CN114774959B - Integrated carbon electrode for producing hydrogen peroxide by air diffusion device and preparation method and application thereof - Google Patents
Integrated carbon electrode for producing hydrogen peroxide by air diffusion device and preparation method and application thereof Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 238
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 186
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 title claims abstract description 116
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- 230000009471 action Effects 0.000 description 1
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- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/02—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form
- C25B11/03—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form perforated or foraminous
- C25B11/031—Porous electrodes
- C25B11/032—Gas diffusion electrodes
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/28—Per-compounds
- C25B1/30—Peroxides
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/054—Electrodes comprising electrocatalysts supported on a carrier
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/055—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material
- C25B11/057—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material consisting of a single element or compound
- C25B11/065—Carbon
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
The invention relates to an integrated carbon electrode for producing hydrogen peroxide by an air diffusion device and a preparation method and application thereof, belonging to the technical field of electrochemistry; the preparation method of the integrated carbon electrode for producing hydrogen peroxide by air bulk-expanding is characterized in that carbon powder, an adhesive and an organic solvent are mixed and concentrated to prepare a precursor, the precursor is cast and pressed to obtain a block-shaped substance, and the block-shaped substance is annealed to obtain the integrated carbon electrode. The integrated carbon electrode is used as an electrochemical cathode to be applied to a horizontally fixed air diffusion device for producing hydrogen peroxide, hydrogen peroxide is synthesized with low energy and high efficiency, the performance is stable, the used electrode has high catalyst load and stable mechanical property, meanwhile, the integrated carbon electrode has diffusion catalytic property, almost no catalyst is dropped and lost in the long-term use process, and the used device is easy to detach and does not need to consider the problems of tightness and material specificity.
Description
Technical Field
The invention relates to the field of electrochemistry, in particular to an integrated carbon electrode for producing hydrogen peroxide by an air diffusion device, a preparation method and application thereof.
Background
Hydrogen peroxide is a green and environment-friendly strong oxidant and has been widely used in the fields of medical treatment, life, industry, environmental management and the like. The anthraquinone process is the mainstream industrial production method at present, and comprises the steps of hydrogenation, oxidation, hydrogen peroxide extraction, working solution purification and circulation, and the like, and has the advantages of high energy consumption, complex steps and easy production of harmful byproducts. Because hydrogen peroxide is unstable, a great amount of hydrogen peroxide is transported and stored, and the safety hazard exists, and only low-concentration hydrogen peroxide is generally needed in actual use. The electrochemical synthesis method is a method for synthesizing hydrogen peroxide by two-electron oxygen reduction reaction on the surface of an electrochemical cathode, and the method can synthesize hydrogen peroxide in situ, so that the method is the hydrogen peroxide synthesis technology with the most development potential in recent years.
In an electrochemical system, a common cathode hydrogen peroxide production mode is a traditional immersed device, namely an electrode is placed in a solution, oxygen is supplied through aeration at the periphery of the electrode, dissolved oxygen is converted into hydrogen peroxide on the surface of the electrode, but the hydrogen peroxide synthesis effect is poor due to the limitation of dissolved oxygen in water.
The gas diffusion electrode refers to a generic name of a porous electrode which has a gas-liquid-solid three-phase reaction interface and has a catalyst for catalyzing a film at the three-phase interface to participate in electrochemical reaction, has a gas pore passage through which gas passes and a thin liquid film which can perform electrochemical reaction, is one of cathode materials widely studied at present, and has the advantages of good air permeability, high gas diffusion mass transfer efficiency and the like. In the electrochemical reaction process, most of gas reaches the position of the thin liquid film through the gas pore canal of the gas diffusion electrode to react, so that the reaction efficiency is greatly improved, and the limit diffusion current density of the electrochemical reaction is further improved.
Currently, common gas diffusion electrodes include laminated, ultrasonic, and coated three-stage gas diffusion electrodes by ultrasonically, coating, or laminating a catalytic support onto the surface of a support layer, wherein the support comprises catalyst particles and a binder. However, since the preparation method of the three-stage gas diffusion electrode limits the catalyst loading amount, it is difficult to form a self-supporting active material layer, and it is often necessary to additionally provide a conductive support layer to enhance mechanical stability. The problem that the combination of the load and the supporting layer is not tight can occur, and the phenomena that the catalyst falls off or the gap between the load is flooded easily occur in the using process, so that the service life of the gas diffusion electrode is shortened.
Disclosure of Invention
The invention aims to overcome the defects that the existing gas diffusion electrode has small load capacity, a surface load is easy to fall off or a water flooding occurs in a gap between the load and the existing immersed device is limited by dissolved oxygen in water, and has poor electrochemical synthesis effect.
