CN104528890B - Ti/SnO2 electrode as well as preparation method and application - Google Patents
Ti/SnO2 electrode as well as preparation method and application Download PDFInfo
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- CN104528890B CN104528890B CN201410802124.1A CN201410802124A CN104528890B CN 104528890 B CN104528890 B CN 104528890B CN 201410802124 A CN201410802124 A CN 201410802124A CN 104528890 B CN104528890 B CN 104528890B
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46109—Electrodes
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/467—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction
- C02F1/4672—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electrooxydation
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
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- C02F2001/46133—Electrodes characterised by the material
- C02F2001/46138—Electrodes comprising a substrate and a coating
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- 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
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
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Abstract
The invention discloses a Ti/SnO2 electrode as well as a preparation method and an application. The preparation method comprises the following steps: preparing sol-gel liquid: heating citric acid and alcohol and uniformly mixing to obtain an acid-alcohol solution; and putting halogenated tin solid powder into the acid-alcohol solution, heating and stirring to obtain the sol-gel solution; preparing a coated electrode: immersing a titanium substrate in the sol-gel solution, carrying out dip coating, taking out, drying, sintering at high temperature and repeatedly carrying out dip coating, drying and sintering at high temperature on the titanium substrate for many times. The preparation method of the Ti/SnO2 electrode disclosed by the invention is simple and feasible, efficient and stable, the re-doping of other metal ions such as antimony, cerium and manganese in SnO2 is not needed according to the current report and the Ti/SnO2 electrode has significantly longer electrode service life than that of the Ti/SnO2-Sb electrode and the like.
Description
Technical field
The present invention relates to organic wastewater Treatment process field, more particularly, to a kind of ti/sno2Electrode and preparation method and should
With ti/sno2Electrode can be used for perfluor organic pollution in Electrooxidation degradation waste water.
Background technology
Perfluoro caprylic acid (pfoa) is the main Types of the perfluorochemical of synthesized use at present, because of its chemical property extremely
Stable, there is hydrophobic oleophobic characteristic, and be widely used as surfactant, foam, lubricant, protective coating, insecticide
And the intermediate of synthetic drug, fluorubber, resin etc..But widely use with it, neutralize in global ecological environment in recent years
Its presence is detected, the harm to ecological environmental and human health impacts is also gradually realized, this type organic in human body animal body
Become the focus of environment in recent years organic pollution research, belong to novel lasting organic pollution.In addition, U.S. Environmental Protection Agency (EPA)
(epa) pfoa stewardship plan regulation U.S. pfoa in 2015 must zero-emission.In terms of control technology, because it is high
Stability and stronger toxicity, conventional biodegrading process (as chemical oxidation, biodegradation etc.) is difficult to prove effective, and seeks mild condition, height
The perfluori piated carboxylic acids mass degradation method of effect low consumption has become the new focus of field of environmental technology research.
Less for the Study on treatment technology of the perfluor organic pollution such as pfoa at present, mainly there are ultrasonic pyrolysis, ultraviolet light
The high energy field action polluted-waters such as solution, plasma oxidation degraded, destroy stablizing of perfluorochemical by exogenous energy input
Structure, promotes carbon-fluorine bond fracture defluorinate, or even final mineralising, but these method high energy consumptions, technical sophistication, cost intensive, mistake
Journey is loaded down with trivial details.In addition, also there being research to carry out the oxidative degradation of pfoa in waste water under hydrothermal reaction condition using strong oxidizing property reagent,
As persulfate or ozone, but oxidation time-consuming, several days time need to be reacted, and defluorinate efficiency is low.Therefore, low cost, behaviour are found
Making the easy, method of efficient stable and technique is urgently one of Environmental Technology leaved for development.
At present, electrochemical oxidation technology is also used for the degraded of the perfluorocarboxylic acids such as pfoa, and it passes through preparation to oxygen evolution reaction
Chemical inertness, thus possessing the anode of oxygen evolution potential, possesses high oxidation potential while suppression analysis oxygen side reaction, thus in electricity
The electronics at relatively oxidizable carboxylic acid end in perfluorocarboxylic acid molecule is directly captured on pole surface；And analyse oxygen intermediate hydroxyl free
Base (oh) is weak physisorption on such anode, and it can assist the decarboxylation defluorinate process promoting perfluorocarboxylic acid, from
And realize the scission of link degraded even mineralising of perfluorocarboxylic acid.Conventional electrode type includes titanio tin ash and mixes antimony electrode, titanio
Lead dioxide electrode, boron-doped diamond electrode.There is anodic stripping in use in lead dioxide electrode, and pb2+
It is heavy metal ion, there is stronger neurotoxicity；Although diamond electrode oxidation susceptibility is good, life-span length, cost of manufacture is high
High.Therefore, ti/sno2Electrode, because of its avirulence and lower cost, is the more oxidative degradation organic pollution of current report
Anode material；However, pure sno2Electric conductivity is very poor, and the energy gap as quasiconductor reaches more than 3.5ev, generally using mixing sb
Method improve its electric conductivity.
