CN114774959A - Integrated carbon electrode for producing hydrogen peroxide by air diffusion device and preparation method and application thereof - Google Patents
Integrated carbon electrode for producing hydrogen peroxide by air diffusion device and preparation method and application thereof Download PDFInfo
- Publication number
- CN114774959A CN114774959A CN202210437576.9A CN202210437576A CN114774959A CN 114774959 A CN114774959 A CN 114774959A CN 202210437576 A CN202210437576 A CN 202210437576A CN 114774959 A CN114774959 A CN 114774959A
- Authority
- CN
- China
- Prior art keywords
- carbon electrode
- integrated carbon
- integrated
- hydrogen peroxide
- electrode
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 225
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 159
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 title claims abstract description 114
- 238000009792 diffusion process Methods 0.000 title claims abstract description 80
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- 239000003054 catalyst Substances 0.000 claims abstract description 48
- 239000002243 precursor Substances 0.000 claims abstract description 33
- 239000000126 substance Substances 0.000 claims abstract description 33
- 239000003960 organic solvent Substances 0.000 claims abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 28
- 238000000137 annealing Methods 0.000 claims abstract description 27
- 239000011230 binding agent Substances 0.000 claims abstract description 25
- 238000011068 loading method Methods 0.000 claims abstract description 14
- 238000002156 mixing Methods 0.000 claims abstract description 12
- 239000000463 material Substances 0.000 claims abstract description 8
- 238000005266 casting Methods 0.000 claims abstract description 7
- 238000003825 pressing Methods 0.000 claims abstract description 6
- 239000007789 gas Substances 0.000 claims description 40
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 28
- 239000000853 adhesive Substances 0.000 claims description 25
- 230000001070 adhesive effect Effects 0.000 claims description 25
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 22
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 22
- 238000004519 manufacturing process Methods 0.000 claims description 21
- 239000011259 mixed solution Substances 0.000 claims description 20
- -1 polytetrafluoroethylene Polymers 0.000 claims description 19
- 238000001035 drying Methods 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 17
- 239000000843 powder Substances 0.000 claims description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 11
- 229910002804 graphite Inorganic materials 0.000 claims description 9
- 239000010439 graphite Substances 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 9
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 8
- 230000015572 biosynthetic process Effects 0.000 claims description 8
- 238000003786 synthesis reaction Methods 0.000 claims description 8
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- 239000002033 PVDF binder Substances 0.000 claims description 6
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 6
- 239000002041 carbon nanotube Substances 0.000 claims description 6
- 229910021389 graphene Inorganic materials 0.000 claims description 6
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 6
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical compound C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 claims description 5
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 claims description 5
- 229910003472 fullerene Inorganic materials 0.000 claims description 5
- 229920000642 polymer Polymers 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 4
- 239000006229 carbon black Substances 0.000 claims description 3
- 230000003197 catalytic effect Effects 0.000 abstract description 10
- 230000008569 process Effects 0.000 abstract description 10
- 238000007789 sealing Methods 0.000 abstract description 4
- 230000005518 electrochemistry Effects 0.000 abstract description 2
- 230000007774 longterm Effects 0.000 abstract 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 20
- 239000001301 oxygen Substances 0.000 description 20
- 229910052760 oxygen Inorganic materials 0.000 description 20
- 239000002245 particle Substances 0.000 description 16
- 239000000839 emulsion Substances 0.000 description 11
- 239000011148 porous material Substances 0.000 description 11
- 239000003792 electrolyte Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 238000006722 reduction reaction Methods 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- 238000003487 electrochemical reaction Methods 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 239000000203 mixture Substances 0.000 description 6
- 229910001220 stainless steel Inorganic materials 0.000 description 6
- 239000010935 stainless steel Substances 0.000 description 6
- 230000007935 neutral effect Effects 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 238000005273 aeration Methods 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- 235000019441 ethanol Nutrition 0.000 description 4
- 229910044991 metal oxide Inorganic materials 0.000 description 4
- 150000004706 metal oxides Chemical class 0.000 description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 239000006230 acetylene black Substances 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 239000007767 bonding agent Substances 0.000 description 3
- 239000003575 carbonaceous material Substances 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 230000002209 hydrophobic effect Effects 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 230000002035 prolonged effect Effects 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 238000009210 therapy by ultrasound Methods 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- 230000009471 action Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000010355 oscillation Effects 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 238000002604 ultrasonography Methods 0.000 description 2
- 238000001075 voltammogram Methods 0.000 description 2
- HXVNBWAKAOHACI-UHFFFAOYSA-N 2,4-dimethyl-3-pentanone Chemical group CC(C)C(=O)C(C)C HXVNBWAKAOHACI-UHFFFAOYSA-N 0.000 description 1
- 239000007832 Na2SO4 Substances 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 1
- 150000004056 anthraquinones Chemical class 0.000 description 1
- 230000027455 binding Effects 0.000 description 1
- 239000013590 bulk material Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000001112 coagulating effect Effects 0.000 description 1
- 239000013256 coordination polymer Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 229920001600 hydrophobic polymer Polymers 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000001360 synchronised effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000012224 working solution Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/02—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form
- C25B11/03—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form perforated or foraminous
- C25B11/031—Porous electrodes
- C25B11/032—Gas diffusion electrodes
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/28—Per-compounds
- C25B1/30—Peroxides
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/054—Electrodes comprising electrocatalysts supported on a carrier
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/055—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material
- C25B11/057—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material consisting of a single element or compound
- C25B11/065—Carbon
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Electrodes For Compound Or Non-Metal Manufacture (AREA)
- Inert Electrodes (AREA)
Abstract
The invention relates to an integrated carbon electrode for producing hydrogen peroxide by an air diffusion device, a preparation method and application thereof, belonging to the technical field of electrochemistry; the preparation method of the integrated carbon electrode for producing hydrogen peroxide by the air diffusion device comprises the steps of mixing carbon powder, a binder and an organic solvent, concentrating to obtain a precursor, casting and pressing the precursor to obtain a block-shaped substance, and annealing the block-shaped substance to obtain the integrated carbon electrode. The integrated carbon electrode is used as an electrochemical cathode and applied to a horizontally fixed air diffusion device to produce hydrogen peroxide, the hydrogen peroxide is synthesized efficiently at low energy and has stable performance, the used electrode catalyst has high loading amount and stable mechanical property, and has diffusion catalytic performance, and the problem of catalyst falling and loss hardly exists in the long-term use process, and the used device is easy to disassemble without considering the problems of sealing performance and material specificity.
