CN118166376A - Membrane electrode for preparing hydrogen peroxide by oxygen reduction, preparation method thereof and membrane electrode reactor - Google Patents
Membrane electrode for preparing hydrogen peroxide by oxygen reduction, preparation method thereof and membrane electrode reactor Download PDFInfo
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- CN118166376A CN118166376A CN202410010405.7A CN202410010405A CN118166376A CN 118166376 A CN118166376 A CN 118166376A CN 202410010405 A CN202410010405 A CN 202410010405A CN 118166376 A CN118166376 A CN 118166376A
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- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 65
- 239000001301 oxygen Substances 0.000 title claims abstract description 65
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- 230000009467 reduction Effects 0.000 title claims abstract description 14
- 238000002360 preparation method Methods 0.000 title abstract description 14
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- 229910000428 cobalt oxide Inorganic materials 0.000 claims description 3
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- CADICXFYUNYKGD-UHFFFAOYSA-N sulfanylidenemanganese Chemical compound [Mn]=S CADICXFYUNYKGD-UHFFFAOYSA-N 0.000 claims description 3
- WWNBZGLDODTKEM-UHFFFAOYSA-N sulfanylidenenickel Chemical compound [Ni]=S WWNBZGLDODTKEM-UHFFFAOYSA-N 0.000 claims description 3
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- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 33
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Abstract
The application relates to a membrane electrode for preparing hydrogen peroxide by oxygen reduction, a preparation method thereof and a membrane electrode reactor. The membrane electrode comprises a cathode diffusion electrode, a cation exchange membrane and an anode oxygen evolution electrode which are arranged in a stacked manner, wherein the cation exchange membrane is positioned between the cathode diffusion electrode and the anode oxygen evolution electrode, and the cathode diffusion electrode, the cation exchange membrane and the anode oxygen evolution electrode are connected in a physical connection mode; the cathode diffusion electrode comprises a cathode porous substrate layer and a cathode active layer, the cathode active layer comprises a cathode catalyst and a cation regulation substance, the anode oxygen evolution electrode comprises an anode porous substrate layer and an anode active layer, and the anode active layer comprises an anode catalyst. The membrane electrode is applicable to preparing hydrogen peroxide by oxygen reduction, and has good hydrogen peroxide selectivity and high Faraday efficiency.
Description
Technical Field
The application relates to the technical field of electrocatalytic and electrochemical reactors, in particular to a membrane electrode for preparing hydrogen peroxide by oxygen reduction, a preparation method thereof and a membrane electrode reactor.
Background
Hydrogen peroxide, as a cleaning oxidizer, affects many industries such as disinfection, water treatment, chemical synthesis, paper bleaching, etc. The method for synthesizing hydrogen peroxide by using electrochemical oxygen reduction has the advantages of strong environmental friendliness, capability of depending on green electricity technology and the like. The reaction raw materials are water, oxygen or air, and two-electron electrocatalytic oxygen reduction reaction is carried out under the drive of electric energy to generate hydrogen peroxide aqueous solution, so that the method has the characteristics of green, clean, high efficiency and the like, and can meet the requirements of miniaturization and discrete manufacturing.
At present, most of the electrosynthesis processes of hydrogen peroxide are carried out in electrolyte solution, so that the generated hydrogen peroxide aqueous solution contains a large amount of acid, alkali or salt electrolytes and the like, and the pure hydrogen peroxide aqueous solution can be obtained only by high-cost separation and purification, and part of the solution system also has great hidden trouble of hydrogen peroxide decomposition, so that the safety production is not facilitated.
Therefore, how to obtain purer hydrogen peroxide water solution and solve the potential safety hazard is a problem to be solved at present.
Disclosure of Invention
Based on this, it is necessary to provide a membrane electrode for preparing hydrogen peroxide by oxygen reduction, a preparation method thereof and a membrane electrode reactor, which can prepare hydrogen peroxide in a pure water environment to obtain purer hydrogen peroxide, and generate hydrogen peroxide using the membrane electrode, which can improve hydrogen peroxide selectivity and faraday efficiency.
The application provides a membrane electrode for preparing hydrogen peroxide by oxygen reduction, which comprises a cathode diffusion electrode, a cation exchange membrane and an anode oxygen evolution electrode which are stacked, wherein the cation exchange membrane is positioned between the cathode diffusion electrode and the anode oxygen evolution electrode, and the cathode diffusion electrode, the cation exchange membrane and the anode oxygen evolution electrode are connected in a physical connection mode;
The cathode diffusion electrode comprises a cathode porous substrate layer and a cathode active layer, the cathode active layer comprises a cathode catalyst and a cation regulation substance, the anode oxygen evolution electrode comprises an anode porous substrate layer and an anode active layer, and the anode active layer comprises an anode catalyst.
In some embodiments, the cation modulating substance comprises a cationic polymer and/or a metal ion complexed crown ether; and/or the cathode catalyst is one or more of an oxidized carbon material, a metal monatomic doped carbon material and a metal nanocluster doped carbon material.
In some embodiments, the cationic polymer comprises one or more of Fumasep anion exchange resin, alykmer anion exchange resin, piperion anion exchange resin, sustainion anion exchange resin, quaternized polyethylenimine, crosslinked polydiallyl dimethyl ammonium chloride, quaternary ammonium poly (n-methyl-piperidine-co-p-terphenyl), quaternary aminopoly (aryl perfluoroalkylene), poly (terphenyl piperidinium-trifluoroacetophenone), poly (diphenyl-co-terphenyl piperidinium) (PDTP), branched poly (terphenyl piperidinium), and poly (fluorenyl-co-terphenyl piperidinium) (PFAP).