In recent years, ti/sno2The report that-sb electrode carries out pfoa degraded is all mainly using stannic chloride and antimony chloride conduct
After presoma repeatedly coats after agglutinating nature yeast mixing on ti electrode, high temperature sintering forms, and also reports in this compound electric
Adulterate on the basis of pole pbo again2、mno2Or ce3+Etc. improving electrode performance, improve its service life.But lasting polynary mix
Miscellaneous will increase the complexity of preparation technology and preparation cost.Therefore, prior art has yet to be improved and developed.
Content of the invention
A kind of in view of above-mentioned the deficiencies in the prior art, it is an object of the invention to provide ti/sno2Electrode and preparation method
And application, ti/sno2Electrode can be used for electroxidation and removes perfluor organic pollution in waste water, ti/sno2The preparation method letter of electrode
Just, described preparation method is only to be used as presoma by stannic fluoride and prepare sol-gel to coat high temperature sintering on titanio material, system
For the ti/sno going out2Electrode has just possessed Electrooxidation degradation pfoa performance, need not according to mix sb common process can make non-conductive
Sno2Possess electroxidation performance, thus solve the ti/sno of existing Electrooxidation degradation perfluor organic pollution2- sb class electrode
Complicated process of preparation, electrode life is not long, the problems such as need multi-element doping to lead to high cost.
Technical scheme is as follows:
A kind of ti/sno2The preparation method of electrode, wherein, comprises the following steps:
The preparation of sol-gel liquid: mix after citric acid and alcohols heating, obtain acid alcohol solution；By tin halides solid
Powder is added in acid alcohol solution, and heated and stirred obtains sol-gel liquid；
The preparation of coated electrode: titanio material is immersed lifting coating in sol-gel, takes out post-drying, then high temperature sintering,
And it is multiple that lifting coating, drying and high temperature sintering are repeated on titanio material.
Wherein, alcohols: citric acid: the mol ratio of tin halides is 140～160:20～30:7～15.
Described ti/sno2The preparation method of electrode, wherein, the preparation process of sol-gel liquid particularly as follows:
Citric acid and alcohols are heated to mixing after 50～80 DEG C, stirring is until citric acid is completely dissolved；Do not stop stirring acid
Alcoholic solution is simultaneously heated to 85～98 DEG C, tin halides pressed powder is added in acid alcohol solution, and stirs under the conditions of 90～98 DEG C
Mix 10～40min.
Described ti/sno2The preparation method of electrode, wherein, in the preparation process of coated electrode, the temperature of drying is 120
DEG C～160 DEG C, the time of drying is 5～15min；The temperature of high temperature sintering is 450 DEG C～550 DEG C, and the time of high temperature sintering is 5
～15min.
Described ti/sno2The preparation method of electrode, wherein, in the preparation process of coated electrode, high temperature the last time
Further comprising the steps of after sintering:
It is maintained at sintering 1～2h in 450 DEG C～550 DEG C environment.
Described ti/sno2The preparation method of electrode, wherein, comprises the following steps:
Pretreatment to titanio material: by titanio material through sand papering, alkali liquor oil removing and oxalic acid oxide film dissolving.
Described ti/sno2The preparation method of electrode, wherein, pretreatment to titanio material particularly as follows:
First with sand paper, titanium substrate surface is polished；Put into alkali cleaning oil removing in naoh solution；Put into ultrasonic cleaner
Middle distilled water cleans；Put into and in Herba Houttuyniae acid solution, remove surface film oxide；After the titanio timber-used distilled water flushing processing, put into
Cleaned with distilled water in ultrasonic cleaner, then be placed in 1～3% oxalic acid solution and save backup.
Described ti/sno2The preparation method of electrode, wherein, titanio material is titanium plate material, web material or bar；Described alcohols
For ethylene glycol, ethanol or diethylene glycol；Described tin halides are stannic fluoride, stannic chloride, Tin tetrabromide. or Tin tetraiodide..
