CN112376072A - Membrane electrode for producing ozone water by using tap water and preparation method thereof - Google Patents

Membrane electrode for producing ozone water by using tap water and preparation method thereof Download PDF

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CN112376072A
CN112376072A CN202011257518.5A CN202011257518A CN112376072A CN 112376072 A CN112376072 A CN 112376072A CN 202011257518 A CN202011257518 A CN 202011257518A CN 112376072 A CN112376072 A CN 112376072A
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membrane
exchange membrane
catalyst layer
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廖雨农
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Dongguan Nanbai Electronic Technology Co ltd
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Abstract

The invention relates to the technical field of environmental electrochemistry, in particular to a membrane electrode for generating ozone water by using tap water and a preparation method thereof. The membrane electrode comprises an ion exchange membrane, an anode catalyst layer arranged on one side of the ion exchange membrane and a cathode catalyst layer arranged on the other side of the ion exchange membrane, wherein the cation exchange membrane is a porous ceramic-based solid polymer electrolyte membrane or a graphite-phase C3N4/PFSA solid electrolyte composite membrane. The invention has wide application, such as drinking water disinfection, municipal sewage treatment, medical disinfection and the like. The membrane electrode of the invention only needs water as the raw material for producing ozone water by using tap water, thus the energy consumption is low; the invention does not need an air pump, and the noise generated by use is low; high-purity ozone is generated, no other by-product is generated, no nitrogen oxide is generated, and no secondary pollution is generated to the environment; can work for a long time, has stable electrolysis efficiency and does not need to additionally add oxygen-containing electrolyte.

Description

Membrane electrode for producing ozone water by using tap water and preparation method thereof
Technical Field
The invention relates to the technical field of environmental electrochemistry, in particular to a membrane electrode for generating ozone water by using tap water and a preparation method thereof.
Background
Ozone can be used for purifying air, bleaching drinking water, sterilizing, treating industrial waste and the like. In practical application, ozone is mainly prepared by a dielectric barrier discharge method, an electrolytic method, an ultraviolet method and the like. The widely applied ozone generation technology at present is a high-voltage discharge ozone generation technology, noise generated by an air pump is large, toxic nitrogen oxides are easily generated in the process of preparing ozone, and the concentration of the prepared ozone is low. The electrolytic water type ozone preparation device is high in current efficiency, the prepared ozone is high in concentration, nitrogen oxide cannot be generated in the electrolytic process, secondary pollution to the environment cannot be generated, however, in the prior art, acid electrolyte is generally required to be utilized, the generated ozone is output as gas, and the ozone is required to be introduced into water through a pipeline to prepare ozone water.
Disclosure of Invention
In order to overcome the defects and shortcomings in the prior art, the invention aims to provide a membrane electrode for producing ozone water by using tap water, wherein the membrane electrode only needs water as a raw material for preparing ozone, has low energy consumption, can generate high-purity ozone, and does not contain any other by-product.
Another object of the present invention is to provide a method for preparing a membrane electrode for producing ozone water using tap water, which is simple in operation, low in production cost, and high in product quality.
The purpose of the invention is realized by the following technical scheme: a membrane electrode for producing ozone water by using tap water comprises an ion exchange membrane, an anode catalyst layer arranged on one side of the ion exchange membrane and a cathode catalyst layer arranged on the other side of the ion exchange membrane, wherein the cation exchange membrane is a porous ceramic-based solid polymer electrolyte membrane or a graphite-phase C3N4/PFSA solid electrolyte composite membrane.
The porous ceramic-based solid polymer electrolyte membrane is used as a cation exchange membrane, electrolyte does not need to be added, and the generation of byproducts is reduced; the conductive coating has good conductivity and high current efficiency; has good chemical stability and thermal stability.
The graphite phase C3N4/PFSA solid electrolyte composite membrane is used as a cation exchange membrane, so that the conductivity is remarkably improved, and the proton conductivity is remarkably improved.
The raw material for producing ozone only needs water, so that the energy consumption is low, the electrolysis efficiency is not influenced by the air quality, drying is not needed, and nitrogen oxides NOx are not generated; the electrolytic tank can work for a long time, has stable electrolytic efficiency, and does not need to additionally add any oxygen-containing electrolyte; high purity ozone and oxygen can be generated without any other by-products.
Further, the anode catalyst layer is made of a boron-carbon diamond heterojunction material, and the cathode catalyst layer is made of a graphene composite material.
The boron-carbon diamond heterojunction material has high mechanical property, good corrosion resistance, good thermal stability and simultaneously extremely high electrochemical stability; the membrane electrode formed by the structure is corrosion resistant, and the problem of falling off of an electrolytic catalyst coating is solved; no hot spot damage risk, strengthening unique structural design, far exceeding the common PEM electrolytic ozone device; the service life of the membrane electrode can continuously work for more than 3 years; the ozone is generated by using low-voltage direct current, the voltage is not higher than 36V, the safety is high, more ozone gas is generated by less energy, the purity of the generated ozone gas is far higher than that of a corona method and an ultraviolet light method, the purity of the generated ozone gas is more than 400% of that of the corona method, and the purity of the generated ozone gas is more than 900% of that of the ultraviolet light method; the ozone generator has the advantages of low power consumption, no maintenance, low frequency, no need of circulating cooling, high purity ozone durability, ozone generation instantaneity and the like.
