CN109264829A - A kind of preparation method of the antimony-doped tin oxide electrode of efficient and long life - Google Patents

A kind of preparation method of the antimony-doped tin oxide electrode of efficient and long life Download PDF

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CN109264829A
CN109264829A CN201811034971.2A CN201811034971A CN109264829A CN 109264829 A CN109264829 A CN 109264829A CN 201811034971 A CN201811034971 A CN 201811034971A CN 109264829 A CN109264829 A CN 109264829A
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electrode
antimony
tin oxide
doped tin
thermal reaction
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CN109264829B (en
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成少安
孙怡
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Zhejiang University ZJU
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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
    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • C02F1/467—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction
    • C02F1/4672—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electrooxydation
    • 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
    • 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
    • C02F2001/46152—Electrodes characterised by the shape or form
    • 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

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Abstract

The present invention relates to material preparation and water-treatment technology fields, it is desirable to provide a kind of preparation method of the antimony-doped tin oxide electrode of efficient and long life.It include: to take SnCl4、SbCl3, HCl and surfactant alcoholic solution as solvent thermal reaction liquid, titanium foam basis material is immersed in solvent thermal reaction liquid, in 170~220 DEG C of insulation reactions after ultrasonic treatment；It is kept the temperature under the conditions of 450~650 DEG C after reaction, cooling foam titanium substrate antimony-doped tin oxide electrode.This method is to modify antimony-doped tin oxide electrode in the inside and outside of foam titanium substrate based on solvent thermal reaction, by control response parameter to obtain different catalysts modification amount, size and distribution and pattern.The present invention prepares electrode and possesses excellent contaminant degradation ability and permanent service life in inside and outside while uniform, the intensive load antimony-doped tin oxide particle of porous foam Titanium base material.It is capable of appropriate and catalyst the size of repairing of conveniently regulating and controlling catalyst, it is easy to operate, be easy to regulation, preparation process low energy consumption, low cost.

Description

A kind of preparation method of the antimony-doped tin oxide electrode of efficient and long life
Technical field
The present invention relates to the technologies of preparing of electrochemical oxidation anode material, and it is advanced which is mainly used in electrochemistry Oxidative system handles difficult-degradation organic sewage, belongs to material preparation and water-treatment technology field.
Background technique
Organic wastewater with difficult degradation thereby becomes one of problem of water treatment field because of its high toxicity, high harmfulness, refractory organics. Advanced electrochemical oxidation process can be under lower electrical potential conditions, and being generated by anode surface electrocatalytic reaction has Strong oxdiative Property the substances such as hydroxyl radical free radical, reacted using free radical with persistent organic pollutants, realize pollutant removing；Treatment process It does not need additionally to add chemicals, reaction condition mild；It is excellent with efficient, inexpensive, easy to operate, being easily enlarged etc. Point possesses huge application prospect in organic wastewater with difficult degradation thereby process field.
Electrode material directly affects electrochemical oxidation technology treatment effect.Currently used electrode material includes Ti/RuO2、 Ti/IrO2, carbon material electrode, brown lead oxide (PbO2) electrode, Characterization of Boron-Doped Diamond Thin Film Electrode (BDD) electrode and Sb doped oxygen Change tin (ATO) electrode etc..In these materials, Ti/RuO2、Ti/IrO2, carbon material electrode have low oxygen evolution potential and free radical Yield, contaminant degradation ability are poor.And PbO2Electrode, which makes and uses process and can discharge Pb ion, causes heavy metal pollution.BDD Electrode production process is complicated, preparation energy consumption is high, and electrode is expensive.Compared with these electrodes, ATO electrode has preparation process letter The advantages that single, cheap, hypotoxicity, however the ATO electrode of conventional method preparation is by basis material and electrode preparation method Limitation, preparing electrode often has low modification amount, causes electrode life very of short duration, significantly limits its practical application.
Traditional ATO electrode mainly uses infusion process, sol-gel process and electrodeposition process on Ti piece or Ti net substrate Modify antimony-doped tin oxide catalyst.Wherein, infusion process and sol-gel process are needed repeatedly during the preparation process by coating- Drying-high temperature sintering process, electrode preparation efficiency is low, energy consumption is high, process is cumbersome；Since solvent steams during heating and calcination Hair, electrode surface will form " chap " structure, aggravate the dissolution of catalyst and fall off, influence electrode life.When raising is urged The modification amount of agent, the preparation time and energy consumption of one side electrode can be multiplied；On the other hand, the inhomogeneities of electrode surface Phenomena such as aggravating, coating caused to fall off.And prepared by ATO electrode for electrodeposition process, decorative layer is poor in conjunction with base material, with The raising of modification amount, during making and using, Catalytic Layer can be very easy to fall off, on the other hand also can electrode be led Electrically it is deteriorated, electrode performance decline, therefore be not suitable for preparing high modification amount ATO electrode.
