CN113149142A - Gas diffusion electrode and preparation method and application thereof - Google Patents
Gas diffusion electrode and preparation method and application thereof Download PDFInfo
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- CN113149142A CN113149142A CN202010075516.8A CN202010075516A CN113149142A CN 113149142 A CN113149142 A CN 113149142A CN 202010075516 A CN202010075516 A CN 202010075516A CN 113149142 A CN113149142 A CN 113149142A
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/467—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction
- C02F1/4672—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electrooxydation
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46109—Electrodes
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46109—Electrodes
- C02F2001/46133—Electrodes characterised by the material
- C02F2001/46138—Electrodes comprising a substrate and a coating
- C02F2001/46142—Catalytic coating
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
Abstract
The application discloses a gas diffusion electrode and a preparation method and application thereof. A gas diffusion electrode comprising a current collector, a diffusion layer and a catalytic layer; the diffusion layer and the catalytic layer are respectively positioned on two sides of the sheet-shaped current collector; the diffusion layer comprises a carbon material and has a porous structure; the catalytic layer includes a carbon material. The electrode is a high-efficiency in-situ electroproduction hydrogen peroxide gas diffusion electrode, is applied to a (catalytic) wet electrocatalysis process, can inhibit hydrogen evolution reaction, can efficiently prepare hydrogen peroxide, and can be used for rapidly degrading organic matters in water in cooperation with an anode.
Description
Technical Field
The application relates to a gas diffusion electrode and a preparation method and application thereof, and belongs to the technical field of electrochemistry.
Background
Among the advanced oxidation treatment technologies of sewage, the electrocatalytic oxidation technology (EO) has the advantages of no secondary pollution, no added reagent, simple operation and the like, and is a water treatment technology with a very promising application prospect.
Many researchers have recently focused on the study of gas diffusion electrodes, Xinmin Yu et al (Xinmin Yu, Minghua Zhou, Gengbo)Ren, et al, A novel gas diffusion systems for effective hydrogen peroxide generation used in electro-Fenton, Chemical Engineering journal.263(2015) 92-100) prepared a carbon nanotube and carbon black co-doped gas diffusion electrode having excellent removal capability to tartrazine; yi Xu et al (Yi Xu, Limei Cao, Wei Sun, et al0via a gas diffusion electrode, Chemical Engineering journal.310(2017) 170-178) prepares a gas diffusion electrode with better removal effect on zero-valent mercury in sewage by using activated carbon powder; ze Chen et al (Ze Chen, Heng Dong, hong bingg Yu, et al. in-situ chemical flow gas depletion section of carbon-based gas diffusion electrodes: Performance, kinetics and mechanism. chemical Engineering journal.307 (2017) 553-561) prepared a gas diffusion electrode containing carbon black, carbon nanotubes for efficient removal of sulfur from water.
Then, the above-mentioned gas diffusion electrode has disadvantages of high cost and low hydrogen peroxide yield.
Disclosure of Invention
According to an aspect of the application, a gas diffusion electrode is provided, the electrode is a high-efficiency in-situ electricity hydrogen peroxide generation gas diffusion electrode, the electrode is applied to (catalysis) wet type electrocatalysis processes, hydrogen evolution reaction can be inhibited, hydrogen peroxide can be efficiently prepared, and organic matters in water can be rapidly degraded in cooperation with an anode.
A gas diffusion electrode comprising a current collector, a diffusion layer and a catalytic layer;
the diffusion layer and the catalytic layer are respectively positioned on two sides of the sheet-shaped current collector;
the diffusion layer comprises a carbon material and has a porous structure;
the catalytic layer includes a carbon material.
Specifically, the middle of the gas diffusion electrode is a sheet-shaped current collector, and a diffusion layer and a catalyst layer are respectively arranged on two sides of the sheet-shaped current collector, so that a sandwich structure is formed.
The gas diffusion electrode prepared by the invention has the advantages of good performance, simple preparation method and long service life, and is firstly applied to the catalytic wet-type electrooxidation technology, the gas diffusion electrode can reduce oxygen into hydrogen peroxide, and hydroxyl radicals catalytically decomposed from the hydrogen peroxide can be used for degrading organic wastewater containing salt in cooperation with the anode.
