 0.13 cm, 0.14 cm or 0.15 cm.

[0024] As a preferred technical solution of the present invention, the average pore diameter of the porous hydrophobic membrane is 100-500 nm, for example, the average pore diameter is 100 nm, 150 nm, 200 nm, 250 nm, 300 nm, 350 nm, 400 nm, 450 nm or 500 nm.

[0025] Preferably, the porous hydrophobic membrane has a thickness of 50 to 80 μm, for example, a thickness of 50 μm, 55 μm, 60 μm, 65 μm, 70 μm, 75 μm or 80 μm.

[0026] The porous hydrophobic membrane in the present invention is used to lead the raw materials out of the pores, while preventing the electrolyte outside the in-situ electrocatalytic electrode from penetrating into the interior of the carrier.

[0027] Preferably, the porous hydrophobic membrane is made of polytetrafluoroethylene or carbon cloth.

[0028] Preferably, the conductive layer has a thickness of 50 to 500 nm, for example, a thickness of 50 nm, 100 nm, 150 nm, 200 nm, 250 nm, 300 nm, 350 nm, 400 nm, 450 nm or 500 nm.

[0029] Preferably, the conductive layer is made of copper and / or platinum.

[0030] As a preferred technical solution of the present invention, the structure of the catalyst in the catalyst layer includes any one of lamellar, dendritic, spherical or honeycomb shapes, or a combination of at least two of them.

[0031] It should be noted that the material in the catalyst layer is related to the catalyst required for the catalytic reaction. The present invention does not make specific requirements and special limitations on the material in the catalyst layer. Those skilled in the art can reasonably set the material in the catalyst layer according to the type of catalytic reaction. For example, molybdenum sulfide is used for thiophene hydrodesulfurization reaction.

[0032] Preferably, the catalyst layer has a thickness of 50 to 500 nm, for example, a thickness of 50 nm, 100 nm, 150 nm, 200 nm, 250 nm, 300 nm, 350 nm, 400 nm, 450 nm or 500 nm.

[0033] Preferably, the material of the catalyst layer includes any one of silver, palladium, graphene oxide or molybdenum sulfide, or a combination of at least two thereof.

[0034] As a preferred technical solution of the present invention, the in-situ electrocatalytic electrode further includes an air inlet channel disposed on the top of the carrier, and the air inlet channel is connected to the cavity.

[0035] Preferably, the diameter of the air inlet passage is 0.2-0.3 cm, for example, the diameter is 0.20 cm, 0.21 cm, 0.22 cm, 0.23 cm, 0.24 cm, 0.25 cm, 0.26 cm, 0.27 cm, 0.28 cm, 0.29 cm or 0.30 cm.

[0036] In a second aspect, the present invention provides a catalytic reaction device, comprising a first reaction module and a second reaction module which are interconnected, the first reaction module and the second reaction module being filled with an electrolyte, the first reaction module being provided with an in-situ electrocatalytic electrode immersed in the electrolyte, the second reaction module being provided with a counter electrode immersed in the electrolyte, the in-situ electrocatalytic electrode and the counter electrode being connected via a wire, a power source being provided on the wire, and the in-situ electrocatalytic electrode adopts the in-situ electrocatalytic electrode as described in the first aspect.

[0037] The present invention utilizes a catalytic reaction device to carry out a catalytic reaction on an in-situ electrocatalytic electrode, generates active reactants in-situ on the surface of the in-situ electrocatalytic electrode, and the active reactants react with raw materials on the surface of the in-situ electrocatalytic electrode, thereby improving the efficiency of the catalytic reaction.

[0038] As a preferred technical solution of the present invention, an exchange layer is provided in the pipeline connecting the first reaction module and the second reaction module, and the exchange layer is used for electrolyte ion exchange.

[0039] The present invention provides an exchange layer to transfer ions between the first reaction module and the second reaction module, so that the first reaction module and the second reaction module respectively perform different reactions.

[0040] Preferably, the exchange layer comprises a sand core or a perfluorosulfonic acid membrane.

[0041] Preferably, the first reaction module comprises a first shell, a first air outlet pipe and an air inlet pipe are provided on the top of the first shell, and the air inlet pipe is connected to the air inlet channel.

[0042] Preferably, the second reaction module comprises a second shell, and a second air outlet pipe is opened on the top of the second shell.

[0043] In a third aspect, the present invention provides a catalytic method, using the catalytic reaction device as described in the second aspect to carry out a catalytic reaction, the catalytic method comprising:

[0044] The electrolyte is electrolyzed on the surface of the in-situ electrocatalytic electrode to produce active reactants, and the introduced raw materials react with the active reactants to generate products under the action of the catalyst layer and the power supply.