The other purpose of the invention is realized by the following technical scheme: a preparation method of a membrane electrode for producing ozone water by using tap water comprises the following steps:
(1) preparing an anode catalyst layer by adopting a boron-carbon diamond heterojunction material;
(2) preparing a cation exchange membrane;
(3) preparing a cathode catalyst layer;
(4) pressing the anode catalyst layer, the cation exchange membrane and the cathode catalyst layer to prepare a membrane electrode;
wherein, the steps (1) to (3) can be carried out simultaneously or the sequence can be changed.
The preparation method is simple, the process is mature, and the membrane electrode prepared by pressing occupies small space, is highly integrated and portable; the structure is stable and the durability is good; the membrane electrode has good ventilation performance, and the cation exchange membrane is not easy to deform in the preparation process.
Further, in the step (1), the preparation method of the anode catalyst layer includes the steps of: decomposing carbon gas and radon gas into carbon and hydrogen atoms and active free radicals at the temperature of 1300-1700 ℃, wherein the hydrogen atoms and the active free radicals are combined with the carbon matrix to form a carbide transition layer; depositing diamond crystal nucleus on the carbide transition layer by carbon atoms; the formed diamond crystal nucleus grows into diamond microcrystal under the pressure of 5-7Gpa, and then grows into a diamond film.
The anode catalyst layer prepared by the method has simple instrument and equipment and convenient operation; the manufacturing cost of the diamond is low, and the film forming process is easy to control; the diamond crystal nucleus grows under the pressure of 5-7Gpa, and the speed and the quality of the deposited film can be effectively improved.
Further, in the step (2), the cation exchange membrane is a porous ceramic-based solid electrolyte composite membrane, and the preparation method of the cation exchange membrane includes the following steps:
a1, preparation of the ceramic-based sulfonated polyimide material: taking 2.8-3.2 parts of diphenyl ether tetracarboxylic dianhydride monoatomic dispersion platinum carbon, 0.8-1.2 parts of diacetyl amide and 2.8-3.2 parts of malonaldehyde according to parts by weight to obtain sulfonated polyimide;
a2, adding sulfonated polyimide into propylene glycol to prepare a sulfonated polyimide solution, wherein the weight ratio of the sulfonated polyimide to the propylene glycol is (7.5-8.5): 0.28 to 0.32, and pressurizing the porous nickel-iron ceramic plate to perform a permeation reaction to prepare the ceramic matrix composite heterogeneous membrane;
a3, soaking the ceramic matrix composite heterogeneous membrane obtained in the step A2 in a hydrochloric acid solution to obtain the cation exchange membrane.
The porous ceramic-based solid electrolyte composite membrane is prepared by the method, and the method is simple to operate; the porous ceramic-based solid electrolyte composite membrane prepared by the method has good conductivity and high current efficiency; the chemical stability and the thermal stability are good; can conduct current and selectively permeate ions to couple reaction and separation.
Further, in the step A2, the pressure for the infiltration reaction is 18-22MPa on the porous nickel-iron ceramic plate.
Further, the cation exchange membrane is a graphite phase C3N4/PFSA solid electrolyte composite membrane, and the preparation method of the cation exchange membrane comprises the following steps: mixing the graphite phase and the perfluorinated sulfonic acid resin according to the weight ratio of 3.8-4.2:0.9-1.1, heating, and performing extrusion molding to form a film, thus obtaining the cation exchange membrane.
The graphite phase C3N4/PFSA solid electrolyte composite membrane prepared by the method has obviously increased conductivity and proton conductivity, probably because acid-base conjugate ion pairs are formed by abundant base groups on the graphite phase C3N4 and sulfonate groups on the PFSA resin, and the proton selectivity and the proton transmission speed are increased.
Further, in the step (2), after the graphite phase and the perfluorosulfonic acid resin are mixed, the mixture is heated to 190 ℃ and 210 ℃ to perform extrusion molding to form the film.
Further, in the step (3), the preparation method of the cathode catalytic material for preparing the cathode catalyst layer includes the following steps: taking a carbon carrier, a non-metal heteroatom reagent and a platinum compound as raw materials, drying for 7-9h at the temperature of 380-420 ℃ after stirring, refluxing and rotary evaporation, grinding to below 50nm, and treating and interacting at the temperature of 950-1050 ℃ to obtain the cathode catalytic material.
The cathode catalyst layer is prepared by adopting the method, and test results show that the platinum element in the catalyst exists in the form of single-atom platinum, the catalytic activity is high, and in acid and alkaline systems, the initial potential and half-wave potential of oxygen reduction are equivalent to those of a commercial carbon-supported platinum catalyst with the platinum content of 20%; and other metal elements are not introduced in the preparation process, so that the stability is better.
Further, the non-metal heteroatom is at least one of nitrogen, oxygen, sulfur, phosphorus, silicon and halogen, and the platinum compound is at least one of platinum hydroxide compound, platinum sulfur compound and platinum chlorine compound.
The invention has the beneficial effects that: the membrane electrode for producing ozone water by using tap water has wide application, such as drinking water disinfection, municipal sewage treatment, medical disinfection and the like. The membrane electrode of the invention only needs water as the raw material for producing ozone water by using tap water, thus the energy consumption is low; the invention does not need an air pump, and the noise generated by use is low; high-purity ozone is generated, no other by-product is generated, no nitrogen oxide is generated, and no secondary pollution is generated to the environment; can work for a long time, has stable electrolysis efficiency and does not need to additionally add oxygen-containing electrolyte.