In a first aspect, the present invention provides a method for preparing an integrated carbon electrode for hydrogen peroxide production by an air diffusion device, which adopts the following technical scheme:
the preparation method of the integrated carbon electrode for producing hydrogen peroxide by using the air diffusion device comprises the steps of mixing carbon powder, an adhesive and an organic solvent, concentrating to obtain a precursor, casting and pressing the precursor to obtain a block-shaped substance, drying the block-shaped substance, and annealing to obtain the integrated carbon electrode.
By adopting the technical scheme, the adhesive and the carbon-based powder are mixed, coagulated, pressed and annealed to prepare the integrated carbon electrode, and the electrode has the functions of diffusion and catalysis; the prepared integrated carbon electrode is in a block shape, has higher mechanical strength, has a stress of 1-8Mpa under a tensile rate of 0.1-0.5, and has stable mechanical properties, so that a stainless steel mesh or the like is not required to be used as a supporting structure, and the problem that carbon powder falls off and runs off almost no more in the use process of the integrated carbon electrode; the existing three-section catalyst layer can be peeled off in a whole piece if the catalyst is too thick, therefore, only one thin catalyst layer can be supported on the surface of the electrode, the catalyst peeling phenomenon does not exist in the integrated carbon electrode, the catalyst amount can be increased at will within the optimal range of hydrogen peroxide production performance, the volume of the catalyst layer is naturally increased, further, the catalyst loading capacity is larger, and the loading capacity can reach 40-178mg/cm 2 。
Preferably, the catalyst loading of the bulk material is 40-178mg/cm 2 。
The original three-section electrode can only load a certain amount of catalyst due to the limitation of the manufacturing process, and if the catalyst is too thick, the catalyst layer can be peeled off in a whole; the integrated carbon electrode prepared by adopting the technical scheme overcomes the limit of the preparation process, increases the catalyst loading capacity, and provides more reaction sites for rapid diffusion and migration of reactants and products in the electrochemical reaction.
Preferably, the annealing treatment is carried out at a temperature of 300-350 ℃ for 1.5-2 hours;
preferably, the annealing treatment is carried out at a temperature of 350 ℃ for 2 hours.
By adopting the technical scheme, the annealing temperature is 300-350 ℃, the annealing temperature is close to or near to the melting temperature of the adhesive, the blocky substances are firstly heated to the annealing temperature, and the adhesive is in a molten state, so that the carbon-based powder is better combined with the adhesive, then the temperature is slowly reduced, acting force is reformed among polymer chains of the adhesive, the structure formed by the adhesive and the carbon-based powder is stable, the adhesive has better mechanical property, the adhesive is more tightly combined with the carbon-based powder, and the falling of the carbon-based powder is reduced.
Preferably, adding the carbon-based powder and the adhesive into an organic solvent, and uniformly mixing by ultrasonic to obtain a mixed solution, concentrating the mixed solution to obtain a precursor, wherein the heating temperature for concentration is 80-85 ℃ and the time is 0.5-1h;
preferably, the precursor is cast on a die, and is uniformly compressed to obtain a blocky substance; and carrying out annealing treatment on the block materials after drying treatment, wherein the temperature of the drying treatment is 75-80 ℃ and the time is 8-10h.
By adopting the technical scheme, the carbon-based powder and the adhesive are added into the organic solvent, and the organic solvent is subjected to ultrasonic treatment to obtain uniform mixed solution, so that the carbon-based powder is uniformly distributed on the integrated carbon electrode, the stability of current when the integrated carbon electrode is used can be improved, and the catalytic performance of the integrated carbon electrode is further improved;
and heating, concentrating and volatilizing part of the organic solvent in the mixed solution to prepare a precursor with smaller fluidity, which is beneficial to shaping the integrated carbon electrode, and the precursor still contains a certain amount of organic solvent;
and casting the precursor on a die to compress and prepare a block-shaped substance, and drying and annealing the organic solvent in the block-shaped substance to volatilize so as to enable the surface and the inside of the integrated carbon electrode to generate micropores, thereby providing a place for efficient transmission of oxygen.
Optionally, the carbon-based powder is selected from one or more of conductive carbon black, graphite, acetylene carbon black, carbon nanotubes, graphene, activated carbon, carbon 60 or fullerenes; optionally, the binder is selected from one or more of polytetrafluoroethylene, polyvinylidene fluoride or perfluorosulfonic acid polymers;
optionally, the input weight ratio of the carbon-based powder to the binder is 1: (1-5);
optionally, the organic solvent is selected from one or more of ethanol, methanol, acetone, isopropanol or n-butanol.
By adopting the technical scheme, the carbon-based material has the advantages of low cost, chemical stability, large specific surface area, good conductivity and the like, is a preferred material for preparing the oxygen reduction electrode, and common carbon-based materials comprise conductive carbon black, activated carbon, acetylene black, carbon nano tubes, graphite, graphene, carbon 60, fullerene and the like; the carbon material can catalyze the oxygen reduction reaction, the adhesive can bond the carbon powder, and the integrated carbon electrode has certain hydrophobicity, is favorable for oxygen transmission, and can be used as a gas diffusion cathode for preparing hydrogen peroxide by an electrochemical synthesis method.