[0045] The present invention generates active reactants on the surface of an in-situ electrocatalytic electrode by electrolyzing a specific electrolyte. Under the action of a catalyst and a power supply voltage, the raw materials directly react with the active reactants generated in situ on the surface of the in-situ electrocatalytic electrode, thereby avoiding the process in which a certain reactant in a traditional catalytic reaction is adsorbed and dissociated on the catalyst surface to form a corresponding active reactant. In addition, the generated product can be controlled by adjusting the voltage, thereby effectively improving the catalytic efficiency.

[0046] It should be noted that the present invention does not make specific requirements and special limitations on reactants and products. The catalytic reactions using the in-situ electrocatalytic electrode provided by the present invention are all within the protection scope of the present invention, for example, catalytic oxidation of ethylene to prepare ethylene oxide.

[0047] It should be noted that the present invention does not make specific requirements and special limitations on the condition parameters such as the required potential of the catalytic reaction. It is well known to those skilled in the art that the reaction conditions required for different reactants are different. The reaction condition parameters required for the catalytic reaction can be reasonably set according to specific experiments. For example, the reaction of thiophene hydrodesulfurization to generate hydrogen sulfide and butane requires a potential of -0.8 V, which is relative to a saturated calomel reference electrode.

[0048] As a preferred technical solution of the present invention, the raw material is ethylene, the electrolyte is any one of potassium hydroxide solution, sodium hydroxide solution or sodium perchlorate solution or a combination of at least two of them, the active reactant is adsorbed oxygen atoms, and the product is ethylene oxide.

[0049] Preferably, the raw material is thiophene, the electrolyte in the first reaction module includes an n-octane solution of thiophene, the electrolyte in the second reaction module includes sulfuric acid, the active reactant is active hydrogen bound to the catalyst surface, and the product includes hydrogen sulfide and butane.

[0050] Preferably, the raw material is oxygen, the electrolyte is potassium hydroxide solution and / or sodium hydroxide solution, the active reactant is active hydrogen bound to the catalyst surface, and the product is hydrogen peroxide.

[0051] The numerical range described in the present invention not only includes the point values ​​listed above, but also includes any point values ​​between the above numerical ranges that are not listed. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the range.

[0052] Compared with the prior art, the present invention has the following beneficial effects:

[0053] The in-situ electrocatalytic electrode provided by the present invention first electrolyzes an electrolyte on the surface of the in-situ electrocatalytic electrode to generate active reactants, forms a stable active reactant area on the surface of the in-situ electrocatalytic electrode, diffuses raw materials to the surface of the catalyst layer through a carrier with a pore structure and a porous hydrophobic membrane, and evenly disperses the raw materials on the surface of the catalyst layer. The raw materials fully contact and react with the active reactants in situ generated on the surface of the in-situ electrocatalytic electrode, thereby reducing the temperature conditions required for the reaction. For example, in the reaction of ethylene catalysis to prepare ethylene oxide, the temperature required for the reaction in the prior art is 200-300°C, while by using the catalytic reaction device described in the present invention, the reaction temperature only needs to be 30°C, and the catalytic reaction efficiency can be effectively improved. BRIEF DESCRIPTION OF THE DRAWINGS

[0054] Figure 1 A schematic structural diagram of an in-situ electrocatalytic electrode provided in a specific embodiment of the present invention;

[0055] Figure 2 A schematic diagram of a catalytic reaction device provided in a specific embodiment of the present invention

[0056] Figure 3a It is a front view of the carrier provided in Embodiment 1, Embodiment 2 and Embodiment 3 of the present invention;

[0057] Figure 3b It is a side view of the carrier provided in Example 1, Example 2 and Example 3 of the present invention.

[0058] Among them, 1-inlet channel; 2-porous hydrophobic membrane; 3-carrier; 4-through hole; 5-conductive layer; 6-catalyst layer; 7-cavity; 8-power supply; 9-conducting wire; 10-inlet pipe; 11-first outlet pipe; 12-second outlet pipe; 13-second shell; 14-first shell; 15-exchange layer; 16-counter electrode; 17-in-situ electrocatalytic electrode. DETAILED DESCRIPTION

[0059] It should be understood that, in the description of the present invention, the terms "center", "longitudinal", "lateral", "up", "down", "front", "back", "left", "right", "vertical", "horizontal", "top", "bottom", "inside", "outside", etc., indicating the orientation or positional relationship are based on the orientation or positional relationship shown in the drawings, and are only for the convenience of describing the present invention and simplifying the description, rather than indicating or implying that the device or element referred to must have a specific orientation, be constructed and operated in a specific orientation, and therefore cannot be understood as a limitation on the present invention. In addition, the terms "first", "second", etc. are only used for descriptive purposes, and cannot be understood as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Therefore, the features defined as "first", "second", etc. may explicitly or implicitly include one or more of the features. In the description of the present invention, unless otherwise specified, "multiple" means two or more.