The preparation method of the membrane electrode for producing ozone water by using tap water has the advantages of simple operation, low production cost and high product quality.
Drawings
FIG. 1 is a schematic structural view of the present invention;
the reference signs are: 1-anode catalyst layer; 2-ion exchange membrane; 3-cathode catalyst layer.
Detailed Description
The present invention will be further described below to facilitate understanding of those skilled in the art, and the embodiments are not to be construed as limiting the present invention.
In a typical embodiment of the present invention, the object of the present invention is achieved by the following technical solutions: a membrane electrode for producing ozone water by using tap water comprises an ion exchange membrane, an anode catalyst layer arranged on one side of the ion exchange membrane and a cathode catalyst layer arranged on the other side of the ion exchange membrane, wherein the cation exchange membrane is a porous ceramic-based solid polymer electrolyte membrane or a graphite-phase C3N4/PFSA solid electrolyte composite membrane.
Further, the anode catalyst layer is made of a boron-carbon diamond heterojunction material, and the cathode catalyst layer is made of a graphene composite material.
A preparation method of a membrane electrode for producing ozone water by using tap water comprises the following steps:
(1) preparing an anode catalyst layer by adopting a boron-carbon diamond heterojunction material;
(2) preparing a cation exchange membrane;
(3) preparing a cathode catalyst layer;
(4) pressing the anode catalyst layer, the cation exchange membrane and the cathode catalyst layer to prepare a membrane electrode;
wherein, the steps (1) to (3) can be carried out simultaneously or the sequence can be changed.
Further, in the step (1), the preparation method of the anode catalyst layer includes the steps of: decomposing carbon gas and radon gas into carbon and hydrogen atoms and active free radicals at the temperature of 1300-1700 ℃, wherein the hydrogen atoms and the active free radicals are combined with the carbon matrix to form a carbide transition layer; depositing diamond crystal nucleus on the carbide transition layer by carbon atoms; the formed diamond crystal nucleus grows into diamond micro-products under the pressure of 5-7Gpa, and then grows into a diamond film.
Further, in the step (2), the cation exchange membrane is a porous ceramic-based solid electrolyte composite membrane, and the preparation method of the cation exchange membrane includes the following steps:
a1, preparation of the ceramic-based sulfonated polyimide material: taking 2.8-3.2 parts of diphenyl ether tetracarboxylic dianhydride monoatomic dispersion platinum carbon, 0.8-1.2 parts of diacetyl amide and 2.8-3.2 parts of malonaldehyde according to parts by weight to obtain sulfonated polyimide;
a2, adding sulfonated polyimide into propylene glycol to prepare a sulfonated polyimide solution, wherein the weight ratio of the sulfonated polyimide to the propylene glycol is (7.5-8.5): 0.28 to 0.32, and pressurizing the porous nickel-iron ceramic plate to perform a permeation reaction to prepare the ceramic matrix composite heterogeneous membrane;
a3, soaking the ceramic matrix composite heterogeneous membrane obtained in the step A2 in a hydrochloric acid solution to obtain the cation exchange membrane.
Further, in the step A2, the pressure for the infiltration reaction is 18-22MPa on the porous nickel-iron ceramic plate.
Further, the cation exchange membrane is a graphite phase C3N4/PFSA solid electrolyte composite membrane, and the preparation method of the cation exchange membrane comprises the following steps: mixing the graphite phase and the perfluorinated sulfonic acid resin according to the weight ratio of 3.8-4.2:0.9-1.1, heating, and performing extrusion molding to form a film, thus obtaining the cation exchange membrane.
Further, in the step (2), after the graphite phase and the perfluorosulfonic acid resin are mixed, the mixture is heated to 190 ℃ and 210 ℃ to perform extrusion molding to form the film.
Further, in the step (3), the preparation method of the cathode catalytic material for preparing the cathode catalyst layer includes the following steps: taking a carbon carrier, a non-metal heteroatom reagent and a platinum compound as raw materials, drying for 7-9h at the temperature of 380-420 ℃ after stirring, refluxing and rotary evaporation, grinding to below 50nm, and treating and interacting at the temperature of 950-1050 ℃ to obtain the cathode catalytic material.
Further, the non-metal heteroatom is at least one of nitrogen, oxygen, sulfur, phosphorus, silicon and halogen, and the platinum compound is at least one of platinum hydroxide compound, platinum sulfur compound and platinum chlorine compound.
Example 1
A membrane electrode for producing ozone water by using tap water comprises an ion exchange membrane 2, an anode catalyst layer 1 arranged on one side of the ion exchange membrane 2 and a cathode catalyst layer 3 arranged on the other side of the ion exchange membrane 2, wherein the cation exchange membrane 2 is a porous ceramic-based solid polymer electrolyte membrane.
The anode catalyst layer 1 is made of a boron-carbon diamond heterojunction material, and the cathode catalyst layer 3 is made of a graphene composite material.
A method for preparing the membrane electrode as described above, comprising the steps of:
(1) preparing an anode catalyst layer 1 by adopting a boron-carbon diamond heterojunction material;
(2) preparing a cation exchange membrane 2;
(3) preparing a cathode catalyst layer 3;
(4) pressing the anode catalyst layer 1, the cation exchange membrane 2 and the cathode catalyst layer 3 to prepare a membrane electrode;
wherein, the steps (1) to (3) can be carried out simultaneously or the sequence can be changed.