In some embodiments, the crown ether complexed with the metal ion comprises one or more of 18-crown-6 complexed with sodium ion, 15-crown-5 complexed with potassium ion, and 12-crown-4 complexed with sodium ion.
In some embodiments, the oxidized carbon material comprises one or more of graphene oxide, carbon nanotubes oxide, and carbon black oxide; and/or the number of the groups of groups,
The metal monoatomic doped carbon material comprises Co and Fe monoatomic doped carbon materials; and/or the number of the groups of groups,
The metal nanocluster-doped carbon material includes one or more of a Ni nanocluster-doped carbon material, a Cu nanocluster-doped carbon material, and a Fe nanocluster-doped carbon material.
In some embodiments, the loading of the cathode catalyst in the cathode diffusion electrode is 0.05-5 mg/cm 2 electrode, and/or the loading of the cation regulating substance in the cathode diffusion electrode is 1-500 μg/cm 2 electrode.
In some embodiments, the mass ratio of the cathode catalyst to the cation modulating species in the cathode diffusion electrode is 1: (0.0016 to 0.06), preferably 1: (0.0032 to 0.06).
In some embodiments, the anode catalyst comprises one or more of iridium oxide, ruthenium oxide, rhodium oxide, iron oxide, cobalt oxide, nickel oxide, perovskite oxide, niFe hydroxide, iron sulfide, cobalt sulfide, nickel sulfide, copper sulfide, manganese sulfide, phosphide of Ni, and phosphide of Fe.
In some embodiments, the anode catalyst loading in the anode oxygen evolution electrode is 0.05-20 mg/cm 2 electrode.
In some embodiments, the cathode active layer includes a cathode catalyst layer and a cation modulating substance layer.
In some embodiments, the porosity of the cathode porous substrate layer is 20% -80%, optionally, the cathode porous substrate layer is carbon paper or carbon cloth;
and/or the porosity of the anode porous substrate layer is 20% -80%, and optionally, the anode porous substrate layer is carbon paper, carbon cloth, metal mesh or foam metal.
In some embodiments, the cation exchange membrane has a membrane thickness of 10 μm to 300 μm, optionally the cation exchange membrane is a Nafion membrane.
In yet another aspect of the present application, there is provided a membrane electrode comprising the steps of:
Step S10, loading the cathode catalyst and the cation regulation and control substance on the cathode porous basal layer to obtain the cathode diffusion electrode;
step S20, loading the anode catalyst on the anode porous basal layer to obtain the anode oxygen evolution electrode; and
And step S30, sequentially stacking the cathode diffusion electrode, the cation exchange membrane and the anode oxygen evolution electrode.
In some embodiments, step S10 includes:
Step S11, placing the cathode catalyst and the cation regulation and control substance into a solvent for mixing to obtain a mixed coating;
and step S13, coating the mixed paint on the cathode porous substrate layer.
In some embodiments, step S10 includes:
step S12, placing the cathode catalyst in a solvent to obtain a cathode catalyst coating;
Step S14, coating the cathode catalyst coating on the cathode porous basal layer to form a cathode catalyst layer;
S16, placing the cation regulating substance in a solvent to obtain a cation regulating substance coating;
And S18, coating the cation control substance coating on the cathode catalyst layer to form a cation control substance layer.
In yet another aspect of the present application, there is provided a membrane electrode reactor including the membrane electrode.
Compared with the prior art, the application at least has the following beneficial effects:
Compared with the traditional membrane electrode, the membrane electrode provided by the application has the advantages that the cation regulating substance is added to the cathode, the interface state of the cathode is changed, a large amount of protons migrated by the anode are blocked, and the proton concentration on the surface of the cathode catalyst is reduced, so that the membrane electrode can accelerate the migration of OOH - ions when the membrane electrode performs electrochemical reaction in pure water, inhibit oxygen from performing 4-electron reduction reaction to generate water, and further improve the selectivity (Faraday efficiency) of hydrogen peroxide.
The membrane electrode adopted by the application has the characteristics of simple structure and good stability, and the used cation regulating substance can form a three-dimensional ion conduction network structure with the catalyst layer, so that the ion conduction resistance of the electrolytic cell is small, the cell voltage is low and the energy consumption is low.
The membrane electrode reactor provided by the application uses pure water, oxygen or air as raw materials, does not use electrolyte solution, is green and clean in process, and can meet the process requirements of disinfection, bleaching and the like.
Drawings
In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the drawings that are needed in the description of the embodiments or the prior art will be briefly described, and it is obvious that the drawings in the description below are some embodiments of the present application, and other drawings can be obtained according to the drawings without inventive effort for a person skilled in the art.
FIG. 1 is a schematic structural diagram of a membrane electrode according to an embodiment;
FIG. 2 is a schematic view of a cathode diffusion electrode according to an embodiment;
FIG. 3 is a schematic view of an anode oxygen evolution electrode according to an embodiment;
FIG. 4 is a schematic structural view of a cathode active layer according to an embodiment;
fig. 5 is a schematic structural diagram of a reaction system for producing hydrogen peroxide by oxygen reduction according to an embodiment.
Wherein, the reference numerals:
10-cathode diffusion electrode, 20-cation exchange membrane, 30-anode oxygen evolution electrode, 12-cathode porous substrate layer, 14-cathode active layer, 32-anode porous substrate layer, 34-anode active layer, 141-cathode catalyst layer, 142-cation regulation substance layer, 1-oxygen or air feeding pipeline, 2-cathode pure water feeding pipeline, 3-gas-liquid mixer, 4-back pressure valve, 5-cathode outlet pipeline, 6-membrane electrode, 7-cathode runner chamber, 8-anode runner chamber, 9-electrochemical workstation (power supply), 10-anode pure water inlet pipeline, 11-anode outlet pipeline.