A kind of ti/sno2Electrode is it is characterised in that described ti/sno2Electrode adopts ti/sno as above2Electrode
Preparation method prepares.
A kind of ti/sno as above2The application of electrode, wherein, by described ti/sno2Electrode is used for Electrooxidation degradation water
Pfoa in phase, specifically includes following steps:
With described ti/sno2Electrode is set to anode, with titanio material as negative electrode, adds supporting electrolyte, using constant current mould
Formula, the pfoa in Electrooxidation degradation aqueous phase.
Described ti/sno2The application of electrode, wherein, current density range is set to 5ma/cm2～25ma/cm2；Described
Supporting electrolyte is naclo4、nacl、nano3, or na2so4.
Beneficial effect: ti/sno provided by the present invention2Electrode and preparation method thereof, simple low consumption, efficient stable, need not
It is reported in sno by existing2In other metal ions such as antimony dopant, cerium, manganese again, compared with ti/sno2The electrodes such as-sb also possess substantially more
Long electrode life, and ti/sno2Electrode can be used for electroxidation and processes perfluor organic pollution.The inventive method is only with halogenation
Stannum prepares the ti base sno of other metal-oxides of undoped p for presoma2Coated electrode, gets final product efficient degradation under electrolysis
Typical case's perfluor organic pollution such as pfoa, for the pollution concentration of mg/l level, its electroxidation decomposition efficiency is in 30min up to 99%
More than, the ti/sno that wherein particularly prepared with stannic fluoride for presoma2Electrode life is long, and electrode performance is stable, can be real
Effective purification of existing fluorine chemical industry correlation waste water.
Brief description
Fig. 1 is the ti-based coating electrode pair pfoa Electrooxidation degradation effect of different tin salt precursor body preparation in the embodiment of the present invention
Fruit is schemed.
Fig. 2 is prepared different titanio sno in the embodiment of the present invention2The sun that coated electrode accelerating lifetime testing is obtained
The pole life-span.
Specific embodiment
The present invention provides a kind of ti/sno2Electrode and preparation method and application, for make the purpose of the present invention, technical scheme and
Effect is clearer, clear and definite, and the present invention is described in more detail below.It should be appreciated that specific embodiment described herein
Only in order to explain the present invention, it is not intended to limit the present invention.
Ti/sno provided by the present invention2The preparation method of electrode, comprises the following steps:
S1, the pretreatment to titanio material: by pure titanio material after sand papering, alkali liquor oil removing and oxalic acid oxide film dissolving, make
For electrode base material；
S2, the preparation of sol-gel liquid: mix tin halides according to a certain ratio after citric acid and alcohols heating mixing, will
Tin halides pressed powder is added in citric acid -ol class mixed liquor, and heated and stirred generates sol-gel liquid for a period of time；
S3, the preparation of coated electrode: titanio material is put into lifting coating in sol-gel, takes out post-drying, then high temperature burns
Knot, and repeated multiple times.
Wherein, titanio material can be selected for titanium plate material, web material and bar.
Described alcohols includes ethylene glycol, ethanol or diethylene glycol.
Described tin halides, as single presoma, can be selected for stannic fluoride, stannic chloride, Tin tetrabromide. or Tin tetraiodide..
, at 120 DEG C～160 DEG C, high temperature sintering temperature is at 450 DEG C～550 DEG C for drying temperature.
Because existing research report thinks pure sno2Non-conductive, need the metal ions such as antimony dopant just can make sno2Conductive work electricity
Pole, but, but ignore using stannic chloride as presoma after high temperature sintering, the sno being formed2Not sterling, still has in it
Chlorine element remains, and actually there is the electric action of residual chlorine doping.Verify through many experiments in the present invention, xrd confirms
Sno2The presence of crystal formation, and it is not detected by the crystal formation of each tin halides, show that halogen is to be doped to sno2In crystal grain, and, pass through
Electroxidation is tested, and confirms that such electrode possesses electroxidation ability.Therefore, the present invention makees presoma, high temperature sintering using tin halides
Prepare the actual ti/sno mixing halogen afterwards2- x electrode (x=f, cl, br, i), sno2Conductive because of halogen residue doping, prepared
Electrode all possesses the performance of Electrooxidation degradation perfluoro caprylic acid.Electrode preparation method provided by the present invention is simple, workable,
The metal-oxides such as calcium halophosphate activated by antimony andmanganese, cerium that need not adulterate again can prepare long-life efficient ti/sno2Electrode, wherein, ti/sno2-f
Electrode electroxidation performance best.