Preferably, the method specifically comprises the following steps:
s1, adding a certain amount of the catalyst particles and the adhesive into the organic solvent, carrying out ultrasonic mixing uniformly to obtain a mixed solution, heating and stirring the mixed solution, and concentrating the mixed solution to obtain a precursor;
s2, casting the precursor onto a die, and compacting to obtain a block-shaped substance;
and S3, drying and annealing the massive substances to obtain the integrated carbon electrode.
In a second aspect, the present application provides an integrated carbon electrode adopting the following technical scheme:
an integrated carbon electrode prepared by the method for preparing the integrated carbon electrode for producing hydrogen peroxide by using the air diffusion device.
By adopting the technical scheme, the mechanical property of the adhesive is improved through annealing treatment, and the integrated carbon electrode formed by mixing the carbon-based powder and the adhesive has stronger mechanical strength without adding a stainless steel net and other supportsA layer; the bonding between the adhesive and the carbon-based powder is tight, so that the problem of catalyst falling in the existing three-stage gas diffusion electrode can be reduced or eliminated; the catalyst loading of the integrated carbon electrode is high, and the loading can reach 40-178mg/cm 2 More oxygen reduction reaction places are provided, and the hydrogen peroxide synthesis efficiency is improved; meanwhile, micropores are distributed in the integrated carbon electrode and on the surface of the integrated carbon electrode, the aperture of the micropores is 0.09-0.14 mu m, the porosity is 40-60%, and the gas mass transfer efficiency and the gas load capacity of the integrated carbon electrode are improved; the catalyst active site in the integrated carbon electrode and the hydrophobic pore canal act together, so that the integrated carbon electrode has synchronous catalytic diffusion performance.
In a third aspect, the present invention provides an air diffusing device, which adopts the following technical scheme:
an air diffusion device, wherein the integrated carbon electrode prepared by any one of the preparation methods is used as a gas diffusion cathode, or the integrated carbon electrode is used as a gas diffusion cathode.
By adopting the technical scheme, the air diffusion device is an air diffusion device which can be matched with the integrated carbon electrode to efficiently produce hydrogen peroxide, and aeration is not needed; moreover, the air diffusion device is easy to detach, and the problems of tightness and material specificity are not required to be considered;
the integrated carbon electrode is used as a gas diffusion cathode in a horizontally fixed air diffusion device, one side is contacted with air and the other side is contacted with electrolyte on the basis of the mechanical property of the electrode, and gas enters a solid-liquid reaction site through an internal pore canal of the integrated carbon electrode to form a gas-liquid-solid three-phase reaction interface, so that the limitation of dissolved oxygen in water is eliminated, aeration is not needed, the energy consumption is low, the yield of hydrogen peroxide is high, and the hydrogen peroxide current efficiency can reach 70% -95% under the neutral condition of 50-200 mA.
In a fourth aspect, the present application provides an integrated carbon electrode prepared by any one of the above methods, or an integrated carbon electrode as described above, or an application of the air diffusion device as described above in the electrochemical synthesis field.
The beneficial effects are that:
(1) The invention provides a preparation method of an integrated carbon electrode for producing hydrogen peroxide by an air diffusion device, which comprises the steps of mixing carbon powder, an adhesive and an organic solvent, pressing, drying, annealing and the like to prepare the integrated carbon electrode with the thickness of 0.2-0.5cm, wherein the stress at the tensile rate of 0.1-0.5 Mpa is 1-8Mpa, the mechanical strength is high, the mechanical property is stable, a stainless steel net and other structures are not required to be used as a supporting structure of the electrode, and the problem that catalyst particles fall off from the integrated carbon electrode in the use process of the integrated carbon electrode is reduced;
(2) The integrated carbon electrode provided by the invention has the functions of catalysis and diffusion, the integrated carbon electrode generates pore channels on the surface and inside through natural evaporation of an organic solvent, more oxygen is provided for electrosynthesis of hydrogen peroxide, oxygen enters the integrated carbon electrode through a hydrophobic pore channel, and oxygen reduction reaction occurs at a catalytic active site of carbon powder in the electrode;
(3) The catalyst loading capacity of the integrated carbon electrode can reach 40-178mg/cm 2 The catalyst has higher catalyst loading capacity and provides more catalytic active sites for hydrogen peroxide electrosynthesis;
(4) The integrated carbon electrode is used as a gas diffusion cathode in an electrochemical reaction system to be applied to a horizontally fixed air diffusion device; in the air diffusion device, an integrated carbon electrode is horizontally arranged on the liquid level of electrolyte, one side of the integrated carbon electrode is in contact with the liquid level, and the other side of the integrated carbon electrode is in direct contact with air, so that a three-phase reaction interface of water, gas and solid is formed, and the limitation of dissolved oxygen in water is eliminated; the integrated carbon electrode and the air diffusion device can be combined to efficiently synthesize hydrogen peroxide, and the hydrogen peroxide current efficiency reaches 70-95% under the neutral condition of 50-200 mA; meanwhile, compared with the existing air diffusion device, the air diffusion device provided by the invention is convenient to assemble and disassemble, does not need to consider the problems of tightness and material specificity, and has higher applicability.