Detailed Description
In order that the application may be readily understood, a more complete description of the application will be rendered by reference to the appended drawings. Preferred embodiments of the present application are shown in the drawings. This application may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. The terminology used herein in the description of the application is for the purpose of describing particular embodiments only and is not intended to be limiting of the application. The term "and/or" as used herein includes any and all combinations of one or more of the associated listed items.
In the present application, "first aspect", "second aspect", "third aspect", etc. are used for descriptive purposes only and are not to be construed as indicating or implying a relative importance or quantity, nor as implying an importance or quantity of the indicated technical features.
In the application, the technical characteristics described in an open mode comprise a closed technical scheme composed of the listed characteristics and also comprise an open technical scheme comprising the listed characteristics.
In the present application, "one or more" means any one, any two or more of the listed items.
In the present application, the numerical ranges are referred to as continuous, and include the minimum and maximum values of the ranges, and each value between the minimum and maximum values, unless otherwise specified. Further, when a range refers to an integer, each integer between the minimum and maximum values of the range is included. Further, when multiple range description features or characteristics are provided, the ranges may be combined. In other words, unless otherwise indicated, all ranges disclosed herein are to be understood to include any and all subranges subsumed therein.
The percentage content referred to in the present application refers to mass percentage for both solid-liquid mixing and solid-solid mixing and volume percentage for liquid-liquid mixing unless otherwise specified.
The percentage concentrations referred to in the present application refer to the final concentrations unless otherwise specified. The final concentration refers to the ratio of the additive component in the system after the component is added.
The temperature parameter in the present application is not particularly limited, and may be a constant temperature treatment or a treatment within a predetermined temperature range. The constant temperature process allows the temperature to fluctuate within the accuracy of the instrument control.
The method step of which the temperature is not emphasized in the present application generally means a method step carried out at ordinary temperature or at room temperature. Herein, normal temperature or room temperature equivalent is replaceable, and the specific temperature is 22-25 ℃.
All embodiments of the application and alternative embodiments may be combined with each other to form new solutions, unless otherwise specified.
All technical features and optional technical features of the application may be combined with each other to form new technical solutions, unless specified otherwise.
All steps of the present application may be performed sequentially or randomly unless otherwise specified. For example, the method comprises steps (a) and (b), meaning that the method may comprise steps (a) and (b) performed sequentially, or may comprise steps (b) and (a) performed sequentially. For example, the method may further include step (c), which means that step (c) may be added to the method in any order, for example, the method may include steps (a), (b) and (c), may include steps (a), (c) and (b), may include steps (c), (a) and (b), and the like.
The terms "comprising" and "including" as used herein mean open ended or closed ended, unless otherwise noted. For example, the terms "comprising" and "comprises" may mean that other components not listed may be included or included, or that only listed components may be included or included.
The term "or" is inclusive in this application, unless otherwise specified. For example, the phrase "a or B" means "a, B, or both a and B. More specifically, either of the following conditions satisfies the condition "a or B": a is true (or present) and B is false (or absent); a is false (or absent) and B is true (or present); or both A and B are true (or present).
The membrane electrode reactor is an important reaction device for preparing hydrogen peroxide in a pure water environment, electrolyte in the reactor is replaced by a cation regulating substance, and purer hydrogen peroxide can be obtained. Advanced membrane electrodes are critical for the preparation of hydrogen peroxide, especially for the efficient synthesis of hydrogen peroxide.
The industrial conversion of electrochemical two-electron oxygen reduction to hydrogen peroxide is challenged by poor selectivity and durability due to the destructive effect of fast electrowetting on the reactive three-phase interface of the air diffusion electrode under high current density operating conditions, especially the faraday efficiency of existing membrane electrodes when used in oxygen reduction to hydrogen peroxide is yet to be improved.
Accordingly, in a first aspect, the present application provides a membrane electrode for preparing hydrogen peroxide by oxygen reduction, referring to fig. 1, which includes a cathode diffusion electrode 10, a cation exchange membrane 20 and an anode oxygen evolution electrode 30 that are stacked, wherein the cation exchange membrane 20 is located between the cathode diffusion electrode 10 and the anode oxygen evolution electrode 30, and the cathode diffusion electrode 10, the cation exchange membrane 20 and the anode oxygen evolution electrode 30 are connected to each other in a physical connection manner. Referring to fig. 2, the cathode diffusion electrode 10 includes a cathode porous base layer 12 and a cathode active layer 14, the cathode active layer 14 containing a cathode catalyst and a cation modulating substance.
Referring to fig. 3, anode oxygen evolution electrode 30 includes an anode porous substrate layer 32 and an anode active layer 34, anode active layer 34 comprising an anode catalyst.
The cation exchange resin comprises a cation exchange resin.
It should be noted that, the mutual connection manner among the cathode diffusion electrode 10, the cation exchange membrane 20 and the anode oxygen evolution electrode 30 is physical connection, and the physical connection is non-embedded physical connection, that is, the cathode diffusion electrode 10 and the cation exchange membrane 20 are in physical contact or closely physical contact, and the closely physical contact is limited to the contact, which means that the contact effect is better, that all the contact surfaces of the two are closely attached, and the contact is on a macroscopic structure, but not the contact surfaces of the two have mutual fusion or mutual penetration or mutual embedding from the molecular structure.
For example, when a heat treatment is used to bond the cathode diffusion electrode and the cation exchange membrane, this results in at least some of the cation control material and the cation exchange resin in the cation exchange membrane fusing or interpenetrating or intercalating with each other, which affects proton migration and increases proton concentration on the cathode catalyst, which is not an objective of the present application.
In some embodiments, the cation modulating substance is a cationic polymer and/or a metal ion complexed crown ether.