Description
Technical Field
The invention relates to the field of electrochemistry, in particular to an integrated carbon electrode for producing hydrogen peroxide by an air diffusion device, a preparation method and application thereof.
Background
Hydrogen peroxide is a strong oxidant with environmental protection, and is widely applied to the fields of medical treatment, life, industry, environmental management and the like. The anthraquinone process is the mainstream industrial production method at present, and comprises the steps of hydrogenation, oxidation, hydrogen peroxide extraction, working solution purification circulation and the like, so that the required energy consumption is high, the steps are complicated, and harmful byproducts are easily generated. Because hydrogen peroxide is unstable, potential safety hazards exist in transporting and storing a large amount of hydrogen peroxide, and only low-concentration hydrogen peroxide is needed in practical use. The electrochemical synthesis method is a method for synthesizing hydrogen peroxide through two-electron oxygen reduction reaction on the surface of an electrochemical cathode, and the method can synthesize the hydrogen peroxide in situ, so the method becomes a hydrogen peroxide synthesis technology with the most development potential in recent years.
In an electrochemical system, a common cathode hydrogen peroxide generation mode is a traditional immersed device, namely, an electrode is placed in a solution, oxygen is supplied by aeration at the periphery of the electrode, and dissolved oxygen is converted into hydrogen peroxide on the surface of the electrode, but the synthesis effect of the hydrogen peroxide is poor due to the limitation of the dissolved oxygen in water.
The gas diffusion electrode is a generic name of a porous electrode which has a gas-liquid-solid three-phase reaction interface and has a catalyst to catalyze a film at the three-phase interface to participate in an electrochemical reaction, has a gas pore passage through which gas passes and also has a thin liquid film capable of generating the electrochemical reaction, is one of cathode materials widely researched at present, and has the advantages of good air permeability, high gas diffusion mass transfer efficiency and the like. In the electrochemical reaction process, most of gas reaches the thin liquid film through the gas pore channel of the gas diffusion electrode for reaction, so that the reaction efficiency is greatly improved, and the ultimate diffusion current density of the electrochemical reaction is further improved.
Currently, common gas diffusion electrodes include three-stage gas diffusion electrodes of the press-fit, ultrasonic, and coated type, by ultrasonically, coating, or press-fitting a support having a catalytic action on the surface of a support layer, wherein the support includes catalyst particles and a binder. However, since the preparation method of the three-stage gas diffusion electrode limits the loading amount of the catalyst, it is difficult to form a self-supporting active material layer, and an additional conductive support layer is often required to enhance mechanical stability. The problem that the combination of the load and the supporting layer is not tight can occur, and the phenomena that the catalyst falls off or a gap in the middle of the load is flooded and the like easily occur in the using process, so that the service life of the gas diffusion electrode is shortened.
Disclosure of Invention
The invention aims to overcome the defects that the existing gas diffusion electrode has small load capacity, surface load is easy to fall off or a gap between the load is flooded with water and the existing immersion device is limited by dissolved oxygen in water and has poor specificity of electrochemical synthesis effect, and provides an integrated carbon electrode for producing hydrogen peroxide by an air diffusion device and a preparation method thereof.
In a first aspect, the invention provides a preparation method of an integrated carbon electrode for producing hydrogen peroxide by an air diffusion device, which adopts the following technical scheme:
a preparation method of an integrated carbon electrode for producing hydrogen peroxide by an air diffusion device comprises the steps of mixing carbon powder, an adhesive and an organic solvent, concentrating to obtain a precursor, casting and pressing the precursor to obtain a blocky substance, drying the blocky substance, and annealing to obtain the integrated carbon electrode.
By adopting the technical scheme, the integrated carbon electrode is prepared by mixing, coagulating, pressing and annealing the adhesive and the carbon powder, and the electrode has the functions of diffusion and catalysis; in addition, the prepared integrated carbon electrode is blocky and has higher mechanical strength, the stress is 1-8Mpa under the tensile rate of 0.1-0.5, and the mechanical property is stable, so that a stainless steel net and the like are not needed to be used as a supporting structure, and the problem of carbon powder falling and loss is hardly caused in the use process of the integrated carbon electrode; the existing three-stage type can only load a thin layer of catalyst on the surface of the electrode because the catalyst layer is stripped off in a whole block if the catalyst is loaded too much and too thickThe layer and the integrated carbon electrode do not have the catalyst peeling phenomenon, the catalyst amount can be randomly increased within the optimal range of the hydrogen peroxide production performance, the catalyst layer volume is also naturally increased, and further, the catalyst loading capacity is larger and can reach 40-178mg/cm2。
Preferably, the loading capacity of the catalyst of the blocky substance is 40-178mg/cm2。
The original three-section type electrode can only load a certain amount of catalyst due to the limitation of the manufacturing process, and if the catalyst is loaded too much and too thick, the catalyst layer can be stripped off in a whole block; the integrated carbon electrode prepared by the technical scheme overcomes the limitation of the preparation process, increases the catalyst loading capacity and provides more reaction sites for rapid diffusion and migration of reactants and products in the electrochemical reaction.
Preferably, the temperature of the annealing treatment is 300-350 ℃, and the time is 1.5-2 h;
preferably, the temperature of the annealing treatment is 350 ℃ and the time is 2 h.