In the step (1), the preparation method of the anode catalyst layer 1 includes the steps of: decomposing carbon gas and radon gas into carbon and hydrogen atoms and active free radicals at 1500 ℃, wherein the hydrogen atoms and the active free radicals are combined with the carbon substrate to form a carbide transition layer; depositing diamond crystal nucleus on the carbide transition layer by carbon atoms; the formed diamond crystal nucleus grows into a diamond micro product under the pressure of 6Gpa, and then grows into a diamond film. The proper pressure in the growth stage can increase the growth speed of the film and improve the quality of the film.
In the step (2), the cation exchange membrane 2 is a porous ceramic-based solid electrolyte composite membrane, and the preparation method of the cation exchange membrane 2 comprises the following steps:
a1, preparation of the ceramic-based sulfonated polyimide material: taking 3 parts of diphenyl ether tetracarboxylic dianhydride monoatomic dispersion platinum carbon, 1 part of diacetyl amide and 3 parts of malonaldehyde according to parts by weight to obtain sulfonated polyimide;
a2, adding sulfonated polyimide into propylene glycol to prepare a sulfonated polyimide solution, wherein the weight ratio of the sulfonated polyimide to the propylene glycol is (8): 0.3, pressurizing the porous nickel-iron ceramic plate for carrying out a permeation reaction to prepare the ceramic matrix composite heterogeneous membrane;
a3, soaking the ceramic matrix composite heterogeneous membrane obtained in the step A2 in a hydrochloric acid solution to obtain the cation exchange membrane 2.
In the step A2, the pressure for the infiltration reaction is 20Mpa on the porous nickel-iron ceramic plate.
In the step (3), the preparation method of the cathode catalytic material used for preparing the cathode catalyst layer 3 includes the following steps: the cathode catalytic material is prepared by taking a carbon carrier, a non-metal heteroatom reagent and a platinum compound as raw materials, drying at the temperature of 400 ℃ for 8 hours after stirring, refluxing and rotary steaming, grinding to the particle size of less than 50nm, and treating at the temperature of 1000 ℃ for interaction.
The nonmetallic heteroatom is nitrogen, and the platinum compound is Pt (OH)2
The membrane electrode of the embodiment only needs water as a raw material for producing ozone water by using tap water, so that the energy consumption is low, the electrolysis efficiency is not influenced by air quality, drying is not needed, and nitrogen oxide NOx is not generated; the corrosion is avoided, and the problem that the electrolytic catalyst coating falls off is solved; when the electrolytic tank is used, the conductivity of water is obviously increased from 0.0891S/cm to 0.2280S/cm, the proton conductivity is increased by 220%, the electrolytic tank can work for a long time, the electrolytic efficiency is stable, and no oxygen-containing electrolyte is required to be additionally added; generating 28% high-purity ozone and 72% oxygen without any other by-products; no hot spot damage risk, strengthening unique structural design, far exceeding the common PEM electrolytic ozone device; the service life of the membrane electrode can continuously work for more than 3 years.
Example 2
A membrane electrode for producing ozone water by using tap water comprises an ion exchange membrane 2, an anode catalyst layer 1 arranged on one side of the ion exchange membrane 2 and a cathode catalyst layer 3 arranged on the other side of the ion exchange membrane 2, wherein the cation exchange membrane 2 is a graphite phase C3N4/PFSA solid electrolyte composite membrane.
The anode catalyst layer 1 is made of a boron-carbon diamond heterojunction material, and the cathode catalyst layer 3 is made of a graphene composite material.
A method for preparing the membrane electrode as described above, comprising the steps of:
(1) preparing an anode catalyst layer 1 by adopting a boron-carbon diamond heterojunction material;
(2) preparing a cation exchange membrane 2;
(3) preparing a cathode catalyst layer 3;
(4) pressing the anode catalyst layer 1, the cation exchange membrane 2 and the cathode catalyst layer 3 to prepare a membrane electrode;
wherein, the steps (1) to (3) can be carried out simultaneously or the sequence can be changed.
In the step (1), the preparation method of the anode catalyst layer 1 includes the steps of: decomposing carbon gas and radon gas into carbon and hydrogen atoms and active free radicals at 1500 ℃, wherein the hydrogen atoms and the active free radicals are combined with the carbon substrate to form a carbide transition layer; depositing diamond crystal nucleus on the carbide transition layer by carbon atoms; the formed diamond crystal nucleus grows into a diamond micro product under the pressure of 6Gpa, and then grows into a diamond film. The proper pressure in the growth stage can increase the growth speed of the film and improve the quality of the film.
In the step (2), the cation exchange membrane 2 is a graphite phase C3N4/PFSA solid electrolyte composite membrane, and the preparation method of the cation exchange membrane 2 comprises the following steps:
in the step (2), the cation exchange membrane 2 is a graphite phase C3N4/PFSA solid electrolyte composite membrane, and the preparation method of the cation exchange membrane 2 comprises the following steps: and mixing the graphite phase and the perfluorinated sulfonic acid resin according to the weight ratio of 4:1, heating, and performing extrusion molding to form a film, thereby obtaining the cation exchange membrane 2.