[0060] It should be noted that in the description of the present invention, unless otherwise clearly specified and limited, the terms "disposed", "connected", and "connected" should be understood in a broad sense, for example, it can be a fixed connection, a detachable connection, or an integral connection; it can be a mechanical connection or an electrical connection; it can be a direct connection, or it can be indirectly connected through an intermediate medium, or it can be the internal communication of two elements. For ordinary technicians in this field, the specific meanings of the above terms in the present invention can be understood by specific circumstances.

[0061] The technical solution of the present invention is further described below with reference to the accompanying drawings and through specific implementation methods.

[0062] In a specific embodiment, Figure 1 As shown, the present invention provides an in-situ electrocatalytic electrode, which includes a carrier 3 with a pore structure, and a porous hydrophobic membrane 2, a conductive layer 5 and a catalyst layer 6 are sequentially stacked on at least one side surface of the carrier 3; the raw material enters the carrier 3 and diffuses through the pores to the porous hydrophobic membrane 2, the conductive layer 5 and the catalyst layer 6.

[0063] The present invention passes the raw materials into the carrier 3, and utilizes the pore structure to diffuse the raw materials to the porous hydrophobic membrane 2, the conductive layer 5 and the catalyst layer 6. The porous hydrophobic membrane 2 draws the raw materials out of the pores and prevents the external electrolyte from penetrating into the carrier 3. The conductive layer 5 is used to transmit electrons participating in the electrochemical reaction process. The present invention diffuses the raw materials to the catalyst layer 6 through the pores, thereby increasing the contact area between the reactants and significantly improving the catalytic efficiency of the reaction.

[0064] The carrier 3 has a cavity 7 structure, and at least one through hole 4 is provided on the surface of the carrier 3 near the porous hydrophobic membrane 2 .

[0065] The present invention designs the carrier 3 to have a cavity 7 structure and a through hole 4 structure, so that the raw material can be buffered in the cavity 7, thereby avoiding the problem of excessive gas pressure during the reaction causing the fluid on the surface of the carrier 3 to form turbulence, thereby reducing the contact area between the reactant and the catalyst layer 6.

[0066] The shape of the carrier 3 is a cuboid, a cube, a cylinder or a trapezoid. The shape of the carrier 3 is a cuboid. The length of the carrier 3 is ≥2.5 cm, the width is ≥2.5 cm, and the height is 1 to 1.5 cm. The wall thickness of the carrier 3 is ≥1 cm. The shape of the cavity 7 is a cuboid, a cube, a cylinder or a trapezoid. The shape of the cavity 7 is a cuboid. The length of the cavity 7 is ≥1.5 cm, the width is ≥1.5 cm, and the height is 0.5 to 0.8 cm. The through holes 4 are evenly distributed on the surface of the carrier 3, and the diameter of the through holes 4 is 0.1 to 0.15 cm.

[0067] The porous hydrophobic membrane 2 has an average pore size of 100 to 500 nm and a thickness of 50 to 80 μm.

[0068] In the present invention, the porous hydrophobic membrane 2 is used to lead the raw materials out of the pores, while preventing the electrolyte outside the in-situ electrocatalytic electrode 17 from penetrating into the inside of the carrier 3.

[0069] The thickness of the conductive layer 5 is 50-500 nm, and the material is copper and / or platinum.

[0070] The structure of the catalyst in the catalyst layer 6 is any one of lamellar, dendritic, spherical or honeycomb, or a combination of at least two of them. The thickness of the catalyst layer 6 is 50 to 500 nm, and the material is any one of silver, palladium, graphene oxide or molybdenum sulfide, or a combination of at least two of them.

[0071] The in-situ electrocatalytic electrode 17 further includes an air inlet channel 1 disposed on the top of the carrier 3 . The air inlet channel 1 is connected to the cavity 7 . The diameter of the air inlet channel 1 is 0.2 to 0.3 cm.

[0072] The material of the carrier 3 is any one of ceramic, polytetrafluoroethylene, polymethyl methacrylate or glass, or a combination of at least two of them. The material of the porous hydrophobic membrane 2 is polytetrafluoroethylene or carbon cloth.