By adopting the technical scheme, the used annealing temperature is between 300-350 ℃, is close to or close to the melting temperature of the adhesive, firstly the blocky substance is heated to the annealing temperature, the adhesive is in a melting state, so that the carbon-series powder is better combined with the adhesive, then the temperature is slowly reduced, and the acting force is formed between the polymer chains of the adhesive again, so that the structure formed by the adhesive and the carbon-series powder is stable, the mechanical property is better, the adhesive and the carbon-series powder are more tightly combined, and the falling of the carbon-series powder is reduced.
Preferably, the carbon-series powder and the adhesive are added into an organic solvent and uniformly mixed by ultrasound to prepare a mixed solution, the mixed solution is concentrated to prepare a precursor, and the heating temperature for concentration is 80-85 ℃ for 0.5-1 h;
preferably, the precursor is cast on a mould and is uniformly compressed to form a blocky substance; and carrying out annealing treatment on the blocky substance after drying treatment, wherein the drying treatment temperature is 75-80 ℃, and the drying treatment time is 8-10 h.
By adopting the technical scheme, the carbon powder and the adhesive are added into the organic solvent, and the organic solvent is subjected to ultrasonic treatment to obtain uniform mixed liquid, so that the carbon powder is favorably and uniformly distributed on the integrated carbon electrode, the stability of current when the integrated carbon electrode is used can be improved, and the catalytic performance of the integrated carbon electrode is further improved;
heating, concentrating and volatilizing a part of organic solvent to prepare a precursor with low liquidity, which is beneficial to shaping of the integrated carbon electrode, and the precursor still contains a certain amount of organic solvent;
the precursor is cast on a mold and is compressed to prepare a block-shaped substance, and organic solvent in the block-shaped substance is dried and volatilized after annealing treatment, so that micron holes are formed on the surface and inside of the integrated carbon electrode, and a place is provided for efficient transmission of oxygen.
Optionally, the carbon-based powder is selected from one or more of conductive carbon black, graphite, acetylene carbon black, carbon nanotubes, graphene, activated carbon, carbon 60 or fullerene; optionally, the binder is selected from one or more of polytetrafluoroethylene, polyvinylidene fluoride or perfluorosulfonic acid type polymers;
optionally, the input weight ratio of the carbon-based powder to the binder is 1: (1-5);
optionally, the organic solvent is selected from one or more of ethanol, methanol, acetone, isopropanol or n-butanol.
By adopting the technical scheme, the carbon-based material has the advantages of low price, chemical stability, large specific surface area, good conductivity and the like, is a preferred material for preparing the oxygen reduction electrode, and common carbon-based materials comprise conductive carbon black, activated carbon, acetylene black, carbon nano tubes, graphite, graphene, carbon 60, fullerene and the like; the carbon material can catalyze the oxygen reduction reaction, the adhesive can bond the carbon powder, and the integrated carbon electrode has certain hydrophobicity, which is beneficial to oxygen transmission, and the integrated carbon electrode made of the carbon powder and the adhesive can be used as a gas diffusion cathode for preparing hydrogen peroxide by an electrochemical synthesis method.
Preferably, the method specifically comprises the following steps:
s1, adding a certain amount of the catalyst particles and the adhesive into the organic solvent, uniformly mixing by ultrasonic to obtain a mixed solution, heating and stirring the mixed solution, and concentrating the mixed solution to obtain a precursor;
s2, casting the precursor onto a mold, and compacting to obtain a block-shaped substance;
and S3, drying and annealing the blocky substance to obtain the integrated carbon electrode.
In a second aspect, the present application provides an integrated carbon electrode that employs the following technical solution:
an integrated carbon electrode, which is prepared by any one of the preparation methods for producing hydrogen peroxide by an air diffusion device.
By adopting the technical scheme, the mechanical property of the adhesive is improved through annealing treatment, and the integrated carbon electrode formed by mixing the carbon powder and the adhesive has stronger mechanical strength without adding supporting layers such as stainless steel meshes and the like; the bonding between the adhesive and the carbon powder is tight, so that the problem of catalyst falling off in the conventional three-section gas diffusion electrode can be reduced or eliminated; the catalyst of the integrated carbon electrode has high load capacity which can reach 40-178mg/cm2More oxygen reduction reaction sites are provided, and the synthesis efficiency of the hydrogen peroxide is improved; meanwhile, micropores are distributed in the integrated carbon electrode and on the surface of the integrated carbon electrode, the aperture of the micropores is 0.09-0.14 mu m, the porosity is 40% -60%, and the gas mass transfer efficiency and the gas loading capacity of the integrated carbon electrode are improved; the active sites of the catalyst in the integrated carbon electrode and the hydrophobic pore channel have the same action, so that the integrated carbon electrode has synchronous catalytic diffusion performance.
In a third aspect, the air diffusion device provided by the invention adopts the following technical scheme:
an air diffusion device using the integrated carbon electrode prepared by any one of the above-described preparation methods as a gas diffusion cathode, or the integrated carbon electrode as a gas diffusion cathode.
By adopting the technical scheme, the air diffusion device is an air diffusion device which can be matched with the integrated carbon electrode to efficiently produce hydrogen peroxide, and aeration is not needed; moreover, the air diffusion device is easy to disassemble without considering the problems of sealing performance and material specificity;
the integrated carbon electrode is used as a gas diffusion cathode to be applied to a horizontally fixed air diffusion device, based on the mechanical property of the electrode, the electrode is stably placed on the liquid surface of electrolyte, one side of the electrode is in contact with air, the other side of the electrode is in contact with the electrolyte, and gas enters a solid-liquid reaction site through an internal pore channel of the integrated carbon electrode to form a gas-liquid-solid three-phase reaction interface, so that the limitation of dissolved oxygen in water is eliminated, aeration is not needed, the energy consumption is low, the yield of hydrogen peroxide is high, and the current efficiency of the hydrogen peroxide can reach 70-95% under the neutral condition of 50-200 mA.