Drawings
In order to more clearly illustrate the technical solutions of the present invention, the following brief description will be made on the accompanying drawings, which are given by way of illustration only and not limitation of the present invention.
FIG. 1 is a flow chart of the preparation of an integrated carbon electrode according to example 1 of the present invention;
FIG. 2 is a physical view showing the appearance of an integrated carbon electrode according to example 1 of the present invention;
FIG. 3 is a scanning electron microscope image of the surface of an integrated carbon electrode provided in example 1 of the present invention;
FIG. 4 is a schematic view of an air diffusing device according to embodiment 14 of the present invention;
FIG. 5 is a graph showing the mechanical properties of the integrated carbon electrodes provided in examples 1-3 of Experimental example 1;
FIG. 6 is a linear voltammogram of the integrated carbon electrode provided in examples 1-3 of Experimental example 2;
FIG. 7 is a graph showing the results of six-cycle experiments on the integrated carbon electrode provided in example 2 of Experimental example 2;
FIG. 8 is a graph showing the results of the use of the integrated carbon electrodes provided in examples 1-3 of Experimental example 2 for the electrosynthesis of hydrogen peroxide for hydrogen peroxide production and amperage;
FIG. 9 is a graph showing the results of the use of the electrodes provided in example 2 and comparative example 2 in experimental example 2 for the electrosynthesis of hydrogen peroxide.
Detailed Description
Preferred embodiments of the present invention will be described in more detail below. While the preferred embodiments of the present invention are described below, it should be understood that the present invention may be embodied in various forms and should not be limited to the embodiments set forth herein. The specific techniques or conditions are not identified in the examples and are performed according to techniques or conditions described in the literature in this field or according to the product specifications. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention. In the examples below, "%" refers to weight percent, unless explicitly stated otherwise.
The application provides a preparation method of an integrated carbon electrode for producing hydrogen peroxide by an air diffusion device, which is characterized in that carbon powder, an adhesive and an organic solvent are mixed and concentrated to prepare a precursor, the precursor is cast and pressed to obtain a block material, and the block material is annealed to obtain the integrated carbon electrode.
In one embodiment, the catalyst loading of the bulk material is 40 to 178mg/cm 2 。
According to the invention, the prepared integrated carbon electrode is in a block shape, the bonding between the bonding agent and between the bonding agent and the carbon-based powder is tight, the mechanical strength is high, the mechanical stability is better, the problem that catalyst particles fall off from the integrated carbon electrode in the use process of the integrated carbon electrode is reduced, and the service life of the integrated carbon electrode is prolonged; meanwhile, the prepared integrated carbon electrode has the functions of catalysis and diffusion, and gas enters the integrated carbon electrode to diffuse through the micropores and is subjected to reduction reaction under the catalysis of carbon powder.
In the invention, the catalyst which can be loaded in the preparation process of the integrated carbon electrode catalyst is high, and more catalytic active sites can be provided for the electrosynthesis of hydrogen peroxide.
According to the invention, the organic solvent is introduced in the preparation process of the integrated carbon electrode, and micropores are formed on the integrated carbon electrode after the organic solvent volatilizes, so that a place is provided for efficient transmission of oxygen, and the gas load of the integrated carbon electrode and the adsorption affinity of oxygen are improved.
In the invention, the hydrophobic polymer material is used as the adhesive, and is mixed with the carbon-based powder and the organic solvent, and the integrated carbon electrode can be prepared by certain treatment, so that the range of the adhesive material, the carbon-based material and the organic solvent which can be selected is wider, and the application range of the preparation method is wider.
In one embodiment, the annealing treatment is performed at a temperature of 300-350 ℃ for a time of 1.5-2 hours;
preferably, the annealing treatment is carried out at a temperature of 350 ℃ for 2 hours.
In the invention, the block-shaped substance is annealed at 250-350 ℃, and the acting force between macromolecular chains in the adhesive is rebuilt, so that the adhesive forms a structure with better mechanical property and has larger mechanical strength, and the structure can be used as a supporting structure of an integrated carbon electrode; in addition, the adhesive is tightly combined with the catalyst particles, so that the condition that the catalyst particles fall off in the use process of the integrated carbon electrode is reduced, and the service life of the integrated carbon electrode is prolonged; meanwhile, in the annealing treatment process, the organic solvent contained in the bulk material is further volatilized, and finally, micropores with the pore size of 0.09-0.14 mu m are formed on the integrated carbon electrode, the distribution of the micropores is uniform, and the porosity of the integrated carbon electrode is 37% -56%.