The purpose of step s1 is to remove the oxide-film of titanium substrate surface, and makes the titanio of uniform grey pitted skin
Body, to increase the adhesion between follow-up coating oxide and matrix.Specifically, can first with sand paper, titanium substrate surface be carried out
Polishing, removes the oxidation film layer on surface, is then placed in alkali cleaning oil removing in naoh solution, places into distilled water ultrasound wave and embathe, remove
Remove the impurity of remained on surface, be subsequently placed in Herba Houttuyniae acid solution and remove surface film oxide, and make uniform grey pitted skin
Titanium base.The titanio timber-used distilled water flushing processing several times after, put in ultrasonic cleaner and cleaned with distilled water, remove table
The impurity of face residual, then be placed in 1～3% oxalic acid solution and save backup.
Experimental result in order to ensure embodiment has comparability, using except tin halides choosing in embodiment of the present invention 1-6
Beyond difference, other experimental procedure conditions are identical, to titanio material pre-treatment step particularly as follows: during titanio material pretreatment, by institute
The certain size titanio material of cutting, is first polished with 180 mesh coarse sandpapers, then is polished with 320 mesh fine sandpapers, remove titanium substrate surface
Oxide-film, is then placed in 80 DEG C of dipping alkali cleaning oil removing 2h in 40% dense naoh solution, subsequently takes out titanio material, put into ultrasonic
Middle distilled water embathes 5min, is subsequently placed into 98 DEG C of heating 2h of constant temperature water bath in 10% oxalic acid solution.
In step s2, in the preparation process of sol-gel liquid, alcohols: citric acid: the mol ratio of stannic fluoride can be in 140-
Select between 160:20-40:1-15.Specifically, first citric acid and alcohols mixed under the conditions of 50～80 DEG C, stir up to entirely
Portion dissolves, and then acid alcohol solution is heated to 85～98 DEG C, in temperature-rise period, does not continuously stop to stir；By tin halides pressed powder
It is added in acid alcohol solution, and stir 10～40min under the conditions of 90～98 DEG C, to obtain sol-gel liquid.
In the embodiment of the present invention 1～6, alcohols is chosen as ethylene glycol, according to ethylene glycol: citric acid: tin halides=140～
The molar ratio range of 160:20～30:7～15, tin halides pressed powder is added in acid alcohol solution, and in 85～95 DEG C of bars
20～40min is stirred, to obtain sol-gel liquid under part.
In step s3, specifically, pretreated titanio material is immersed in 1～5min in sol-gel liquid so as to surface
Even application has sol-gel liquid, and lifting is taken out titanio material, this titanio material is placed in baking oven, in 120 DEG C～160 DEG C of bar
Under part, dry 5～15min, after making that surface solvent is slow and volatilizing, take out be placed in 450 DEG C～550 DEG C Muffle furnaces sintering 5～
15min.Until after titanio material Slow cooling, carrying out lifting coating and heat treatment operation again, repeatedly, best high temperature burns
Knot more than 20 times.After the completion of high temperature sintering when last, by titanio material be maintained in 450 DEG C～550 DEG C environment sintering 1～
2h.
In the embodiment of the present invention 1～6, pretreated titanium plate is immersed in 1min in sol gel solution.Lifting is taken out
Afterwards, this titanium plate is placed in baking oven, under conditions of 140 DEG C, dries 10min, after making the slow volatilization of surface solvent, taking-up is placed in
10min is sintered in 500 DEG C of Muffle furnaces.Until after titanium plate Slow cooling, carrying out dip coating and heat treatment operation again, repeat 20
Secondary.After the completion of Muffle furnace sintering when the 20th time, titanium plate is maintained at sintering 2h in 500 DEG C of environment.
A kind of ti/sno is also provided in the present invention2Electrode, also provides ti/sno in the described present invention2Electrode is using above-mentioned
Method preparation.Described ti/sno2The application of electrode, by described ti/sno2Electrode is used for the perfluorinate in Electrooxidation degradation aqueous phase
Compound, specifically includes following steps:
With ti/sno provided by the present invention2Electrode is set to anode, with titanio material as negative electrode, adds supporting electrolyte, adopts
With constant current mode, the perfluorochemical in Electrooxidation degradation aqueous phase.