In a fourth aspect, the present application provides an integrated carbon electrode prepared by any one of the above-mentioned preparation methods, or an application of the integrated carbon electrode or the air diffusion device in the field of electrochemical synthesis.
Has the advantages that:
(1) the invention provides a preparation method of an integrated carbon electrode for producing hydrogen peroxide by an air diffusion device, which comprises the steps of mixing carbon powder, an adhesive and an organic solvent, and carrying out pressing, drying, annealing and the like to prepare the integrated carbon electrode with the thickness of 0.2-0.5cm, wherein the stress under the tensile rate of 0.1-0.5 is 1-8Mpa, the mechanical strength is higher, the mechanical property is stable, structures such as a stainless steel net and the like are not required to be used as a supporting structure of the electrode, and the problem that catalyst particles fall off from the integrated carbon electrode in the using process of the integrated carbon electrode is solved;
(2) the integrated carbon electrode provided by the invention has both catalysis and diffusion functions, the integrated carbon electrode generates pore channels on the surface and in the integrated carbon electrode through natural evaporation of an organic solvent, so that more oxygen is provided for hydrogen peroxide electrosynthesis, oxygen enters the integrated carbon electrode through a hydrophobic pore channel, and an oxygen reduction reaction occurs at a catalytic active site of carbon powder in the electrode;
(3) integrationThe catalyst loading capacity of the carbon electrode can reach 40-178mg/cm2The catalyst has higher catalyst loading capacity, and provides more catalytic active sites for hydrogen peroxide electrosynthesis;
(4) the integrated carbon electrode is used as a gas diffusion cathode in an electrochemical reaction system and applied to a horizontally fixed air diffusion device; in the air diffusion device, the integrated carbon electrode is horizontally arranged on the liquid level of the electrolyte, one side of the integrated carbon electrode is in contact with the liquid level, and the other side of the integrated carbon electrode is in direct contact with air, so that a water, gas and solid three-phase reaction interface is formed, and the limitation of dissolved oxygen in water is eliminated; the integrated carbon electrode and the air diffusion device can efficiently synthesize hydrogen peroxide through electrosynthesis under the combined action, and the current efficiency of the hydrogen peroxide reaches 70-95% under the neutral condition of 50-200 mA; meanwhile, compared with the existing air diffusion device, the air diffusion device provided by the invention is convenient to disassemble and assemble, does not need to consider the problems of sealing performance and material specificity, and has higher applicability.
Drawings
In order to illustrate the technical solution of the present invention more clearly, the drawings will be briefly described below, and it is apparent that the drawings in the following description relate only to some embodiments of the present invention and are not intended to limit the present invention.
FIG. 1 is a flow chart illustrating the preparation of an integrated carbon electrode according to the present invention provided in example 1;
FIG. 2 is a physical diagram of the integrated carbon electrode provided in example 1 of the present invention;
FIG. 3 is a scanning electron microscope image of the surface of the integrated carbon electrode provided in example 1 of the present invention;
FIG. 4 is a schematic view of an air diffusing device provided in example 14 of the present invention;
FIG. 5 is a graph of the mechanical properties of the integrated carbon electrodes provided in examples 1-3 of Experimental example 1;
FIG. 6 is a linear voltammogram of the integrated carbon electrodes provided in examples 1 to 3 of Experimental example 2;
FIG. 7 is a graph of the results of a six cycle experiment for the integrated carbon electrode provided in example 2 of Experimental example 2;
FIG. 8 is a graph showing the results of hydrogen peroxide production and current efficiency in the electrosynthesis of hydrogen peroxide using the integrated carbon electrode provided in examples 1-3 of Experimental example 2;
fig. 9 is a graph showing the results of the application of the electrodes provided in example 2 and comparative example 2 to hydrogen peroxide in the electrosynthesis of hydrogen peroxide and the current efficiency in experimental example 2.
Detailed Description
Preferred embodiments of the present invention will be described in more detail below. While the following describes preferred embodiments of the present invention, it should be understood that the present invention may be embodied in various forms and should not be limited by the embodiments set forth herein. The examples do not specify particular techniques or conditions, and are performed according to the techniques or conditions described in the literature in the art or according to the product specifications. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available. In the following examples, "%" means weight percent, unless otherwise specified.
The application provides a preparation method of an integrated carbon electrode for producing hydrogen peroxide by an air diffusion device, which is characterized in that carbon powder, a binder and an organic solvent are mixed and concentrated to prepare a precursor, the precursor is cast and pressed to obtain a blocky substance, and the blocky substance is annealed to obtain the integrated carbon electrode.
In one embodiment, the catalyst loading of the bulk material is 40-178mg/cm2。
According to the invention, the prepared integrated carbon electrode is in a block shape, the bonding agent and the bonding agent as well as the bonding agent and the carbon powder are tightly combined, the mechanical strength is high, the mechanical stability is better, the problem that catalyst particles fall off from the integrated carbon electrode in the use process of the integrated carbon electrode is reduced, and the service life of the integrated carbon electrode is prolonged; meanwhile, the prepared integrated carbon electrode has the functions of catalysis and diffusion, and gas enters the integrated carbon electrode to diffuse through the micropores and is subjected to reduction reaction under the catalysis of carbon powder.
In the invention, the supported catalyst amount is high in the preparation process of the integrated carbon electrode catalyst, and more catalytic active sites can be provided for hydrogen peroxide electrosynthesis.
According to the invention, the organic solvent is introduced in the preparation process of the integrated carbon electrode, and the organic solvent is volatilized to form the micron pores on the integrated carbon electrode, so that a place is provided for the efficient transmission of oxygen, and the gas loading capacity and the oxygen adsorption affinity of the integrated carbon electrode are improved.
In the invention, the hydrophobic polymer material is used as the binder, is mixed with the carbon-based powder and the organic solvent, and is subjected to certain treatment to prepare the integrated carbon electrode.