[0073] The present invention also provides a catalytic reaction device, such as Figure 2 As shown, the catalytic reaction device includes a first reaction module and a second reaction module which are interconnected, the first reaction module and the second reaction module are filled with electrolyte, the first reaction module is provided with an in-situ electrocatalytic electrode 17 immersed in the electrolyte, the second reaction module is provided with a counter electrode 16 immersed in the electrolyte, the in-situ electrocatalytic electrode 17 is connected to the counter electrode 16 through a wire 9, a power supply 8 is provided on the wire 9, and the in-situ electrocatalytic electrode 17 adopts the above-mentioned in-situ electrocatalytic electrode 17.

[0074] The present invention utilizes a catalytic reaction device to carry out a catalytic reaction on the in-situ electrocatalytic electrode 17. The electrolyte generates active reactants in-situ on the surface of the in-situ electrocatalytic electrode 17, and reacts with the raw materials on the surface of the in-situ electrocatalytic electrode 17, thereby improving the efficiency of the catalytic reaction.

[0075] An exchange layer 15 is arranged in the pipeline connecting the first reaction module and the second reaction module. The exchange layer 15 includes a sand core or a perfluorosulfonic acid membrane.

[0076] The present invention provides an exchange layer 15 for transferring ions between the first reaction module and the second reaction module, so that the first reaction module and the second reaction module respectively perform different reactions.

[0077] The first reaction module includes a first shell 14 , a first air outlet pipe 11 and an air inlet pipe 10 are opened on the top of the first shell 14 , and the air inlet pipe 10 is connected to the air inlet channel 1 . The second reaction module includes a second shell 13 , a second air outlet pipe 12 is opened on the top of the second shell 13 .

[0078] In another specific embodiment, the present invention provides a catalytic method, which uses the above-mentioned catalytic reaction device to carry out a catalytic reaction, and the catalytic method comprises:

[0079] The electrolyte is electrolyzed on the surface of the in-situ electrocatalytic electrode 17 to produce active reactants, and the introduced raw materials react with the active reactants under the action of the catalyst layer 6 and the power source 8 to generate products.

[0080] The present invention uses an in-situ electrocatalytic electrode 17 to allow the electrolyte to generate active reactants on the surface of the in-situ electrocatalytic electrode 17, which undergo a catalytic reaction with the raw materials under the action of the catalyst and the voltage of the power supply 8. The reaction is carried out on the surface of the in-situ electrocatalytic electrode 17, avoiding the process in which a certain reactant in the traditional catalytic reaction is adsorbed and dissociated on the catalyst surface to form a corresponding active reactant, and the generated product is easy to control, thereby effectively improving the catalytic efficiency.

[0081] Example 1

[0082] This embodiment provides a catalytic reaction device, based on a catalytic reaction device described in a specific embodiment, wherein the exchange layer 15 includes a sand core. Figure 3a and Figure 3b As shown, the two side surfaces of the carrier 3 in the in-situ electrocatalytic electrode 17 are sequentially stacked with a porous hydrophobic membrane 2, a conductive layer 5 and a catalyst layer 6. The carrier 3 is in the shape of a rectangular parallelepiped, with a length of 2.5 cm, a width of 4 cm and a height of 1.5 cm. The cavity 7 is in the shape of a rectangular parallelepiped, with a length of 1.5 cm, a width of 3 cm and a height of 0.8 cm, and the diameter of the through hole 4 is 0.1 cm.

[0083] The average pore size of the porous hydrophobic membrane 2 is 200nm and the thickness is 50μm. The thickness of the conductive layer 5 is 150nm and the material is platinum. The structure of the catalyst in the catalyst layer 6 includes lamellar and dendritic structures, the mass ratio of the lamellar and dendritic catalysts is 1:1, the thickness of the catalyst layer 6 is 200nm, and the material is silver. The diameter of the air intake channel 1 is 0.3cm. The material of the carrier 3 is ceramic, and the material of the porous hydrophobic membrane 2 is carbon cloth.

[0084] Example 2

[0085] This embodiment provides a catalytic reaction device, based on a catalytic reaction device described in a specific embodiment, wherein the exchange layer 15 includes a perfluorosulfonic acid membrane. Figure 3a and Figure 3b As shown, the two side surfaces of the carrier 3 in the in-situ electrocatalytic electrode 17 are sequentially stacked with a porous hydrophobic membrane 2, a conductive layer 5 and a catalyst layer 6. The carrier 3 is in the shape of a rectangular parallelepiped, with a length of 6 cm, a width of 2.5 cm and a height of 1 cm. The cavity 7 is in the shape of a rectangular parallelepiped, with a length of 4 cm, a width of 2 cm and a height of 0.5 cm, and the diameter of the through hole 4 is 0.12 cm.