In one embodiment, the carbon-based powder and the binder are added into an organic solvent and mixed uniformly by ultrasonic to obtain a mixed solution, the mixed solution is concentrated to obtain a precursor, and the heating temperature for concentration is 80-85 ℃ and the time is 0.5-1h.
In one embodiment, the precursor is cast on a die, and is uniformly compressed to form a block-shaped substance; and carrying out annealing treatment on the block materials after drying treatment, wherein the temperature of the drying treatment is 75-80 ℃ and the time is 8-10h.
In one embodiment, the carbon-based powder is selected from one or more of conductive carbon black, graphite, acetylene carbon black, carbon nanotubes, graphene, activated carbon, carbon 60, or fullerenes;
optionally, the binder is selected from one or more of polytetrafluoroethylene, polyvinylidene fluoride or perfluorosulfonic acid polymers;
optionally, the input weight ratio of the carbon-based powder to the binder is 1: (1-5);
optionally, the organic solvent is selected from one or more of ethanol, methanol, acetone, isopropanol or n-butanol.
In the invention, the carbon-based powder is selected as the catalyst particles of the integrated carbon electrode, and the carbon-based powder has the advantages of low cost, chemical stability, good specific surface area, good electric conduction performance and the like, and can be used as the catalytic material of the oxygen reduction electrode and applied to the electrochemical reaction for synthesizing hydrogen peroxide.
In the invention, one or more of hydrophobic high molecular materials polytetrafluoroethylene, polyvinylidene fluoride or perfluorinated sulfonic acid polymer is used as a binder, and carbon-based powder is added into the binder, and the carbon-based powder and the binder form an integrated gas diffusion electrode under the bonding action of the binder.
In the present invention, the input weight ratio of the carbon-based powder to the binder is controlled so that the input weight ratio of the carbon-based powder to the binder is 1: (1-5), and the mass concentration of the binder is 40-80%, the integrated carbon electrode has more catalytic sites and more proper conductivity, and mainly catalyzes 2e - The oxygen reduction reaction is favorable for the generation of hydrogen peroxide, and the hydrophobicity of the integrated carbon electrode is proper at the moment, so that a gas-liquid-solid three-phase reaction interface is formed on the integrated carbon electrode.
According to the invention, the carbon-based powder and the adhesive are uniformly mixed by ultrasonic, the precursor is obtained by heating and concentrating, the precursor is pressed to obtain a blocky substance, and the blocky substance is dried and annealed to obtain the integrated carbon electrode, so that the integrated carbon electrode can be prepared by the method, has the thickness of 0.2-0.5cm, has high mechanical strength and stable mechanical property, is less in possibility of falling off of the carbon-based powder in the use process, and prolongs the service life of the integrated carbon electrode while improving the catalyst loading capacity of the integrated carbon electrode.
In one embodiment, the method specifically comprises the following steps:
s1, adding a certain amount of the catalyst particles and the adhesive into the organic solvent, carrying out ultrasonic mixing uniformly to obtain a mixed solution, heating and stirring the mixed solution, and concentrating the mixed solution to obtain a precursor;
s2, casting the precursor onto a die, and compacting to obtain a block-shaped substance;
and S3, drying and annealing the massive substances to obtain the integrated carbon electrode.
The application provides an integrated carbon electrode, which is prepared by the preparation method of the integrated carbon electrode for producing hydrogen peroxide by using the air diffusion device.
In the invention, the integrated carbon electrode is provided with micropores, the aperture of the micropores is 0.09-0.14 mu m, and the porosity of the integrated carbon electrode is 37-56%.
The application provides an air diffusion device, wherein an integrated carbon electrode prepared by any one of the preparation methods is used as a gas diffusion cathode, or the integrated carbon electrode is used as the gas diffusion cathode.
The air diffusion device is an air diffusion device which can be matched with the integrated carbon electrode to efficiently produce hydrogen peroxide, and has the advantages of no need of aeration, easy disassembly, no need of considering the sealing performance, material specificity and the like.
The application provides an integrated carbon electrode prepared by any one of the preparation methods, or the integrated carbon electrode, or the application of the air diffusion device in the electrochemical synthesis field.
Example 1. An Integrated carbon electrode and method for producing the same
An integrated carbon electrode is provided in this embodiment, which includes a carbon-based powder and a binder; wherein, the carbon-based powder and the adhesive are respectively conductive carbon black and polytetrafluoroethylene, and the polytetrafluoroethylene and the carbon-based powder are mixed and treated to form an integrated carbon electrode, and catalyst particles and micropores are dispersed in the integrated carbon electrode and on the surface of the integrated carbon electrode.