In the step (2), the graphite phase and the perfluorinated sulfonic acid resin are mixed and heated to 200 ℃ for extrusion molding to form a film.
In the step (3), the preparation method of the cathode catalytic material used for preparing the cathode catalyst layer 3 includes the following steps: the cathode catalytic material is prepared by taking a carbon carrier, a non-metal heteroatom reagent and a platinum compound as raw materials, drying at the temperature of 400 ℃ for 8 hours after stirring, refluxing and rotary steaming, grinding to the particle size of less than 50nm, and treating at the temperature of 1000 ℃ for interaction.
The nonmetallic heteroatom is oxygen, and the platinum compound is Pt (OH)2
In the embodiment, the graphite phase C3N4/PFSA solid electrolyte composite membrane is used as the cathode, the electrical conductivity of the membrane electrode is significantly increased, and the proton conductivity is increased by 220%, presumably because the acid-base conjugated ion pair is formed by the abundant base group on the graphite phase C3N4 and the sulfonate on the PFSA, and the proton selectivity and the proton transmission speed are increased. This example is capable of producing 29% high purity ozone and 71% oxygen.
Example 3
A membrane electrode for producing ozone water by using tap water comprises an ion exchange membrane 2, an anode catalyst layer 1 arranged on one side of the ion exchange membrane 2 and a cathode catalyst layer 3 arranged on the other side of the ion exchange membrane 2, wherein the cation exchange membrane 2 is a porous ceramic-based solid polymer electrolyte membrane.
The anode catalyst layer 1 is made of a boron-carbon diamond heterojunction material, and the cathode catalyst layer 3 is made of a graphene composite material.
A method for preparing the membrane electrode as described above, comprising the steps of:
(1) preparing an anode catalyst layer 1 by adopting a boron-carbon diamond heterojunction material;
(2) preparing a cation exchange membrane 2;
(3) preparing a cathode catalyst layer 3;
(4) pressing the anode catalyst layer 1, the cation exchange membrane 2 and the cathode catalyst layer 3 to prepare a membrane electrode;
wherein, the steps (1) to (3) can be carried out simultaneously or the sequence can be changed.
In the step (1), the preparation method of the anode catalyst layer 1 includes the steps of: decomposing carbon gas and radon gas into carbon and hydrogen atoms and active free radicals at 1300 ℃, wherein the hydrogen atoms and the active free radicals are combined with the carbon substrate to form a carbide transition layer; depositing diamond crystal nucleus on the carbide transition layer by carbon atoms; the formed diamond crystal nucleus grows into a diamond micro product under the pressure of 5Gpa, and then grows into a diamond film. The proper pressure in the growth stage can increase the growth speed of the film and improve the quality of the film.
In the step (2), the cation exchange membrane 2 is a porous ceramic-based solid electrolyte composite membrane, and the preparation method of the cation exchange membrane 2 comprises the following steps:
a1, preparation of the ceramic-based sulfonated polyimide material: taking 2.8 parts of diphenyl ether tetracarboxylic dianhydride monoatomic dispersion platinum carbon, 0.8 part of diacetyl amide and 2.8 parts of malonaldehyde according to parts by weight to obtain sulfonated polyimide;
a2, adding sulfonated polyimide into propylene glycol to prepare a sulfonated polyimide solution, wherein the weight ratio of the sulfonated polyimide to the propylene glycol is (7.5): 0.28, pressurizing the porous nickel-iron ceramic plate for carrying out infiltration reaction to prepare the ceramic matrix composite heterogeneous membrane;
a3, soaking the ceramic matrix composite heterogeneous membrane obtained in the step A2 in a hydrochloric acid solution to obtain the cation exchange membrane 2.
In the step A2, the pressure for the infiltration reaction is 18Mpa on the porous nickel-iron ceramic plate.
In the step (3), the preparation method of the cathode catalytic material used for preparing the cathode catalyst layer 3 includes the following steps: the cathode catalytic material is prepared by taking a carbon carrier, a non-metal heteroatom reagent and a platinum compound as raw materials, drying at 380 ℃ for 9 hours after stirring, refluxing and rotary evaporation, grinding to below 50nm, and treating and interacting at 950 ℃.
The non-metal heteroatom is sulfur, and the platinum compound is PtS.
This example was able to generate 27% high purity ozone and 73% oxygen.
Example 4
A membrane electrode for producing ozone water by using tap water comprises an ion exchange membrane 2, an anode catalyst layer 1 arranged on one side of the ion exchange membrane 2 and a cathode catalyst layer 3 arranged on the other side of the ion exchange membrane 2, wherein the cation exchange membrane 2 is a porous ceramic-based solid polymer electrolyte membrane.
The anode catalyst layer 1 is made of a boron-carbon diamond heterojunction material, and the cathode catalyst layer 3 is made of a graphene composite material.
A method for preparing the membrane electrode as described above, comprising the steps of:
(1) preparing an anode catalyst layer 1 by adopting a boron-carbon diamond heterojunction material;
(2) preparing a cation exchange membrane 2;
(3) preparing a cathode catalyst layer 3;
(4) pressing the anode catalyst layer 1, the cation exchange membrane 2 and the cathode catalyst layer 3 to prepare a membrane electrode;
wherein, the steps (1) to (3) can be carried out simultaneously or the sequence can be changed.