Wherein, set current density range is in 5ma/cm2～25ma/cm2.Described supporting electrolyte can be naclo4、
nacl、nano3, or na2so4.Described ti/sno2The application of electrode, it is possible to achieve the fast anode oxygen of the organic pollution such as pfoa
Change decarboxylation defluorinate chain rupture, or even thorough mineralising, for the pollution concentration of mg/l level, its electroxidation decomposition efficiency 30min up to
More than 99%, the waste water containing pfoa of oxidable process 10mg/l～500mg/l, the time that removes is short, and removal efficiency is high.
In the embodiment of the present invention 1～6, electroxidation process is carried out to 50ml 100mg/l perfluoro caprylic acid waste water, pending
Water body starting ph is 3.7, with electric current density 20ma/cm2Constant-current electrolysis, is electrolysed 30min under stirring.Hplc-ms/ms's
Analysis result shows the removal effect of pfoa up to more than 99.9% (see Fig. 1), defluorinate rate more than 70%, the ti/sno of fluorine doped2
Electrode life is more than 400h.
The introducing of above-mentioned tin halides prepares sno in the present invention2Synchronously halogen doping is achieved, its high efficiency reason during electrode
With above-mentioned ti/sno2The best ti/sno of electroxidation performance in-x electrode2Parsed (see Fig. 1) as a example-f electrode.First, with
Report most sno at present2Mix sb electrode to compare, present invention introduces f more much higher than sb electronegativity, electron-withdrawing power is strong, electricity
Sub- animal migration declines, the ti/sno of preparation2- f electrode compares ti/sno2- sb electrode has higher interface resistance.In addition, from electricity
Analyze in sub- effect, fluorine and oxygen are all the high elements of electronegativity, all easily formation anion or band are negative with during other element compounds
Electricity；Because electrostatic interaction can produce repulsion after therefore fluorine is negatively charged with oxygen, this makes oxygen containing hydrone be difficult in fluorine-containing solid
On interface, infiltration is sprawled, and oxygen containing hydroxyl radical free radical is also difficult to produce strong adsorption in fluorine-containing electrode surface.Above-mentioned reason makes
Obtain ti/sno2The electrode of the halogen-containing doping such as-f compares ti/sno2- sb has higher oxygen evolution potential, thus having compared with ti/sno2-
Sb electrode more preferable electroxidation ability and the efficiency of degraded pfoa.
Embodiment is provided below embodiment of the present invention is described in detail.
Embodiment 1:snf4Presoma prepares ti/sno2Pfoa in-f anodizing degrading waste water
Heating oil removing in concentrated alkali solution is put into through thick, fine sandpaper after the titanium plate of cut lengths 50 × 60 × 3mm is polished, then
Change in water and be cleaned by ultrasonic, be subsequently placed in Herba Houttuyniae acid solution and remove surface film oxide.First by ethylene glycol and lemon during coating solution preparation
Lemon acid heating mixed dissolution, ethylene glycol in molar ratio: citric acid: stannic fluoride=140:30:9, add snf4To in solution, heating
Stirring obtains sol-gel liquid.Subsequently, pretreated ti plate is immersed in sol gel solution.Take out post-drying high temperature again
Sintering, its coating and heat treatment step are repeated 20 times.After the completion of Muffle furnace sintering when the 20th time, titanium plate is maintained at 500 DEG C of rings
2h is sintered in border.
ti/sno2After the completion of the preparation of-f electrode, carry out the pfoa solution electrolytic trial of 50ml 100mg/l, 20ma/cm2Electricity
Under current density, electroxidation 30min can achieve that more than 99.9% pfoa decomposes, and hplc-ms/ms test shows pfoa defluorinate rate
More than 70%.With ti/sno2- sb electrode is compared, ti/sno manufactured in the present embodiment2- f electrode electroxidation the time shortens 1 times, fall
Solution efficiency considerably higher (see Fig. 1).In addition, ti/sno2- f anode accelerating lifetime testing shows that its electrode performance is stable, converts the longevity
Life can exceed 400h hence it is evident that being more than ti/sno2- sb electrode (see Fig. 2).
Embodiment 2:sncl4Presoma prepares ti/sno2Pfoa in-cl anodizing degrading waste water
With sncl4Prepare ti/sno for presoma2- cl electrode, other conditions, with embodiment 1, are a difference in that in molar ratio
Ethylene glycol: citric acid: stannic chloride=140:30:9, add sncl4·5h2O, in solution, prepares sol-gel liquid.Its preparation
The result becoming electrode rear oxidation pfoa is as shown in figure 1, the degradation efficiency of pfoa is slightly below ti/sno2- f electrode, but also substantially high
In traditional ti/sno2- sb electrode, in addition, ti/sno2The life-span of-cl electrode is more than 180h (see Fig. 2).