[0086] The average pore size of the porous hydrophobic membrane 2 is 300nm and the thickness is 55μm. The thickness of the conductive layer 5 is 300nm and the material is copper. The structure of the catalyst in the catalyst layer 6 is lamellar, the thickness of the catalyst layer 6 is 50nm, and the material is graphene oxide. The diameter of the air inlet channel 1 is 0.25cm. The material of the carrier 3 is polytetrafluoroethylene, and the material of the porous hydrophobic membrane 2 is polytetrafluoroethylene.

[0087] Example 3

[0088] This embodiment provides a catalytic reaction device, based on a catalytic reaction device described in a specific embodiment, wherein the exchange layer 15 includes a perfluorosulfonic acid membrane. Figure 3a and Figure 3b As shown, the two side surfaces of the carrier 3 in the in-situ electrocatalytic electrode 17 are sequentially stacked with a porous hydrophobic membrane 2, a conductive layer 5 and a catalyst layer 6. The carrier 3 is in the shape of a rectangular parallelepiped, with a length of 10 cm, a width of 12 cm and a height of 1.25 cm, the cavity 7 is in the shape of a rectangular parallelepiped, with a length of 8 cm, a width of 10 cm and a height of 0.65 cm, and the diameter of the through hole 4 is 0.13 cm.

[0089] The average pore size of the porous hydrophobic membrane 2 is 100nm and the thickness is 75μm. The thickness of the conductive layer 5 is 50nm and the material is copper. The structure of the catalyst in the catalyst layer 6 is a combination of lamellar and spherical, the mass ratio of the lamellar and spherical catalysts is 1:1, the thickness of the catalyst layer 6 is 300nm, and the material is molybdenum sulfide. The diameter of the air intake channel 1 is 0.2cm. The material of the carrier 3 is polymethyl methacrylate, and the material of the porous hydrophobic membrane 2 is polytetrafluoroethylene.

[0090] Example 4

[0091] This embodiment provides a catalytic reaction device, based on a catalytic reaction device described in a specific embodiment, wherein the exchange layer 15 includes a sand core. A porous hydrophobic membrane 2, a conductive layer 5 and a catalyst layer 6 are sequentially stacked on one side surface of the carrier 3. The shape of the carrier 3 is a cube, and the wall thickness of the carrier 3 is 3 cm; the shape of the cavity 7 is a cuboid, and the length of the cavity 7 is 4 cm, the width is 6 cm, the height is 0.75 cm, and the diameter of the through hole 4 is 0.14 cm.

[0092] The porous hydrophobic membrane 2 has an average pore size of 500 nm and a thickness of 80 μm. The conductive layer 5 has a thickness of 200 nm and is made of platinum. The catalyst layer 6 has a honeycomb structure, a thickness of 100 nm and is made of palladium. The diameter of the air inlet channel 1 is 0.2 cm.

[0093] The material of the carrier 3 is glass, and the material of the porous hydrophobic membrane 2 is carbon cloth.

[0094] Example 5

[0095] This embodiment provides a catalytic reaction device, based on a catalytic reaction device described in a specific embodiment, wherein the exchange layer 15 includes a perfluorosulfonic acid membrane. The two side surfaces of the carrier 3 are sequentially stacked with a porous hydrophobic membrane 2, a conductive layer 5 and a catalyst layer 6. The shape of the carrier 3 is a cylinder, and the wall thickness of the carrier 3 is 5 cm; the shape of the cavity 7 is a cylinder, and the diameter of the through hole 4 is 0.15 cm.

[0096] The average pore size of the porous hydrophobic membrane 2 is 400 nm, and the thickness is 70 μm. The thickness of the conductive layer 5 is 400 nm, and the material is platinum. The catalyst in the catalyst layer 6 is spherical, and the thickness of the catalyst layer 6 is 500 nm, and the material includes silver and palladium.

[0097] The diameter of the air inlet channel 1 is 0.24 cm. The material of the carrier 3 is a combination of ceramic and glass, the mass ratio of ceramic to glass is 1:1, and the material of the porous hydrophobic membrane 2 is carbon cloth.

[0098] Example 6

[0099] This embodiment provides a catalytic reaction device, based on a catalytic reaction device described in a specific embodiment, wherein the exchange layer 15 includes a sand core. The three side surfaces of the carrier 3 are sequentially stacked with a porous hydrophobic membrane 2, a conductive layer 5 and a catalyst layer 6. The shape of the carrier 3 is a trapezoid, and the wall thickness of the carrier 3 is 1 cm; the shape of the cavity 7 is a trapezoid, and the diameter of the through hole 4 is 0.13 cm.