In one embodiment, the annealing treatment temperature is 300-350 ℃, and the time is 1.5-2 h;
preferably, the temperature of the annealing treatment is 350 ℃ and the time is 2 h.
In the invention, the blocky substance is annealed at the temperature of 250-350 ℃, and the acting force between macromolecular chains in the adhesive is reconstructed, so that the adhesive forms a structure with better mechanical property and higher mechanical strength and can be used as a supporting structure of an integrated carbon electrode; in addition, the adhesive is tightly combined with the catalyst particles, so that the condition that the catalyst particles fall off in the use process of the integrated carbon electrode is reduced, and the service life of the integrated carbon electrode is prolonged; meanwhile, in the annealing treatment process, the organic solvent contained in the blocky substance is further volatilized, and finally micron pores with the pore size of 0.09-0.14 mu m are formed on the integrated carbon electrode, the distribution of the micron pores is uniform, and the porosity of the integrated carbon electrode is 37% -56%.
In one embodiment, the carbon powder and the adhesive are added into an organic solvent and uniformly mixed by ultrasound to prepare a mixed solution, the mixed solution is concentrated to prepare a precursor, and the heating temperature for concentration is 80-85 ℃, and the time is 0.5-1 h.
In one embodiment, the precursor is cast on a mould and is uniformly compacted to form a block-shaped substance; and carrying out annealing treatment on the blocky substance after drying treatment, wherein the drying treatment temperature is 75-80 ℃ and the time is 8-10 h.
In one embodiment, the carbon-based powder is selected from one or more of conductive carbon black, graphite, acetylene carbon black, carbon nanotubes, graphene, activated carbon, carbon 60, or fullerene;
optionally, the binder is selected from one or more of polytetrafluoroethylene, polyvinylidene fluoride or perfluorosulfonic acid type polymers;
optionally, the input weight ratio of the carbon-based powder to the binder is 1: (1-5);
optionally, the organic solvent is selected from one or more of ethanol, methanol, acetone, isopropanol or n-butanol.
In the invention, carbon powder is selected as the catalyst particles of the integrated carbon electrode, has the advantages of low price, chemical stability, good specific surface area and electrical conductivity and the like, and can be used as a catalytic material of an oxygen reduction electrode and applied to electrochemical reaction for synthesizing hydrogen peroxide.
In the invention, one or more of hydrophobic high molecular materials of polytetrafluoroethylene, polyvinylidene fluoride or perfluorosulfonic acid type polymers are used as a binding agent, and carbon-based powder is added into the binding agent, and the carbon-based powder and the binding agent form an integrated gas diffusion electrode under the binding action of the binding agent.
In the present invention, the input weight ratio of the carbon-based powder to the binder is controlled to be in a range of 1: (1-5) and when the mass concentration of the binder is 40-80%, the integrated carbon electrode has more catalytic sites and more appropriate conductivity, mainly catalyzing 2e-The oxygen reduction reaction is favorable for the generation of hydrogen peroxide, and the integrated carbon electrode has proper hydrophobicity, so that a gas-liquid-solid three-phase reaction interface is formed on the integrated carbon electrode.
According to the method, the integrated carbon electrode can be prepared, the thickness reaches 0.2-0.5cm, the mechanical strength is high, the mechanical property is stable, the possibility of falling off of the carbon powder in the using process is low, the catalyst loading capacity of the integrated carbon electrode is improved, and the service life of the integrated carbon electrode is prolonged.
In one embodiment, the method specifically comprises the following steps:
s1, adding a certain amount of catalyst particles and the adhesive into the organic solvent, uniformly mixing by ultrasonic waves to obtain a mixed solution, heating and stirring the mixed solution, and concentrating the mixed solution to obtain a precursor;
s2, casting the precursor onto a mold, and compacting to obtain a block-shaped substance;
and S3, drying and annealing the blocky substance to obtain the integrated carbon electrode.
The application provides an integrated carbon electrode, which is prepared by any one of the preparation methods for the integrated carbon electrode for producing hydrogen peroxide by an air diffusion device.
In the invention, the integrated carbon electrode is provided with micropores, the pore diameter of the micropores is 0.09-0.14 μm, and the porosity of the integrated carbon electrode is 37% -56%.
The application provides an air diffusion device, which uses the integrated carbon electrode prepared by any one of the preparation methods as a gas diffusion cathode, or uses the integrated carbon electrode as a gas diffusion cathode.
In the invention, the air diffusion device is an air diffusion device which can be matched with the integrated carbon electrode to efficiently generate hydrogen peroxide, and has the advantages of no need of aeration, easy disassembly, no need of considering the problems of sealing property and material specificity and the like.
The application provides an integrated carbon electrode prepared by any one of the preparation methods, or the integrated carbon electrode, or the air diffusion device, and an application thereof in the field of electrochemical synthesis.
Example 1. an Integrated carbon electrode and method of making the same
The present embodiment provides an integrated carbon electrode including a carbon-based powder and a binder; the carbon powder and the adhesive are respectively conductive carbon black and polytetrafluoroethylene, the polytetrafluoroethylene and the carbon powder are mixed and processed to form an integrated carbon electrode, and catalyst particles and micropores are dispersed in and on the surface of the integrated carbon electrode.
As shown in fig. 1, this embodiment further provides a method for preparing an integrated carbon electrode for producing hydrogen peroxide by using an air diffusion device, in which conductive carbon black and polytetrafluoroethylene are added to an organic solvent according to a mass ratio of 1:3 to obtain a mixed solution, the mixed solution is concentrated to obtain a precursor, the precursor is cast and pressed to obtain a block-shaped substance with a thickness of 0.4cm, and finally, the block-shaped substance is annealed to obtain the integrated carbon electrode, where the organic solvent is absolute ethyl alcohol, and a catalyst loading amount of the integrated carbon electrode is 171.4mg/cm2(ii) a The preparation of the integrated carbon electrode specifically comprises the following steps:
s1, weighing 1.2g of conductive carbon black and 6g of 60% polytetrafluoroethylene emulsion, adding into 40mL of absolute ethyl alcohol, and carrying out ultrasonic treatment for 30min to obtain a uniform mixed solution;
s2, placing the mixed solution in a water bath kettle at 85 ℃, stirring, heating and concentrating for 1h until the mixed solution is agglomerated to form a precursor;
s3, casting the precursor onto a stainless steel-containing plate, and pressing the stainless steel-containing plate by using a solid stainless steel cylinder to obtain a blocky substance;
s4, placing the blocky substance in an oven at 80 ℃ for 10 hours, and drying;
and S5, placing the dried block-shaped substance in a muffle furnace at 350 ℃ for annealing treatment for 2h to obtain the integrated carbon electrode.