In the step (1), the preparation method of the anode catalyst layer 1 includes the steps of: decomposing carbon gas and radon gas into carbon and hydrogen atoms and active free radicals at 1700 ℃, and combining the hydrogen atoms and the active free radicals with the carbon matrix to form a carbide transition layer; depositing diamond crystal nucleus on the carbide transition layer by carbon atoms; the formed diamond crystal nucleus grows into a diamond micro product under the pressure of 7Gpa, and then grows into a diamond film. The proper pressure in the growth stage can increase the growth speed of the film and improve the quality of the film.
In the step (2), the cation exchange membrane 2 is a porous ceramic-based solid electrolyte composite membrane, and the preparation method of the cation exchange membrane 2 comprises the following steps:
a1, preparation of the ceramic-based sulfonated polyimide material: according to the parts by weight, 3.2 parts of diphenyl ether tetracarboxylic dianhydride monoatomic dispersion platinum carbon, 1.2 parts of diacetyl amide and 3.2 parts of malonaldehyde are taken to obtain sulfonated polyimide;
a2, adding sulfonated polyimide into propylene glycol to prepare a sulfonated polyimide solution, wherein the weight ratio of the sulfonated polyimide to the propylene glycol is (8.5): 0.32, pressurizing the porous nickel-iron ceramic plate for carrying out infiltration reaction to prepare the ceramic matrix composite heterogeneous membrane;
a3, soaking the ceramic matrix composite heterogeneous membrane obtained in the step A2 in a hydrochloric acid solution to obtain the cation exchange membrane 2.
In the step A2, the pressure for the infiltration reaction is 22MPa on the porous nickel-iron ceramic plate.
In the step (3), the preparation method of the cathode catalytic material used for preparing the cathode catalyst layer 3 includes the following steps: the cathode catalytic material is prepared by taking a carbon carrier, a non-metal heteroatom reagent and a platinum compound as raw materials, drying for 7 hours at the temperature of 420 ℃ after stirring, refluxing and rotary steaming, grinding to the particle size of less than 50nm, and treating and interacting at the temperature of 1050 ℃ to obtain the cathode catalytic material.
The nonmetal heteroatom is silicon, and the platinum compound is PtS2
This example is capable of generating 26% high purity ozone and 74% oxygen.
Example 5
A membrane electrode for producing ozone water by using tap water comprises an ion exchange membrane 2, an anode catalyst layer 1 arranged on one side of the ion exchange membrane 2 and a cathode catalyst layer 3 arranged on the other side of the ion exchange membrane 2, wherein the cation exchange membrane 2 is a graphite phase C3N4/PFSA solid electrolyte composite membrane.
The anode catalyst layer 1 is made of a boron-carbon diamond heterojunction material, and the cathode catalyst layer 3 is made of a graphene composite material.
A method for preparing the membrane electrode as described above, comprising the steps of:
(1) preparing an anode catalyst layer 1 by adopting a boron-carbon diamond heterojunction material;
(2) preparing a cation exchange membrane 2;
(3) preparing a cathode catalyst layer 3;
(4) pressing the anode catalyst layer 1, the cation exchange membrane 2 and the cathode catalyst layer 3 to prepare a membrane electrode;
wherein, the steps (1) to (3) can be carried out simultaneously or the sequence can be changed.
In the step (1), the preparation method of the anode catalyst layer 1 includes the steps of: decomposing carbon gas and radon gas into carbon and hydrogen atoms and active free radicals at 1500 ℃, wherein the hydrogen atoms and the active free radicals are combined with the carbon substrate to form a carbide transition layer; depositing diamond crystal nucleus on the carbide transition layer by carbon atoms; the formed diamond crystal nucleus grows into a diamond micro product under the pressure of 6Gpa, and then grows into a diamond film. The proper pressure in the growth stage can increase the growth speed of the film and improve the quality of the film.
In the step (2), the cation exchange membrane 2 is a graphite phase C3N4/PFSA solid electrolyte composite membrane, and the preparation method of the cation exchange membrane 2 comprises the following steps: and mixing the graphite phase and the perfluorinated sulfonic acid resin according to the weight ratio of 3.8:0.9, heating, and performing extrusion molding to form a film, thereby obtaining the cation exchange membrane 2.
In the step (2), the graphite phase and the perfluorinated sulfonic acid resin are mixed and heated to 190 ℃ for extrusion molding to form the film.
In the step (3), the preparation method of the cathode catalytic material used for preparing the cathode catalyst layer 3 includes the following steps: the cathode catalytic material is prepared by taking a carbon carrier, a non-metal heteroatom reagent and a platinum compound as raw materials, drying at the temperature of 400 ℃ for 8 hours after stirring, refluxing and rotary steaming, grinding to the particle size of less than 50nm, and treating at the temperature of 1000 ℃ for interaction.
The nonmetal heteroatom is fluorine, and the platinum compound is PtCl4
This example is capable of generating 28% high purity ozone and 72% oxygen.
Example 6
A membrane electrode for producing ozone water by using tap water comprises an ion exchange membrane 2, an anode catalyst layer 1 arranged on one side of the ion exchange membrane 2 and a cathode catalyst layer 3 arranged on the other side of the ion exchange membrane 2, wherein the cation exchange membrane 2 is a graphite phase C3N4/PFSA solid electrolyte composite membrane.
The anode catalyst layer 1 is made of a boron-carbon diamond heterojunction material, and the cathode catalyst layer 3 is made of a graphene composite material.