Optionally, the current collector is a metal mesh;
the diffusion layer comprises carbon I and a binder I;
the catalytic layer comprises carbon II and a binder II.
Optionally, the metal mesh comprises any one of a titanium mesh, an iron mesh, a nickel mesh, a copper mesh and stainless steel;
the carbon I and the carbon II are independently selected from at least one of graphite powder, acetylene black, activated carbon powder, carbon nano tubes and micron carbon spheres;
the binder I and the binder II are independently selected from at least one of polyvinylidene fluoride, polyvinyl chloride, polytetrafluoroethylene, polypropylene and polybutylene.
Optionally, the thickness ratio of the diffusion layer to the current collector to the catalyst layer is 1-8: 1-3: 1-8;
preferably, in the diffusion layer, the pore diameter of the porous structure is 0.01-0.1 mm.
According to another aspect of the present application, there is also provided a method of manufacturing a gas diffusion electrode, the method comprising:
s100, obtaining a mixture I containing carbon I, a binder I, a pore-forming agent and a dispersing agent I, namely a diffusion layer precursor;
s200, obtaining a mixture II containing carbon II, a binder II and a dispersant II, namely a catalyst layer precursor;
s300, respectively coating the diffusion layer precursor and the catalyst layer precursor on two sides of the sheet-shaped current collector, cold pressing, and roasting to obtain the gas diffusion electrode.
Optionally, the pore-forming agent is an ammonium salt; the ammonium salt is at least one of ammonium sulfate, ammonium carbonate, ammonium chloride, ammonium bicarbonate, ammonium acetate, ammonium fluoride and ammonium bromide;
the dispersing agent I and the dispersing agent II are alcohol compounds;
the alcohol compound is selected from at least one of methanol, ethanol, propanol, n-propanol, isopropanol, isobutanol and n-butanol.
Optionally, in step S100, mixing carbon i, a binder i, a pore-forming agent and a dispersant i, wherein the mixing temperature is 60 to 90 ℃;
the mass ratio of the binder I to the carbon I is 1: 1-10: 1;
the mass ratio of the pore-forming agent to the carbon I is 0.1: 1-1: 1;
the mass ratio of the dispersing agent I to the carbon I is 1: 1-40: 1.
Specifically, the upper limit of the mass ratio of the binder i to the carbon i is independently selected from 2: 1. 5: 1. 8: 1. 10: 1; the lower limit of the mass ratio of binder i to carbon i is independently selected from 1: 1. 2: 1. 5: 1. 8: 1.
the upper limit of the mass ratio of the pore-forming agent to the carbon I is selected from 0.2: 1. 0.5: 1. 0.8: 1. 1: 1; the lower limit of the mass ratio of the pore-forming agent to the carbon I is selected from 0.1: 1. 0.2: 1. 0.5: 1. 0.8: 1.
The upper limit of the mass ratio of the dispersant I to the carbon I is independently selected from 10: 1. 20: 1. 30: 1. 40: 1; the lower limit of the mass ratio of the dispersant I to the carbon I is independently selected from 1: 1. 10: 1. 20: 1. 30: 1.
specifically, step S100 is a diffusion layer preparation step, wherein carbon powder I, a binder I, a pore-forming agent and a dispersing agent I are mixed, and the mixture is stirred at a temperature of 60-90 ℃ and heated in a water bath until the mixture is pasty.
Optionally, the carbon I is powder, and the mesh number of the carbon powder is between 100 and 300.
Optionally, in step S200, mixing carbon ii, binder ii and dispersant ii, wherein the mixing temperature is 60 to 90 ℃;
the mass ratio of the binder II to the carbon II is 1: 1-10: 1;
the mass ratio of the dispersing agent II to the carbon II is 1: 1-40: 1.
Specifically, step S200 is preparation of the catalyst layer, mixing carbon powder II, a binder II and a dispersant II, stirring and heating in a water bath at 60-90 ℃ until the mixture is pasty.
Optionally, the carbon II is powder, and the mesh number of the carbon powder is between 100 and 300.
