CN108130582A - A kind of preparation method of 2.5 dimension anodes of high catalytic activity carried magnetic particle - Google Patents

A kind of preparation method of 2.5 dimension anodes of high catalytic activity carried magnetic particle Download PDF

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Publication number
CN108130582A
CN108130582A CN201711386825.1A CN201711386825A CN108130582A CN 108130582 A CN108130582 A CN 108130582A CN 201711386825 A CN201711386825 A CN 201711386825A CN 108130582 A CN108130582 A CN 108130582A
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titanium
oxide
magnetic
antimony
preparation
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邵丹
张昕蕾
谈国强
王颖
于婉茹
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Shaanxi University of Science and Technology
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Shaanxi University of Science and Technology
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D15/00—Electrolytic or electrophoretic production of coatings containing embedded materials, e.g. particles, whiskers, wires
    • 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
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/34—Pretreatment of metallic surfaces to be electroplated
    • C25D5/38—Pretreatment of metallic surfaces to be electroplated of refractory metals or nickel
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D9/00—Electrolytic coating other than with metals
    • C25D9/04—Electrolytic coating other than with metals with inorganic materials
    • C25D9/08—Electrolytic coating other than with metals with inorganic materials by cathodic processes
    • 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

Abstract

A kind of preparation method of 2.5 dimension anodes of high catalytic activity carried magnetic particle; titanium oxide layer is first prepared on magnetic particles of ferroferric oxide using the method for impregnating thermal oxide; the tin dioxide layer of Sb doped is further coated on the particle covered again by impregnating thermal oxidation method in titanium oxide, the tin dioxide layer for making Sb doped and the titanium oxide layer being attached on magnetic-particle matrix combine closely to form solid solution.Magnetic force is used to attract magnetic-particle and forms 2.5 dimension magnetic-particle loading anodes to be attached to tubular electrode surface.Due to the flexibility of magnetic force, it is easy to operate can to recycle the present invention in situ for magnetic-particle on novel electrode.Experiment condition requirement is relatively low, and technical process is easy to control, and prepared composite anode has high electrocatalytic active, and oxygen evolution potential is high, and service life is long, is suitably applied the extensive electrolysis wastewater of industrialization.

Description

A kind of preparation method of 2.5 dimension anodes of high catalytic activity carried magnetic particle
Technical field
The invention belongs to electrochemical catalysis electrode fabrication fields, and in particular to a kind of high catalytic activity carried magnetic The preparation method of 2.5 dimension anodes of grain.
Background technology
Water be the mankind depend on for existence with the limitation of the valuable natural resources and social sustainable development of social development because Element.China's gross amount of water resources enriches, but relative quantity is less, and distribution of water resources unevenness is extremely serious, many areas in China, particularly The water resource in city and industry prosperity area is very short.And in recent years, with the rapid industrial development in our country, wastewater discharge Also increase year by year therewith, and water pollution increasingly tends to diversification.The pollution sources of organic wastewater are increasing, contained therein The existence and health of high concentration and organic principle serious threat difficult to degrade to the mankind.For example, paper industry is to caused by environment Pollution problem it is urgently to be resolved hurrily.Although traditional method for treating water can purify water, the concentration of useless Organic substance in water is reduced, it is right It is beyond one's ability in the processing of high concentrated organic wastewater.Under relatively, organic wastewater is handled with the method for electrochemical catalytic degradation More conducively control and pollute it is few even pollution-free, there are obvious advantage in terms of the flexibility of economy and processing, therefore electrochemical The method for learning processing waste water is increasingly paid close attention to.
Electrochemical oxidation, also known as electroxidation and electrochemical catalytic oxidation are the one of which of high-level oxidation technology.Compared to Traditional multiple water treatment technology, electrochemical oxidation process processing industrial wastewater have its unique advantage, such as multi-functional (anti- It is electronics to answer object), low device dependence (only needs power supply and electrolytic cell optionally), and (plug and play can be located in situ for flexibility Reason), environment friendly (clean electronics) and potential economic validity (depend on suitable anode material and electrolytic cell are set Meter).In recent years, the research and development both at home and abroad about electrochemicial oxidation organic pollutants is rapid, report layer goes out not Thoroughly.
The key of electrochemical oxidation technology is exactly electrode material, and the performance of anode material is more for cathode material It is important.This is because anode surface and its neighbouring solution region are the main regions of electrochemical oxidation reactions first.Compared to other Factor, the activity of anode material, influence of the catalysis oxidation selectivity to handling result are the most significant.Secondly Anodic Region can generate oxidizing species, and its neighbouring solution is in highly acid, and anode is caused to be in a strong corrosive region, and Cathode material peripheral region environment is not very severe relatively.It therefore will to the stability of anode material and service life in actual process Seek cathode material to be far longer than.
So the selection for anode material is very crucial.Stannic oxide (SnO2) it is a kind of semiconductor material with wide forbidden band, Its energy gap is about 3.6eV.Pure SnO2Conductivity at normal temperatures is very low, and electrochemical properties and chemical property are stablized, not It is suitable as anode material.And element antimony (Sb) is used to SnO2Carry out the Sb-SnO obtained after suitably adulterating2Material causes it Conductivity greatly improves.Sb doping improves SnO2The mechanism of conductivity has numerous studies into line justification, is attributable to 5 valency Sb originals Son is instead of SnO24 valency Sn atoms in lattice, an electronics having more enter conduction band, make conduction band electron concentration improve caused by. General Sb dopings have a optimum range, and excessively high Sb doping can destroy SnO instead2Lattice structure so that conductivity is counter to drop It does not rise.
Brown lead oxide has good electric conductivity, higher oxygen evolution potential and the stronger catalysis oxidation energy of metalloid Power, while acid-alkali-corrosive-resisting, stability are good, cost price is cheap, are widely used in the research of electrochemical treatment of wastewater and answer In.
At present, traditional stibium doping stannic oxide electrode has preferable electro catalytic activity, but it causes due to being heat-treated Face crack is more, and electrolyte easily penetrates into during use, is passivated Titanium base and causes electrode inactivation that can not be continuing with, surely It is qualitative poor.And traditional lead dioxide electrode, though having a longer life expectancy, its catalytic activity is relatively low, and brown lead oxide coating It is poor with Titanium base binding force, cause coating easy to fall off, reduce electrode stability energy.
Invention content
2.5 the purpose of the present invention is to provide a kind of high catalytic activity carried magnetic particle tie up the preparation method of anodes, The preparation method experiment condition requirement it is relatively low, obtained stannic oxide composite lead dioxide anode material have oxygen evolution potential, High electrocatalytic active, long-life.