Alternatively, the cationic polymer includes one or more of an ammonium-based polymer resin, an imidazolium-based polymer resin, a phosphonium, and an organometallic cationic-based polymer resin, further alternatively, specific examples of the cationic polymer include, but are not limited to, fumasep anion exchange resins, alykmer anion exchange resins, piperion anion exchange resins, sustainion anion exchange resins, quaternized polyethylenimine, crosslinked polydiallyl dimethyl ammonium chloride, quaternary ammonium poly (n-methyl-piperidine-co-p-terphenyl), quaternary ammonium poly (aryl perfluoroalkylenes), poly (terphenyl piperidinium-trifluoroacetophenone), poly (diphenyl-co-terphenyl piperidinium) (PDTP), branched poly (terphenyl piperidinium), and poly (fluorenyl-co-terphenyl piperidinium) (PFAP), and combinations thereof.
Fumasep the main component of anion exchange resin is polysulfone-based quaternary ammonium salt polymer. Alykmer the anion exchange resin comprises polyarylpiperidine as the main component. Piperion the anion exchange resin comprises polyarylpiperidine as the main component. Sustainion the main component of the anion exchange resin is imidazole functionalized polystyrene.
Alternatively, the crown ether complexed with the metal ion includes one or more of 18-crown-6 complexed with sodium ion, 15-crown-5 complexed with potassium ion, and 12-crown-4 complexed with sodium ion.
In some embodiments, the cathode catalyst is an oxidation treated carbon material, a metal monatomic doped carbon material, or a metal nanocluster doped carbon material.
Optionally, the oxidized carbon material comprises one or more of graphene oxide, carbon nanotube oxide, and carbon black oxide.
Optionally, the metal monatomic doped carbon material comprises a Co, fe monatomic doped carbon material.
Optionally, the metal nanocluster-doped carbon material includes one or more of a Ni nanocluster-doped carbon material, a Cu nanocluster-doped carbon material, and an Fe nanocluster-doped carbon material.
Further optionally, the carbon material comprises one or more of carbon black, graphene, carbon nanotubes, oxidized carbon black, oxidized graphene, and oxidized carbon nanotubes.
In some embodiments, the cathode catalyst loading in the cathode diffusion electrode 10 is 0.05-5 mg/cm 2 electrode, such as but not limited to 0.05 mg/cm 2 electrode, 0.1 mg/cm 2 electrode, 0.5 mg/cm 2 electrode, 1mg/cm 2 electrode, 1.5 mg/cm 2 electrode, 2 mg/cm 2 electrode, 2.5 mg/cm 2 electrode, 3 mg/cm 2 electrode, 3.5 mg/cm 2 electrode, 4 mg/cm 2 electrode, 4.5 mg/cm 2 electrode, 5 mg/cm 2 electrode, and ranges between any two of the foregoing.
In some embodiments, the loading of the cation modulating species in the cathode diffusion electrode 10 is 1-500 μg/cm 2 electrode, such as, but not limited to, 1 μg/cm 2 electrode, 10 μg/cm 2 electrode, 50 μg/cm 2 electrode, 100 μg/cm 2 electrode, 150 μg/cm 2 electrode, 200 μg/cm 2 electrode, 250 μg/cm 2 electrode, 300 μg/cm 2 electrode, 350 μg/cm 2 electrode, 400 μg/cm 2 electrode, 450 μg/cm 2 electrode, 500 μg/cm 2 electrode, and ranges between any two of the foregoing.
In some embodiments, the mass ratio of cathode catalyst to cation-modulating species in cathode diffusion electrode 10 is 1: (0.0016 to 0.06), for example, but not limited to 1:0.0016、1:0.0018、1:0.002、1:0.003、1:0.0032、1:0.005、1:0.01、1:0.016、1:0.02、1:0.03、1:0.04、1:0.048、1:0.05、1:0.06 and the range between any two of the above ratios. Optionally, the mass ratio of the cathode catalyst to the cation control material in the cathode diffusion electrode 10 is 1: (0.0032-0.06), further optionally 1: (0.01 to 0.06). In the optional range, the proton concentration on the surface of the cathode catalyst is more favorable for producing hydrogen peroxide, the selectivity of the hydrogen peroxide is better, and the Faraday effect of the membrane electrode reactor is higher.
In some embodiments, the cathode active layer 14 is formed from a mixed coating material comprising a cathode catalyst and a cation modulating substance that do not form significant delamination after drying.
In other embodiments, referring to fig. 4, the cathode active layer 14 is a composite layer comprising two layers of a cathode catalyst layer 141 and a cation control material layer 142, the cathode catalyst layer 141 being disposed proximate to the cathode porous substrate layer 12 and the cation control material layer 142 being disposed distal to the cathode porous substrate layer 12. The cathode catalyst layer is formed by drying a coating material containing only a cathode catalyst, and the cation regulating substance layer is formed by drying a coating material containing only a cation regulating substance. The proton concentration on the surface of the membrane electrode cathode catalyst of the embodiment is lower, the selectivity of hydrogen peroxide is better, and the Faraday efficiency of the membrane electrode reactor is higher.
In some embodiments, the porosity of the cathode porous substrate layer 12 is 20% -80%, such as, but not limited to, 20%, 30%, 40%, 50%, 60%, 70%, 80%, and ranges between any two of the foregoing.
In some embodiments, the cathode porous substrate layer 12 is carbon paper or carbon cloth.
In some embodiments, the anode porous substrate layer 12 has a porosity of 20% -80%, such as, but not limited to, 20%, 30%, 40%, 50%, 60%, 70%, 80%, and ranges between any two of the foregoing.
In some embodiments, the anode porous substrate layer 32 is carbon paper, carbon cloth, metal mesh, or metal foam. Specific examples of the metal mesh or the metal foam include titanium mesh, nickel foam and stainless steel mesh.