FIGS. 2 and 3 are an appearance entity image and a surface scanning electron microscope image of the integrated carbon electrode prepared by the above preparation method, respectively; as can be seen from fig. 3, the surface of the integrated carbon electrode is porous, which is beneficial to the transportation of two electron oxygen reduction related reactants on the surface of the electrode.
The present example is different from example 1 in that the amounts of the conductive carbon black and the 60% polytetrafluoroethylene emulsion charged are 1.2g and 2.0g, respectively, and the charged mass ratio of the conductive carbon black and the polytetrafluoroethylene is 1: 1.
Example 3. an Integrated carbon electrode and method of making the same
The present example is different from example 1 in that the amounts of the conductive carbon black and the 60% polytetrafluoroethylene emulsion charged were 1.2g and 10g, respectively, and the charged mass ratio of the conductive carbon black to the polytetrafluoroethylene was 1: 5.
Example 4. an Integrated carbon electrode and method of making the same
This example is different from example 1 in that the amounts of the conductive carbon black and the 60% polytetrafluoroethylene emulsion charged were 0.3g and 1.5g, and the catalyst supporting amount of the integrated carbon electrode was 42.8mg/cm2。
Example 5. an Integrated carbon electrode and method of making the same
This example is different from example 1 in that the charged amounts of the conductive carbon black and the 60% polytetrafluoroethylene emulsion were 0.9g and 4.5g, and the catalyst supporting amount of the integrated carbon electrode was 128.5mg/cm2。
Example 6. an Integrated carbon electrode and method of making the same
The difference between this example and example 1 is that the annealing temperature is 320 ℃ and the annealing time is 1.5 hours.
Example 7. an Integrated carbon electrode and method of making the same
This example differs from example 1 in that the heating temperature for concentration was 80 ℃ and the time was 0.5 h.
Example 8 an Integrated carbon electrode and method of making the same
The difference between this example and example 1 is that the drying temperature is 75 ℃ and the drying time is 8 h.
Example 9. an Integrated carbon electrode and method of making the same
This example is different from example 1 in that the catalyst particles are activated carbon, the binder is polyvinylidene fluoride, the organic solvent is isopropyl ketone, and the input amounts of the activated carbon and the 40% polyvinylidene fluoride emulsion are 0.3g and 2.25g, respectively.
Example 10 an Integrated carbon electrode and method of making the same
This example is different from example 1 in that the catalyst particles were graphite and carbon nanotubes, the organic solvent was acetone, and the input amounts of graphite, carbon nanotubes, and 60% polytetrafluoroethylene emulsion were 0.15g, and 2.5g, respectively.
Example 11. an Integrated carbon electrode and method of making the same
The present example is different from example 1 in that the catalyst particles were activated carbon and graphene, and the amounts of the activated carbon, graphene and 60% polytetrafluoroethylene emulsion charged were 0.3g, 0.6g and 7.5g, respectively.
Example 12. an Integrated carbon electrode and method of making the same
The present example is different from example 1 in that the catalyst particles are acetylene black and carbon 60, the organic solvent is n-butanol, and the input amounts of the acetylene black, carbon 60 and 60% perfluorosulfonic acid type emulsion are 0.3g, 0.3g and 3.0g, respectively.
Example 13 an Integrated carbon electrode and method of making the same
This example is different from example 1 in that the catalyst particles are fullerenes and the organic solvent is methanol.
EXAMPLE 14 an air diffusion device and its use in the production of hydrogen peroxide
As shown in fig. 4, an air diffusion device includes an electrolytic cell, an anode, a cathode, and a power source; the anode is a metal oxide electrode, the cathode is an integrated carbon electrode provided in any one of embodiments 1 to 13, the anode and the cathode are respectively communicated with the positive electrode and the negative electrode of a power supply, the electrolytic cell is filled with electrolyte, the anode is immersed in the electrolyte and is positioned in the electrolytic cell close to the bottom of the cell, the cathode is fixed on the liquid level of the electrolyte, one surface of the cathode is in contact with air, and the other surface of the cathode is in contact with the electrolyte.
When the synthesis of hydrogen peroxide is carried out, Na is used2SO4The solution was added as an electrolyte to the cell of an air diffusion device with a titanium-based metal oxide as the anode, examples1-13 as cathode, setting current at 100mA, and electrifying for 60min under neutral condition.
Comparative example 1 gas diffusion cathode and preparation thereof
The gas diffusion cathode consists of a diffusion catalytic layer and a supporting layer, and the preparation method specifically comprises the following steps:
the gas diffusion cathode takes carbon paper as a support net frame, and the carbon paper is coated with a mixture consisting of catalyst particles and a binder, and the preparation method specifically comprises the following steps:
(1) weighing 1.2g of conductive carbon black and 6.0g of 60% polytetrafluoroethylene emulsion according to a certain mass, uniformly mixing, adding 40mL of ethanol, and performing ultrasonic oscillation for 30min to uniformly disperse to obtain a conductive carbon black/binder mixture;
(2) uniformly and ultrasonically coating the conductive carbon black/binder mixture on the surface of carbon paper to obtain a precursor;
(3) placing the precursor in an oven at 80 ℃ for 10h, and drying;
(4) and placing the dried precursor in a muffle furnace at 350 ℃ for annealing treatment for 2h to obtain the gas diffusion electrode.