As shown in fig. 1, this embodiment also provides a method for preparing an integrated carbon electrode for hydrogen peroxide production by an air diffusion device, which comprises adding conductive carbon black and polytetrafluoroethylene into an organic solvent according to a mass ratio of 1:3 to obtain a mixed solution, concentrating the mixed solution to obtain a precursor, casting and pressing the precursor to obtain a bulk material with a thickness of 0.4cm, and finally annealing the bulk material to obtain the integrated carbon electrode, wherein the organic solvent is absolute ethyl alcohol, and the catalyst loading capacity of the integrated carbon electrode is 171.4mg/cm 2 The method comprises the steps of carrying out a first treatment on the surface of the The preparation of the integrated carbon electrode specifically comprises the following steps:
s1, weighing 1.2g of conductive carbon black and 6g of 60% polytetrafluoroethylene emulsion, adding the mixture into 40mL of absolute ethyl alcohol, and carrying out ultrasonic treatment for 30min to obtain uniform mixed solution;
s2, placing the mixed solution in a water bath kettle at 85 ℃, stirring, heating and concentrating for 1h until the mixed solution is agglomerated to form a precursor;
s3, casting the precursor on a plate containing stainless steel, and pressing the solid stainless steel cylinder to obtain a block substance;
s4, placing the block materials in an oven at 80 ℃ for 10 hours, and drying;
and S5, placing the dried block material in a muffle furnace at 350 ℃ for annealing treatment for 2 hours to obtain the integrated carbon electrode.
FIGS. 2 and 3 are a physical appearance diagram and a surface scanning electron microscope diagram, respectively, of the integrated carbon electrode prepared by the above-described preparation method; as can be seen from fig. 3, the surface of the integrated carbon electrode has a porous structure, which is beneficial to transport of two electron oxygen reduction related reactants on the surface of the electrode.
Example 2 an Integrated carbon electrode and method of making the same
This example is different from example 1 in that the amounts of conductive carbon black and 60% polytetrafluoroethylene emulsion added are 1.2g and 2.0g, respectively, and the mass ratio of conductive carbon black to polytetrafluoroethylene added is 1:1.
Example 3 an Integrated carbon electrode and method of making the same
This example is different from example 1 in that the amounts of conductive carbon black and 60% polytetrafluoroethylene emulsion added are 1.2g and 10g, respectively, and the ratio of conductive carbon black to polytetrafluoroethylene added is 1:5.
Example 4 an Integrated carbon electrode and method of making the same
This example is different from example 1 in that the input amounts of the conductive carbon black and 60% polytetrafluoroethylene emulsion were 0.3g and 1.5g, and the catalyst loading amount of the integrated carbon electrode was 42.8mg/cm 2 。
Example 5 an Integrated carbon electrode and method of making the same
This example is different from example 1 in that the amounts of the conductive carbon black and 60% polytetrafluoroethylene emulsion added are 0.9g and4.5g, catalyst loading of 128.5mg/cm for the integrated carbon electrode 2 。
Example 6 an Integrated carbon electrode and method of making the same
This example differs from example 1 in that the annealing treatment is carried out at 320℃for 1.5 hours.
Example 7 an Integrated carbon electrode and method of making the same
This example differs from example 1 in that the heating temperature for concentration is 80℃and the time is 0.5h.
Example 8 an Integrated carbon electrode and method of making the same
This example differs from example 1 in that the temperature of the drying is 75℃and the time is 8 hours.
Example 9 an Integrated carbon electrode and method of making the same
This example differs from example 1 in that the catalyst particles were activated carbon, the binder was polyvinylidene fluoride, and the organic solvent was isopropyl alcohol, and the amounts of the activated carbon and 40% polyvinylidene fluoride emulsion added were 0.3g and 2.25g, respectively.
Example 10 an Integrated carbon electrode and method of making the same
This example differs from example 1 in that the catalyst particles were graphite and carbon nanotubes, the organic solvent was acetone, and the amounts of graphite, carbon nanotubes, and 60% polytetrafluoroethylene emulsion added were 0.15g, and 2.5g, respectively.
Example 11 an Integrated carbon electrode and method of making the same
The present example is different from example 1 in that the catalyst particles are activated carbon and graphene, and the amounts of the activated carbon, graphene and 60% polytetrafluoroethylene emulsion added are 0.3g, 0.6g and 7.5g, respectively.
Example 12 an Integrated carbon electrode and method of making the same
This example differs from example 1 in that the catalyst particles were acetylene black and carbon 60, the organic solvent was n-butanol, and the amounts of acetylene black, carbon 60, and 60% perfluorosulfonic acid emulsion charged were 0.3g, and 3.0g, respectively.
Example 13 an Integrated carbon electrode and method of making the same
This example differs from example 1 in that the catalyst particles are fullerenes and the organic solvent is methanol.