In some embodiments, the anode catalyst comprises one or more of iridium oxide, ruthenium oxide, rhodium oxide, iron oxide, cobalt oxide, nickel oxide, perovskite oxide, niFe hydroxide, iron sulfide, cobalt sulfide, nickel sulfide, copper sulfide, manganese sulfide, phosphide of Ni, and phosphide of Fe.
The anode catalyst loading in the anode oxygen evolution electrode 30 may be 0.05-20 mg/cm 2 electrode, such as, but not limited to, 0.05 mg/cm 2 electrode, 0.1 mg/cm 2 electrode, 0.5 mg/cm 2 electrode, 1mg/cm 2 electrode, 5 mg/cm 2 electrode, 10 mg/cm 2 electrode, 15 mg/cm 2 electrode, 20 mg/cm 2 electrode, and ranges between any two of the foregoing.
In some embodiments, anode porous substrate layer 32 is carbon paper or carbon cloth, and the anode catalyst loading in anode oxygen evolution electrode 30 is 0.05-5 mg/cm 2 electrode, such as, but not limited to, 0.05 mg/cm 2 electrode, 0.1 mg/cm 2 electrode, 0.5 mg/cm 2 electrode, 1mg/cm 2 electrode, 2 mg/cm 2 electrode, 3 mg/cm 2 electrode, 4 mg/cm 2 electrode, 5 mg/cm 2 electrode, and ranges between any two of the foregoing.
In some embodiments, anode porous substrate layer 32 is a metal mesh or foam, and the anode catalyst loading in anode oxygen evolution electrode 30 is 0.05-20 mg/cm 2 electrode, such as, but not limited to, 0.05 mg/cm 2 electrode, 0.1 mg/cm 2 electrode, 0.5 mg/cm 2 electrode, 1mg/cm 2 electrode, 5 mg/cm 2 electrode, 10 mg/cm 2 electrode, 15 mg/cm 2 electrode, 20 mg/cm 2 electrode, and ranges between any two of the foregoing.
In some embodiments, the cation exchange membrane 20 has a thickness of 10 μm to 300 μm, which may include, for example, but not limited to, 10 μm, 50 μm, 100 μm, 150 μm, 200 μm, 250 μm, 300 μm, and ranges between any two of the foregoing.
In some embodiments, the cation exchange membrane 20 is a Nafion membrane. The Nafion membrane may include, but is not limited to, nafion 117 membrane, nafion 211 membrane, nafion 212 membrane.
The second aspect of the present application also provides a method for preparing a membrane electrode according to any one of the embodiments of the first aspect, comprising the steps of:
Step S10, loading a cathode catalyst and a cation control substance on a cathode porous basal layer 12 to obtain a cathode diffusion electrode 10;
Step S20, anode catalyst is supported on the anode porous base layer 32 to obtain an anode oxygen evolution electrode 30; and
In step S30, the cathode diffusion electrode 10, the cation exchange membrane 20, and the anode oxygen evolution electrode 30 are stacked in this order.
In some embodiments, step S10 includes:
Step S11, placing a cathode catalyst and a cation regulation and control substance into a solvent for mixing to obtain a mixed coating;
in step S13, the mixed paint is coated on the cathode porous base layer 12 to form the cathode active layer 14.
As a possible embodiment, the solvent in step S11 is a mixed solvent of isopropyl alcohol and water. Optionally, the volume ratio of the isopropanol to the water is 4:1-1:1.
As one possible implementation mode, the concentration of the cathode catalyst in the mixed paint is 1-100 mg/mL.
As one possible implementation mode, the concentration of the cation regulating substance in the mixed paint is 1-500 mug/mL.
In other embodiments, step S10 includes:
step S12, placing a cathode catalyst in a solvent to obtain a cathode catalyst coating;
Step S14, coating a cathode catalyst coating material on the cathode porous base layer 12 to form a cathode catalyst layer 141;
s16, placing the cation regulating substance in a solvent to obtain a cation regulating substance coating;
in step S18, a cation controlling substance paint is coated on the cathode catalyst layer 141 to form a cation controlling substance layer 142.
As a possible embodiment, the solvent in step S12 is a mixed solvent of isopropyl alcohol and water. Optionally, the volume ratio of the isopropanol to the water is 4:1-1:1.
As one possible implementation, the concentration of the cathode catalyst in the cathode catalyst coating is 1-10 mg/mL.
As a possible embodiment, the solvent in step S16 is a mixed solvent of isopropyl alcohol and water. Optionally, the volume ratio of the isopropanol to the water is 4:1-1:1.
As one possible implementation mode, the concentration of the cation control material in the cation control material coating is 1-500 mug/mL.
The third aspect of the application also provides a membrane electrode reactor comprising a membrane electrode according to any one of the embodiments of the first aspect of the application.
The membrane electrode reactor also includes other components besides the membrane electrode, such as a cathode flow channel chamber and an anode flow channel chamber. The components are assembled in the order of the cathode flow channel chamber, the cathode diffusion electrode, the cation exchange membrane, the anode oxygen evolution electrode and the anode flow channel chamber, good surface contact between adjacent components is required to be ensured, and the cathode diffusion electrode, the cation exchange membrane and the anode oxygen evolution electrode are required to be tightly attached, but are still physically connected.
In some embodiments, the cathode flow channel chamber is fabricated from graphite or a corrosion resistant metal, including but not limited to one or more of titanium metal, stainless steel, hastelloy. The width of the internal channel of the cathode flow channel chamber can be 1-12 mm, and the depth of the channel can be 0.5-5 mm.
In some embodiments, the anode flow channel chamber is fabricated from graphite or a corrosion resistant metal, including but not limited to one or more of titanium metal, stainless steel, hastelloy. The width of the internal channel of the anode flow channel cavity can be 1-12 mm, and the depth of the channel can be 0.5-5 mm.