Solvent thermal reaction method of modifying is as a kind of brand-new material preparation method, with easy to operate, reaction speed is fast, item The advantages such as part is mild, prepare product good dispersion, crystallinity is high, granularity is controllable.And titanium foam material and biography rich in micron openings System titanium sheet or titanium net material are compared, inside and outside that attachment place can be provided for catalyst with high-specific surface area, because This is a kind of base material of suitable antimony-doped tin oxide electrode.The method of the present invention is based on solvent thermal reaction method of modifying, Titanium foam substrate material surface and inside uniformly, intensive load ATO catalyst, prepare a kind of performance efficiency, service life it is permanent, at This cheap electrode material；It, being capable of conveniently regulating and controlling by controlling solvent thermal reaction liquid concentration and ingredient, reaction temperature and time etc. Modification amount, size and distribution pattern of catalyst etc..The method of the present invention preparation process is simple, preparation cost is low, and preparation process is low Pollution, can be applied to the electrochemistry oxygen polarizing electrode of actual production efficient and long life.
Summary of the invention
The technical problem to be solved by the present invention is to overcome the shortcomings of existing technology of preparing, provide one kind using titanium foam as base The preparation method of the efficient and long life antimony-doped tin oxide electrode of body material.
In order to solve the technical problem, solution of the invention is:
A kind of preparation method of the antimony-doped tin oxide electrode of efficient and long life is provided, is based on solvent thermal reaction in foam Antimony-doped tin oxide electrode is modified in the inside and outside of titanium substrate, by control response parameter to obtain different catalysts modification amount, ruler Very little and distribution and pattern；This method specifically includes:
(1) SnCl is taken4、SbCl3, HCl and surfactant alcoholic solution, be placed in water heating kettle as solvent thermal reaction liquid； In solvent thermal reaction liquid, SnCl4·5H2The molar concentration of O is 0.2~1.5mol/L；SbCl3With SnCl4·5H2Mole of O Concentration ratio is 1: 0.09~0.03；The molar concentration of hydrochloric acid is 0.6~2.4mol/L；The concentration of surfactant be 0~ 0.3mol/L；
(2) it will be immersed in solvent thermal reaction liquid by pretreated titanium foam basis material, and be ultrasonically treated 5min；By water After hot kettle sealing, 8~36h of insulation reaction under the conditions of 170~220 DEG C；It is cooled to room temperature after reaction, takes out water heating kettle simultaneously It is placed in Muffle furnace, 1~3h is kept the temperature under the conditions of 450~650 DEG C；It is cooled to room temperature after the completion of heat preservation, obtains foam titanium substrate Antimony-doped tin oxide electrode.
In the present invention, the pretreatment of titanium foam refers to: after successively being polished using 400 mesh and 800 mesh sand paper, with deionized water It cleans up；Then it is to impregnate 0.5h in 40wt%NaOH solution in 80 DEG C, mass concentration, takes out and cleaned with deionized water；Again It goes in the oxalic acid solution that mass concentration is 10wt% and boils 0.5h, clean up, be immersed in ethanol solution under ultrasound condition It is spare.
In the present invention, the Muffle furnace in step (2) uses program-controlled heating, and heating rate is 1~25 DEG C/min.
In the present invention, the solvent thermal reaction liquid is using methanol, ethyl alcohol or ethylene glycol as solvent.
In the present invention, the surfactant is any one in citric acid, glucose or dodecyl sodium sulfate.
In the present invention, when titanium foam basis material is immersed in solvent thermal reaction liquid, tilt titanium foam basis material It places.Inclination submergence is beneficial to improve catalyst in the adhesion amount of foam titanium substrate, and slant setting catalyst can be yet It is grown on basis material, tilt angle is not required.