Example 14 an air diffusion device and its use in the production of Hydrogen peroxide
As shown in fig. 4, an air diffusion device includes an electrolytic cell, an anode, a cathode, and a power source; the anode is a metal oxide electrode, the cathode is an integrated carbon electrode provided in any one of embodiments 1-13, the anode and the cathode are respectively communicated with the anode and the cathode of a power supply, electrolyte is contained in the electrolytic cell, the anode is immersed in the electrolyte and is positioned in the electrolytic cell at a position close to the bottom of the cell, the cathode is fixed on the liquid surface of the electrolyte, one surface of the cathode is contacted with air, and the other surface of the cathode is contacted with the electrolyte.
In the case of hydrogen peroxide synthesis, na is used 2 SO 4 The solution was added as an electrolyte to an electrolytic cell of an air diffusion device, with titanium-based metal oxide as an anode, and the integrated carbon electrodes provided in examples 1-13 as cathodes, set a current of 100mA, and were energized under neutral conditions for 60min.
Comparative example 1A gas diffusion cathode and its preparation
The gas diffusion cathode consists of a diffusion catalytic layer and a supporting layer, and the preparation specifically comprises the following steps:
the gas diffusion cathode takes carbon paper as a supporting net frame, and coats the mixture composed of catalyst particles and a binder on the carbon paper, and the preparation method specifically comprises the following steps:
(1) 1.2g of conductive carbon black and 6.0g of 60% polytetrafluoroethylene emulsion are weighed according to a certain mass, uniformly mixed, 40mL of ethanol is added, and ultrasonic oscillation is carried out for 30min to uniformly disperse to obtain a conductive carbon black/binder mixture;
(2) Uniformly ultrasonically coating the conductive carbon black/binder mixture on the surface of carbon paper to obtain a precursor;
(3) Placing the precursor in an oven at 80 ℃ for 10 hours, and drying;
(4) And (3) placing the dried precursor in a muffle furnace at 350 ℃ for annealing treatment for 2 hours to obtain the gas diffusion electrode.
Comparative example 2A gas diffusion cathode and its preparation
The gas diffusion cathode takes graphite felt as a supporting net frame, and is prepared by carrying out ultrasonic treatment on the graphite felt, coating catalyst particles and a mixture formed by a binder, wherein the preparation method specifically comprises the following steps of:
(1) 1.2g of conductive carbon black and 6.0g of 60% polytetrafluoroethylene emulsion are weighed according to a certain mass, uniformly mixed, 40mL of ethanol is added, and ultrasonic oscillation is carried out for 30min to uniformly disperse to obtain a conductive carbon black/binder mixture;
(2) Uniformly ultrasonically coating the conductive carbon black/binder mixture on the surface of a graphite felt to obtain a precursor;
(3) Placing the precursor in an oven at 80 ℃ for 10 hours, and drying;
(4) And (3) placing the dried precursor in a muffle furnace at 350 ℃ for annealing treatment for 2 hours to obtain the gas diffusion cathode.
Experimental example 1 mechanical Properties of electrode
The mechanical properties of the electrodes provided in examples 1-3 were tested using a YES-2000 press tester, the results of which are shown in fig. 5, as can be seen: when the elongation percentage is 50%, the maximum stress of the integrated carbon electrode provided by the examples 1, 2 and 3 increases along with the increase of the polytetrafluoroethylene addition amount, wherein the maximum stress of the example 3 reaches 7.73MPa, which shows that the integrated carbon electrode prepared by the examples 1-3 has strong deformation resistance and stable mechanical property.
Experimental example 2 electrochemical Properties of electrode
The electrochemical performance of the integrated carbon electrodes provided in examples 1-3 was characterized using the CHI electrochemical workstation and the hydrogen peroxide production performance of the integrated carbon electrodes provided in examples 1-3 and the gas diffusion cathodes provided in comparative examples 1-2 was investigated, and the experimental results are shown in fig. 6-9.
Fig. 6 is a linear voltammogram of the integrated carbon electrode provided in examples 1-3, and as can be seen from fig. 6, the current response increases with increasing conductive carbon black content, indicating that the higher the catalyst loading of the integrated carbon electrode, the better its conductivity and more reactive sites.
The integrated carbon electrode provided in example 1 was used as the cathode of the air diffusion device provided in example 14, and was continuously run 6 times for 60 minutes each time, and the experimental results are shown in fig. 7. As can be seen from fig. 7, the hydrogen peroxide yield was maintained at 450mg/L and the average current efficiency was maintained at 80% in six cycle experiments, indicating that the hydrogen peroxide production performance was stable in six cycle experiments.
The integrated carbon electrode provided in examples 1-3 was used as the cathode of the air diffusion device provided in example 14, titanium and metal oxide were used as the anode, and Na was used as the anode 2 SO 4 The electrolyte was set to 100mA, and was energized under neutral conditions for 60 minutes, and the experimental results are shown in FIG. 8. As can be seen from fig. 8, the hydrogen peroxide yield of the integrated carbon electrode provided in example 1 was 453.2mg/L h, and the current efficiency was maintained above 70%, which is superior to examples 2 and 3.