[0100] The average pore size of the porous hydrophobic membrane 2 is 350nm, and the thickness is 65μm. The thickness of the conductive layer 5 is 350nm, and the material is copper. The structure of the catalyst in the catalyst layer 6 is a combination of lamellar, spherical and honeycomb, and the mass ratio of the lamellar, spherical and honeycomb catalysts is 1:1:1. The thickness of the catalyst layer 6 is 400nm, and the material is a combination of graphene oxide and molybdenum sulfide, and the mass ratio of graphene oxide to molybdenum sulfide is 1:1.

[0101] The diameter of the air inlet channel 1 is 0.21 cm. The material of the carrier 3 is a combination of polytetrafluoroethylene and polymethyl methacrylate, the mass ratio of polytetrafluoroethylene to polymethyl methacrylate is 1:1, and the material of the porous hydrophobic membrane 2 is polytetrafluoroethylene.

[0102] Application Example 1

[0103] The catalytic reaction device described in Example 1 is used to catalyze the preparation of ethylene oxide by ethylene, and the catalytic method specifically includes:

[0104] (I) applying a potential of 0.6 V to the in-situ electrocatalytic electrode 17 via a power source 8, the potential being relative to a mercury / mercuric oxide reference electrode, and a potassium hydroxide solution having a concentration of 1 mol / L being electrolyzed on the surface of the in-situ electrocatalytic electrode 17 to generate adsorbed oxygen atoms;

[0105] (II) Ethylene with a volume fraction of 20% is introduced. Ethylene enters the carrier 3 and diffuses through the porous hydrophobic membrane 2 to the catalyst layer 6 on the surface of the conductive layer 5. Under the action of the potential and the catalyst layer 6, it reacts with the adsorbed oxygen atoms to generate ethylene oxide.

[0106] Application Example 2

[0107] The catalytic reaction device described in Example 1 is used to catalyze the preparation of ethylene oxide by ethylene, and the catalytic method specifically includes:

[0108] Ethylene is used to catalyze the preparation of ethylene oxide, and the catalytic method comprises:

[0109] (I) applying a potential of 0.9 V to the in-situ electrocatalytic electrode 17 via a power source 8, the potential being relative to a mercury / mercuric oxide reference electrode, and a sodium hydroxide solution having a concentration of 1 mol / L being electrolyzed on the surface of the in-situ electrocatalytic electrode 17 to generate adsorbed oxygen atoms;

[0110] (II) Ethylene with a volume fraction of 25% is introduced. Ethylene enters the carrier 3 and diffuses through the porous hydrophobic membrane 2 to the catalyst layer 6 on the surface of the conductive layer 5. Under the action of the potential and the catalyst layer 6, it reacts with the adsorbed oxygen atoms to generate ethylene oxide.

[0111] Application Example 3

[0112] The catalytic reaction device described in Example 1 is used to catalyze the preparation of ethylene oxide by ethylene, and the catalytic method specifically includes:

[0113] Ethylene is used to catalyze the preparation of ethylene oxide, and the catalytic method comprises:

[0114] (I) applying a 1.1V potential to the in-situ electrocatalytic electrode 17 via a power source 8, the potential being relative to a mercury / mercuric oxide reference electrode, and a sodium perchlorate solution having a concentration of 0.1 mol / L being electrolyzed on the surface of the in-situ electrocatalytic electrode 17 to generate adsorbed oxygen atoms;

[0115] (II) Ethylene with a volume fraction of 27% is introduced. Ethylene enters the carrier 3 and diffuses through the porous hydrophobic membrane 2 to the catalyst layer 6 on the surface of the conductive layer 5. Under the action of the potential and the catalyst layer 6, it reacts with the adsorbed oxygen atoms to generate ethylene oxide.

[0116] Application Example 4

[0117] The catalytic reaction device described in Example 2 is used to catalyze the preparation of hydrogen peroxide using oxygen, and the catalytic method specifically includes:

[0118] (I) applying a -1.0 V potential to the in-situ electrocatalytic electrode 17 via a power source 8, the potential being relative to a mercury / mercuric oxide reference electrode, and a potassium hydroxide solution having a concentration of 0.1 mol / L being electrolyzed on the surface of the in-situ electrocatalytic electrode 17 to produce a transition state of hydrogen;

[0119] (II) Oxygen is introduced into the carrier 3 and diffuses through the porous hydrophobic membrane 2 to the catalyst layer 6 on the surface of the conductive layer 5. Under the action of the potential and the catalyst layer 6, oxygen reacts with the transition state of hydrogen to generate hydrogen peroxide.