To achieve the above object, the technical solution adopted by the present invention is：
A kind of preparation method of 2.5 dimension anodes of high catalytic activity carried magnetic particle, includes the following steps：
1) preparation of magnetic-particle middle layer：
Magnetic particles of ferroferric oxide is added in precursor liquid, after precursor liquid evaporation is heated under stirring, passes through hot oxygen Change method forms titanium oxide layer on magnetic particles of ferroferric oxide surface；
2) preparation of magnetic-particle coating：
The magnetic particles of ferroferric oxide of surface attachment titanium oxide layer in the precursor liquid containing tin and antimony is impregnated, is heated After stirring is evaporated to precursor liquid, antimony is prepared on the magnetic particles of ferroferric oxide of loading titanium oxide layer by thermal oxidation method and is mixed Miscellaneous stannic oxide active coating, and repeat the step 4~6 time；
3) preparation of Titanium base middle layer：
Pretreated Titanium base is immersed in faint yellow precursor liquid, drying is taken out after the uniform fold precursor liquid of surface, and Titanium oxide layer is formed on Titanium base surface by thermal oxidation method, the titanium oxide that electrochemical reduction method is recycled to cover Titanium base surface Layer is restored, and forms hydrogenation titanium；
4) preparation of Titanium base stibium doping stannic oxide coating：
Titanium base with hydrogenation titanium is connected as cathode with power cathode, at room temperature, with graphite electricity Extremely anode is connected with positive pole, and Sb doped titanium is made using electro-deposition-thermal oxidation method in stanniferous and antimony electroplate liquid Base stannic oxide electrode；
5) preparation of Titanium base brown lead oxide coating：
It is connected using Sb doped titanium-based stannic oxide electrode as anode with positive pole, using copper plate electrode as anode and electricity Source cathode is connected, and Sb doped titanium-based stannic oxide dioxide composite is made using electrodeposition process in the electroplate liquid containing plumbi nitras Lead electrode；
6) assembling of electrode
The surface for preparing step 2) using physisorphtion covers four oxidations three of stibium doping stannic oxide active coating Ferromagnetic particle is attached to the outer surface of Sb doped titanium-based stannic oxide dioxide composite lead electrode, forms 2.5 dimension magnetic-particles Loading anode.
Of the invention further improve be, step 1) and 3) in, precursor liquid is made by procedure below：By volume hundred Score meter adds in the ethyl alcohol and 1~5% volume of 35~55% volume fractions into the butyl titanate of 40~64% volume fractions The nitric acid of score, stirring 10-20min is uniform to solution, obtains precursor liquid.
Further improve of the invention is that thermal oxidation method detailed process is in step 1)：It is calcined at 250~350 DEG C 1.5h。
Further improve of the invention is that precursor liquid and magnetic particles of ferroferric oxide volume ratio are 1 in step 1):(1 ~2).
Further improve of the invention is that the precursor liquid containing tin and antimony in step 2) is made by procedure below：It will Butter of tin, antimony trichloride are added in nitric acid, obtain precursor liquid, in the precursor liquid, butter of tin a concentration of 1.0mol/L, and three Antimony chloride a concentration of 0.1mol/L, concentration of nitric acid 0.1mol/L；The ferroso-ferric oxide of surface attachment titanium oxide layer in step 2) Magnetic-particle and the precursor liquid containing tin and antimony and volume ratio be 1:2.
Further improve of the invention is that the actual conditions of thermal oxidation method are in step 2)：With the liter of 5~10 DEG C/min Warm rate is from room temperature to 400~700 DEG C and calcines 2~6h, is then down to room temperature with the rate of temperature fall of 1~3 DEG C/min.
Further improve of the invention is that in step 3), the detailed process of the pretreatment of Titanium base is as follows：It will with sand paper Titanium base surface is polished smooth to remove its surface oxide layer, in the alkaline solution containing sodium hydroxide heat 5~10min with Remove Titanium base surface and oil contaminant impurity, and will treated that Titanium base impregnates in oxalic acid solution boils 1~2h, etching matrix table Fresh titanium is exposed in face, is cleaned and dried with deionized water.
Further improve of the invention is that thermal oxidation method detailed process is in step 3)：It is calcined at 250~350 DEG C 1.5h；
The detailed process of electrochemical reduction method is in step 3)：The Titanium base of surface covering titanium oxide layer is being contained into sodium sulphate In electrolyte, 10~20mA/cm of constant current density2Lower energization carries out 10~30min of reduction, forms hydrogenation titanium.
Further improve of the invention is that in step 4), stanniferous and antimony electroplate liquid is made by procedure below：By four Stannic chloride, antimony trichloride, ethylene glycol and normal propyl alcohol are uniformly mixed, and are then adjusted pH value and are less than 5, obtain stanniferous and antimony plating Liquid, wherein, tin, antimony molar ratio are 10:1, the volume ratio of ethylene glycol and normal propyl alcohol is (1~2):1, butter of tin and ethylene glycol Than for 2.0mol：1L；
In step 4), the detailed process for preparing stibium doping stannic oxide coating is：In stanniferous and antimony electroplate liquid, in perseverance 5~15mA/cm of current density2Under be electroplated in matrix surface and be co-deposited tin and antimony, electrodeposition time is 20~60min；Then certainly Room temperature is down to room after being warming up to 400~700 DEG C and 2~6h of calcining with 5~10 DEG C/min heating rates with 1~3 DEG C/min rates Temperature.
Further improve of the invention is, in step 5), prepares Sb doped titanium-based stannic oxide composite lead dioxide electricity The detailed process of pole is：It is 5 in molar ratio:1, plumbi nitras and copper nitrate are added to the water, then add in sodium fluoride, stirring is equal It is even, obtain the electroplate liquid containing plumbi nitras；Wherein, the concentration of sodium fluoride is 0.01~0.05mol/L, a concentration of the 0.5 of plumbi nitras ~1.5mol/L, a concentration of 0.1~0.5mol/L of copper nitrate；In the electroplate liquid containing plumbi nitras, at 50~70 DEG C, with copper Piece is as cathode, in 5~15mA/cm of constant current density2Under be electroplated on the Titanium base for having loaded stibium doping stannic oxide coating 1~2h of brown lead oxide is deposited, Sb doped titanium-based stannic oxide dioxide composite lead electrode is made.
Relative to the prior art, the invention has the advantages that：
The present invention first prepares titanium oxide layer, then lead to using the method for dipping-thermal oxide on magnetic particles of ferroferric oxide The tin dioxide layer that Sb doped is further coated on the particle that dipping-thermal oxidation method is covered in titanium oxide is crossed, makes the two of Sb doped Stannic oxide layer combines closely to form solid solution with the titanium oxide layer being attached on magnetic-particle matrix.With a permanent magnet (NdFeB) it is core, the antimony for containing hydrogenated titanium prepared using dipping-thermal decomposition and electrodeposition process is mixed in outer cover Miscellaneous stannic oxide composite lead dioxide cylindrical electrode set uses magnetic force that magnetic-particle is attracted to be attached to tubular electrode surface shape Into 2.5 dimension magnetic-particle loading anodes.This method is simple for process, and experiment condition requirement is relatively low, and prepared composite anode is passing It unites supported active magnetic-particle on the basis of 2 dimensional plane electrodes, increases the true catalysis area of electrode, make the work of electrode surface Property site increase, it is high so as to improve the electro catalytic activity of electrode and oxygen evolution potential, using brown lead oxide as main electrode outer coating It can effectively extend that electrode life is long, 2.5 maintain the organic matter removal efficiency of system and energy consumption all than traditional electrode ideal. Simultaneously because the flexibility of magnetic force, magnetic-particle can recycle in situ on novel electrode.Electrode life is obviously prolonged, and is suitably applied Industrialize extensive electrolysis wastewater.This novel environmental close friend electrode has broad application prospects in Green Chemistry industry. 2.5 dimension anodes of the high catalytic activity carried magnetic particle of the present invention are suitably applied answering for the extensive electrolysis wastewater of industrialization With.
Description of the drawings
Fig. 1 is the structure chart that the embodiment of the present invention 1 prepares electrode；
Fig. 2 is the SEM of scroll-like titanium-based stibium doping stannic oxide dioxide composite lead electrode prepared by the embodiment of the present invention 1 Figure；
Fig. 3 is the SEM figures of stibium doping stannic oxide coated ferroferric oxide magnetic particle prepared by the embodiment of the present invention 2；
Fig. 4 is the XRD of scroll-like titanium-based stibium doping stannic oxide dioxide composite lead electrode prepared by the embodiment of the present invention 3 Figure；
Fig. 5 is that scroll-like titanium-based stibium doping stannic oxide dioxide composite lead electrode prepared by the embodiment of the present invention 4 is magnetic Load the cyclic voltammetry curve of stibium doping stannic oxide coated ferroferric oxide magnetic particle；
Fig. 6 is that scroll-like titanium-based stibium doping stannic oxide dioxide composite lead electrode prepared by the embodiment of the present invention 4 is magnetic Load the quantity of electric charge curve of stibium doping stannic oxide coated ferroferric oxide magnetic particle；
Fig. 7 is that scroll-like titanium-based stibium doping stannic oxide dioxide composite lead electrode prepared by the embodiment of the present invention 5 is magnetic Load the COD removal rates of stibium doping stannic oxide coated ferroferric oxide magnetic particle.
Specific embodiment
With reference to embodiment and attached drawing, the invention will be further described.
It is heretofore described 2.5 dimension refer to it is that a kind of plane is combined with particle, between 2 tie up (plane electrode system) and 3 2.5 dimension structures between (mosaic electrode system) structure are tieed up, enhance the recuperability of mosaic electrode with this.
Embodiment 1
1) by volume percent, by the butyl titanate of 64% volume fraction, the ethyl alcohol of 35% volume fraction and 1% body The nitric acid mixing of fraction, stirs 10min, faint yellow precursor liquid is obtained, by ferriferrous oxide particles in faint yellow precursor liquid Dipping, ferriferrous oxide particles are 1 with precursor liquid volume ratio:1, precursor liquid evaporation is heated under stirring, the time of stirring is 60min is then placed in Muffle furnace and calcines 1.5h at 300 DEG C, and silver gray titanium oxide layer is made on ferriferrous oxide particles surface；
2) butter of tin, antimony trichloride are added in nitric acid, obtain precursor liquid, in the precursor liquid, butter of tin concentration For 1.0mol/L, antimony trichloride a concentration of 0.1mol/L, concentration of nitric acid 0.1mol/L.Silver gray titanium oxide layer is adhered on surface Ferriferrous oxide particles be impregnated into precursor liquid, surface adhere to silver gray titanium oxide layer ferriferrous oxide particles and precursor liquid Volume ratio be 1:2, it is put into after drying in Muffle furnace and calcines 4h at 500 DEG C, Sb doped is made on ferriferrous oxide particles surface Tin dioxide layer repeats this step 6 time；
3) using the titanium sheet of 3mm thickness as matrix, titanium sheet is cut into 7cm × 8.7cm sizes with scissors；Successively 200 purposes The fine sandpaper of coarse sandpaper and 40 mesh polishes smooth titanium plate surface, removes surface oxide layer, exposes metallic luster, and rolled up and be It is cylindric.Cylindric Titanium base is put into heating in the sodium hydroxide solution of mass fraction 10% and boils 10min removal surface oils It is dirty；It is subsequently placed in heating in the oxalic acid of mass fraction 10% and boils 1.5h progress acid etches surface, rinsed well with deionized water It is for use afterwards；
4) by volume percent, by the butyl titanate of 64% volume fraction, the ethyl alcohol of 35% volume fraction and 1% body The nitric acid mixing of fraction, stirs 10min, obtains faint yellow precursor liquid, the cylindric Titanium base of clean dried is immersed yellowish In color precursor liquid, make cylindric Titanium base surface uniform fold precursor liquid, 300 DEG C of calcinings of Muffle furnace are put into after drying at room temperature 1.5h is cooled to room temperature rear Titanium base surface and forms titanium oxide layer；
5) surface is covered by titanium oxide for electrolyte with the electrolyte (i.e. the aqueous solution of 0.05mol/L) containing sodium sulphate The cylindric Titanium base of layer constant current density 10mA/cm in the electrolyte containing sodium sulphate2It is lower energization carry out reduction 10~ 15min forms hydrogenation titanium；
6) butter of tin, antimony trichloride, ethylene glycol and normal propyl alcohol are uniformly mixed, then adjust pH value and be less than 5, contained The electroplate liquid of tin and antimony, wherein, tin, antimony molar ratio are 10:1, the volume ratio of ethylene glycol and normal propyl alcohol is 1:1, butter of tin with The ratio of ethylene glycol is 2.0mol：1L.
Using electro-deposition-thermal oxidation method in stanniferous and antimony electroplate liquid, the Titanium base conduct with hydrogenation titanium Cathode, using graphite as anode, in constant current density 15mA/cm2Under on the Titanium base of as-reduced containing hydrogenated titanium Plating is co-deposited tin and antimony metal 15~20min of simple substance, then with the heating rate of 5 DEG C/min from room temperature to 500 DEG C simultaneously Room temperature is down to, and the step is repeated 6 times with the rate of temperature fall of 3 DEG C/min after calcining 4h, obtains Sb doped titanium-based stannic oxide Electrode；
7) it is 5 in molar ratio:1, plumbi nitras and copper nitrate are added to the water, then add in sodium fluoride, is stirred evenly, is obtained To the electroplate liquid containing plumbi nitras.Wherein, the concentration of sodium fluoride is 0.01mol/L, a concentration of 0.5mol/L of plumbi nitras.Utilize electricity Sedimentation is in the electroplate liquid containing plumbi nitras, using Sb doped titanium-based stannic oxide electrode as anode, using copper sheet as cathode, 50~70 DEG C, constant current density 15mA/cm2Under on Sb doped titanium-based stannic oxide electrode electroplating deposition 1~2h of brown lead oxide, Obtain Sb doped titanium-based stannic oxide dioxide composite lead electrode；
8) with a permanent magnet (NdFeB) for core, the Sb doped titanium-based stannic oxide compound two in permanent magnet outer cover Lead dioxide electrode, the surface for preparing step 2) using physisorphtion cover four oxidations of stibium doping stannic oxide active coating Three ferromagnetic particles are attached to the outer surface of Sb doped titanium-based stannic oxide dioxide composite lead electrode, form magnetic of 2.5 dimensions Particle loading anode.
Embodiment 2
1) by volume percent, by the butyl titanate of 40% volume fraction, the ethyl alcohol of 55% volume fraction and 5% body The nitric acid mixing of fraction, stirs 20min, obtains faint yellow precursor liquid, ferriferrous oxide particles are impregnated in precursor liquid, four Fe 3 O particle is 2 with precursor liquid volume ratio:1, precursor liquid evaporation is heated under stirring, the time of stirring is 70min, then It is put into Muffle furnace and calcines 1.5h at 250 DEG C, silver gray titanium oxide layer is made on ferriferrous oxide particles surface；
2) butter of tin, antimony trichloride are added in nitric acid, obtain precursor liquid, in the precursor liquid, butter of tin concentration For 1.0mol/L, antimony trichloride a concentration of 0.1mol/L, concentration of nitric acid 0.1mol/L.Silver gray titanium oxide layer is adhered on surface Ferriferrous oxide particles be impregnated into precursor liquid again, surface attachment silver gray titanium oxide layer ferriferrous oxide particles with before The volume ratio for driving liquid is 1:2, it is put into after drying in Muffle furnace and calcines 4h at 500 DEG C, antimony is made on ferriferrous oxide particles surface Doping stannic oxide layer repeats this step 6 time；
3) using the titanium sheet of 3mm thickness as matrix, titanium sheet is cut into 7cm × 8.7cm sizes with scissors；Successively 200 purposes The fine sandpaper of coarse sandpaper and 40 mesh polishes smooth titanium plate surface, removes surface oxide layer, exposes metallic luster, and rolled up and be It is cylindric.Cylindric Titanium base is put into heating in the sodium hydroxide solution of mass fraction 10% and boils 10min removal surface oils It is dirty；It is subsequently placed in heating in the oxalic acid of mass fraction 10% and boils 1.5h progress acid etches surface, rinsed well with deionized water It is for use afterwards；
4) by volume percent, by the butyl titanate of 40% volume fraction, the ethyl alcohol of 55% volume fraction and 5% body The nitric acid mixing of fraction, stirs 20min, obtains faint yellow precursor liquid, the cylindric Titanium base of clean dried is immersed yellowish In color precursor liquid, make cylindric Titanium base surface uniform fold precursor liquid, 300 DEG C of calcinings of Muffle furnace are put into after drying at room temperature 1.5h is cooled to room temperature rear Titanium base surface and forms titanium oxide layer；
5) surface is covered by titanium oxide for electrolyte with the electrolyte (i.e. the aqueous solution of 0.10mol/L) containing sodium sulphate The cylindric Titanium base of layer constant current density 10mA/cm in the electrolyte containing sodium sulphate2It is lower energization carry out reduction 10~ 15min forms hydrogenation titanium；
6) butter of tin, antimony trichloride, ethylene glycol and normal propyl alcohol are uniformly mixed, then adjust pH value and be less than 5, contained The electroplate liquid of tin and antimony, wherein, tin, antimony molar ratio are 10:1, the volume ratio of ethylene glycol and normal propyl alcohol is 1:1, butter of tin with The ratio of ethylene glycol is 2.0mol：1L.
Using electro-deposition-thermal oxidation method in stanniferous and antimony electroplate liquid, the Titanium base conduct with hydrogenation titanium Cathode, using graphite as anode, in constant current density 15mA/cm2Under on the Titanium base of as-reduced containing hydrogenated titanium Plating is co-deposited tin and antimony metal 15~20min of simple substance, then with the heating rate of 6 DEG C/min from room temperature to 400 DEG C simultaneously Room temperature is down to, and the step is repeated 6 times with the rate of temperature fall of 2 DEG C/min after calcining 6h, obtains Sb doped titanium-based stannic oxide Electrode；
7) it is 6 in molar ratio:1, plumbi nitras and copper nitrate are added to the water, then add in sodium fluoride, is stirred evenly, is obtained To the electroplate liquid containing plumbi nitras.Wherein, the concentration of sodium fluoride is 0.01mol/L, a concentration of 0.5mol/L of plumbi nitras.Utilize electricity Sedimentation is in the electroplate liquid containing plumbi nitras, using Sb doped titanium-based stannic oxide electrode as anode, using copper sheet as cathode, 50~70 DEG C, constant current density 15mA/cm2Under on Sb doped titanium-based stannic oxide electrode electroplating deposition 1~2h of brown lead oxide, Obtain Sb doped titanium-based stannic oxide dioxide composite lead electrode；
8) with a permanent magnet (NdFeB) for core, the Sb doped titanium-based stannic oxide compound two in permanent magnet outer cover Lead dioxide electrode, the surface for preparing step 2) using physisorphtion cover four oxidations of stibium doping stannic oxide active coating Three ferromagnetic particles are attached to the outer surface of Sb doped titanium-based stannic oxide dioxide composite lead electrode, form magnetic of 2.5 dimensions Particle loading anode.
Embodiment 3
1) by volume percent, by the butyl titanate of 50% volume fraction, the ethyl alcohol of 37% volume fraction and 3% body The nitric acid mixing of fraction, stirs 10min, faint yellow precursor liquid is obtained, by ferriferrous oxide particles in faint yellow precursor liquid Dipping, ferriferrous oxide particles are 1 with precursor liquid volume ratio:1, after precursor liquid evaporation is heated under stirring, the time of stirring is 80min is then placed in 350 DEG C of calcining 1.5h in Muffle furnace, silver gray titanium oxide layer is made on ferriferrous oxide particles surface；
2) butter of tin, antimony trichloride are added in nitric acid, obtain precursor liquid, in the precursor liquid, butter of tin concentration For 1.0mol/L, antimony trichloride a concentration of 0.1mol/L, concentration of nitric acid 0.1mol/L.Silver gray titanium oxide layer is adhered on surface Ferriferrous oxide particles be impregnated into precursor liquid again, surface attachment silver gray titanium oxide layer ferriferrous oxide particles with before The volume ratio for driving liquid is 1:2, it is put into after drying in Muffle furnace and calcines 4h at 500 DEG C, antimony is made on ferriferrous oxide particles surface Doping stannic oxide layer repeats this step 6 time；
3) using the titanium sheet of 3mm thickness as matrix, titanium sheet is cut into 7cm × 8.7cm sizes with scissors；Successively 200 purposes The fine sandpaper of coarse sandpaper and 40 mesh polishes smooth titanium plate surface, removes surface oxide layer, exposes metallic luster, and rolled up and be It is cylindric.Cylindric Titanium base is put into heating in the sodium hydroxide solution of mass fraction 10% and boils 10min removal surface oils It is dirty；It is subsequently placed in heating in the oxalic acid of mass fraction 10% and boils 1.5h progress acid etches surface, rinsed well with deionized water It is for use afterwards；
4) by volume percent, by the butyl titanate of 50% volume fraction, the ethyl alcohol of 37% volume fraction and 3% body The nitric acid mixing of fraction, stirs 10min, obtains faint yellow precursor liquid, obtain faint yellow precursor liquid；By the cylinder of clean dried Shape Titanium base is immersed in faint yellow precursor liquid, makes cylindric Titanium base surface uniform fold precursor liquid, horse is put into after drying at room temperature Not 300 DEG C of calcining 1.5h of stove, are cooled to room temperature rear Titanium base surface and form titanium oxide layer；
5) surface is covered by titanium oxide for electrolyte with the electrolyte (i.e. the aqueous solution of 0.07mol/L) containing sodium sulphate The cylindric Titanium base of layer constant current density 10mA/cm in the electrolyte containing sodium sulphate2It is lower energization carry out reduction 10~ 15min forms hydrogenation titanium；
6) butter of tin, antimony trichloride, ethylene glycol and normal propyl alcohol are uniformly mixed, then adjust pH value and be less than 5, contained The electroplate liquid of tin and antimony, wherein, tin, antimony molar ratio are 10:1, the volume ratio of ethylene glycol and normal propyl alcohol is 1:1, butter of tin with The ratio of ethylene glycol is 2.0mol：1L.
Using electro-deposition-thermal oxidation method in stanniferous and antimony electroplate liquid, the Titanium base conduct with hydrogenation titanium Cathode, using graphite as anode, in constant current density 20mA/cm2Under on the Titanium base of as-reduced containing hydrogenated titanium Plating is co-deposited tin, antimony metal 15~20min of simple substance, is then warming up to 700 DEG C with 7 DEG C/min heating rates from room temperature and calcines Room temperature is down to 1 DEG C/min rates after 2h.And be repeated 6 times the step, obtain Sb doped titanium-based stannic oxide electrode；
7) it is 5 in molar ratio:1, plumbi nitras and copper nitrate are added to the water, then add in sodium fluoride, is stirred evenly, is obtained To the electroplate liquid containing plumbi nitras.Wherein, the concentration of sodium fluoride is 0.01mol/L, a concentration of 0.5mol/L of plumbi nitras.Utilize electricity Sedimentation is in the electroplate liquid containing plumbi nitras, using Sb doped titanium-based stannic oxide electrode as anode, using copper sheet as cathode, Constant current density 15mA/cm2Under on Sb doped titanium-based stannic oxide electrode electroplating deposition 1~2h of brown lead oxide, obtain antimony and mix Miscellaneous titanium-based stannic oxide dioxide composite lead electrode；
8) with a permanent magnet (NdFeB) for core, the Sb doped titanium-based stannic oxide compound two in permanent magnet outer cover Lead dioxide electrode, the surface for preparing step 2) using physisorphtion cover four oxidations of stibium doping stannic oxide active coating Three ferromagnetic particles are attached to the outer surface of Sb doped titanium-based stannic oxide dioxide composite lead electrode, form magnetic of 2.5 dimensions Particle loading anode.
Embodiment 4
1) by volume percent, by the butyl titanate of 60% volume fraction, the ethyl alcohol of 37% volume fraction and 3% body The nitric acid mixing of fraction, stirs 15min, faint yellow precursor liquid is obtained, by ferriferrous oxide particles in faint yellow precursor liquid Dipping, ferriferrous oxide particles are 1 with precursor liquid volume ratio:1, after precursor liquid evaporation is heated under stirring, the time of stirring is 60min is then placed in 300 DEG C of calcining 1.5h in Muffle furnace, silver gray titanium oxide layer is made on ferriferrous oxide particles surface；
2) butter of tin, antimony trichloride are added in nitric acid, obtain precursor liquid, in the precursor liquid, butter of tin concentration For 1.0mol/L, antimony trichloride a concentration of 0.1mol/L, concentration of nitric acid 0.1mol/L.Silver gray titanium oxide layer is adhered on surface Ferriferrous oxide particles be impregnated into precursor liquid again, surface attachment silver gray titanium oxide layer ferriferrous oxide particles with before The volume ratio for driving liquid is 1:2, it is put into after drying in Muffle furnace and calcines 4h at 500 DEG C, antimony is made on ferriferrous oxide particles surface Doping stannic oxide layer repeats this step 4 time；
3) using titanium sheet as matrix, titanium sheet is cut into 4cm × 1cm sizes with scissors；Successively with the coarse sandpaper of 200 mesh and 40 Purpose fine sandpaper polishes smooth titanium plate surface, removes surface oxide layer, exposes metallic luster, and flaky matrix is put into quality point 10min removal surface and oil contaminants are boiled in heating in the sodium hydroxide solution of number 10%；It is subsequently placed in the oxalic acid of mass fraction 10% Heating boils 1.5h and carries out acid etch surface, for use after being rinsed well with deionized water；
4) by volume percent, by the butyl titanate of 60% volume fraction, the ethyl alcohol of 37% volume fraction and 3% body The nitric acid mixing of fraction, stirs 15min, obtains faint yellow precursor liquid, the cylindric Titanium base of clean dried is immersed yellowish In color precursor liquid, make cylindric Titanium base surface uniform fold precursor liquid, 300 DEG C of calcinings of Muffle furnace are put into after drying at room temperature 1.5h is cooled to room temperature rear Titanium base surface and forms titanium oxide layer；
5) surface is covered by titanium oxide for electrolyte with the electrolyte (i.e. the aqueous solution of 0.05mol/L) containing sodium sulphate The cylindric Titanium base of layer constant current density 10mA/cm in the electrolyte containing sodium sulphate2It is lower energization carry out reduction 10~ 15min forms hydrogenation titanium；
6) butter of tin, antimony trichloride, ethylene glycol and normal propyl alcohol are uniformly mixed, then adjust pH value and be less than 5, contained The electroplate liquid of tin and antimony, wherein, tin, antimony molar ratio are 10:1, the volume ratio of ethylene glycol and normal propyl alcohol is 1:1, butter of tin with The ratio of ethylene glycol is 2.0mol：1L.
Using electro-deposition-thermal oxidation method in stanniferous and antimony electroplate liquid, the Titanium base conduct with hydrogenation titanium Cathode, using graphite as anode, in constant current density 15mA/cm2Under on the Titanium base of as-reduced containing hydrogenated titanium Plating is co-deposited tin, antimony metal 15~20min of simple substance, then to 600 DEG C and is forged from room temperature with the heating rate of 8 DEG C/min Room temperature is down to, and the step is repeated 6 times with the rate of temperature fall of 3 DEG C/min after burning 3h, obtains Sb doped titanium-based stannic oxide electricity Pole；
7) it is 5 in molar ratio:1, plumbi nitras and copper nitrate are added to the water, then add in sodium fluoride, is stirred evenly, is obtained To the electroplate liquid containing plumbi nitras.Wherein, the concentration of sodium fluoride is 0.01mol/L, a concentration of 0.5mol/L of plumbi nitras.Utilize electricity Sedimentation is in the electroplate liquid containing plumbi nitras, using Sb doped titanium-based stannic oxide electrode as anode, using copper sheet as cathode, Constant current density 15mA/cm2Under on Sb doped titanium-based stannic oxide electrode electroplating deposition 1~2h of brown lead oxide, obtain antimony and mix Miscellaneous titanium-based stannic oxide dioxide composite lead electrode；
8) permanent magnet (NdFeB) is fixed on to the titanium sheet one side for having loaded coating, is made by using physisorphtion made The magnetic particles of ferroferric oxide of standby surface covering stibium doping stannic oxide is attached to Sb doped titanium-based stannic oxide compound two One surface of lead dioxide electrode piece forms 2.5 dimension magnetic-particle loading anodes.
Embodiment 5
1) by volume percent, by the butyl titanate of 45% volume fraction, the ethyl alcohol of 50% volume fraction and 5% body The nitric acid mixing of fraction, stirs 15min, faint yellow precursor liquid is obtained, by ferriferrous oxide particles in faint yellow precursor liquid Dipping, ferriferrous oxide particles are 1 with precursor liquid volume ratio:1, after precursor liquid evaporation is heated under stirring, the time of stirring is 80min is then placed in 300 DEG C of calcining 1.5h in Muffle furnace, silver gray titanium oxide layer is made on ferriferrous oxide particles surface；
2) butter of tin, antimony trichloride are added in nitric acid, obtain precursor liquid, in the precursor liquid, butter of tin concentration For 1.0mol/L, antimony trichloride a concentration of 0.1mol/L, concentration of nitric acid 0.1mol/L.Silver gray titanium oxide layer is adhered on surface Ferriferrous oxide particles be impregnated into precursor liquid again, surface attachment silver gray titanium oxide layer ferriferrous oxide particles with before The volume ratio for driving liquid is 1:2, it is put into after drying in Muffle furnace and calcines 4h at 500 DEG C, antimony is made on ferriferrous oxide particles surface Doping stannic oxide layer repeats this step 5 time；
3) using the titanium sheet of 3mm thickness as matrix, titanium sheet is cut into 7cm × 8.7cm sizes with scissors；Successively 200 purposes The fine sandpaper of coarse sandpaper and 40 mesh polishes smooth titanium plate surface, removes surface oxide layer, exposes metallic luster, and rolled up and be It is cylindric.Cylindrical base member is put into heating in the sodium hydroxide solution of mass fraction 10% and boils 10min removal surface and oil contaminants；So It is placed on heating in the oxalic acid of mass fraction 10% and boils 1.5h progress acid etches surface, treated after being rinsed well with deionized water With；
4) by volume percent, by the butyl titanate of 45% volume fraction, the ethyl alcohol of 50% volume fraction and 5% body The nitric acid mixing of fraction, stirs 15min, obtains faint yellow precursor liquid, the cylindric Titanium base of clean dried is immersed yellowish In color precursor liquid, make cylindric Titanium base surface uniform fold precursor liquid, 300 DEG C of calcinings of Muffle furnace are put into after drying at room temperature 1.5h is cooled to room temperature rear Titanium base surface and forms titanium oxide layer；
5) surface is covered by titanium oxide for electrolyte with the electrolyte (i.e. the aqueous solution of 0.10mol/L) containing sodium sulphate The cylindric Titanium base of layer constant current density 10mA/cm in the electrolyte containing sodium sulphate2It is lower energization carry out reduction 10~ 15min forms hydrogenation titanium；
6) butter of tin, antimony trichloride, ethylene glycol and normal propyl alcohol are uniformly mixed, then adjust pH value and be less than 5, contained The electroplate liquid of tin and antimony, wherein, tin, antimony molar ratio are 10:1, the volume ratio of ethylene glycol and normal propyl alcohol is 1:1, butter of tin with The ratio of ethylene glycol is 2.0mol：1L.
Using electro-deposition-thermal oxidation method in stanniferous and antimony electroplate liquid, using graphite as anode, in constant current density 15mA/cm2Under on the Titanium base of as-reduced containing hydrogenated titanium plating be co-deposited tin, antimony metal 15~20min of simple substance, Then room is down to the rate of temperature fall of 2 DEG C/min from room temperature to 650 DEG C and after calcining 4h with the heating rate of 10 DEG C/min Temperature, and the step is repeated 6 times, obtain Sb doped titanium-based stannic oxide electrode；
7) it is 5 in molar ratio:1, plumbi nitras and copper nitrate are added to the water, then add in sodium fluoride, is stirred evenly, is obtained To the electroplate liquid containing plumbi nitras.Wherein, the concentration of sodium fluoride is 0.01mol/L, a concentration of 0.5mol/L of plumbi nitras.Utilize electricity Sedimentation is in the electroplate liquid containing plumbi nitras, using Sb doped titanium-based stannic oxide electrode as anode, using copper sheet as cathode, 50~70 DEG C, constant current density 15mA/cm2Under on Sb doped titanium-based stannic oxide electrode electroplating deposition 1~2h of brown lead oxide, Obtain Sb doped titanium-based stannic oxide dioxide composite lead electrode；
8) with a permanent magnet (NdFeB) for core, the Sb doped titanium-based stannic oxide compound two in permanent magnet outer cover Lead dioxide electrode, the surface for preparing step 2) using physisorphtion cover four oxidations of stibium doping stannic oxide active coating Three ferromagnetic particles are attached to the outer surface of Sb doped titanium-based stannic oxide dioxide composite lead electrode, form magnetic of 2.5 dimensions Particle loading anode.
Fig. 1 ties up magnetic-particle loading anode structure diagram by the high catalytic activity 2.5 that embodiment 1 constructs, wherein Scroll-like titanium-based stibium doping stannic oxide dioxide composite lead electrode (Ti/TiH containing hydrogenation titaniumx/Sb-SnO2/ PbO2Tubular motor) permanent magnet (NdFeB) 1 is inserted at 2 centers, and is passed through magnetic absorption stibium doping stannic oxide and coated four oxygen Change three ferromagnetic particle (Fe3O4/TiOx/Sb-SnO2Magnetic-particle) 3 in Titanium base electrode surface, it is a kind of between 2 dimensions to be formed 2.5 dimension structures of (sheet plate electrode) and 3 dimensions (particulate electrode).
Fig. 2 is the SEM of scroll-like titanium-based stibium doping stannic oxide dioxide composite lead electrode prepared by the embodiment of the present invention 1 Figure, it can be seen that the typical tetragonal pyramid bodily form is presented in electrode surface after load coating, and surface is uniform, fine and close, is conducive to electricity Pole life-time dilatation.
Fig. 3 is the SEM figures of stibium doping stannic oxide coated ferroferric oxide magnetic particle prepared by the embodiment of the present invention 2, It can be seen that the Size Distribution of particle is wider (about from 10 μm to 50 μm).Particle it is in irregular shape, Surface Microtexture is coarse, Ferriferrous oxide particles wrap up more even compact by stibium doping stannic oxide coating, this be advantageously possible for catalysis reaction into Row.
Fig. 4 is the XRD of scroll-like titanium-based stibium doping stannic oxide dioxide composite lead electrode prepared by inventive embodiments 3 Figure, it can be seen that brown lead oxide 2 θ for 25.2 °, 32.0 °, 36.2 °, 48.8 °, 58.8 °, 62.2 ° of diffraction maximums it is corresponding (110) β type brown lead oxide in crystal face, (101) crystal face, (200) crystal face, (211) crystal face, (222) crystal face, (301) crystal face standard spectrogram The diffraction maximum of (JCPDS PDF#65-2826) fits like a glove, and the coating of covering is β-brown lead oxide, no dephasign.Illustrate Titanium base It has been completely covered by brown lead oxide with middle layer, and coating covering is uniform, fine and close, electrolyte permeability can be effectively prevent to make matrix Passivation promotes electrode stability.
Fig. 5 and Fig. 6 is scroll-like titanium-based stibium doping stannic oxide dioxide composite lead electrode prepared by the embodiment of the present invention 4 The cyclic voltammetry curve and quantity of electric charge curve of magnetic loading stibium doping stannic oxide coated ferroferric oxide magnetic particle, from figure It can be seen that the OEP values of all electrodes will not reduce (~1.8V vs.Ag/AgCl) with the increase of coating load amount substantially, Illustrate oxidability of the load without reduction electrode of particle.However, the closed area of cyclic voltammetry curve is converted into charge Amount, finds in sodium sulphate medium, and load capacity quantity of electric charge in 0.25g is maximum (closed area is maximum), in sodium lignin sulfonate The quantity of electric charge is maximum (closed area is maximum) during middle load capacity 0.5g, it may be possible to due to the increase and catalysis of electrode real table area Increasing for active site is caused, and thus deducibility electrode is best in the catalytic activity of load capacity 0.25-0.5g.Specifically, Higher potential region (>2.0V vs.Ag/AgCl), the increase of particle reduces the current-responsive of electrode, due in system Have no the presence of organic matter, the reason of this phenomenon may be due to coating thick or high potential section oxygen evolution reaction by Certain inhibition is arrived.
Fig. 7 is that scroll-like titanium-based stibium doping stannic oxide dioxide composite lead electrode prepared by the embodiment of the present invention 5 is magnetic Load the COD removal rates of stibium doping stannic oxide coated ferroferric oxide magnetic particle, it can be seen that wooden with the electrode degrading During plain sodium sulfonate, the COD removal rates after carried magnetic particle are apparently higher than the COD removal rates of unsupported mosaic electrode, illustrate this 2.5 dimension structures are conducive to improve the catalytic activity of electrode.
The present invention first prepares titanium oxide layer, then lead to using the method for dipping-thermal oxide on magnetic particles of ferroferric oxide The tin dioxide layer that Sb doped is further coated on the particle that dipping-thermal oxidation method is covered in titanium oxide is crossed, makes the two of Sb doped Stannic oxide layer combines closely to form solid solution with the titanium oxide layer being attached on magnetic-particle matrix.With a permanent magnet (NdFeB) it is core, the antimony for containing hydrogenated titanium prepared using dipping-thermal decomposition and electrodeposition process is mixed in outer cover Miscellaneous stannic oxide composite lead dioxide cylindrical electrode set uses magnetic force that magnetic-particle is attracted to be attached to tubular electrode surface shape Into 2.5 dimension magnetic-particle loading anodes.Its organic matter removal efficiency and energy consumption are all than traditional electrode ideal.Simultaneously because magnetic force Flexibility, it is easy to operate can to recycle the present invention in situ for magnetic-particle on novel electrode.Experiment condition requires relatively low, technical process Easy to control, prepared composite anode has high electrocatalytic active, and oxygen evolution potential is high, and service life is long, is suitably applied industry Change extensive electrolysis wastewater.
The foregoing is merely one embodiment of the present invention, are not all of or unique embodiment, this field are common Technical staff is the present invention by reading description of the invention and any equivalent transformation taken technical solution of the present invention Claim covered.

Claims (10)

1. the preparation method of 2.5 dimension anodes of a kind of high catalytic activity carried magnetic particle, which is characterized in that including following step Suddenly：
1) preparation of magnetic-particle middle layer：
Magnetic particles of ferroferric oxide is added in precursor liquid, after precursor liquid evaporation is heated under stirring, passes through thermal oxidation method Titanium oxide layer is formed on magnetic particles of ferroferric oxide surface；
2) preparation of magnetic-particle coating：
The magnetic particles of ferroferric oxide of surface attachment titanium oxide layer is impregnated in the precursor liquid containing tin and antimony, heating stirring After being evaporated to precursor liquid, Sb doped two is prepared on the magnetic particles of ferroferric oxide of loading titanium oxide layer by thermal oxidation method Tin oxide active coating, and repeat the step 4~6 time；
3) preparation of Titanium base middle layer：
Pretreated Titanium base is immersed in faint yellow precursor liquid, drying is taken out after the uniform fold precursor liquid of surface, and pass through Thermal oxidation method Titanium base surface formed titanium oxide layer, recycle electrochemical reduction method to the titanium oxide layer that Titanium base surface is covered into Row reduction forms hydrogenation titanium；
4) preparation of Titanium base stibium doping stannic oxide coating：
Using with hydrogenation titanium Titanium base be connected as cathode with power cathode, at room temperature, using graphite electrode as Anode is connected with positive pole, and Sb doped titanium-based two is made using electro-deposition-thermal oxidation method in stanniferous and antimony electroplate liquid Tin oxide electrode；
5) preparation of Titanium base brown lead oxide coating：
It is connected using Sb doped titanium-based stannic oxide electrode as anode with positive pole, is born by anode and power supply of copper plate electrode Pole is connected, and Sb doped titanium-based stannic oxide composite lead dioxide electricity is made using electrodeposition process in the electroplate liquid containing plumbi nitras Pole；
6) assembling of electrode
The surface for preparing step 2) using physisorphtion covers the ferroso-ferric oxide magnetic of stibium doping stannic oxide active coating Property particle be attached to the outer surface of Sb doped titanium-based stannic oxide dioxide composite lead electrode, form 2.5 dimension magnetic-particles loads Anode.
2. a kind of preparation method of 2.5 dimension anodes of high catalytic activity carried magnetic particle according to claim 1, special Sign is, step 1) and 3) in, precursor liquid is made by procedure below：By volume percent, to 40~64% volumes point The ethyl alcohol of 35~55% volume fractions and the nitric acid of 1~5% volume fraction are added in several butyl titanates, stirs 10-20min It is uniform to solution, obtain precursor liquid.
3. a kind of preparation method of 2.5 dimension anodes of high catalytic activity carried magnetic particle according to claim 1, special Sign is that thermal oxidation method detailed process is in step 1)：1.5h is calcined at 250~350 DEG C.
4. a kind of preparation method of 2.5 dimension anodes of high catalytic activity carried magnetic particle according to claim 1, special Sign is that precursor liquid and magnetic particles of ferroferric oxide volume ratio are 1 in step 1):(1~2).
5. a kind of preparation method of 2.5 dimension anodes of high catalytic activity carried magnetic particle according to claim 1, special Sign is that the precursor liquid containing tin and antimony in step 2) is made by procedure below：Butter of tin, antimony trichloride are added to nitre In acid, precursor liquid is obtained, in the precursor liquid, a concentration of 1.0mol/L of butter of tin, a concentration of 0.1mol/L of antimony trichloride, nitric acid A concentration of 0.1mol/L；The magnetic particles of ferroferric oxide of surface attachment titanium oxide layer and the forerunner containing tin and antimony in step 2) Liquid and volume ratio be 1:2.
6. a kind of preparation method of 2.5 dimension anodes of high catalytic activity carried magnetic particle according to claim 1, special Sign is that the actual conditions of thermal oxidation method are in step 2)：With the heating rate of 5~10 DEG C/min from room temperature to 400~ 700 DEG C and 2~6h of calcining, room temperature is then down to the rate of temperature fall of 1~3 DEG C/min.
7. a kind of preparation method of 2.5 dimension anodes of high catalytic activity carried magnetic particle according to claim 1, special Sign is, in step 3), the detailed process of the pretreatment of Titanium base is as follows：Titanium base surface is polished smooth to remove with sand paper Its surface oxide layer heats 5~10min to remove Titanium base surface and oil contaminant impurity in the alkaline solution containing sodium hydroxide, And will treated that Titanium base impregnates in oxalic acid solution boils 1~2h, fresh titanium is exposed in etching matrix surface, use Deionized water is cleaned and is dried.