Specifically, the upper limit of the mass ratio of the binder ii to the carbon ii is independently selected from 2: 1. 5: 1. 8: 1. 10: 1; the lower limit of the mass ratio of binder ii to carbon ii is independently selected from 1: 1. 2: 1. 5: 1. 8: 1.
the upper limit of the mass ratio of dispersant II to carbon II is independently selected from 10: 1. 20: 1. 30: 1. 40: 1; the lower limit of the mass ratio of dispersant II to carbon II is independently selected from 1: 1. 10: 1. 20: 1. 30: 1.
optionally, in step S300, the cold pressing conditions are: the pressure is 5-25 MPa; the time is 30-120 s;
the roasting conditions are as follows: roasting at the temperature of 150-300 ℃; the roasting time is 0.5-2 h; the heating rate is 1-5 ℃/min.
Specifically, in step S300, the paste-like diffusion layer precursor is coated on one side of the current collector substrate, and the paste-like catalyst layer precursor is coated on the other side of the current collector substrate, and the high-efficiency in-situ electricity-generated hydrogen peroxide gas diffusion electrode is obtained by cold pressing and baking.
Specifically, the upper limit of the pressure of the cold pressing is independently selected from 10MPa, 15MPa, 20MPa, 25 MPa; the lower limit of the pressure of cold pressing is independently selected from 5MPa, 10MPa, 15MPa, 20 MPa.
The upper limit of the calcination temperature is independently selected from 200 ℃, 240 ℃, 280 ℃, 300 ℃; the lower limit of the calcination temperature is independently selected from the group consisting of 150 deg.C, 200 deg.C, 240 deg.C, and 280 deg.C.
The upper limit of the temperature rise speed is independently selected from 2 ℃/min, 3 ℃/min, 4 ℃/min and 5 ℃/min; the lower limit of the temperature rise rate is independently selected from 1 ℃/min, 2 ℃/min, 3 ℃/min and 4 ℃/min.
Optionally, before coating the diffusion layer precursor and the catalytic layer precursor on two sides of the sheet-shaped current collector respectively, the method further comprises pretreating the current collector.
Pretreatment of the pooled stream comprises: and soaking the current collector in an acetone and NaOH solution for ultrasonic treatment, cleaning with deionized water, and airing for later use.
Specifically, the current collector, i.e., the electrode substrate, was placed in acetone and 0.3mol L-1Carrying out ultrasonic treatment on NaOH solution (v/v is 1: 0.2-1: 1) for 10-30 min, then placing the solution in deionized water for ultrasonic treatment for 10-30 min, and airing for later use.
According to another aspect of the application, a method for generating hydrogen peroxide by in-situ electricity is further provided, and the hydrogen peroxide is generated by the gas diffusion electrode obtained by any one of the above gas diffusion electrodes and the gas diffusion electrode prepared by any one of the above preparation methods.
According to still another aspect of the present application, there is also provided a method for degrading organic wastewater, wherein the organic wastewater is subjected to wet electrooxidation degradation by using the gas diffusion electrode according to any one of the above-mentioned aspects and the gas diffusion electrode obtained by the preparation method according to any one of the above-mentioned aspects.
Optionally, the gas diffusion electrode is a cathode, and under the condition of an oxygen source, the gas diffusion electrode is cooperated with the anode to perform wet-type electro-oxidative degradation on the organic wastewater;
the anode is selected from any one of a carbon electrode, a diamond film electrode, a noble metal electrode, a lead dioxide electrode, a tin dioxide electrode and a mixed metal oxide electrode.
Specifically, the noble metal electrode includes any one of a platinum electrode and a gold electrode.
Specifically, the mixed metal oxide electrode includes any one of a ruthenium iridium oxide electrode, a ruthenium tantalum oxide electrode, an iridium tantalum oxide electrode, and a ruthenium titanium oxide electrode.
Optionally, the conditions of the wet electro-oxidative degradation are: the temperature is 200-350 ℃; the reaction pressure is 5MPa to 10 MPa; the current density is 5 to 20mA/cm2. Specifically, in the wet electro-oxidative degradation process, the upper limit of the temperature is independently selected from 220 ℃, 250 ℃, 280 ℃, 300 ℃ and 350 ℃; the lower limit of the temperature is independently selected from 200 deg.C, 220 deg.C, 250 deg.C, 280 deg.C, 300 deg.C.
In the wet electro-oxidative degradation process, the upper limit of the reaction pressure is independently selected from 2MPa, 4MPa, 6MPa and 10 MPa; the lower limit of the reaction pressure is independently selected from 1MPa, 2MPa, 4MPa, 6 MPa.
The upper limit of the current density during the wet electro-oxidative degradation is independently 10mA/cm2、 20mA/cm2(ii) a The lower limit of the current density is independently 5mA/cm2、10mA/cm2。
Optionally, in the process of carrying out catalytic wet-type electrooxidation degradation on the organic wastewater, a catalyst is also contained;
the catalyst comprises a supported iron catalyst or a supported copper catalyst.
The supported iron catalyst comprises Fe/C, Fe/Al2O3Fe/red mud, Fe/molecular sieve;
the supported copper catalyst comprises Cu/C, Cu/A12O3Cu/red mud, Cu/molecular sieve;
the organic wastewater contains organic matters such as isophorone, phenol, m-cresol, methyl orange, acrylic acid, acetic acid, glyphosate and the like.
The invention discloses a preparation method of a high-efficiency in-situ electroproduction hydrogen peroxide gas diffusion electrode, which is characterized in that a metal net is used as a substrate and a current collecting layer, polytetrafluoroethylene is used as a binder and a hydrophobic agent, ammonium salt is used as a pore forming agent, carbon powder and binder tablets are used as electrode catalyst layers, the carbon powder, the binder and the pore forming agent tablets are used as electrode diffusion layers, the catalyst layers and the diffusion layers are cold-pressed to two ends of the substrate, and the gas diffusion electrode is obtained by high-temperature roasting.
The beneficial effects that this application can produce include:
1) the high-efficiency in-situ electricity-generated hydrogen peroxide gas diffusion electrode prepared by the invention has the characteristics of simple preparation, low price, longer service life and the like.
2) The efficient in-situ electroproduction hydrogen peroxide gas diffusion electrode prepared by the invention can convert oxygen generated by anode electrolysis into hydrogen peroxide and inhibit hydrogen evolution reaction, and because (catalytic) wet-type electro-oxidation is a high-pressure environment, the generation of hydrogen is inhibited, a system can be ensured to carry out wastewater degradation reaction within a safe pressure range, the production safety is improved, especially for industrial production, and the energy consumption required by side reaction in the electrolysis process is reduced.
3) The high-efficiency in-situ electricity-generated hydrogen peroxide gas diffusion electrode prepared by the invention can efficiently prepare hydrogen peroxide at the cathode and can rapidly degrade organic matters in water in cooperation with the anode.
Detailed Description
The present application will be described in detail with reference to examples, but the present application is not limited to these examples.
A high-efficiency in-situ hydrogen peroxide gas generation diffusion electrode comprises a current collector, a diffusion layer and a catalyst layer.
A preparation method of a high-efficiency in-situ electricity-generated hydrogen peroxide gas diffusion electrode comprises the following specific steps:
pretreating the current collector, namely the electrode substrate, which can be a titanium mesh, an iron mesh, a nickel mesh, a copper mesh, stainless steel and other metal meshes, and putting the substrate into acetone and 0.3mol L-1Carrying out ultrasonic treatment on NaOH solution (v/v is 1: 0.2-1: 1) for 10-30 min, then placing the treated solution in deionized water for ultrasonic treatment for 10-30 min, and airing for later use;
and (II) preparing a diffusion layer, namely mixing carbon powder, a binder, a pore-forming agent and a dispersing agent, stirring at 60-90 ℃, and heating in a water bath until the mixture is pasty.
And (III) preparing a catalyst layer, namely mixing carbon powder, a binder and a dispersing agent, stirring and heating the mixture in water bath at the temperature of 60-90 ℃ until the mixture is pasty.
And (IV) cold pressing preparation of the gas diffusion electrode, namely cold pressing the diffusion layer and the catalytic layer to two ends of the current collecting layer under the pressure of 5-25 MPa.
And (V) roasting the gas diffusion electrode, namely roasting the electrode prepared by cold pressing in a muffle furnace at the temperature of 150-300 ℃ at the heating rate of 1-5 ℃/min.
Preferably, the carbon powder can be one or more of graphite powder, acetylene black, activated carbon powder, carbon nanotubes, micron carbon spheres and the like, and the mesh number of the carbon powder is between 100 and 300.
Preferably, the binder can be one or more of polyvinylidene fluoride, polyvinyl chloride, polytetrafluoroethylene and the like, and the mass ratio of the binder to the carbon powder is 1: 1-10: 1.
Preferably, the pore-forming agent can be one or more of ammonium salts such as ammonium sulfate, ammonium carbonate and ammonium chloride, and the mass ratio of the pore-forming agent to the carbon powder is 0.1: 1-1: 1.
Preferably, the dispersing agent can be one or more of methanol, ethanol, propanol and the like, and the mass ratio of the dispersing agent to the carbon powder is 1: 1-40: 1.
The gas diffusion electrode can be used for degrading the salt-containing organic wastewater in cooperation with anode catalytic wet electrooxidation.
Preferably, the anode may be a carbon electrode, a diamond film electrode, a noble metal electrode, a lead dioxide electrode, a tin dioxide electrode, a mixed metal oxide electrode, or the like.
Preferably, a granular catalyst with the mesh number of 40-70 meshes can be added in the catalytic wet electro-oxidation process.
Further preferably, the catalyst added is a supported iron or copper catalyst.
In the examples, the organic matter degrading performance of the samples was measured by using an Shimadzu total organic carbon analyzer.
In the examples, the conversion of organic substances was measured by HPLC-P1201 type high performance liquid chromatography.
In the examples, an ultraviolet spectrometer was used for hydrogen peroxide testing.
Isoflurolone removal rate ═ (C)0-Ct)/C0×100％
C0Is the initial organic concentration, CtInitial organic matter concentration at time t
Total organic carbon removal (TOC)0-TOCt)/TOC0×100％
TOC0As initial total organic carbon, TOCtTotal organic carbon at time t.
In the application, the catalytic wet electrocatalytic oxidation device is an intermittent reaction device; the intermittent reaction device comprises a reactor, a pressurizing device, a heating device and an electrode pair; the reactor is a high-pressure reaction kettle; a gas charging port is arranged on the high-pressure reaction kettle and is used for introducing an oxygen source into the high-pressure reaction kettle; the pressurizing device is positioned outside the reactor and used for pressurizing the oxygen source; the heating device is positioned outside the reactor and used for heating the high-pressure reaction kettle; wherein, the organic wastewater is contained in the high-pressure reaction kettle, and an oxygen source is introduced for electro-catalytic treatment and wet oxidation treatment.
Optionally, the pair of electrodes includes at least one cathode and at least one anode.
Optionally, the cathode and the anode are oppositely arranged in parallel; alternatively, the first and second electrodes may be,
the cathode and the anode are opposite in arc-shaped front surface and are coaxially arranged with the reactor; alternatively, the first and second electrodes may be,
the cathode and the anode are coaxially and annularly arranged.
Optionally, the reactor also contains a catalyst;
the catalyst is placed at the upper end of the interior of the reactor; alternatively, the first and second electrodes may be,
the catalyst is placed at the lower end of the interior of the reactor; alternatively, the first and second electrodes may be,
the catalyst is placed throughout the interior of the reactor.
Optionally, the combination of the catalyst and the electrode pair comprises any one of the following modes:
the first method is as follows: the catalyst and the electrode are arranged at the lower end of the reactor;
the second method comprises the following steps: the catalyst is arranged at the lower end in the reactor, and the electrode is arranged at the upper end in the reactor;
the third method comprises the following steps: the catalyst is arranged at the lower end in the reactor, and the electrode is arranged at the upper end and the lower end in the reactor;
the method is as follows: the catalyst and the electrode are arranged at the upper end of the reactor;
the fifth mode is as follows: the catalyst is arranged at the upper end in the reactor, and the electrode is arranged at the lower end in the reactor;
the method six: the catalyst is arranged at the upper end in the reactor, and the electrode is arranged at the upper end and the lower end in the reactor;
the method is as follows: the catalyst is in the whole reactor, and the electrode pair is arranged at the upper end of the inside of the reactor;
the method eight: the catalyst is in the whole reactor, and the electrode is arranged at the lower end of the inside of the reactor;
the method is nine: the catalyst is in the whole reactor, and the electrode pair is arranged at the upper end and the lower end in the reactor.
Example 1 preparation of gas diffusion electrode and electric hydrogen peroxide production test
Selecting a titanium mesh as a current collector, and putting the current collector into acetone and 0.3mol L of solution-1Carrying out ultrasonic treatment on NaOH (v/v is 1:1) for 10min, then placing the treated solution in deionized water for ultrasonic treatment for 20min, and airing for later use;
preparing a diffusion layer, namely mixing carbon powder, a binder, a pore-forming agent and a dispersing agent, stirring at 60 ℃, heating in a water bath until the mixture is pasty, wherein the carbon powder is 200-mesh activated carbon powder, the binder is polyvinylidene fluoride (the polymerization degree is 1500), the mass ratio of the polyvinylidene fluoride to the carbon powder is 1:1, the pore-forming agent is ammonium carbonate, the mass ratio of the ammonium carbonate to the carbon powder is 0.5:1, and the mass ratio of the methyl alcohol to the carbon powder is 20: 1;
(III) preparing the catalyst layer, which is similar to the preparation method of the diffusion layer, except that no pore-forming agent is added;
fourthly, preparing a gas diffusion electrode by cold pressing, namely cold pressing the diffusion layer and the catalytic layer to two ends of the current collecting layer under the pressure of 10MPa for 60 s;
and (V) roasting the gas diffusion electrode, namely placing the electrode prepared by cold pressing in a muffle furnace for roasting at the temperature of 240 ℃, the roasting time of 1h and the heating rate of 2 ℃/min to obtain the gas diffusion electrode, and recording the gas diffusion electrode as a sample No. 1.
In sample # 1, the thickness ratio of the diffusion layer, the current collector, and the catalytic layer was 1: 3: 1.
in the diffusion layer, the aperture of the porous structure is 0.01-0.1 mm.
A ruthenium iridium electrode (RuIr-03, Dajunke bell environment) is taken as an anode, a gas diffusion electrode sample 1# prepared in the embodiment is taken as a cathode, a 0.1mol/L aqueous solution of sodium sulfate is taken as an electrolyte, and wet electrocatalysis is carried out in a catalysis modePerforming an electricity-generated hydrogen peroxide experiment in an oxidation device, wherein the pressure of the charged oxygen is 2MPa, the temperature is raised to 200 ℃, the reaction pressure is 5.5MPa, and the current density is 20mA/cm2The time is 2 hours, and the concentration of the prepared hydrogen peroxide is 1236 mg/L.
Example 2 preparation of gas diffusion electrode and electric hydrogen peroxide production test
Unlike example 1, the carbon powder used was a mixture of carbon nanotubes and activated carbon powder at a mass ratio of 1:1, and the binder used was polytetrafluoroethylene (polymerization degree of 1000), and the gas diffusion electrode obtained was prepared and designated as sample # 2.
In sample 2#, the thickness ratio of the diffusion layer, the current collector, and the catalytic layer was 5: 3: 4.
in the diffusion layer, the aperture of the porous structure is 0.05-0.1 mm.
The prepared 2# electrode is used as a cathode, a ruthenium iridium electrode (RuIr-03, Dajunke bell environment) is used as an anode, 0.1mol/L aqueous solution of sodium sulfate is used as electrolyte, an electrogenesis hydrogen peroxide experiment is carried out in a catalytic wet type electrocatalytic oxidation device, the pressure of charged oxygen is 2MPa, the temperature is raised to 250 ℃, the reaction pressure is 7.8MPa, and the current density is 20mA/cm2The time is 2h, and the concentration of the prepared hydrogen peroxide is 1532 mg/L.
Example 3 preparation of gas diffusion electrode and electric hydrogen peroxide production test
Different from example 1, the carbon powder used was acetylene black, the binder used was polytetrafluoroethylene (degree of polymerization 1500), the dispersant used was ethanol, cold pressing pressure was 15MPa, cold pressing time was 100s, firing temperature was 200 ℃, and firing time was 1.5h, and the gas diffusion electrode obtained was prepared and designated as sample # 3.
In sample 3#, the thickness ratio of the diffusion layer, the current collector, and the catalytic layer was 8: 1: 8.
in the diffusion layer, the aperture of the porous structure is 0.01-0.1 mm.
The prepared electrode is taken as a cathode, a ruthenium iridium electrode (RuIr-03, Dalianke bell environment) is taken as an anode, a 0.1mol/L aqueous solution of sodium sulfate is taken as an electrolyte, and the electrolysis is carried out in a catalytic wet type electrocatalytic oxidation deviceIn the experiment of producing hydrogen peroxide, the pressure of the oxygen is 4MPa, the temperature is increased to 300 ℃, the reaction pressure is 5MPa, and the current density is 5mA/cm2The time is 2h, and the concentration of the prepared hydrogen peroxide is 1124 mg/L.
Example 4 preparation of gas diffusion electrode
Preparation of sample 4# gas diffusion electrode: different from the example 1, the mass ratio of the binder to the carbon powder is 10:1, the mass ratio of the pore-forming agent to the carbon powder is 1:1, the mass ratio of the dispersant to the carbon powder is 40:1, the cold pressing pressure is 25MPa, the cold pressing time is 30s, the roasting temperature is 280 ℃, the roasting time is 0.8h, and the temperature rising rate is 1 ℃/min, so that the sample No. 4 gas diffusion electrode is obtained.
Preparation of sample # 5 gas diffusion electrode: different from the embodiment 1, the mass ratio of the binder to the carbon powder is 5:1, the mass ratio of the pore-forming agent to the carbon powder is 0.1:1, the mass ratio of the dispersant to the carbon powder is 1:1, the cold pressing pressure is 20MPa, the cold pressing time is 40s, the roasting temperature is 300 ℃, the roasting time is 0.5h, and the temperature rising rate is 5 ℃/min, so that the sample No. 5 gas diffusion electrode is obtained.
Example 6 degradation of waste Water test
An experiment of degrading wastewater with 1000ppm of isophorone by the aid of cathode and anode is carried out in a catalytic wet electrocatalytic oxidation device by taking the electrode in example 1 as a cathode, a lead dioxide electrode (PbTi-03, Dalianke environment) as an anode and 0.1mol/L of aqueous solution of sodium sulfate as electrolyte, wherein the pressure of oxygen gas is 2MPa, the temperature is increased to 260 ℃, the reaction pressure is 6.0MPa, and the current density is 10mA/cm2The time is 2h, the removal rate of the isophorone is 100%, and the removal rate of the total organic carbon is 47.20%.
Comparative example
The difference from the present embodiment is: taking a titanium mesh as a cathode; the removal rate of isophorone was 21.3%, and the total removal rate of organic carbon was 8.21%.
The experimental effect of example 6 is much higher than that of the comparative example.
Example 7 degradation of waste Water test
The electrode of example 1 was used as a cathode, and a lead dioxide electrode (PbTi)03, Dajunke bell environment) as an anode, adding 1g/L of Fe/AC catalyst (Fe/AC-01, Dajunke bell environment), taking 0.1mol/L of sodium sulfate aqueous solution as electrolyte, carrying out a wastewater experiment with 1000ppm of isofluranone degraded by cathode and anode in a catalytic wet electrocatalytic oxidation device, charging oxygen at 2MPa, heating to 260 ℃, wherein the reaction pressure is 6.5MPa, and the current density is 10mA/cm2The time is 2 hours, the removal rate of the isophorone is 100%, and the removal rate of the total organic carbon is 94.32%.
Although the present invention has been described with reference to a few preferred embodiments, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (10)
1. A gas diffusion electrode, comprising a current collector, a diffusion layer and a catalytic layer;
the diffusion layer and the catalytic layer are respectively positioned on two sides of the sheet-shaped current collector;
the diffusion layer comprises a carbon material and has a porous structure;
the catalytic layer includes a carbon material.
2. The gas diffusion electrode of claim 1, wherein the current collector is a metal mesh;
the diffusion layer comprises carbon I and a binder I;
the catalytic layer comprises carbon II and a binder II.