The following are specific examples. The present application is further described in detail to assist those skilled in the art and researchers in further understanding the present application, and the technical conditions and the like are not to be construed as limiting the present application in any way. Any modification made within the scope of the claims of the present application is within the scope of the claims of the present application.
Unless otherwise indicated, the starting materials and reagents used in the following examples were either commercially available or may be prepared by known methods. The experimental methods without specific conditions noted in the examples were carried out according to conventional conditions, such as those described in the literature, books, or recommended by the manufacturer.
Example 1
The 1mg Ni nm cluster supported oxidized carbon black catalyst was weighed and mixed with 1.6 μ g Fumasep anion exchange resin in a solvent of a mixture of 0.6. 0.6 mL isopropyl alcohol and 0.4. 0.4 mL water. The catalyst was dispersed in an ultrasonic cleaner to form a uniform coating, and the coating was uniformly sprayed on a GDL carbon paper of 1 cm X1 cm with a spray pen to prepare a cathode diffusion electrode having a catalyst loading of 0.2 mg/cm 2.
An IrO 2 -loaded 1 cm x1 cm titanium mesh was used as the anode oxygen evolution electrode. IrO 2 was supported at a level of 2 mg/cm 2.
The cation exchange membrane adopts a nafion 117 membrane with the area of 1.2 cm multiplied by 1.2 cm.
The membrane electrode assembly is assembled into a membrane electrode reactor in the order of a cathode flow channel chamber, a cathode diffusion electrode, a cation exchange membrane, an anode oxygen evolution electrode and an anode flow channel chamber.
Example 2
The 2 mg oxidized carbon black catalyst was weighed out and mixed with 100 μ g Piperion anion exchange resin in a solvent of 0.7. 0.7 mL isopropyl alcohol and 0.3. 0.3 mL water. The catalyst was dispersed in an ultrasonic cleaner to form a uniform coating, and the coating was uniformly sprayed on a 2 cm ×2 cm GDL carbon paper with a spray pen to prepare a cathode diffusion electrode having a catalyst loading of 0.4 mg/cm 2.
RuO 2 loaded on 2 cm ×2 cm foam nickel is adopted as an anode oxygen evolution electrode, and the RuO 2 loading is 1 mg/cm 2.
The cation exchange membrane adopts a nafion 211 membrane with the area of 2.5 cm multiplied by 2.5 cm.
The cathode flow channel chamber, the cathode diffusion electrode, the cation exchange membrane, the anode oxygen evolution electrode and the anode flow channel chamber are assembled in sequence.
Example 3
1 Mg Co monoatomic catalyst was weighed out and mixed with 50 μg of quaternary ammonium poly (n-methyl-piperidine-co-p-terphenyl) in a solvent of 0.7. 0.7 mL isopropanol and 0.3. 0.3 mL water. The catalyst was dispersed in an ultrasonic cleaner to form a uniform coating, and the coating was uniformly sprayed on a carbon paper of 2 cm ×2 cm with a spray pen to prepare a cathode diffusion electrode having a catalyst loading of 0.2 mg/cm 2.
NiFe hydroxide grown on 1cm X1 cm of nickel foam was used as the anode oxygen evolution electrode with a loading of about 10 mg/cm 2.
The cation exchange membrane adopts a nafion117 membrane with the area of 2.2 cm multiplied by 2.2 cm.
The cathode flow channel chamber, the cathode diffusion electrode, the cation exchange membrane, the anode oxygen evolution electrode and the anode flow channel chamber are assembled in sequence.
Example 4
500Mg of Fe nanocluster-doped carbon nanotubes were weighed and mixed with 1.6 mg Alkmer anion exchange resin, the solvent being 8. 8 mL isopropanol and 2. 2 mL water. The catalyst was dispersed in an ultrasonic cleaner to form a uniform coating, which was uniformly sprayed on a GDL commercial carbon cloth of 20 cm ×20 cm using an ultrasonic coater to produce a cathode diffusion electrode with a catalyst loading of 1 mg/cm 2.
An IrO 2 -loaded 20 cm ×20 cm titanium mesh is used as an anode oxygen evolution electrode, and the IrO 2 loading is 2 mg/cm 2.
The cation exchange membrane adopts a nafion117 membrane with the area of 22.5 cm multiplied by 22.5 cm.
The cathode flow channel chamber, the cathode diffusion electrode, the cation exchange membrane, the anode oxygen evolution electrode and the anode flow channel chamber are assembled in sequence.
Example 5
100 Mg carbon nanotube oxide catalyst was weighed and mixed with 160 μg poly (fluorenyl-co-terphenylpiperidinium) (PFAP), solvent 7.8 mL isopropanol and 2mL water. The catalyst was dispersed in an ultrasonic cleaner to form a uniform coating, which was uniformly sprayed on a 10X 10cm GDL commercial carbon cloth using an ultrasonic coater, the carbon was placed on a 80℃hot plate to produce a cathode diffusion electrode with a catalyst loading of 0.15 mg/cm 2.
FeP/Ni 2 P loaded on foam nickel is used as an anode oxygen evolution electrode, the loading capacity is 2 mg/cm 2, and the area is 10 multiplied by 10cm.
The cation exchange membrane adopts a nafion212 membrane with the area of 12 multiplied by 12cm.
The cathode flow channel chamber, the cathode diffusion electrode, the cation exchange membrane, the anode oxygen evolution electrode and the anode flow channel chamber are assembled into a membrane electrolyzer in the order of the cathode flow channel chamber, the cathode diffusion electrode, the cation exchange membrane, the anode oxygen evolution electrode and the anode flow channel chamber.