Comparative example 2 gas diffusion cathode and preparation thereof
The gas diffusion cathode takes a graphite felt as a supporting net frame, and the graphite felt is subjected to ultrasonic treatment and is coated with a mixture consisting of catalyst particles and a binder, and the preparation method specifically comprises the following steps:
(1) weighing 1.2g of conductive carbon black and 6.0g of 60% polytetrafluoroethylene emulsion according to a certain mass, uniformly mixing, adding 40mL of ethanol, and performing ultrasonic oscillation for 30min to uniformly disperse to obtain a conductive carbon black/binder mixture;
(2) uniformly and ultrasonically coating the conductive carbon black/binder mixture on the surface of a graphite felt to obtain a precursor;
(3) placing the precursor in an oven at 80 ℃ for 10h, and drying;
(4) and placing the dried precursor in a muffle furnace at 350 ℃ for annealing treatment for 2h to obtain the gas diffusion cathode.
Experimental example 1 mechanical properties of electrode
Mechanical testing was performed on the electrodes provided in examples 1-3 using a YES-2000 press tester, and the results are shown in fig. 5, where it can be seen that: when the elongation is 50%, the maximum stress of the integrated carbon electrodes provided in examples 1, 2 and 3 increases with the addition of polytetrafluoroethylene, wherein the maximum stress of example 3 reaches 7.73MPa, which indicates that the integrated carbon electrodes prepared in examples 1 to 3 have strong deformation resistance and stable mechanical properties.
Experimental example 2 electrochemical Performance of electrode
Electrochemical properties of the integrated carbon electrodes provided in examples 1-3 were characterized using the CHI electrochemical workstation and the hydrogen peroxide generation properties of the integrated carbon electrodes provided in examples 1-3 and the gas diffusion cathodes provided in comparative examples 1-2 were investigated and the results are shown in fig. 6-9.
Fig. 6 is a linear voltammogram of the integrated carbon electrodes provided in examples 1 to 3, and it can be seen from fig. 6 that as the content of the conductive carbon black increases, the current response increases, indicating that as the catalyst loading of the integrated carbon electrode is higher, the integrated carbon electrode has better conductivity and more reactive sites.
The integrated carbon electrode provided in example 1 was used as the cathode of the air diffusion device provided in example 14, and the operation was performed for 60min 6 times continuously, and the experimental results are shown in fig. 7. As can be seen from FIG. 7, the hydrogen peroxide production was maintained at 450mg/L and the average current efficiency was maintained at 80% in the six-cycle experiment, indicating that the hydrogen peroxide production performance was stable in the six-cycle experiment.
The integrated carbon electrodes provided in examples 1-3 were used as the cathode, titanium and metal oxide as the anode, and Na was used as the anode of the air diffusion device provided in example 142SO4The current is set as 100mA for the electrolyte, the current is electrified for 60min under the neutral condition, and the experimental result is shown in figure 8. As can be seen from fig. 8, the integrated carbon electrode provided in example 1 had a hydrogen peroxide yield of 453.2mg/L × h, and the current efficiency was maintained at 70% or more, which is better than those of examples 2 and 3.
The electrodes provided in example 1 and comparative examples 1 to 2 were used as gas diffusion cathodes, and titanium and metal oxides asAs anode with Na2SO4The current is set as 100mA for the electrolyte, the current is electrified for 60min under the neutral condition, and the experimental result is shown in figure 9.
As can be seen from FIG. 9, CB-PTFE/CP is the gas diffusion cathode of comparative example 1, which has a current efficiency of about 60%, H2O2The yield was 5.3mg x h-1*cm-1CB-PTFE/GF is the gas diffusion cathode of comparative example 2, which has a current efficiency of about 55%, H2O2The yield was 4.3mg x h-1*cm-1(ii) a While CB-PTFE was the integrated carbon electrode of example 1, the current efficiency was about 90%, H2O2The yield was 7.5mg h-1*cm-1Compared with comparative example 1 and comparative example 2, the electrosynthesis of hydrogen peroxide using the integrated carbon electrode provided in example 1 has higher hydrogen peroxide yield and current efficiency.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various features described in the above embodiments may be combined in any suitable manner without departing from the scope of the invention. The invention is not described in detail in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.
Claims (10)
1. A preparation method of an integrated carbon electrode for producing hydrogen peroxide by an air diffusion device is characterized by comprising the following steps: mixing and concentrating carbon powder, a binder and an organic solvent to prepare a precursor, casting and pressing the precursor to obtain a blocky substance, and drying and annealing the blocky substance to obtain the integrated carbon electrode.
2. The method for preparing an integrated carbon electrode for hydrogen peroxide generation of an air diffusion device according to claim 1, wherein: the catalyst loading of the blocky material is 40-178mg/cm2。
3. The method as claimed in claim 1, wherein the annealing treatment is performed at a temperature of 300-350 ℃ for a period of 1.5-2 h;
preferably, the temperature of the annealing treatment is 350 ℃ and the time is 2 h.
4. The method of claim 1, wherein the carbon electrode is selected from the group consisting of: adding the carbon powder and the adhesive into an organic solvent, uniformly mixing by ultrasonic waves to obtain a mixed solution, concentrating the mixed solution to obtain a precursor, wherein the heating temperature for concentration is 80-85 ℃, and the time is 0.5-1 h.
5. The preparation method of the integrated carbon electrode for the hydrogen peroxide production of the air diffusion device according to claim 1, wherein the precursor is cast on a mold and is uniformly compressed to form a block-shaped substance; and carrying out annealing treatment on the blocky substance after drying treatment, wherein the drying treatment temperature is 75-80 ℃ and the time is 8-10 h.