A method for preparing the membrane electrode as described above, comprising the steps of:
(1) preparing an anode catalyst layer 1 by adopting a boron-carbon diamond heterojunction material;
(2) preparing a cation exchange membrane 2;
(3) preparing a cathode catalyst layer 3;
(4) pressing the anode catalyst layer 1, the cation exchange membrane 2 and the cathode catalyst layer 3 to prepare a membrane electrode;
wherein, the steps (1) to (3) can be carried out simultaneously or the sequence can be changed.
In the step (1), the preparation method of the anode catalyst layer 1 includes the steps of: decomposing carbon gas and radon gas into carbon and hydrogen atoms and active free radicals at 1500 ℃, wherein the hydrogen atoms and the active free radicals are combined with the carbon substrate to form a carbide transition layer; depositing diamond crystal nucleus on the carbide transition layer by carbon atoms; the formed diamond crystal nucleus grows into a diamond micro product under the pressure of 6Gpa, and then grows into a diamond film. The proper pressure in the growth stage can increase the growth speed of the film and improve the quality of the film.
In the step (2), the cation exchange membrane 2 is a graphite phase C3N4/PFSA solid electrolyte composite membrane, and the preparation method of the cation exchange membrane 2 comprises the following steps: and mixing the graphite phase and the perfluorinated sulfonic acid resin according to the weight ratio of 4.2:1.1, heating, and performing extrusion molding to form a film, thereby obtaining the cation exchange membrane 2.
In the step (2), the graphite phase and the perfluorinated sulfonic acid resin are mixed and heated to 210 ℃ for extrusion molding to form a film.
In the step (3), the preparation method of the cathode catalytic material used for preparing the cathode catalyst layer 3 includes the following steps: the cathode catalytic material is prepared by taking a carbon carrier, a non-metal heteroatom reagent and a platinum compound as raw materials, drying at the temperature of 400 ℃ for 8 hours after stirring, refluxing and rotary steaming, grinding to the particle size of less than 50nm, and treating at the temperature of 1000 ℃ for interaction.
The non-metal heteroatom is chlorine, and the platinum compound is PtCl2
This example was able to generate 27% high purity ozone and 73% oxygen.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention, and not for limiting the protection scope of the present invention, although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.

Claims (10)

1.一种利用自来水产生臭氧水的膜电极,其特征在于:包括离子交换膜、设置于离子交换膜一侧的阳极催化剂层和设置于离子交换膜另一侧的阴极催化剂层,所述阳离子交换膜为多孔陶瓷基固体聚合物电解质膜或石墨相C3N4/PFSA固体电解质复合膜。1. a membrane electrode utilizing tap water to produce ozone water, is characterized in that: comprising ion exchange membrane, the anode catalyst layer arranged on one side of the ion exchange membrane and the cathode catalyst layer arranged on the other side of the ion exchange membrane, the cationic The exchange membrane is a porous ceramic-based solid polymer electrolyte membrane or a graphite phase C3N4/PFSA solid electrolyte composite membrane. 2.根据权利要求1所述的利用自来水产生臭氧水的膜电极,其特征在于:所述阳极催化剂层采用硼碳金刚石异质结材料制成,所述阴极催化剂层采用石墨烯复合材料制成。2. The membrane electrode utilizing tap water to generate ozone water according to claim 1, wherein the anode catalyst layer is made of boron-carbon diamond heterojunction material, and the cathode catalyst layer is made of graphene composite material . 3.一种权利要求2所述的膜电极的制备方法,其特征在于:包括如下步骤:3. The preparation method of a membrane electrode according to claim 2, characterized in that: comprising the steps of: (1)采用硼碳金刚石异质结材料,制备阳极催化剂层;(1) using boron carbon diamond heterojunction material to prepare anode catalyst layer; (2)制备阳离子交换膜;(2) preparing a cation exchange membrane; (3)制备阴极催化剂层;(3) preparing a cathode catalyst layer; (4)将阳极催化剂层、阳离子交换膜和阴极催化剂层压合,制得膜电极;(4) laminating the anode catalyst layer, the cation exchange membrane and the cathode catalyst layer to obtain a membrane electrode; 其中,所述步骤(1)-(3)可同时进行或调换前后顺序。Wherein, the steps (1)-(3) can be performed at the same time or the sequence before and after can be reversed. 4.根据权利要求3所述的膜电极的制备方法,其特征在于:所述步骤(1)中,阳极催化剂层的制备方法包括如下步骤:将碳气体和氡气在1300-1700℃温度下分解成碳、氢原子和活性游离基团,氢原子以及活性游离基团与碳基体结合先形成一层碳化物过渡层;碳原子在碳化物过渡层沉积金刚石晶核;形成的金刚石晶核在5-7Gpa压力下长大成金刚石微品,继而长大成金刚石薄膜。