[0120] Application Example 5

[0121] The catalytic reaction device described in Example 2 is used to catalyze the preparation of hydrogen peroxide using oxygen, and the catalytic method specifically includes:

[0122] (I) applying a potential of -1.2 V to the in-situ electrocatalytic electrode 17 via a power source 8, the potential being relative to a mercury / mercuric oxide reference electrode, and a sodium hydroxide solution having a concentration of 0.1 mol / L being electrolyzed on the surface of the in-situ electrocatalytic electrode 17 to produce a transition state of hydrogen;

[0123] (II) Oxygen is introduced into the carrier 3 and diffuses through the porous hydrophobic membrane 2 to the catalyst layer 6 on the surface of the conductive layer 5. Under the action of the potential and the catalyst layer 6, oxygen reacts with the transition state of hydrogen to generate hydrogen peroxide.

[0124] Application Example 6

[0125] The catalytic reaction device described in Example 3 is used to carry out a process for hydrodesulfurization of thiophene, and the catalytic method specifically includes:

[0126] (I) The electrolyte in the first reaction module is an n-octane solution of thiophene, and the electrolyte in the second reaction module is sulfuric acid. A potential of -0.4 V is applied to the in-situ electrocatalytic electrode 17 by a power supply 8, and the potential is relative to a saturated calomel reference electrode. The hydrogen ions in the second reaction module are enriched to the surface of the in-situ electrocatalytic electrode 17 through the perfluorosulfonic acid membrane and converted into active hydrogen;

[0127] (II) Thiophene in the first reaction module directly contacts the surface of the in-situ electrocatalytic electrode 17 and reacts with active hydrogen under the action of the potential and the catalyst layer 6 to generate hydrogen sulfide and butane.

[0128] Application Example 7

[0129] The catalytic reaction device described in Example 3 is used to carry out efficient hydrodesulfurization of thiophene, and the catalytic method specifically includes:

[0130] (I) The electrolyte in the first reaction module is an octane solution containing thiophene, and the electrolyte in the second reaction module is sulfuric acid. A potential of -0.8 V is applied to the in-situ electrocatalytic electrode 17 by a power supply 8, and the potential is relative to a saturated calomel reference electrode. The hydrogen ions in the second reaction module are enriched to the surface of the in-situ electrocatalytic electrode 17 through the perfluorosulfonic acid membrane and converted into active hydrogen;

[0131] (II) Thiophene in the first reaction module directly contacts the surface of the in-situ electrocatalytic electrode 17 and reacts with active hydrogen under the action of the potential and the catalyst layer 6 to generate hydrogen sulfide and butane.

[0132] The in-situ electrocatalytic electrode 17 provided by the present invention first electrolyzes the electrolyte on the surface of the in-situ electrocatalytic electrode 17 to generate active reactants, forms a stable active reactant region on the surface of the in-situ electrocatalytic electrode 17, diffuses the raw materials to the surface of the catalyst layer 6 through the carrier 3 with a pore structure and the porous hydrophobic membrane 2, so that the raw materials are evenly dispersed on the surface of the catalyst layer 6, and the raw materials react with the active reactants generated in situ on the surface of the catalyst layer 6. The raw materials and the active reactants are fully contacted and reacted, thereby effectively improving the efficiency of the catalytic reaction.

[0133] The applicant declares that the above is only a specific implementation mode of the present invention, but the protection scope of the present invention is not limited thereto. Those skilled in the art should understand that any changes or substitutions that can be easily thought of by those skilled in the art within the technical scope disclosed by the present invention shall fall within the protection scope and disclosure scope of the present invention.