Inventive principle description:
The present invention is using alcohol as solvent, and under the conditions of specific reaction temperature, solvent evaporation is formed in closed reaction kettle Hyperbaric environment advantageously reduces reaction activity and chemical reaction barrier, so that under the conditions of a relatively low temperature, it is real Existing SnCl4And SbCl3With the O in closed environment2The granules of stannic oxide of Sb doped is precipitated in reaction.Wherein, the formation of tin oxide crystal Main to pass through nucleation and growth phase, in nucleation stage, system is in the micro cell domain of titanium foam and reaction solution two-phase interface Inside overcome energy battier, forms the cenotype nucleus of stable tin oxide；After New phase formation, it is higher new nearby to there is free energy Transition region between old two-phase, reaction occurs in nucleus and solution interface, so that nucleus is gradually grown up.Titanium foam material internal is rich It is inside and outside to provide site for nucleus formation and growth containing micron openings, therefore can be realized in titanium foam material It is inside and outside while loading antimony-doped tin oxide catalyst.
The factors such as reaction solution concentration, solvent type, PH, reaction temperature and reaction time will affect antimony-doped tin oxide crystalline substance The nucleation and growth course of grain, therefore by factors such as control reaction solution concentration, ingredient, reaction temperature, reaction time, it can be right Catalyst modification amount, pattern, distribution and size etc. are regulated and controled.On the other hand, hyperbaric environment limits the thickness of ion diffusion layer Degree, while the crystal grain rapid synthesis of place, can quickly generating to avoid crystal grain, be to realize to catalyst content, size and shape Looks, which control effectively, provides possibility.
Electrode catalyst based on the method for the present invention preparation can uniform, the intensive inside for being supported on foam titanium substrate and Outer surface, Catalytic Layer have preferable cladding ability to Ti substrate, can be avoided the exposed oxidation of Ti piece and cause electrode performance and stabilization Property decline；Catalyst has high-specific surface area, is conducive to generate higher concentration number of free radical in degradation process, promotes pollutant Degradation；The electrode finally prepared shows excellent degradation property and permanent service life.
Compared with prior art, the present invention has the beneficial effect that:
1, compared with traditional infusion process, solution-gel method and electro-deposition method, the method for the present invention be can be realized in porous bubble Inside and outside while uniform, the intensive load antimony-doped tin oxide particle of foam Titanium base material, prepare electrode possess it is excellent Contaminant degradation ability and permanent service life.
2, the method for the present invention is capable of the repairing in right amount in 15~450mg/cm of conveniently regulating and controlling catalyst2；Overcome conventional method Catalyst modification amount is low, the disadvantages of being difficult to.
3, the method for the present invention is capable of the size of conveniently regulating and controlling catalyst between 500nm~3000nm；Catalyst is prepared to gather around There are high-specific surface area and electro-chemical activity.
4, the method for the present invention is easy to operate, is easy to regulate and control, preparation process low energy consumption, low cost, can be suitable for practical raw Produce the three-dimensional antimony-doped tin oxide electrode of efficient and long life.
Detailed description of the invention
Fig. 1 is in specific embodiment 2, and the solvent thermal reaction time is the scanning that 12h prepares electrode surface enlargement ratio 5000 Electronic Speculum (SEM) photo.
Fig. 2 is that the scanning electron microscope (SEM) that addition citric acid prepares electrode surface enlargement ratio 5000 in specific embodiment 3 is shone Piece.
Fig. 3 is to prepare electrode X ray diffracting spectrum (XRD) in specific embodiment 2 and specific embodiment 3.
Fig. 4 is the foam Titanium base ATO electricity in specific embodiment 4, comparative example 1 and comparative example 2 using distinct methods preparation The degradation curve of pole material processing methylene blue simulated wastewater.
Specific embodiment
Below in conjunction with drawings and concrete examples, the invention will be further described, and its object is to preferably explain the present invention Rather than limitation of the present invention.
Specific embodiment 1
Use the method for the present invention preparation using the titanium foam of different size as the three-dimensional antimony-doped tin oxide electrode of base material.
Preferred dimension is 20mm × 20mm, and thickness is respectively 0.4mm (10 μm of aperture), 1.5mm (150 μm of aperture), 5mm The titanium foam material in (200 μm of aperture) and 10mm (300 μm of aperture), (final products will be respectively used to Asia to each two pieces of every kind of specification Methyl blue simulated wastewater degradation test and electrode accelerating lifetime testing)；Successively polished using 400 mesh and 800 mesh sand paper, gone from It is to impregnate 0.5h in 40wt%NaOH solution in 80 DEG C, mass concentration after sub- water cleans up；It impregnates after completing through deionized water It cleans, goes in the oxalic acid solution that mass concentration is 10wt% and boil 0.5h；Then ultrasonic cleaning is clean, is immersed in ethanol solution In it is spare.