8. a kind of preparation method of 2.5 dimension anodes of high catalytic activity carried magnetic particle according to claim 1, special Sign is that thermal oxidation method detailed process is in step 3)：1.5h is calcined at 250~350 DEG C；
The detailed process of electrochemical reduction method is in step 3)：By the Titanium base of surface covering titanium oxide layer in the electrolysis containing sodium sulphate In liquid, 10~20mA/cm of constant current density2Lower energization carries out 10~30min of reduction, forms hydrogenation titanium.
9. a kind of preparation method of 2.5 dimension anodes of high catalytic activity carried magnetic particle according to claim 1, special Sign is, in step 4), stanniferous and antimony electroplate liquid is made by procedure below：By butter of tin, antimony trichloride, ethylene glycol and Normal propyl alcohol is uniformly mixed, and is then adjusted pH value and is less than 5, obtains stanniferous and antimony electroplate liquid, wherein, tin, antimony molar ratio are 10:1, The volume ratio of ethylene glycol and normal propyl alcohol is (1~2):1, the ratio of butter of tin and ethylene glycol is 2.0mol：1L；
In step 4), the detailed process for preparing stibium doping stannic oxide coating is：In stanniferous and antimony electroplate liquid, in constant current 5~15mA/cm of density2Under be electroplated in matrix surface and be co-deposited tin and antimony, electrodeposition time is 20~60min；Then from room temperature Room temperature is down to 1~3 DEG C/min rates after being warming up to 400~700 DEG C and 2~6h of calcining with 5~10 DEG C/min heating rates.
10. a kind of preparation method of 2.5 dimension anodes of high catalytic activity carried magnetic particle according to claim 1, It is characterized in that, in step 5), the detailed process for preparing Sb doped titanium-based stannic oxide dioxide composite lead electrode is：In molar ratio It is 5:1, plumbi nitras and copper nitrate are added to the water, then add in sodium fluoride, is stirred evenly, obtains the plating containing plumbi nitras Liquid；Wherein, the concentration of sodium fluoride is 0.01~0.05mol/L, a concentration of 0.5~1.5mol/L of plumbi nitras, copper nitrate it is dense It spends for 0.1~0.5mol/L；It is close in constant current using copper sheet as cathode at 50~70 DEG C in the electroplate liquid containing plumbi nitras Spend 5~15mA/cm2Under on the Titanium base for having loaded stibium doping stannic oxide coating 1~2h of electroplating deposition brown lead oxide, be made Sb doped titanium-based stannic oxide dioxide composite lead electrode.
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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109728314A (en) * 2018-12-13 2019-05-07 浙江大学 A kind of the flow battery structure and method of the magnetic-particle adhesive electrodes of externally-applied magnetic field
CN109825855A (en) * 2019-03-26 2019-05-31 扬州大学 Electrochemical deposition method removes the three-diemsnional electrode of iron ion in sulfuric acid solution
CN111333155A (en) * 2020-03-17 2020-06-26 重庆工业职业技术学院 Preparation method of electrode with magnetic oxide coating
CN112093860A (en) * 2020-09-14 2020-12-18 陕西科技大学 2.5-dimensional iridium dioxide/stannic oxide magnetic assembly electrode and preparation method and application thereof
CN114133003A (en) * 2021-12-31 2022-03-04 西安建筑科技大学 Construction method of magnetic sandwich titanium-based composite anode

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1099907A (en) * 1993-09-04 1995-03-08 中国科学院青海盐湖研究所 Active lead dioxide electrode and preparing method and use
CN101417831A (en) * 2008-11-11 2009-04-29 北京师范大学 Novel ti-supported lead dioxide electric pole and preparation method thereof
CN105239095A (en) * 2015-09-30 2016-01-13 淮南师范学院 Method for preparing Ti/Sb-SnO2/Nd-nano TiO2-PbO2 electrode and degrading reactive blue 117 through Ti/Sb-SnO2/Nd-nano TiO2-PbO2 electrode
CN107302102A (en) * 2017-05-19 2017-10-27 南京理工大学 A kind of 3-D ordered multiporous lead dioxide membrane electrode and preparation method thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1099907A (en) * 1993-09-04 1995-03-08 中国科学院青海盐湖研究所 Active lead dioxide electrode and preparing method and use
CN101417831A (en) * 2008-11-11 2009-04-29 北京师范大学 Novel ti-supported lead dioxide electric pole and preparation method thereof
CN105239095A (en) * 2015-09-30 2016-01-13 淮南师范学院 Method for preparing Ti/Sb-SnO2/Nd-nano TiO2-PbO2 electrode and degrading reactive blue 117 through Ti/Sb-SnO2/Nd-nano TiO2-PbO2 electrode
CN107302102A (en) * 2017-05-19 2017-10-27 南京理工大学 A kind of 3-D ordered multiporous lead dioxide membrane electrode and preparation method thereof

Non-Patent Citations (5)

* Cited by examiner, † Cited by third party
Title
DAN SHAO ET AL.: "A Highly Stable Ti/TiHx/Sb-SnO2 Anode: Preparation,Characterization and Application", 《INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH》 *
DAN SHAO ET AL.: "An improved stable Ti/Sb–SnO2 electrode with high performance in electrochemical oxidation processes", 《RSC ADV.》 *
DAN SHAO ET AL.: "Fe3O4/Sb-SnO2 Granules Loaded on Ti/Sb-SnO2 Electrode Shell by Magnetic Force: Good Recyclability and High Electro-oxidation Performance", 《ACS SUSTAINABLE CHEMISTRY & ENGINEERING》 *
DAN SHAO ET AL.: "Magnetic assembled anode combining PbO2 and Sb-SnO2 organically as an effective and sustainable electro-catalyst for wastewater treatment with adjustable attribution and construction", 《ACS APPLIED MATERIALS & INTERFACES》 *
宋秀丽 等: "Ti/SnO2+Sb2Ox/PbO2耐酸阳极的寿命及电催化性能", 《人工晶体学报》 *

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109728314A (en) * 2018-12-13 2019-05-07 浙江大学 A kind of the flow battery structure and method of the magnetic-particle adhesive electrodes of externally-applied magnetic field
CN109825855A (en) * 2019-03-26 2019-05-31 扬州大学 Electrochemical deposition method removes the three-diemsnional electrode of iron ion in sulfuric acid solution
CN111333155A (en) * 2020-03-17 2020-06-26 重庆工业职业技术学院 Preparation method of electrode with magnetic oxide coating
CN111333155B (en) * 2020-03-17 2022-03-01 重庆工业职业技术学院 Preparation method of electrode with magnetic oxide coating
CN112093860A (en) * 2020-09-14 2020-12-18 陕西科技大学 2.5-dimensional iridium dioxide/stannic oxide magnetic assembly electrode and preparation method and application thereof
CN114133003A (en) * 2021-12-31 2022-03-04 西安建筑科技大学 Construction method of magnetic sandwich titanium-based composite anode
CN114133003B (en) * 2021-12-31 2022-11-11 西安建筑科技大学 Construction method of magnetic sandwich titanium-based composite anode

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