Claims

1. A catalytic method, characterized in that: The catalytic method specifically comprises: The electrolyte is electrolyzed on the surface of the in-situ electrocatalytic electrode to produce active reactants, and the introduced raw materials react with the active reactants to generate products under the action of the catalyst layer and the power source; The raw material is ethylene, the electrolyte includes any one of potassium hydroxide solution, sodium hydroxide solution or sodium perchlorate solution or a combination of at least two of them, the active reactant includes adsorbed oxygen atoms, and the product is ethylene oxide; The catalytic method uses the following catalytic device to perform a catalytic reaction, the catalytic device includes a first reaction module and a second reaction module that are interconnected, the first reaction module and the second reaction module are filled with an electrolyte, the first reaction module is provided with an in-situ electrocatalytic electrode immersed in the electrolyte, the second reaction module is provided with a counter electrode immersed in the electrolyte, the in-situ electrocatalytic electrode and the counter electrode are connected by a wire, and the wire is provided with a power supply; The raw material is thiophene, the electrolyte in the first reaction module includes an n-octane solution of thiophene, the electrolyte in the second reaction module includes sulfuric acid, the active reactant includes active hydrogen bound to the catalyst surface, and the product includes hydrogen sulfide and butane; The raw material includes oxygen, the electrolyte includes potassium hydroxide solution and / or sodium hydroxide solution, the active reactant includes active hydrogen bound to the catalyst surface, and the product includes hydrogen peroxide; The in-situ electrocatalytic electrode comprises a carrier with a pore structure, and a porous hydrophobic membrane, a conductive layer and a catalyst layer are sequentially stacked on at least one side surface of the carrier. The raw material enters the carrier and diffuses through the pores to the porous hydrophobic membrane, the conductive layer and the catalyst layer.

2. The catalytic method according to claim 1, characterized in that: The carrier is a cavity structure, and at least one through hole is provided on the surface of one side of the carrier close to the porous hydrophobic membrane.

3. The catalytic method according to claim 1, characterized in that: The material of the carrier includes any one of ceramic, polytetrafluoroethylene, polymethyl methacrylate or glass, or a combination of at least two of them.

4. The catalytic method according to claim 1, characterized in that: The wall thickness of the carrier is ≥1 cm.

5. The catalytic method according to claim 1, characterized in that: The shape of the carrier includes a cuboid, a cube, a cylinder or a trapezoid.

6. The catalytic method according to claim 5, characterized in that: The carrier is in the shape of a cuboid, the length of the carrier is ≥2.5 cm, the width of the carrier is ≥2.5 cm, and the height of the carrier is 1 to 1.5 cm.

7. The catalytic method according to claim 2, characterized in that: The shape of the cavity includes a cuboid, a cube, a cylinder or a trapezoid.

8. The catalytic method according to claim 7, characterized in that: The shape of the cavity is a cuboid, the length of the cavity is ≥1.5 cm, the width of the cavity is ≥1.5 cm, and the height of the cavity is 0.5-0.8 cm.

9. The catalytic method according to claim 2, characterized in that: The through holes are evenly distributed on the surface of the carrier.

10. The catalytic method according to claim 2, characterized in that: The diameter of the through hole is 0.1-0.15 cm.

11. The catalytic method according to claim 1, characterized in that: The average pore size of the porous hydrophobic membrane is 100-500 nm.

12. The catalytic method according to claim 1, characterized in that: The thickness of the porous hydrophobic membrane is 50-80 μm.

13. The catalytic method according to claim 1, characterized in that: The material of the porous hydrophobic membrane includes polytetrafluoroethylene and / or carbon cloth.

14. The catalytic method according to claim 1, characterized in that: The thickness of the conductive layer is 50-500 nm.

15. The catalytic method according to claim 1, characterized in that: The conductive layer is made of copper and / or platinum.

16. The catalytic method according to claim 1, characterized in that: The structure of the catalyst in the catalyst layer includes any one of lamellar, dendritic, spherical or honeycomb structures or a combination of at least two of them.

17. The catalytic method according to claim 1, characterized in that The thickness of the catalyst layer is 50-500 nm.

18. The catalytic method according to claim 1, characterized in that: The material of the catalyst layer includes any one of silver, palladium, graphene oxide or molybdenum sulfide, or a combination of at least two thereof.

19. The catalytic method according to claim 2, characterized in that: The in-situ electrocatalytic electrode further comprises an air inlet channel arranged on the top of the carrier, and the air inlet channel is connected to the cavity.

20. The catalytic method according to claim 19, characterized in that The diameter of the air inlet channel is 0.2-0.3 cm.

21. The catalytic method according to claim 1, characterized in that: An exchange layer is arranged in the pipeline connecting the first reaction module and the second reaction module, and the exchange layer is used for ion exchange in the electrolyte.

22. The catalytic method according to claim 21, characterized in that: The exchange layer includes a sand core or a perfluorosulfonic acid membrane.

23. The catalytic method according to claim 1, characterized in that: The first reaction module comprises a first shell, a first air outlet pipe and an air inlet pipe are provided on the top of the first shell, and the air inlet pipe is connected to the air inlet channel.

24. The catalytic method according to claim 1, characterized in that: The second reaction module includes a second shell, and a second air outlet pipe is opened on the top of the second shell.

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