Configure four parts of solvent thermal reaction liquid, the configuration method of every part of solvent thermal reaction liquid are as follows: drawing 3mL mass concentration is 37.5% concentrated hydrochloric acid is added dropwise in 27ml alcohol solvent, is uniformly mixed；Weigh 4.2g SnCl4·5H2O、0.25g SbCl3It is added in the mixed solution of ethyl alcohol and hydrochloric acid, uniform stirring is until form clear solution；In the solvent thermal reaction liquid, The molar concentration of hydrochloric acid is 1.2mol/L；SnCl4·5H2The molar concentration of O is 0.4mol/L；SbCl3With SnCl4·5H2O's rubs Your concentration ratio is 1:0.09.
It will tilt respectively and be immersed in solvent thermal reaction liquid by pretreated titanium foam basis material, after ultrasonic 5min, Water heating kettle is sealed at 180 DEG C, insulation reaction 36h is removed and placed in Muffle furnace after being cooled to room temperature, in 550 DEG C of items 2h is kept the temperature under part, Muffle furnace uses program-controlled heating, and heating rate is 1 DEG C/min, and i.e. obtaining property is cooled to room temperature after the completion of heat preservation The foam titanium substrate antimony-doped tin oxide electrode that energy is efficient, the service life is permanent.
Using the urging as the antimony-doped tin oxide electrode of base material of the titanium foam with a thickness of 0.4mm, 1.5mm, 5mm and 10mm Agent modification amount is respectively 15mg/cm2、70mg/cm2、190mg/cm2And 450mg/cm2.The modification of catalyst modification amount catalyst The quality that amount can modify front and back titanium foam base material by precise is learnt.
The degradation test of methylene blue simulated wastewater, test experiments step are carried out using the electrode prepared in embodiment 1 are as follows:
Configuration concentration is methylene blue (MB) solution of 100mg/L, and 0.25M Na is added2SO4Conductivity is adjusted, it will be upper Solution is stated to be added in the electrolytic cell that volume is 120ml；Electrolytic cell anode using preparation ATO electrode, cathode use having a size of The platinum plate electrode of 20mm × 20mm, anode and cathode spacing are 2cm, and electrolytic cell bottom rotor mixing speed is 500rpm；Degradation electric current Density is 20mA/cm2.Timing liquid-transfering gun sampling analysis (0h, 1h, 2h, 3h, 4h) from electrolytic cell；It is dynamic using level-one degradation Mechanics is fitted the degradation results of MB, using the antimony prepared with a thickness of 0.4mm, 1.5mm, 5mm and 10mm titanium foam as substrate The level-one degradation rate constant of doped stannum oxide electrode is respectively 0.92h-1、0.96h-1、1.13h-1And 0.98h-1；Show to be based on The foam titanium substrate antimony-doped tin oxide electrode of the method for the present invention preparation has excellent contaminant degradation performance.
Accelerating lifetime testing is carried out to the electrode prepared in embodiment 1, testing procedure is the H for being 0.5M by concentration2SO4It is molten Liquid is added in accelerating lifetime testing electrolytic cell, and anode is using the electrode of preparation, and cathode is using having a size of 20mm × 20mm's Platinum plate electrode, test electrolytic current density are 100mA/cm2, anode and cathode both end voltage is recorded using data collecting instrument, data are adopted 5min is divided between collection, when anode and cathode both end voltage rises to 10V, it is believed that electrode failure, record electrolysis time are to test electricity The accelerated aging time of pole.Using the antimony-doped tin oxide prepared with a thickness of 0.4mm, 1.5mm, 5mm and 10mm titanium foam as substrate The accelerated aging of electrode is respectively 86h, 200h, 300h and 380h；Show that the electrode of the method for the present invention preparation has permanent make Use the service life.
Specific embodiment 2
Regulated and controled by controlling the different solvent thermal reaction time using titanium foam as base material using the method for the present invention The modification amount and size of antimony-doped tin oxide electrode catalyst.
Selecting four chip sizes is 20mm × 20mm × 0.8mm, and the titanium foam material that aperture is 50 μm successively uses 400 mesh It polishes with 800 mesh sand paper, is to be impregnated in 40wt%NaOH solution in 80 DEG C, mass concentration after deionized water cleans up 0.5h；It impregnates and is cleaned after completing through deionized water, go in the oxalic acid solution that mass concentration is 10wt% and boil 0.5h；Then surpass Sound cleans up, and is immersed in spare in ethanol solution.