6. The method of claim 1, wherein the carbon electrode is selected from the group consisting of: the carbon powder is selected from one or more of conductive carbon black, graphite, acetylene carbon black, carbon nano tube, graphene, activated carbon, carbon 60 or fullerene;
optionally, the binder is selected from one or more of polytetrafluoroethylene, polyvinylidene fluoride or perfluorosulfonic acid type polymers; optionally, the input weight ratio of the carbon-based powder to the binder is 1: (1-5);
optionally, the organic solvent is selected from one or more of ethanol, methanol, acetone, isopropanol or n-butanol.
7. The method for manufacturing an integrated carbon electrode for hydrogen peroxide generation for an air diffusion device according to any one of claims 1 to 6, wherein: the method specifically comprises the following steps:
s1, adding a certain amount of the carbon-series powder and the adhesive into the organic solvent, uniformly mixing by ultrasonic waves to obtain a mixed solution, heating and stirring the mixed solution, and concentrating the mixed solution to obtain a precursor;
s2, casting the precursor onto a mould, and compacting to obtain a block-shaped substance;
and S3, drying and annealing the block-shaped substance to obtain the integrated carbon electrode.
8. An integrated carbon electrode, comprising: the integrated carbon electrode for the air diffusion device to produce hydrogen peroxide is prepared by the preparation method of any one of claims 1 to 7.
9. An air diffusion device characterized by using the integrated carbon electrode produced by the production method according to any one of claims 1 to 7 as a gas diffusion cathode, or the integrated carbon electrode according to claim 8 as a gas diffusion cathode.
10. An integrated carbon electrode prepared by the method according to any one of claims 1 to 7, or an integrated carbon electrode according to claim 8, or an air diffusion device according to claim 9, for use in electrochemical synthesis.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210437576.9A CN114774959B (en) | 2022-04-25 | 2022-04-25 | Integrated carbon electrode for producing hydrogen peroxide by air diffusion device and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210437576.9A CN114774959B (en) | 2022-04-25 | 2022-04-25 | Integrated carbon electrode for producing hydrogen peroxide by air diffusion device and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114774959A true CN114774959A (en) | 2022-07-22 |
| CN114774959B CN114774959B (en) | 2024-02-20 |
Family
ID=82432470
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210437576.9A Active CN114774959B (en) | 2022-04-25 | 2022-04-25 | Integrated carbon electrode for producing hydrogen peroxide by air diffusion device and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114774959B (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108866569A (en) * | 2018-07-03 | 2018-11-23 | 青岛理工大学 | A kind of preparation method of teflon heat modification gas-diffusion electrode |
| CN110306205A (en) * | 2019-07-09 | 2019-10-08 | 郑州大学 | A kind of gas-diffusion electrode and preparation method thereof |
-
2022
- 2022-04-25 CN CN202210437576.9A patent/CN114774959B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108866569A (en) * | 2018-07-03 | 2018-11-23 | 青岛理工大学 | A kind of preparation method of teflon heat modification gas-diffusion electrode |
| CN110306205A (en) * | 2019-07-09 | 2019-10-08 | 郑州大学 | A kind of gas-diffusion electrode and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114774959B (en) | 2024-02-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108977847B (en) | Mesoporous carbon air diffusion electrode and preparation method and application thereof | |
| CN109216717B (en) | Catalyst, method for preparing the same, cathode and electrochemical system | |
| CN110143647B (en) | Preparation method and application of carbon nanotube-nafion/foam metal gas diffusion electrode | |
| EP1169743B1 (en) | Gas difffusion substrates | |
| Hu et al. | Oxygen reduction on Ag–MnO2/SWNT and Ag–MnO2/AB electrodes | |
| CN101736360B (en) | Gas diffusion electrode and preparation method thereof | |
| CN109524674B (en) | Method for improving performance of cathode catalyst layer of membrane electrode of fuel cell | |
| JP4575330B2 (en) | Anode for fuel cell, method for producing the same, and fuel cell having the same | |
| CN101328591B (en) | Preparation of self-assembled membrane electrode for producing hydrogen peroxide by electrochemistry | |
| Mehdinia et al. | Nanostructured polyaniline-coated anode for improving microbial fuel cell power output | |
| CN104659379B (en) | Nanometer iron-manganese composite oxide loaded gas diffusion electrode and preparation and application thereof | |
| CN102029151B (en) | Modified polyol method for preparing Pt/C catalyst | |
| CN110586127B (en) | Preparation method and application of platinum-cobalt bimetallic hollow nanospheres | |
| CN108630950A (en) | Monatomic air cathode, battery, electro-chemical systems and bioelectrochemical system | |
| CN1697221A (en) | Catalyst for fuel cell and fuel cell comprising the same | |
| Song et al. | Biochar-supported Fe3C nanoparticles with enhanced interfacial contact as high-performance binder-free anode material for microbial fuel cells | |
| CN109939716B (en) | Nitrogen vacancy carbon-based catalyst for hydrogen production and preparation method thereof | |
| CN101002353A (en) | Highly hydrophilic support, catalyst-supporting support, electrode for fuel cell, method for producing the same, and polymer electrolyte fuel cell including the same | |
| CN114774959A (en) | Integrated carbon electrode for producing hydrogen peroxide by air diffusion device and preparation method and application thereof | |
| CN116387532A (en) | Hydrogen electrode and preparation method and application thereof | |
| Ma et al. | Cu Single-Atom Decorated Three-Dimensional Nitrogen–Carbon Framework as an Oxygen Reduction Reaction Catalyst for High-Performance Zinc–Air Batteries | |
| CN114369847A (en) | Iron-nickel alloy @ tungsten carbide/carbon composite catalyst, and preparation method and electrocatalysis application thereof | |
| CN109873171B (en) | Composite electrode for microbial electrochemical system and preparation method thereof | |
| CN112779558A (en) | Method for cathodic electrosynthesis of hydrogen peroxide by using PTFE (polytetrafluoroethylene) partially-hydrophobic modified graphite felt | |
| CN104916858A (en) | Membrane tubular bioelectrochemical system |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |