CN108975462A - A kind of ferrite modification MXene laminar gas diffusion electrode and the preparation method and application thereof - Google Patents

A kind of ferrite modification MXene laminar gas diffusion electrode and the preparation method and application thereof Download PDF

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CN108975462A
CN108975462A CN201810966274.4A CN201810966274A CN108975462A CN 108975462 A CN108975462 A CN 108975462A CN 201810966274 A CN201810966274 A CN 201810966274A CN 108975462 A CN108975462 A CN 108975462A
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mxene
ferrite
diffusion electrode
gas diffusion
modification
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CN108975462B (en
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姚晶晶
李海普
杨兆光
刘博宇
代喜梅
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Central South University
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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
    • 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
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/722—Oxidation by peroxides
    • 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
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/78—Treatment of water, waste water, or sewage by oxidation with ozone
    • 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
    • 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
    • C02F2101/36—Organic compounds containing halogen
    • C02F2101/363—PCB's; PCP's
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2201/00—Apparatus for treatment of water, waste water or sewage
    • C02F2201/46—Apparatus for electrochemical processes
    • C02F2201/461—Electrolysis apparatus
    • C02F2201/46105—Details relating to the electrolytic devices
    • C02F2201/4619—Supplying gas to the electrolyte
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2201/00—Apparatus for treatment of water, waste water or sewage
    • C02F2201/78—Details relating to ozone treatment devices
    • C02F2201/782—Ozone generators

Abstract

The invention discloses a kind of preparation methods of ferrite modification MXene laminar gas diffusion electrode, comprising the following steps: 1) preparation of Mxene material；2) ferrite modifies MXene material；3) prepared by laminar gas diffusion electrode.The invention also discloses ferrite modification MXene laminar gas diffusion electrode and its applications.Ferrite modification MXene laminar gas diffusion electrode can prepare electrochemical cathode material, be used for electrochemistry/ozone coupling water treatment system.Preparation method materials are convenient, technological operation is simple, at low cost, pole strength is big, the active high, good dispersion of electrochemical catalysis, are a kind of low energy consumption, efficient water treatment technology.It is had broad application prospects using the electrochemical cathode of the modification of ferrite prepared by present invention MXene in three-phase reaction interface degradation treatment PPCPs pollutant.

Description

A kind of ferrite modification MXene laminar gas diffusion electrode and preparation method thereof with Using
Technical field
The invention belongs to water treatment fields, and in particular to ferrite modifies MXene laminar gas diffusion electrode and its preparation Methods and applications are in particular to dropped using ferrite modification MXene laminar gas diffusion electrode in electrochemistry/ozone coupling system Solve the application in terms of PPCPs pollutant.
Background technique
In recent years, people gradually detect the drug and personal care articles of trace in the natural waters such as river, lake (Pharmaceuticals and personal care products, PPCPs), human body or animal-use drug are PPCPs most main The source wanted, PPCPs have the characteristics that stronger persistence, bioactivity, bioaccumulation, are largely deposited in environment for a long time In can generate endocrine disrupting, threaten the health of the mankind.Effluent of municipal sewage plant discharge is PPCPs to environmental transport and transfer Most important approach, in sewage treatment plant periphery basin PPCPs heavy contamination；The processing packet of PPCPs pollutant in water environment Included physical method, chemical method, bioanalysis etc., but due to PPCPs component extensively in sewage concentration it is low, conventional processing technique is gone Except the ability of this pollutant is extremely limited.Therefore it needs to study the better technique of degradation effect, further increases sewage treatment Water quality.
In electrochemistry/ozone coupling system, electrode material is the principal element for influencing coupling effect.Gas-diffusion electrode Refer to a kind of special three-phase porous membrane electrode, is generally combined using hydrophilic porous carbon material through hydrophobic binder and pressed again System roasts, and has better chemical property and electro catalytic activity compared with traditional plate electrode.Gas-diffusion electrode Film layer in there is cellular structure abundant, which includes the micropore that electrode catalytic materials itself carry, catalyst granules it Between formation hydrophilic pores, by binder package aggregation between weep hole and electrode baking during formed it is big Hole forms gas, liquid, solid three phase boundary between hydrophilic pores and weep hole.Three-phase reaction interface is not only gas near cathode Reduction reaction provide place, also be conducive to liquid phase reactor object migration.Weep hole constructed by hydrophobic binder is gas expansion It dissipates and channel is provided, the gap between hydrophilic carbon material is covered with electrolyte, forms thin liquid layer, and gas is spread from weep hole Into thin liquid layer, then from the active site that thin liquid layer is diffused into catalyst.The more common system in battery of gas-diffusion electrode The monitoring of polluted gas in standby and air, some scholars are applied in water pollution processing in recent years.
Ferrite refers to that the special oxide that iron and several metallic element are combined, crystal form mainly have spinelle Type, Magnetoplumbate-type and carbuncle type, wherein Mn ferrite (Fe2MnO4) it is one of most widely used magnetic material.Based on ferrite Large specific surface area, good catalytic action, magnetic the features such as being convenient for recycling by force, application in the treatment of waste water obtains The further investigation of scientific research personnel.MXene is a kind of two-dimentional transition metal carbide or carbonitride, passes through hf etching ternary Transition metal atoms layer in lamellar compound obtains, and has the characteristics that class graphene-structured, high surface area, high conductivity, again It is flexibly adjustable to have component, the advantages such as minimum nanometer thickness is controllable have potential advantages in electro-catalysis field.
Summary of the invention
Goal of the invention: technical problem to be solved by the invention is to provide a kind of ferrites to modify MXene laminar gas The preparation method of diffusion electrode.Preparation method materials are convenient, technological operation is simple, at low cost, pole strength is big, electrochemistry is urged Change that activity is high, good dispersion, is a kind of low energy consumption, efficient water treatment technology.
The ferrite that the present invention also technical problems to be solved are obtained there is provided the preparation method modifies MXene layers Shape gas-diffusion electrode.Ferrite modification MXene laminar gas diffusion electrode prepared by the present invention can be used as electrochemical cathode Material is used for electrochemistry/ozone coupling water treatment system, promotes the generation of living radical in reaction process as cathode, mentions The treatment efficiency of high electro-catalysis system.
Mxene material in the preparation of the electrode is obtained by hydrofluoric acid solution etching MAX phase material, ferrite be manganese, copper, The ferrites such as nickel, cobalt or multielement combined type ferrite.
There is provided ferrite modification MXene laminar gas diffusion electrode to answer for the last technical problems to be solved of the present invention With.Using the electrochemical cathode of the modification of ferrite prepared by present invention MXene in three-phase reaction interface degradation treatment PPCPs class Pollutant has broad application prospects.
Technical solution: in order to solve the above-mentioned technical problem, the technical scheme adopted by the invention is as follows: a kind of ferrite modification The preparation method of MXene laminar gas diffusion electrode, comprising the following steps:
1) preparation of Mxene material: taking MAX phase material to be immersed in HF aqueous solution, dry, and washing and centrifugation for several times, remove Surface residual debris impurity is removed, it is dry, until reaching constant quality obtains Mxene material；
2) ferrite modifies MXene material: ultrasound, filtering after the MXene material that step 1) obtains being added in ferrite It washs to neutrality；Then it roasts, it is stand-by that ferrite modification MXene material is obtained after cooling；
3) prepared by laminar gas diffusion electrode: ferrite modification MXene material and rush that step 2) obtains are led agent, pore-creating After agent, binder and dehydrated alcohol mixture ultrasound, stirring to mixture is in paste under water bath with thermostatic control, and cream gel object is taken Out, it is placed on axis press repeatedly axis pressure in the form of sheets, flaky substance is wrapped in continuation axis in nickel foam and is depressed into not water content, then It rolls to obtain electrode using roller bearing machine, the electrode rolled is placed in thermostatic drying chamber after drying, under 10-20MPa pressure Compression moulding is subsequently placed in tube furnace and roasts under inert gas conditions, finally impregnates in boiling water, is drying to obtain after taking-up To the laminar gas diffusion electrode of ferrite modification MXene.
Wherein, step 1) the MXene material can be two-dimentional transition metal carbide or carbonitride.
Wherein, the Mxene material is that the MAX phase material of certain mass is fully immersed in equipped with the stainless of HF aqueous solution In steel reaction kettle polytetrafluoroethylliner liner, places 72 hours, then use obtained material super in 40 DEG C of thermostatic drying chamber Pure water and centrifugation for several times, remove surface residual debris impurity until cleaning solution pH be not less than 6, then in 60 DEG C of vacuum drying ovens It is sufficiently dry, until reaching constant quality.
Wherein, the MAX phase material of the step 1) is Ti3AlC2、Ti3SiC2、Ti2One of AlC, but be not limited to above It is several.
Wherein, the ferrite of the step 2) is that can promote electron transfer, and catalysis ozone, hydrogen peroxide are decomposed to generate and be lived The ferrites such as manganese, copper, nickel, the cobalt of free love base and multielement combined type ferrite, the ferrite are not limited to Mn ferrite (Fe2MnO4) this kind of.
Wherein, the ferritic preparation of the step 2) can be the addition Fe (NO into ultrapure water3)3·9H2O solid and MCl2(M=Mn, Cu or Co) solid, then with magnetic stirrer so that its be uniformly mixed and be completely dissolved to obtain mix it is molten Liquid, and polyethylene glycol is added thereto and continues to stir to obtain the final product.It is described to contain Fe3+Solid chemical compound be not limited to Fe (NO3)3·9H2O This kind, suitable for ferrite preparation.
Wherein, the mass ratio of the ferrite in the step 2) and MXene material is 1:3~1:9.
Wherein, the quality sum of the ferrite and MXene material be laminar gas diffusion electrode quality 19%~ 45%.
Wherein, it is acetylene black or/and carbon black that the rush, which leads agent, and the pore creating material is sodium sulphate or/and sodium bicarbonate, described Binder is polytetrafluoroethylene (PTFE) or/and polyvinylidene fluoride or/and polyvinyl alcohol, but unlimited above several classes.
Specifically, a kind of preparation method of above-mentioned ferrite modification MXene laminar gas diffusion electrode includes following step It is rapid:
1) preparation of MXene material: the MAX phase material for weighing certain mass and the hydrofluoric acid solution for measuring certain volume add Enter into round-bottomed flask, after the ultrasonic treatment of 1h, react 72h in 40 DEG C of isothermal reaction kettle, after solution is cooling, uses Milli-Q water and centrifugation for several times, remove surface residual debris impurity until cleaning solution pH is not less than 6, then in 60 DEG C of vacuum drying ovens It is sufficiently drying, until reaching constant quality；The mass volume ratio of the MAX phase material and hydrofluoric acid solution is 1.0g:(50 ~200mL)；
2) ferrite modifies MXene material: Fe (NO being added into the ultrapure water of certain volume3)3·9H2O solid and MCl2 (M=Mn, Cu or Co) solid, with magnetic stirrer so that it is uniformly mixed and is completely dissolved to obtain mixed solution, mixing Solution Fe3+ and M2+Molar concentration rate is 2:1, and the polyethylene glycol that certain volume is added to mixed solution continues to stir 90min, is gathered The effect of ethylene glycol is prevent ferrite crystal oversized.It is dry complete that certain mass is added in mixed solution Then suspension was placed 48h under vacuum drying oven after 4 hours by MXene material, ultrasound；Then it is filtered again by 0.22 μm of micropore Film is filtered and is washed to neutrality；Ferrite modification MXene material after washing is placed in 60 DEG C of thermostatic drying chambers and is dried, then It is placed in electric tube furnace, is passed through inert gas as protection gas, is roasted 3 hours under the conditions of 600 DEG C, it is stand-by after cooling.
3) prepared by laminar gas diffusion electrode: the ferrite modification MXene material of certain mass ratio, rush being led agent, made After hole agent, binder and dehydrated alcohol mixture ultrasound 30min, stirring to mixture is in paste under 60 DEG C of waters bath with thermostatic control, will Cream gel object takes out, and is placed on axis press repeatedly axis pressure in the form of sheets, and flaky substance is wrapped in continuation axis in nickel foam and is depressed into It is almost dry, the electrode rolled is placed in 40 DEG C of thermostatic drying chamber after drying, the compression moulding under 10-20MPa pressure, It is subsequently placed in tube furnace under 350 DEG C of inert gas conditions and roasts 2 hours, it is small that 0.5 is finally impregnated in 100 DEG C of boiling water When, it is dry after taking-up.
Binder, rush in electrode production process of the present invention lead MXene material after agent, pore creating material and ferrite are modified Equal ingredients can adjust proportion as needed.
Preferably, binder, rush lead MXene quality of materials ratio after agent, pore creating material and ferrite are modified are as follows: (2~4): (3~7): (50~70): (19~45).
The content of present invention further includes the ferrite modification MXene laminar gas diffusion electrode that the preparation method obtains.
The content of present invention further includes the ferrite modification MXene laminar gas diffusion electrode in electrochemical cathode material In application.
Specific application is that, using netted platinum electrode as anode, mesh can be 20~60 mesh；Ferrite modifies MXene Laminar gas diffusion electrode is cathode, and yin-yang the two poles of the earth are placed in parallel in two sides up and down, are isolated with insulation silica gel pad, and rise Sealing function.
The content of present invention further includes the ferrite modification MXene laminar gas diffusion electrode in water pollution processing Using.
Ferrite modification MXene electrochemical cathode of the present invention can load different catalyst as excellent according to target contaminant Change.
The present invention also provides a kind of electrochemistry/ozone coupling water treatment system, which includes being sequentially connected Oxygen tank, ozone generator, ozone concentration detector, reaction unit (degradation room), peristaltic pump, mother liquor tank and tail gas absorption dress It sets, wherein include ferrite modification Mxene electrode, platinum gauze anode and insulated enclosure floor in the degradation room.
Wherein, for netted platinum electrode as anode, anode can be graphite electrode, stainless steel electrode, Ti electrode, noble metal electrode Or boron-doped diamond electrode etc., Fe2MnO4- MXene stratiform diffusion electrode is cathode, and yin-yang the two poles of the earth are placed in parallel in two sides up and down, It is isolated with insulation silica gel pad, and is sealed.
Wherein, it is respectively set between oxygen tank and ozone generator and between ozone concentration detector and degradation room There is gas flowmeter, reaction unit (decomposition apparatus) is connected with D.C. regulated power supply.It can be air that ozone generator, which supplies source, Or oxygen, ozonation aerated device can be micro-pore aeration material, hydraulic ejector or duct type air and liquid mixer etc., be located at ferrite Modify region immediately below MXene electrochemical cathode.Under electrochemistry/ozone coupling catalytic action, which pollutes PPCPs class Object is thoroughly degraded.
The present invention also provides a kind of using above-mentioned ferrite modification MXene laminar gas diffusion electrode in electrochemistry/smelly Oxygen couples the application in terms of water treatment system, method particularly includes: the solution containing target contaminant is pressurized using peristaltic pump, Speedup makes water body enter reaction unit (decomposition apparatus) with Reasonable Speed；Circulation flows through cathode electrode surface；Oxygen is sent out through ozone Life device generates ozone, and ozone gas is uniformly slow after the microporous diaphragm aerator at decomposition apparatus gas access slows down dispersion Liquid/solid contact layer is entered behind stratiform diffusion electrode bottom, is entered finally into solution, ozone concentration and flow lead to respectively It crosses ozone concentration monitor and gas flowmeter is measured, the tail gas after reaction discharges after the absorption of absorbing off-gas ozone device.
The utility model has the advantages that the present invention provides a kind of preparation method behaviour of ferrite modification MXene laminar gas diffusion electrode Make simple, material source is abundant, and at low cost, pole strength is big, and electrochemical catalysis activity is high, good dispersion, be a kind of low energy consumption, Efficient water treatment technology effectively, economically, environmentally friendly can carry out water process, in electrochemistry/ozone coupling water treatment system Middle degradation PPCPs pollutant has broad application prospects.
Specifically, compared with prior art, the invention has the advantages that
1, modification is modified to MXene using ferrite, chemical property and the catalytic ozonation for improving electrode are living Property, laminar gas diffusion electrode electrochemistry/ozone coupling technology has treatment effeciency as a kind of advanced oxidation technology , there is preferable application prospect in high, many advantages, such as occupied area is small, low energy consumption in terms of PPCPs is degraded in processing.
2, the modified reusing of ferrite modification MXene, stability and catalytic performance are all significantly improved, can Different ferrites is selected as needed, the MXene material that also more than one can be selected to be modified in same reaction unit, and meanwhile it is high The different PPCPs pollutants of effect degradation, have a wide range of application, and effluent quality is high.
3, ferrite is a kind of to be catalyzed O simultaneously3And H2O2A kind of new catalyst for generating OH is decomposed, iron oxygen is utilized Body modifies gas-diffusion electrode, can improve the degradation capability of system to greatest extent, also can be by gas diffusion electricity The MXene of pole, composition proportion optimize selection, prepare the laminar gas diffusion electrode for being best suited for Fourier Series expansion technique, especially It is suitble to the PPCPs pollutant of processing composition component complexity.
4, the laminar gas diffusion electrode of ferrite modification MXene helps to improve electrochemistry/ozone coupling system pair The degradation property of PPCPs pollutant: ferrite can occur catalytic action with ozone and hydrogen peroxide simultaneously and generate OH, meanwhile, The special space structure of ferrite makes that electron transmission occurs inside metallic particles；MXene material itself as carrier has spy Different nanostructure can not only provide reaction compartment for ozone, also can provide channel for electron transmission, accelerate ferrite with it is smelly Electron transmission between oxygen, hydrogen peroxide and crystals promotes the generation of redox reaction.
5, the present invention is by electrochemistry/ozone coupling water treatment system Automatic Control Unit to ozone concentration detector, remnants Oxide concentration detector, water pump, air pump, power supply etc. carry out signal acquisition and controlling, it can be achieved that treatment process full-automatic, intelligence Energyization control；Also mathematical simulation can be realized to reaction system by OH automatic capture collecting and detecting device, establishes efficiently science Water treatment system.
Detailed description of the invention
Fig. 1 ferrite modifies MXene electrochemical cathode preparation flow schematic diagram；
Fig. 2 electrochemistry/ozone coupling water treatment system circulation degradation PPCPs pollutant schematic diagram；1, oxygen tank 2, gas Flowmeter body 3, ozone generator 4, ozone concentration detector 5, ferrite modify Mxene electrode under-layer 6, insulated enclosure layer 7, platinum Screen anode 8, ferrite modification Mxene electrode at the middle and upper levels 9, D.C. regulated power supply 10, peristaltic pump 11, device for absorbing tail gas 12, Mother liquor tank.
Fig. 3 ferrite modifies MXene electrochemical cathode stability schematic diagram；
Fig. 4 electrochemistry/ozone coupling water treatment system adds the pass of concentration to PPCPs pollutants removal rate and gas phase ozone System's figure；
Relationship of Fig. 5 electrochemistry/ozone coupling water treatment system to PPCPs pollutants removal rate and cathode-current density Figure；
Relationship of Fig. 6 electrochemistry/ozone coupling water treatment system to PPCPs pollutants removal rate and reaction solution temperature Figure.
Specific embodiment
Below by specific embodiment, the present invention is further described, it is noted that for the ordinary skill of this field For personnel, without departing from the principle of the present invention, several variations and modifications can also be made, these also should be regarded as belonging to Protection scope of the present invention.
The preparation of 1 ferrite of embodiment modification MXene laminar gas diffusion electrode
(1) preparation of MXene material: 2.0g Ti is weighed3AlC2Material and the hydrofluoric acid solution for measuring 200mL are added to circle In the flask of bottom, after the ultrasonic treatment of 1h, 72h is reacted in 40 DEG C of isothermal reaction kettle, after solution is cooling, uses ultrapure water It washs and is centrifuged for several times, removing surface residual debris impurity is not less than 6 up to cleaning solution pH, then abundant again in 60 DEG C of vacuum drying ovens It is dry, until reaching constant quality obtains MXene material.
2) ferrite modifies MXene material: accurately weighing 808mg Fe (NO3)3·9H2O solid and 125.84mg MnCl2 Solid.Fe (NO is added into the ultrapure water of 100mL3)3·9H2O solid and MnCl2Solid, with magnetic stirrer so that its It is uniformly mixed and is completely dissolved to obtain mixed solution, wherein Fe (NO3)3For 0.02mol/L, MnCl2For 0.01mol/L, thereto The polyethylene glycol that 5mL is added continues to stir 90min, and the effect of polyethylene glycol is prevent ferrite crystal oversized, Dry complete 1089mg MXene material is added in the mixed solution of 100ml, ultrasound is after 4 hours then by suspension in room temperature Lower placement is for 24 hours；Then pass through 0.22 μm of filtering with microporous membrane again and wash to neutrality；By the ferrite modification after washing MXene material is placed in 50 DEG C of thermostatic drying chambers and dries, and is subsequently placed in electric tube furnace, is passed through nitrogen as protection gas, 600 It is roasted 3 hours under the conditions of DEG C, grinds the Fe to get modification for use after cooling2MnO4- MXene material.
3) preparation of ferrite modification MXene laminar gas diffusion electrode: the Fe of modification is weighed2MnO4- MXene material (700mg), acetylene black and pore creating material (Na2SO4) in the beaker of 50ml, add the dehydrated alcohol and polytetrafluoroethylene (PTFE) cream of 5ml Liquid (PTFE), ultrasound are uniformly mixed it, wherein Fe2MnO4Fe in-MXene2MnO4Mass percent be 17.5%, acetylene black 3.5wt%, Na2SO44.7wt%, PTFE 60.6wt%, Fe2MnO4- MXene 31.2wt%, then exists Stirring to mixture is in paste under 70 DEG C of waters bath with thermostatic control, and cream gel object is taken out, is placed on axis press repeatedly axis pressure in the form of sheets, Flaky substance is wrapped in continuation axis in nickel foam and is depressed into intimate drying, then rolls to obtain electrode using roller bearing machine, will roll Good electrode is placed in 40 DEG C of thermostatic drying chamber after drying, is cut into the circle of diameter 5cm, is pressed under 20MPa pressure Type is subsequently placed in tube furnace under 350 DEG C of inert gas conditions and roasts 2 hours, it is small that 1 is finally impregnated in 100 DEG C of boiling water When, drying for standby modifies the laminar gas diffusion electrode of MXene to get ferrite after taking-up.
Acetylene black is a kind of hydrophobic porous conductive material, porosity with higher and biggish specific surface area, energy Increase electrode surface or the internal catalysis to gas restores site；Sodium sulphate (Na2SO4) it is pore creating material, in electrode production process In, Na2SO4Sub-fraction is dissolved in ethyl alcohol, most of to exist in the form of crystallite, after the electrode after roasting is impregnated with deionized water, Na2SO4It being dissolved in water, slightly soluble part generates aperture, and crystallite part generates macropore, so that double-pore structure is formed in the electrodes, Improve the gas permeability of gas-diffusion electrode, improves gas effciency；The ptfe emulsion of 60wt%, PTFE are a kind of common Binder and water delivery materials, on the one hand PTFE, which is added, can increase binding force in electrode between each material, increase electrode and stablize Property, while also can increase the hydrophobicity of electrode, improve three-phase reaction interface.
2 ferrite of embodiment modifies MXene laminar gas diffusion electrode
1) preparation of MXene material: 3.0g Ti is weighed3AlC2Material and the hydrofluoric acid solution for measuring 150mL are added to circle In the flask of bottom, after the ultrasonic treatment of 1h, 72h is reacted in 40 DEG C of isothermal reaction kettle, after solution is cooling, uses ultrapure water It washs and is centrifuged for several times, removing surface residual debris impurity is not less than 6 up to cleaning solution pH, then abundant again in 60 DEG C of vacuum drying ovens It is dry, until reaching constant quality obtains MXene material.
2) ferrite modifies MXene material: accurately weighing 808mg Fe (NO3)3·9H2O solid and 125.84mg MnCl2 Fe (NO is added into the ultrapure water of certain volume for solid3)3·9H2O solid and MnCl2Solid, with magnetic stirrer with It is uniformly mixed it and is completely dissolved to obtain mixed solution, wherein Fe (NO3)3For 0.02mol/L, MnCl2For 0.01mol/L, to The polyethylene glycol that wherein 5mL is added in mixed solution continues to stir 90min, and the effect of polyethylene glycol is the ruler for preventing ferrite crystal It is very little excessive.2079mg MXene material is added in the mixed solution of 100ml, after 4 hours ultrasonic and then by suspension at room temperature It places for 24 hours；Then pass through 0.22 μm of filtering with microporous membrane again and wash to neutrality；Catalyst after washing is placed in 50 DEG C of perseverances It dries, is subsequently placed in electric tube furnace in warm drying box, be passed through nitrogen as protection gas, roasted 3 hours under the conditions of 600 DEG C, The Fe for use to get modification is ground after cooling2MnO4- MXene material.
3) preparation of ferrite modification MXene laminar gas diffusion electrode: the Fe of modification is weighed2MnO4- MXene material (2000mg), acetylene black and pore creating material (Na2SO4) in the beaker of 50ml, add 10ml dehydrated alcohol and polytetrafluoroethylene (PTFE) cream Liquid, ultrasound are uniformly mixed it, wherein Fe2MnO4Fe in-MXene2MnO4Mass percent be 10%, acetylene black 2wt%, Na2SO43wt%, PTFE 50wt%, Fe2MnO4- MXene 45wt%, then stirred under 70 DEG C of waters bath with thermostatic control to Mixture is in paste, and cream gel object is taken out, axis pressure is placed on axis press repeatedly in the form of sheets, flaky substance is wrapped in foam Continue axis on nickel and be depressed into intimate drying, then rolls to obtain electrode using roller bearing machine, the electrode rolled is placed in 40 DEG C of perseverance After drying in warm drying box, it is cut into the circle of diameter 5cm, the compression moulding under 20MPa pressure is subsequently placed in tube furnace Roast under 350 DEG C of inert gas conditions 2 hours, finally impregnated 1 hour in 100 DEG C of boiling water, after taking-up drying for standby to get The laminar gas diffusion electrode of ferrite modification MXene.
3 ferrite of embodiment modifies MXene laminar gas diffusion electrode
1) preparation of MXene material: 1.0g Ti is weighed3AlC2Material and the hydrofluoric acid solution for measuring 300mL are added to circle In the flask of bottom, after the ultrasonic treatment of 1h, 72h is reacted in 40 DEG C of isothermal reaction kettle, after solution is cooling, uses ultrapure water It washs and is centrifuged for several times, removing surface residual debris impurity is not less than 6 up to cleaning solution pH, then abundant again in 60 DEG C of vacuum drying ovens It is dry, until reaching constant quality obtains MXene material.
2) ferrite modifies MXene material: accurately weighing 1616mg Fe (NO3)3·9H2O solid and 251.68mg MnCl2Fe (NO is added into the ultrapure water of certain volume for solid3)3·9H2O solid and MnCl2Solid is stirred with magnetic stirring apparatus It mixes so that it is uniformly mixed and is completely dissolved to obtain mixed solution, wherein Fe (NO3)3For 0.04mol/L, MnCl2For 0.02mol/ L, the polyethylene glycol that 10mL is added in mixed solution thereto continue to stir 90min, and the effect of polyethylene glycol is to prevent ferrite brilliant Body it is oversized.2079mg MXene material is added in the above-mentioned mixed solution of 100ml, then ultrasound will suspend after 4 hours Liquid is placed for 24 hours at room temperature；Then pass through 0.22 μm of filtering with microporous membrane again and wash to neutrality；By the catalyst after washing It is placed in 50 DEG C of thermostatic drying chambers and dries, be subsequently placed in electric tube furnace, be passed through nitrogen as protection gas, under the conditions of 600 DEG C Roasting 3 hours grinds the Fe to get modification for use after cooling2MnO4- MXene material.The 1386mg in the mixed solution of 100ml Then MXene material, ultrasound place suspension for 24 hours at room temperature after 4 hours；Then pass through 0.22 μm of miillpore filter mistake again It filters and washs to neutrality；Catalyst after washing is placed in 50 DEG C of thermostatic drying chambers and is dried, is subsequently placed in electric tube furnace, is led to Enter nitrogen as protection gas, is roasted 3 hours under the conditions of 600 DEG C, grind the Fe to get modification for use after cooling2MnO4-MXene Material.
3) preparation of ferrite modification MXene laminar gas diffusion electrode: the Fe of modification is weighed2MnO4- MXene material (1000mg), acetylene black and pore creating material (Na2SO4) in the beaker of 50ml, add 20ml dehydrated alcohol and polytetrafluoroethylene (PTFE) cream Liquid, ultrasound are uniformly mixed it, wherein Fe2MnO4Fe in-MXene2MnO4Mass percent be 25%, acetylene black 4wt%, Na2SO47wt%, PTFE 70wt%, Fe2MnO4- MXene 19wt%, then stirred under 70 DEG C of waters bath with thermostatic control to Mixture is in paste, and cream gel object is taken out, axis pressure is placed on axis press repeatedly in the form of sheets, flaky substance is wrapped in foam Continue axis on nickel and be depressed into intimate drying, then rolls to obtain electrode using roller bearing machine, the electrode rolled is placed in 40 DEG C of perseverance After drying in warm drying box, it is cut into the circle of diameter 5cm, the compression moulding under 20MPa pressure is subsequently placed in tube furnace Roast under 350 DEG C of inert gas conditions 2 hours, finally impregnated 1 hour in 100 DEG C of boiling water, after taking-up drying for standby to get The laminar gas diffusion electrode of ferrite modification MXene.
Application Example
By the ferrite modification MXene laminar gas diffusion electrode of Examples 1 to 3 preparation in electrochemistry/ozone coupling water Application in terms of processing system
Electrochemistry/ozone coupling water treatment system includes oxygen tank 1, gas flowmeter 2, ozone generator 3, ozone concentration Detector 4, ferrite modification Mxene electrode under-layer 5, insulated enclosure layer 6, platinum gauze anode 7, ferrite modify Mxene electrode 8, D.C. regulated power supply 9, peristaltic pump 10, device for absorbing tail gas 11 and mother liquor tank 12 at the middle and upper levels.Wherein, netted platinum electrode is as sun Pole, anode can be graphite electrode, stainless steel electrode, Ti electrode, noble metal electrode or boron-doped diamond electrode etc., Fe2MnO4- MXene stratiform diffusion electrode is cathode, and yin-yang the two poles of the earth are placed in parallel in two sides up and down, are isolated with insulation silica gel pad, and It seals.Ozone generator, which supplies source, to be air or oxygen, and ozonation aerated device can be micro-pore aeration material, waterpower Ejector or duct type air and liquid mixer etc. are placed in region immediately below ferrite modification MXene electrochemical cathode.In electrification Under/ozone coupling catalytic action, thoroughly degraded to PPCPs pollutant
Using ferrite modification MXene laminar gas diffusion electrode in the processing of electrochemistry/ozone coupling water treatment system Method is as follows: being pressurized using peristaltic pump to the solution containing target contaminant, speedup, water body is made to enter reaction with Reasonable Speed Device；Circulation flows through the laminar gas diffusion electrode surface of ferrite modification MXene；Oxygen generates ozone through ozone generator, Ozone gas uniformly flows slowly over ferrite after the microporous diaphragm aerator at decomposition apparatus gas access slows down dispersion and repairs Adorn MXene laminar gas diffusion electrode bottom after enter liquid/solid contact layer, enter finally into solution, ozone concentration and Flow passes through ozone concentration monitor respectively and gas flowmeter is measured, and the tail gas after reaction is inhaled through absorbing off-gas ozone device It is discharged after receipts.
PPCPs pollutant detects extensively in earth surface water source, and long-term preservation causes damages to aquatile, wherein four Ring element is not limited to this using tetracycline as target contaminant as water head site priority acccess control antibiotic, example of the present invention Pollutant takes a certain amount of tetracycline antibiotic to be added to potassium dihydrogen phosphate-sodium hydroxide buffer solution storage that pH value is 7 In standby liquid 1000mg/L.Initial concentration solution is 100mg/L, the Na of reaction solution 2000mL, electrolyte 0.15mol/L2SO4, it is compacted Dynamic revolution speed 150r/min and degradation time 25min, using the concentration of object in high performance liquid chromatography measurement reaction process, just Starting point concentration is Co, sampling interval 5min, and measuring concentration is C, and removal rate is calculated as (Co-C)/Co, investigates iron oxygen respectively Body modifies MXene electrochemical cathode stability (electrode access times are 1,5,8 and 10) schematic diagram, and more different numbers respectively sample The difference of time point and final removal rate；Electrochemistry/ozone coupling water treatment system is smelly to PPCPs pollutants removal rate and gas phase Oxygen adds the relational graph of concentration (concentration is respectively 10,30,50 and 70mg/L)；Electrochemistry/ozone coupling water treatment system pair PPCPs pollutants removal rate and cathode-current density (5,20,30 and 40mA/cm2) relational graph；Electrochemistry/ozone coupling water Relational graph of the processing system to PPCPs pollutants removal rate and reaction solution temperature (10,20 and 30 DEG C), the result finally handled Referring to Fig. 3~6.
Ferrite modifies MXene electrochemical cathode, and there is no too for degradation rate of the DIA in Fourier Series expansion technique after using 30 times Big variation, and to the removal rate of object in 25min up to 80% (Fig. 3)；Other primary conditions are constant, in gas phase ozone Adding concentration is 70mg/L, and removal rate is 81% (Fig. 4)；Other primary conditions are constant, are 40mA/cm in cathode-current density2, Removal rate is 78% (Fig. 5)；Other primary conditions are constant, are 30 DEG C in reaction solution temperature, removal rate is 80% (Fig. 6).
It above are only the preferred embodiment of the invention, be not restricted to the present invention.Those skilled in the art is come It says, other various forms of variations or variation can also be made on the basis of the above description.There is no need and unable to all Embodiment illustrate.And the obvious changes or variations that thus scheme is extended out are still in protection of the invention Within the scope of.