Four parts of solvent thermal reaction liquid are configured, the configuration method of solvent thermal reaction liquid is to draw 1.5mL mass concentration to be 37.5% concentrated hydrochloric acid is added dropwise in 28.5ml alcohol solvent, is uniformly mixed；Weigh 6.3g SnCl4·5H2O、0.188g SbCl3It is added in the mixed solution of ethyl alcohol and hydrochloric acid, uniform stirring is until form clear solution；In the solvent thermal reaction liquid, The molar concentration of hydrochloric acid is 0.6mol/L；SnCl4·5H2The molar concentration of O is 0.4mol/L；SbCl3With SnCl4·5H2O's rubs Your concentration ratio is 1:0.045.
It will tilt respectively and be immersed in solvent thermal reaction liquid by pretreated titanium foam basis material, after ultrasonic 5min, Water heating kettle is sealed at 200 DEG C, difference insulation reaction 8h, 12h, for 24 hours and after 36h, is removed and placed after being cooled to room temperature In Muffle furnace, 3h is kept the temperature under the conditions of 450 DEG C, Muffle furnace uses program-controlled heating, and heating rate is 5 DEG C/min, after the completion of heat preservation It is cooled to room temperature and obtains performance efficiency, service life permanent foam titanium substrate antimony-doped tin oxide electrode.Reaction time be 8h, 12h, for 24 hours, the catalyst modification amount of 36h electrode be respectively 13mg/cm2、16mg/cm2、31mg/cm2、46mg/cm2；Electrode is repaired Decorations amount is positively correlated with the solvent thermal reaction time, can be regulated and controled to electrode modification amount by controlling the solvent thermal reaction time.
The characterization of electrode of the present invention:
It is that foam titanium substrate antimony-doped tin oxide prepared by 36h and 12h is electric to the solvent thermal reaction time using scanning electron microscope Pole surface is observed (see Fig. 1), it can be seen that the solvent thermal reaction time is 36h, prepares electrode surface catalyst at hollow Ellipsoid or dome-type distribution, size is between 2~3 μm, and at 1 μm or so, catalyst morphology is complete in internal aperture, is evenly distributed； The solvent thermal reaction time is 12h, prepares the different spheroid shape distribution of electrode surface Cheng great Yi, and size is less than the solvent thermal reaction time Electrode is prepared for 36h, size is between 0.5~1.8 μm；, by controlling the reaction time, catalyst size can be adjusted Control.
Using X-ray diffractometer to the different solvents thermal response time prepare electrode carry out XRD characterization, gained XRD spectra (see Fig. 3).Sample XRD diagram and tetragonal phase stannic oxide standard card 2 θ=26.597 °, 33.889 °, 37.968 °, 38.994 °, 42.655°、51.795°、54.78°、57.852°、61.908°、62.629°、64.767°、65.994°、69.272°、 Diffraction maximum at 71.308 °, 74.481 ° and 78.744 ° is consistent completely, shows that modifier is tetragonal phase stannic oxide, does not go out The associated diffraction peak of existing antimony shows that antimony successfully adulterates and enters stannic oxide lattice, do not occur the associated diffraction peak of Ti, show electrode Finishing coat is fine and close, can completely cover titanium substrate, this is conducive to improve electrode stability.As the solvent thermal reaction time mentions Height, XRD diffraction peak intensity increase, and diffraction peak width narrows, and show that catalyst size and crystallinity are got higher；Therefore it can pass through control The solvent-thermal method reaction time regulates and controls the size and crystallinity of catalyst.
Specific embodiment 3
Using the method for the present invention, using methanol as reaction solution solvent, addition citric acid is prepared as surfactant to steep Foam titanium is the antimony-doped tin oxide electrode of basis material.
Preferred dimension is the titanium foam material of 20mm × 20mm, is successively polished using 400 mesh and 800 mesh sand paper, gone from It is to impregnate 0.5h in 40wt%NaOH solution in 80 DEG C, mass concentration after sub- water cleans up；It impregnates after completing through deionized water It cleans, goes in the oxalic acid solution that mass concentration is 10wt% and boil 0.5h；Then ultrasonic cleaning is clean, is immersed in ethanol solution In it is spare.