3. The gas diffusion electrode of claim 2, wherein the metal mesh comprises any one of a titanium mesh, an iron mesh, a nickel mesh, a copper mesh, stainless steel;
the carbon I and the carbon II are independently selected from at least one of graphite powder, acetylene black, activated carbon powder, carbon nano tubes and micron carbon spheres;
the binder I and the binder II are independently selected from at least one of polyvinylidene fluoride, polyvinyl chloride, polytetrafluoroethylene, polypropylene and polybutylene.
4. The gas diffusion electrode according to claim 1, wherein the thickness ratio of the diffusion layer, the current collector and the catalyst layer is 1-8: 1-3: 1-8;
preferably, in the diffusion layer, the pore diameter of the porous structure is 0.01-0.1 mm.
5. A method of making a gas diffusion electrode, the method comprising:
s100, obtaining a mixture I containing carbon I, a binder I, a pore-forming agent and a dispersing agent I, namely a diffusion layer precursor;
s200, obtaining a mixture II containing carbon II, a binder II and a dispersant II, namely a catalyst layer precursor;
s300, respectively coating the diffusion layer precursor and the catalyst layer precursor on two sides of a sheet-shaped current collector, and carrying out cold pressing and roasting to obtain a gas diffusion electrode;
preferably, the pore-forming agent is ammonium salt; the ammonium salt is at least one of ammonium sulfate, ammonium carbonate, ammonium chloride, ammonium bicarbonate, ammonium acetate, ammonium fluoride and ammonium bromide;
preferably, the dispersant I and the dispersant II are alcohol compounds;
the alcohol compound is selected from at least one of methanol, ethanol, propanol, n-propanol, isopropanol, isobutanol and n-butanol.
6. The preparation method according to claim 5, wherein in step S100, carbon I, a binder I, a pore-forming agent and a dispersant I are mixed, and the mixing temperature is 60-90 ℃;
the mass ratio of the binder I to the carbon I is 1: 1-10: 1;
the mass ratio of the pore-forming agent to the carbon I is 0.1: 1-1: 1;
the mass ratio of the dispersing agent I to the carbon I is 1: 1-40: 1;
preferably, in step S200, mixing carbon ii, binder ii and dispersant ii, wherein the mixing temperature is 60 to 90 ℃;
the mass ratio of the binder II to the carbon II is 1: 1-10: 1;
the mass ratio of the dispersing agent II to the carbon II is 1: 1-40: 1;
preferably, in step S300, the cold pressing conditions are: the pressure is 5-25 MPa; the time is 30-120 s;
the roasting conditions are as follows: roasting at the temperature of 150-300 ℃; the roasting time is 0.5-2 h; the heating rate is 1-5 ℃/min.
7. The method for generating hydrogen peroxide by in-situ electricity is characterized by utilizing the gas diffusion electrode of any one of claims 1 to 4 and the gas diffusion electrode prepared by the preparation method of any one of claims 5 to 6 to generate hydrogen peroxide by in-situ electricity.
8. A method for degrading organic wastewater, which is characterized in that the gas diffusion electrode of any one of claims 1 to 4 and the gas diffusion electrode obtained by the preparation method of any one of claims 5 to 6 are used for carrying out wet electrooxidation degradation on the organic wastewater.
9. The method according to claim 8, wherein the gas diffusion electrode is a cathode, and under the condition of an oxygen source, the gas diffusion electrode is cooperated with an anode to carry out wet electrooxidation degradation on the organic wastewater;
the anode is selected from any one of a carbon electrode, a diamond film electrode, a noble metal electrode, a lead dioxide electrode, a tin dioxide electrode and a mixed metal oxide electrode.
10. The method according to claim 9, characterized in that the conditions of the wet electro-oxidative degradation are: the reaction temperature is 200-350 ℃; reaction ofThe pressure is 5MPa to 10 MPa; the current density is 5 to 20mA/cm2。
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| CN113789538A (en) * | 2021-11-15 | 2021-12-14 | 广东工业大学 | Gas diffusion cathode with suspension catalyst layer and electrochemical reactor |
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