4 . The method for preparing membrane electrodes according to claim 3 , wherein in the step (1), the method for preparing the anode catalyst layer comprises the following steps: adding carbon gas and radon gas at a temperature of 1300-1700° C. 5 . It is decomposed into carbon, hydrogen atoms and active free groups. The hydrogen atoms and active free groups are combined with the carbon matrix to form a carbide transition layer; the carbon atoms deposit diamond nuclei in the carbide transition layer; the formed diamond nuclei are in Under the pressure of 5-7Gpa, it grows into a diamond micro-product, and then grows into a diamond film. 5.根据权利要求3所述的膜电极的制备方法,其特征在于:所述步骤(2)中,所述阳离子交换膜为多孔陶瓷基固体电解质复合膜,所述阳离子交换膜的制备方法包括如下步骤:5 . The method for preparing a membrane electrode according to claim 3 , wherein in the step (2), the cation exchange membrane is a porous ceramic-based solid electrolyte composite membrane, and the preparation method for the cation exchange membrane comprises the following steps: 6 . Follow the steps below: A1、陶瓷基磺化聚酰亚胺材料的制备:按重量份计,取二苯醚四甲酸二酐单原子分散铂碳2.8-3.2份、双乙酰胺0.8-1.2份、丙二醛2.8-3.2,得到磺化聚酰亚胺;A1. Preparation of ceramic-based sulfonated polyimide material: in parts by weight, take 2.8-3.2 parts of diphenyl ether tetracarboxylic dianhydride monoatomic dispersed platinum carbon, 0.8-1.2 parts of bisacetamide, 2.8-1.2 parts of malondialdehyde 3.2, obtain sulfonated polyimide; A2、将磺化聚酰亚胺加入到丙二醇中,制成磺化聚酰亚胺溶液,所述磺化聚酰亚胺与丙二醇的重量比为7.5-8.5:0.28-0.32,并在多孔镍铁陶瓷板上加压进行渗透反应,制成陶瓷基复合异相膜;A2. The sulfonated polyimide is added to propylene glycol to prepare a sulfonated polyimide solution. The weight ratio of the sulfonated polyimide to propylene glycol is 7.5-8.5:0.28-0.32, and the sulfonated polyimide is dissolved in porous nickel. The iron ceramic plate is pressurized for infiltration reaction to make a ceramic matrix composite heterogeneous membrane; A3、将步骤A2中得到的陶瓷基复合异相膜在盐酸溶液中浸泡,制得阳离子交换膜。A3. Soak the ceramic matrix composite heterogeneous membrane obtained in step A2 in a hydrochloric acid solution to obtain a cation exchange membrane. 6.根据权利要求5所述的膜电极的制备方法,其特征在于:所述步骤A2中,在多孔镍铁陶瓷板上加压进行渗透反应的压力为18-22Mpa。6 . The method for preparing a membrane electrode according to claim 5 , wherein in the step A2 , the pressure at which the osmotic reaction is carried out under pressure on the porous nickel-iron ceramic plate is 18-22 Mpa. 7 . 7.根据权利要求3所述的膜电极的制备方法,其特征在于:所述步骤(2)中,所述阳离子交换膜为石墨相C3N 4/PFSA固体电解质复合膜,所述阳离子交换膜的制备方法包括如下步骤:将石墨相和全氟磺酸树脂按照重量比3.8-4.2:0.9-1.1混合,加热,进行挤塑成膜,制得阳离子交换膜。7. The preparation method of membrane electrode according to claim 3, characterized in that: in the step (2), the cation exchange membrane is a graphite phase C3N4/PFSA solid electrolyte composite membrane, and the cation exchange membrane is The preparation method includes the following steps: mixing the graphite phase and the perfluorosulfonic acid resin according to a weight ratio of 3.8-4.2:0.9-1.1, heating, and extruding to form a film to obtain a cation exchange membrane. 8.根据权利要求3所述的制备方法,其特征在于:所述步骤(2)中,石墨相和全氟磺酸树脂混合后,加热到190-210℃,进行挤塑成膜。8 . The preparation method according to claim 3 , wherein in the step (2), after the graphite phase and the perfluorosulfonic acid resin are mixed, they are heated to 190-210° C. to form a film by extrusion molding. 9 . 9.根据权利要求2所述的膜电极的制备方法,其特征在于:所述步骤(3)中,所述制备阴极催化剂层采用的阴极催化材料的制备方法包括如下步骤:以碳载体,非金属杂原子试剂和铂化合物为原料,通过搅拌回流、旋蒸后在380-420℃温度下干燥7-9h,研磨至50nm以下,在950-1050℃温度下处理相互作用得到阴极催化材料。9 . The method for preparing a membrane electrode according to claim 2 , wherein in the step (3), the method for preparing the cathode catalytic material used for preparing the cathode catalyst layer comprises the following steps: using a carbon carrier, a non-metallic Metal heteroatom reagents and platinum compounds are used as raw materials. After stirring and refluxing, rotary evaporation, drying at 380-420 °C for 7-9 hours, grinding to below 50 nm, and interaction at 950-1050 °C to obtain cathode catalytic materials. 10.根据权利要求9所述的膜电极的制备方法,其特征在于:所述非金属杂原子为氮、氧、硫、磷、硅、卤素中的至少一种,所述铂化合物为铂氢氧化合物、铂硫化合物、铂氯化合物中的至少一种。10 . The method for preparing a membrane electrode according to claim 9 , wherein the non-metallic heteroatom is at least one of nitrogen, oxygen, sulfur, phosphorus, silicon and halogen, and the platinum compound is platinum hydrogen. 11 . At least one of oxygen compounds, platinum sulfur compounds, and platinum chloride compounds.
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113899071A (en) * 2021-10-25 2022-01-07 西安建筑科技大学 An electric heating water boiler and water treatment and purification method

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