Example 6
The preparation method was substantially the same as in example 3, except that the cathode catalyst was changed to graphene oxide and the anion exchange resin was changed to Sustainion.
Example 7
The preparation method is basically the same as that of example 3, except that the cathode catalyst is replaced with graphene oxide and the cation controlling substance is replaced with 18-crown-6 complexed with sodium ions.
Example 8
The same procedure as in example 3 was followed except that the cathode catalyst was replaced with a Fe monoatomically doped carbon material and the cation controlling species was replaced with 15-crown-5 complexed with potassium ions. Example 9
The same procedure as in example 3 was followed except that the cathode catalyst was replaced with a Fe monoatomically doped carbon material and the cation controlling species was replaced with a quaternary aminopoly (arylperfluoroalkylene).
Example 10
The preparation was substantially the same as in example 3, except that the cation controlling substance was changed to poly (terpiperidinium-trifluoroacetophenone).
Example 11
The preparation method was substantially the same as in example 2, except that the anode oxygen evolution electrode used a carbon paper-supported IrO 2,IrO2 load of 0.5 mg/cm 2.
Example 12
The preparation method was substantially the same as in example 3, except that the cathode catalyst was replaced with a nano Pt catalyst.
Examples 13 to 15
The preparation method was substantially the same as in example 3 except that the mass of the anion exchange resin was different, and the specific mass of the anion exchange resin was added in accordance with the mass ratio of the cathode catalyst to the anion exchange resin shown in Table 1, wherein the mass of the Co monoatomic catalyst was 1 mg.
Example 16
The same preparation method as in example 3 was basically used, except that the cathode catalyst and the anion exchange resin in the cathode diffusion electrode were not mixed, but were separately prepared as a coating material layered on carbon paper, and the specific cathode diffusion electrode was prepared as follows:
The 1mg Co monoatomic catalyst was placed in a solvent of 0.7. 0.7 mL isopropyl alcohol and 0.3. 0.3 mL water, which were dispersed in an ultrasonic cleaner to form a uniform coating, and the coating was uniformly sprayed on carbon paper of 2 cm ×2 cm with a spray pen to obtain a cathode catalyst layer.
50 Μg of quaternary ammonium poly (n-methyl-piperidine-co-p-terphenyl) was placed in a solvent of 0.7 mL isopropyl alcohol and 0.3 mL water, dispersed in an ultrasonic cleaner to form a uniform coating, and the coating was uniformly sprayed on a cathode catalyst layer with a spray pen to prepare a cathode diffusion electrode having a catalyst loading of 0.2 mg/cm 2.
The procedure is as in example 3.
Comparative example 1
The same procedure as in example 1 was followed except that the anion exchange resin in the cathode diffusion electrode, i.e., the carbon paper of the cathode diffusion electrode was omitted and only the oxidized carbon black catalyst supported by the Ni nanoclusters was sprayed.
Comparative example 2
The same preparation method as in example 1 was used, except that the anion diffusion resin in the cathode diffusion electrode was replaced with a cation exchange resin nafion, i.e., a mixed solution of the Ni nanocluster-supported oxidized carbon black catalyst and the cation exchange resin was sprayed on the carbon paper of the cathode diffusion electrode.
The parameters relating to the membrane electrode reactors in examples 1 to 15 are shown in Table 1:
TABLE 1
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Application examples
The membrane electrode reactors, the related pipelines and the circuits prepared in the corresponding examples and the comparative examples are sequentially connected according to the application examples 1-16 and the application comparative examples 1-2 as shown in fig. 5 to serve as a reaction system for preparing hydrogen peroxide by oxygen reduction, and oxygen and pure water are mixed into a cathode runner chamber through a T-shaped three-way pipeline, wherein the flow rate of the oxygen is 25 sccm, the flow rate of the pure water in the application examples 1-3, the application examples 6-16 and the application comparative examples 1-2 is 1 mL/min, and the flow rate of the pure water in the application examples 4-5 is 10 mL/min. The cathode pressure was atmospheric pressure. The reactant of the anode is pure water, and the flow rate is 2 mL/min. After the fluid is stably input into the reactor for 10 minutes, the electrochemical workstation is used for setting reaction current, so that the reaction is carried out, a collecting bottle is placed at a cathode outlet for collecting a reaction liquid product, hydrogen peroxide generated by titration of Ce 4+ ion standard solution is analyzed, the hydrogen peroxide concentration C H2O2 is analyzed, and Faraday efficiency FE is calculated according to the following formula:
Where C Ce 4+ Total (S) is the concentration of Ce 4+ participating in the reaction, V Ce 4+ is the volume of Ce 4+ added at the time of titration, C Ce 4+ The remainder is is the concentration of residual Ce 4+ measured using ultraviolet spectroscopy after the end of titration, V H2O2 is the volume of H 2O2 reaction product participating in the titration, F is Faraday constant, 96485C/mol, j is the set constant current magnitude, and t is the reaction time. Wherein j is 200 mA/cm 2 and t is set to 1 hour.
The membrane electrode reactors, current densities, electrolysis times, and volumes V H2O2, concentrations C H2O2, and corresponding faraday efficiencies FE of the hydrogen peroxide solutions produced, corresponding to application examples 1-16 and application comparative example 1 are listed in table 2 below:
TABLE 2
The technical features of the above-described embodiments may be arbitrarily combined, and all possible combinations of the technical features in the above-described embodiments are not described for brevity of description, however, as long as there is no contradiction between the combinations of the technical features, they should be considered as the scope of the description.
The above examples merely represent a few embodiments of the present application, which facilitate a specific and detailed understanding of the technical solutions of the present application, but are not to be construed as limiting the scope of the application. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the application, which are all within the scope of the application. It should be understood that, based on the technical solutions provided by the present application, those skilled in the art may obtain technical solutions through logical analysis, reasoning or limited experiments, which are all within the scope of protection of the appended claims. The scope of the patent is therefore intended to be covered by the appended claims, and the description and drawings may be interpreted as illustrative of the contents of the claims.