Claims (13)

1. a kind of preparation method of ferrite modification MXene laminar gas diffusion electrode, which comprises the following steps:
1) preparation of Mxene material: taking MAX phase material to be immersed in HF aqueous solution, dry, and washing and centrifugation for several times, remove table Face residue impurity, it is dry, until reaching constant quality obtains Mxene material；
2) ferrite modifies MXene material: ultrasound, filtration washing after the MXene material that step 1) obtains being added in ferrite To neutrality；Then it roasts, it is stand-by that ferrite modification MXene material is obtained after cooling；
3) prepared by laminar gas diffusion electrode: by ferrite that step 2 obtains modification MXene material and rush lead agent, pore creating material, After binder and dehydrated alcohol mixture ultrasound, stirring to mixture is in paste under water bath with thermostatic control, and cream gel object is taken out, It is placed on axis press repeatedly axis pressure in the form of sheets, flaky substance is wrapped in continuation axis in nickel foam and is depressed into not water content, is then adopted It rolls to obtain electrode with roller bearing machine, the electrode rolled is placed in thermostatic drying chamber after drying, pushed in 10-20MPa pressure Type is made, is subsequently placed in tube furnace and roasts under inert gas conditions, is finally impregnated in boiling water, drying to obtain after taking-up The laminar gas diffusion electrode of ferrite modification MXene.
2. a kind of preparation method of ferrite modification MXene laminar gas diffusion electrode according to claim 1, feature It is, the MAX phase material of the step 1) is Ti3AlC2、Ti3SiC2、Ti2One of AlC.
3. a kind of preparation method of ferrite modification MXene laminar gas diffusion electrode according to claim 1, feature It is, the ferrite of the step 2 is the ferrite or multielement combined type ferrite of manganese, copper, nickel or cobalt.
4. a kind of preparation method of ferrite modification MXene laminar gas diffusion electrode according to claim 1, feature It is, the ferritic preparation of the step 2 can be the addition Fe (NO into ultrapure water3)3•9H2O solid and MCl2Solid, M= Mn, Cu or Co, then with magnetic stirrer so that it is uniformly mixed and is completely dissolved to obtain mixed solution, and thereto plus Enter polyethylene glycol to continue to stir to obtain the final product.
5. a kind of preparation method of ferrite modification MXene laminar gas diffusion electrode according to claim 1, feature It is, the mass ratio of the ferrite in the step 2 and MXene material is 1:3 ~ 1:9.
6. a kind of preparation method of ferrite modification MXene laminar gas diffusion electrode according to claim 1, feature It is, the quality sum of the ferrite and MXene material is the 19% ~ 45% of laminar gas diffusion electrode quality.
7. a kind of preparation method of ferrite modification MXene laminar gas diffusion electrode according to claim 1, feature It is, it is acetylene black or/and carbon black that the rush, which leads agent, and the pore creating material is sodium sulphate or/and sodium bicarbonate, the binder are Polytetrafluoroethylene (PTFE) or/and polyvinylidene fluoride or/and polyvinyl alcohol.
8. the ferrite that the described in any item preparation methods of claim 1 ~ 7 obtain modifies MXene laminar gas diffusion electrode.
9. ferrite modification MXene laminar gas diffusion electrode according to any one of claims 8 is in electrochemical cathode material or water pollution Application in processing.
10. a kind of electrochemistry/ozone coupling water treatment system, which includes the oxygen tank being sequentially connected, ozone generation Device, ozone concentration detector, reaction unit, peristaltic pump, mother liquor tank and device for absorbing tail gas include iron oxygen in the reaction unit Body modifies Mxene stratiform diffusion electrode, platinum gauze anode and insulated enclosure layer.
11. electrochemistry according to claim 10/ozone coupling water treatment system, which is characterized in that the platinum gauze sun Extremely one of graphite electrode, stainless steel electrode, Ti electrode, noble metal electrode or boron-doped diamond electrode, the ferrite Modification Mxene stratiform diffusion electrode be cathode, yin-yang the two poles of the earth be placed in parallel in up and down two sides, with insulation silica gel pad be subject to every From.
12. using ferrite modification MXene laminar gas diffusion electrode according to any one of claims 8 in electrochemistry/ozone coupling water Application in terms of processing system.
13. application according to claim 12, which is characterized in that the application specifically includes: using peristaltic pump to containing mesh Mark pollutant solution be pressurized, speedup, so that water body is entered reaction unit with Reasonable Speed；Circulation flows through ferrite modification Mxene stratiform diffusion electrode surface；Oxygen generates ozone through ozone generator, and ozone expands by ferrite modification Mxene stratiform Liquid/solid contact layer is entered after dissipating electrode base, is entered finally into solution, ozone concentration and flow pass through ozone concentration respectively Monitor and gas flowmeter are measured, and the tail gas after reaction discharges after the absorption of absorbing off-gas ozone device.
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