The electrodes provided in example 1 and comparative examples 1-2 were used as gas diffusion cathodes, titanium and metal oxides as anodes, and Na 2 SO 4 The electrolyte was set to 100mA, and was energized under neutral conditions for 60 minutes, and the experimental results are shown in FIG. 9.
As can be seen from FIG. 9, CB-PTFE/CP is the gas diffusion cathode of comparative example 1, which has a current efficiency of about 60%, H 2 O 2 Yield 5.3mg h -1 *cm -1 CB-PTFE/GF is the gas diffusion cathode of comparative example 2, which has a current efficiency of about 55%, H 2 O 2 Yield 4.3mg h -1 *cm -1 The method comprises the steps of carrying out a first treatment on the surface of the CB-PTFE is the integrated carbon electrode of example 1, and has a current efficiency of about 90%, H 2 O 2 Yield 7.5mg h -1 *cm -1 The electrosynthesis of hydrogen peroxide using the integrated carbon electrode provided in example 1 has higher hydrogen peroxide yield and current efficiency than comparative examples 1 and 2.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited to the specific details of the above embodiments, and various simple modifications can be made to the technical solution of the present invention within the scope of the technical concept of the present invention, and all the simple modifications belong to the protection scope of the present invention.
In addition, the specific features described in the above embodiments may be combined in any suitable manner without contradiction. The various possible combinations of the invention are not described in detail in order to avoid unnecessary repetition.
Moreover, any combination of the various embodiments of the invention can be made without departing from the spirit of the invention, which should also be considered as disclosed herein.
Claims (10)
1. The preparation method of the integrated carbon electrode for producing hydrogen peroxide by using the air diffusion device is characterized by comprising the following steps of: mixing carbon powder, an adhesive and an organic solvent, concentrating to obtain a precursor, casting and pressing the precursor to obtain a block material, drying the block material, and annealing at 300-350 ℃ for 1.5-2h to obtain the integrated carbon electrode.
2. The method for producing an integrated carbon electrode for hydrogen peroxide production by an air diffusing apparatus according to claim 1, wherein: the catalyst loading of the bulk material is 40-178mg/cm 2 。
3. The method for producing an integrated carbon electrode for hydrogen peroxide production by an air diffusing apparatus according to claim 1, wherein the annealing treatment is performed at a temperature of 350 ℃ for a time of 2 hours.
4. The method for producing an integrated carbon electrode for hydrogen peroxide production by an air diffusing apparatus according to claim 1, wherein: adding the carbon-based powder and the adhesive into an organic solvent, and uniformly mixing by ultrasonic to obtain a mixed solution, concentrating the mixed solution to obtain a precursor, wherein the heating temperature for concentration is 80-85 ℃ and the time is 0.5-1h.
5. The method for producing an integrated carbon electrode for hydrogen peroxide production by an air diffusion device according to claim 1, wherein the precursor is cast onto a mold and uniformly compressed to form a bulk substance; and carrying out annealing treatment on the block materials after drying treatment, wherein the temperature of the drying treatment is 75-80 ℃ and the time is 8-10h.
6. The method for producing an integrated carbon electrode for hydrogen peroxide production by an air diffusing apparatus according to claim 1, wherein: the carbon-based powder is selected from one or more of conductive carbon black, graphite, acetylene carbon black, carbon nanotubes, graphene, activated carbon, carbon 60 or fullerene;
the adhesive is selected from one or more of polytetrafluoroethylene, polyvinylidene fluoride or perfluorinated sulfonic acid type polymers; the input weight ratio of the carbon-based powder to the binder is 1: (1-5);
the organic solvent is selected from one or more of ethanol, methanol, acetone, isopropanol or n-butanol.
7. The method for producing an integrated carbon electrode for hydrogen peroxide production of an air diffusing apparatus according to any one of claims 1 to 6, wherein: the method specifically comprises the following steps:
s1, adding a certain amount of the carbon-based powder and the adhesive into the organic solvent, carrying out ultrasonic mixing uniformly to obtain a mixed solution, heating and stirring the mixed solution, and concentrating the mixed solution to obtain a precursor;
s2, casting the precursor onto a die, and compacting to obtain a block-shaped substance;
and S3, drying and annealing the massive substances to obtain the integrated carbon electrode.
8. An integrated carbon electrode, characterized in that: is prepared by the method for preparing the integrated carbon electrode for producing hydrogen peroxide by the air diffusion device according to any one of claims 1 to 7.
9. An air diffusion device, characterized in that an integrated carbon electrode prepared by the preparation method of any one of claims 1 to 7 is used as a gas diffusion cathode, or an integrated carbon electrode of claim 8 is used as a gas diffusion cathode.
10. An integrated carbon electrode prepared by the preparation method of any one of claims 1 to 7, or an integrated carbon electrode of claim 8, or an air diffusion device of claim 9, for use in the field of electrochemical synthesis.
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