Claims (15)
1. The membrane electrode for preparing hydrogen peroxide by oxygen reduction is characterized by comprising a cathode diffusion electrode, a cation exchange membrane and an anode oxygen evolution electrode which are arranged in a stacked manner, wherein the cation exchange membrane is positioned between the cathode diffusion electrode and the anode oxygen evolution electrode, and the cathode diffusion electrode, the cation exchange membrane and the anode oxygen evolution electrode are connected in a physical connection mode;
The cathode diffusion electrode comprises a cathode porous substrate layer and a cathode active layer, the cathode active layer comprises a cathode catalyst and a cation regulation substance, the anode oxygen evolution electrode comprises an anode porous substrate layer and an anode active layer, and the anode active layer comprises an anode catalyst.
2. The membrane electrode of claim 1, wherein the cation modulating species comprises a cationic polymer and/or a metal ion complexed crown ether; and/or the number of the groups of groups,
The cathode catalyst is one or more of an oxidized carbon material, a metal monoatomic doped carbon material and a metal nanocluster doped carbon material.
3. The membrane electrode of claim 2, wherein the cationic polymer comprises one or more of Fumasep anion exchange resin, alykmer anion exchange resin, piperion anion exchange resin, sustainion anion exchange resin, quaternized polyethylenimine, crosslinked polydiallyl dimethyl ammonium chloride, quaternary ammonium poly (n-methyl-piperidine-co-p-terphenyl), quaternary ammonium poly (aryl perfluoroalkylene), poly (terphenyl piperidinium-trifluoroacetophenone), poly (diphenyl-co-terphenyl piperidinium) (PDTP), branched poly (terphenyl piperidinium), and poly (fluorenyl-co-terphenyl piperidinium) (PFAP);
The crown ethers complexed with metal ions include one or more of 18-crown-6 complexed with sodium ions, 15-crown-5 complexed with potassium ions, and 12-crown-4 complexed with sodium ions.
4. The membrane electrode of claim 2, wherein the oxidized carbon material comprises one or more of graphene oxide, carbon nanotube oxide, and carbon black oxide; and/or the number of the groups of groups,
The metal monoatomic doped carbon material comprises a Co or Fe monoatomic doped carbon material; and/or the number of the groups of groups,
The metal nanocluster-doped carbon material includes one or more of a Ni nanocluster-doped carbon material, a Cu nanocluster-doped carbon material, and a Fe nanocluster-doped carbon material.
5. The membrane electrode according to claim 1, wherein the loading of the cathode catalyst in the cathode diffusion electrode is 0.05-5 mg/cm 2 electrode and/or the loading of the cation regulating substance in the cathode diffusion electrode is 1-500 μg/cm 2 electrode.
6. The membrane electrode according to any one of claims 1 to 5, wherein the mass ratio of the cathode catalyst to the cation control substance in the cathode diffusion electrode is 1: (0.0016 to 0.06).
7. The membrane electrode of claim 1, wherein the anode catalyst comprises one or more of iridium oxide, ruthenium oxide, rhodium oxide, iron oxide, cobalt oxide, nickel oxide, perovskite oxide, niFe hydroxide, iron sulfide, cobalt sulfide, nickel sulfide, copper sulfide, manganese sulfide, ni phosphide, and Fe phosphide.
8. The membrane electrode according to claim 1 or 7, wherein the anode catalyst loading in the anode oxygen evolution electrode is 0.05-20 mg/cm 2 electrode.
9. The membrane electrode of claim 1, wherein the cathode active layer comprises a cathode catalyst layer and a cation modulating substance layer, the cathode catalyst layer disposed proximate the cathode porous substrate layer, the cation modulating substance layer disposed distal the cathode porous substrate layer.
10. The membrane electrode according to claim 1, wherein the porosity of the cathode porous substrate layer is 20% -80%, optionally the cathode porous substrate layer is carbon paper or carbon cloth;
and/or the porosity of the anode porous substrate layer is 20% -80%, and optionally, the anode porous substrate layer is carbon paper, carbon cloth, metal mesh or foam metal.
11. The membrane electrode of claim 1, wherein the cation exchange membrane has a thickness of 10 μm to 300 μm, optionally the cation exchange membrane is a Nafion membrane.
12. The method for preparing a membrane electrode according to any one of claims 1 to 11, comprising the steps of:
Step S10, loading the cathode catalyst and the cation regulation and control substance on the cathode porous basal layer to obtain the cathode diffusion electrode;
step S20, loading the anode catalyst on the anode porous basal layer to obtain the anode oxygen evolution electrode; and
And step S30, sequentially stacking the cathode diffusion electrode, the cation exchange membrane and the anode oxygen evolution electrode.
13. The method of preparing a membrane electrode according to claim 12, wherein step S10 comprises:
Step S11, placing the cathode catalyst and the cation regulation and control substance into a solvent for mixing to obtain a mixed coating;
and step S13, coating the mixed paint on the cathode porous substrate layer.
14. The method of preparing a membrane electrode according to claim 12, wherein step S10 comprises:
step S12, placing the cathode catalyst in a solvent to obtain a cathode catalyst coating;
Step S14, coating the cathode catalyst coating on the surface of the cathode porous substrate layer to form a cathode catalyst layer;
S16, placing the cation regulating substance in a solvent to obtain a cation regulating substance coating;
And S18, coating the cation regulating substance coating on the surface of the cathode catalyst layer to form a cation regulating substance layer.
15. A membrane electrode reactor comprising a membrane electrode according to any one of claims 1 to 11.
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