The configuration method of solvent thermal reaction liquid is to draw the concentrated hydrochloric acid that 6mL mass concentration is 37.5% to be added dropwise to 24ml In methanol solvate, it is uniformly mixed；Weigh 6.3g SnCl4·5H2O、0.125g SbCl3, 1.73g citric acid be added to ethyl alcohol and In the mixed solution of hydrochloric acid, uniform stirring is until form clear solution；In the solvent thermal reaction liquid, the molar concentration of hydrochloric acid is 2.4mol/L；SnCl4·5H2The molar concentration of O is 0.6mol/L；SbCl3With SnCl4·5H2The molar concentration rate of O is 1: 0.03；The molar concentration of citric acid is 0.3mol/L.
It will tilt respectively and be immersed in solvent thermal reaction liquid by pretreated titanium foam basis material, after ultrasonic 5min, Water heating kettle is sealed at 210 DEG C, insulation reaction for 24 hours after, removed and placed in Muffle furnace after being cooled to room temperature, at 650 DEG C Under the conditions of keep the temperature 1h, Muffle furnace uses program-controlled heating, and heating rate is 5 DEG C/min, is cooled to room temperature after the completion of heat preservation and obtains Performance efficiency, service life permanent foam titanium substrate antimony-doped tin oxide electrode；The modification amount that this method prepares electrode is about 20mg/ cm2。
The characterization of electrode of the present invention:
Electrode surface is observed (see Fig. 2) using scanning electron microscope, it can be seen that addition citric acid is as surface-active Agent, electrode surface flatness increase, this is conducive to improve catalyst to the coverage of basis material, improve the stability of electrode； XRD characterization (see Fig. 3) is carried out to electrode using X-ray diffractometer, electrode diffraction maximum is prepared using citric acid as surfactant It broadens, shows that catalyst size and crystallinity reduce.
Specific embodiment 4
Using the method for the present invention, using ethylene glycol as reaction solution solvent, addition glucose be used as surfactant, prepare with Titanium foam is the antimony-doped tin oxide electrode of basis material.
Preferred dimension is the titanium foam material of 20mm × 20mm, is successively polished using 400 mesh and 800 mesh sand paper, gone from It is to impregnate 0.5h in 40wt%NaOH solution in 80 DEG C, mass concentration after sub- water cleans up；It impregnates after completing through deionized water It cleans, goes in the oxalic acid solution that mass concentration is 10wt% and boil 0.5h；Then ultrasonic cleaning is clean, is immersed in ethanol solution In it is spare.
The configuration method of solvent thermal reaction liquid is to draw the concentrated hydrochloric acid that 3mL mass concentration is 37.5% to be added dropwise to 27ml In methanol solvate, it is uniformly mixed；Weigh 8.4g SnCl4·5H2O、0.5g SbCl3, 0.54g glucose be added to ethyl alcohol and salt In the mixed solution of acid, uniform stirring is until form clear solution；In the solvent thermal reaction liquid, the molar concentration of hydrochloric acid is 1.2mol/L；SnCl4·5H2The molar concentration of O is 0.8mol/L；SbCl3With SnCl4·5H2The molar concentration rate of O is 1: 0.09；The molar concentration of glucose is 0.1mol/L.
It will tilt respectively and be immersed in solvent thermal reaction liquid by pretreated titanium foam basis material, after ultrasonic 5min, Water heating kettle is sealed at 220 DEG C, after insulation reaction 8h, is removed and placed in Muffle furnace after being cooled to room temperature, in 650 DEG C of items 1h is kept the temperature under part, Muffle furnace uses program-controlled heating, and heating rate is 15 DEG C/min, and i.e. obtaining property is cooled to room temperature after the completion of heat preservation The foam titanium substrate antimony-doped tin oxide electrode that energy is efficient, the service life is permanent, the modification amount that this method prepares electrode is about 13mg/ cm2。
The degradation test of methylene simulated wastewater is carried out using electrode of the present invention, test specific steps are sub- with specific embodiment 1 Methyl blue degradation curve is shown in Fig. 5.As can be seen that electrode of the present invention shows excellent contaminant degradation performance, knot of degrading to it Fruit carries out the fitting of level-one degradation kinetics, and level-one degradation kinetics constant has reached 0.91h-1。
Specific embodiment 5
Using the method for the present invention, using ethyl alcohol as reaction solution solvent, addition dodecyl sodium sulfate as surfactant, Preparation is using titanium foam as the antimony-doped tin oxide electrode of basis material.
The configuration method of solvent thermal reaction liquid is to draw the concentrated hydrochloric acid that 6ml mass concentration is 37.5% to be added dropwise to 24ml In alcohol solvent, it is uniformly mixed；Weigh 15.8g SnCl4·5H2O、0.94g SbCl3, 0.43g dodecyl sodium sulfate be added To in the mixed solution of ethyl alcohol and hydrochloric acid, uniform stirring is until form clear solution；In the solvent thermal reaction liquid, mole of hydrochloric acid Concentration is 2.4mol/L；SnCl4·5H2The molar concentration of O is 1.5mol/L；SbCl3With SnCl4·5H2The molar concentration rate of O is 1:0.09；The molar concentration of dodecyl sodium sulfate is 0.05mol/L.
It will tilt respectively and be immersed in solvent thermal reaction liquid by pretreated titanium foam basis material, after ultrasonic 5min, Water heating kettle is sealed at 170 DEG C, after insulation reaction 16h, is removed and placed in Muffle furnace after being cooled to room temperature, at 650 DEG C Under the conditions of keep the temperature 1h, Muffle furnace uses program-controlled heating, and heating rate is 5 DEG C/min, is cooled to room temperature after the completion of heat preservation and obtains Performance efficiency, service life permanent foam titanium substrate antimony-doped tin oxide electrode；The modification amount of this electrode is about 38mg/cm2。
Specific embodiment 6
Using the method for the present invention, using methanol as reaction solution solvent, surfactant is not added, is prepared using titanium foam as base The antimony-doped tin oxide electrode of body material.
The configuration method of solvent thermal reaction liquid is to draw the concentrated hydrochloric acid that 3mL mass concentration is 37.5% to be added dropwise to 27mL In alcohol solvent, it is uniformly mixed；Weigh 2.1g SnCl4·5H2O、0.125g SbCl3The mixing for being added to ethyl alcohol and hydrochloric acid is molten In liquid, uniform stirring is until form clear solution；In the solvent thermal reaction liquid, the molar concentration of hydrochloric acid is 1.2mol/L； SnCl4·5H2The molar concentration of O is 0.2mol/L；SbCl3With SnCl4·5H2The molar concentration rate of O is 1:0.09.
It will tilt respectively and be immersed in solvent thermal reaction liquid by pretreated titanium foam basis material, after ultrasonic 5min, Water heating kettle is sealed at 170 DEG C, after insulation reaction 36h, is removed and placed in Muffle furnace after being cooled to room temperature, at 650 DEG C Under the conditions of keep the temperature 1h, Muffle furnace uses program-controlled heating, and heating rate is 25 DEG C/min, is cooled to room temperature after the completion of heat preservation and obtains Performance efficiency, service life permanent foam titanium substrate antimony-doped tin oxide electrode.
Comparative example 1
Use infusion process preparation using titanium foam as the antimony-doped tin oxide electrode of base material, specific steps are as follows: selection rule Lattice are basis material of 20mm × 20mm × 0.8mm titanium foam as electrode；The pre-treatment step of titanium foam is the same as specific implementation Example 1.
The configuration method of dipping solution are as follows: weigh 17.52g SnCl4·5H2O；0.18g SbCl3It is dissolved in 50ml isopropyl In alcoholic solvent, and 2ml concentrated hydrochloric acid is added dropwise, to promote to dissolve；It will be immersed in dipping solution by pretreated titanium foam, ultrasound After 2min, takes out to be sent into 100 DEG C of drying boxes and toast 10min in air atmosphere, 550 DEG C of Muffle furnaces after dry 10min, take out After cool down；Last electrode obtained is toasted 60min in 550 DEG C, taken out by repeated impregnations-ultrasound-drying-baking procedure 9 times It is afterwards prepared by infusion process using titanium foam as the antimony-doped tin oxide electrode of base material.The modification amount of the electrode is 4.2mg/ cm2, catalyst be mainly distributed on titanium foam intrinsic silicon, and it is very low in titanium foam matrix surface abundance.
To the degradation test of electrode methylene simulated wastewater is prepared, specific experiment step is the same as specific embodiment 1, methylene blue drop Solution curve is shown in Fig. 4；The fitting of level-one degradation kinetics is carried out to its degradation results, level-one degradation kinetics constant is 0.62h-1； Electrode accelerating lifetime testing is carried out to electrode is prepared, for concrete operation step with specific embodiment 1, electrode accelerated aging is 34h.
Comparative example 2
Use electro-deposition method preparation using titanium foam as the antimony-doped tin oxide electrode of base material, specific steps are as follows: choosing Selecting specification is basis material of 20mm × 20mm × 0.8mm titanium foam as electrode；The pre-treatment step of titanium foam is the same as specific Embodiment 1.
The configuration method of electric depositing solution is to weigh 2.6g SnCl4·5H2O；0.164g SbCl3It is molten with 1.2g tartaric acid Solution is in 80ml deionized water；Electrodeposition process are as follows: will make in electric depositing solution by pretreated titanium foam vertical immersion For working electrode, the graphite flake that diameter is 3.5cm is arranged symmetrically in titanium foam two sides and is used as to electrode, positive pole and to electrode It is connected, power cathode is connected with working electrode, deposition current 40mA, electrodeposition time 20min；After electro-deposition is completed, At room temperature after natural drying, it is transferred in Muffle furnace and toasts 3h at 600 DEG C, Muffle furnace uses program-controlled heating, heating rate 5 DEG C/min, be cooled to room temperature obtain electro-deposition method preparation using titanium foam as the antimony-doped tin oxide electrode of substrate.The electricity The modification amount of the catalyst of pole is about 10mg/cm2；Catalyst is mainly distributed on titanium foam surface, and is distributed inside titanium foam It measures extremely low.
The degradation test of methylene simulated wastewater is carried out to electrode is prepared, specific experiment step is the same as specific embodiment 1, methylene Blue degradation curve is shown in Fig. 4；The fitting of level-one degradation kinetics is carried out to its degradation results, level-one degradation kinetics constant is 0.45h-1；Electrode accelerating lifetime testing is carried out to electrode is prepared, concrete operation step accelerates the longevity with specific embodiment 1, electrode Life is 5h.

Claims (6)

1. a kind of preparation method of the antimony-doped tin oxide electrode of efficient and long life, which is characterized in that be based on solvent thermal reaction Antimony-doped tin oxide electrode is modified in the inside and outside of foam titanium substrate, by control response parameter to obtain different catalysts modification Amount, size and distribution and pattern；This method specifically includes:
(1) SnCl is taken4、SbCl3, HCl and surfactant alcoholic solution, be placed in water heating kettle as solvent thermal reaction liquid；Molten In agent thermal response liquid, SnCl4·5H2The molar concentration of O is 0.2~1.5mol/L；SbCl3With SnCl4·5H2The molar concentration of O Than being 1: 0.09~0.03；The molar concentration of hydrochloric acid is 0.6~2.4mol/L；The concentration of surfactant is 0~0.3mol/L；
(2) it will be immersed in solvent thermal reaction liquid by pretreated titanium foam basis material, and be ultrasonically treated 5min；By water heating kettle After sealing, 8~36h of insulation reaction under the conditions of 170~220 DEG C；It is cooled to room temperature, takes out water heating kettle and places after reaction In Muffle furnace, 1~3h is kept the temperature under the conditions of 450~650 DEG C；It is cooled to room temperature after the completion of heat preservation, obtains foam titanium substrate antimony and mix Miscellaneous tin oxide electrode.
2. the method according to claim 1, wherein the pretreatment of titanium foam refers to: successively using 400 mesh and After the polishing of 800 mesh sand paper, cleaned up with deionized water；It then is to be impregnated in 40wt%NaOH solution in 80 DEG C, mass concentration 0.5h is taken out and is cleaned with deionized water；It is gone in the oxalic acid solution that mass concentration is 10wt% again and boils 0.5h, under ultrasound condition It cleans up, is immersed in spare in ethanol solution.
3. the method according to claim 1, wherein the Muffle furnace in step (2) uses program-controlled heating, heating speed Rate is 1~25 DEG C/min.
4. the method according to claim 1, wherein the solvent thermal reaction liquid is with methanol, ethyl alcohol or second two Alcohol is as solvent.
5. the method according to claim 1, wherein the surfactant is citric acid, glucose or 12 Any one in sodium alkyl sulfonate.
6. the method according to claim 1, wherein titanium foam basis material is immersed in solvent thermal reaction liquid When, make titanium foam basis material slant setting.
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CN114772683A (en) * 2022-04-26 2022-07-22 南京理工大学 Titanium-based antimony-doped tin dioxide microporous whole-body electrode applied to oily wastewater treatment and preparation method and application thereof
CN114772683B (en) * 2022-04-26 2023-06-13 南京理工大学 Titanium-based antimony-doped tin dioxide microporous whole electrode and preparation method and application thereof

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