Embodiment 3:snbr4Presoma prepares ti/sno2Pfoa in-br anodizing degrading waste water
With snbr4Prepare ti/sno for presoma2- br electrode, other conditions, with embodiment 1, are a difference in that in molar ratio
Ethylene glycol: citric acid: Tin tetrabromide .=140:30:9, add snbr4To in solution, prepare sol-gel liquid.Prepared by the present embodiment
Ti/sno2- br electrode is used for the result of Electrooxidation degradation pfoa as shown in figure 1, the degradation efficiency of pfoa is less than ti/sno2-f
Electrode, but also apparently higher than traditional ti/sno2- sb electrode, in addition, ti/sno2The life-span of-br electrode is shorter, and only 17h is (see figure
2).
Embodiment 4:sni4Presoma prepares ti/sno2Pfoa in-i anodizing degrading waste water
With sni4Prepare ti/sno for presoma2- i electrode, other conditions, with embodiment 1, are a difference in that second in molar ratio
Glycol: citric acid: Tin tetraiodide .=140:30:9, add sni4To in solution, prepare sol-gel liquid.Manufactured in the present embodiment
ti/sno2- i electrode is used for the result of Electrooxidation degradation pfoa as shown in figure 1, the degradation efficiency of pfoa is less than ti/sno2- f electricity
Pole, but also apparently higher than traditional ti/sno2- sb electrode, in addition, ti/sno2The short life of-i electrode, only 7h (see Fig. 2).
Embodiment 5:sn (ch3)4Presoma prepares ti/sno2Pfoa in anodizing degrading waste water
With sn (ch3)4Prepare ti/sno for presoma2Electrode, other conditions, with embodiment 1, are a difference in that in molar ratio
Ethylene glycol: citric acid: tetramethyl tin=140:30:9, add sn (ch3)4To in solution, prepare sol-gel liquid.The present embodiment
The ti/sno of preparation2-ch3Electrode is used for the result of Electrooxidation degradation pfoa as shown in figure 1, the degradation efficiency of pfoa is less than ti/
sno2- f electrode, but also apparently higher than traditional ti/sno2- sb electrode.
However, using sn (ch3)4Ti/sno for presoma preparation2Electrode, in electrolytic process, its groove pressure (30.1v) is bright
Aobvious is higher than above-mentioned ti/sno2-f(15.1v)、ti/sno2-cl(15.4v)、ti/sno2-br(16.4v)、ti/sno2-i
(22.4v) electrode and ti/sno2- sb (14.5v) electrode.This is mainly by sn (ch3)4The sno firing2Its methyl meeting of coating
Generate oxycarbide and dissipation of gasifying, the coating of formation can be more nearly pure sno2Performance, thus resistance is big, its groove causing
Press through height and can lead to high energy consumption during practical application.Thus comparison understands that above-mentioned halogen doping improves sno2Electric conductivity, reduce
Electrolysis energy consumption.
Embodiment 6:ti/sno2Perfluoro-heptanoic acid in-f electrode Electrooxidation degradation waste water
The experiment condition of the present embodiment with embodiment 1, is a difference in that the perfluor processing one of short chain perfluorocarboxylic acid substantially
Enanthic acid waste water, the initial concentration of perfluoro-heptanoic acid is 100ppm, and in different time water sample in electrolytic process, the concentration of perfluoro-heptanoic acid is divided
Analysis to be completed using superelevation liquid chromatograph-bis- mass spectrums, after the water sample analysis result of electro-oxidation process shows to be electrolysed 30min, perfluor
The clearance of enanthic acid is more than 99%.
Embodiment 7:ti/sno2Perfluoro-pelargonic acid in-f electrode Electrooxidation degradation waste water
The experiment condition of the present embodiment with embodiment 1, is a difference in that the perfluor processing one of long-chain perfluorocarboxylic acid substantially
N-nonanoic acid waste water, the initial concentration of perfluoro-pelargonic acid is 100ppm, and in different time water sample in electrolytic process, the concentration of perfluoro-pelargonic acid is divided
Analysis to be completed using superelevation liquid chromatograph-bis- mass spectrums, after the water sample analysis result of electro-oxidation process shows to be electrolysed 30min, perfluor
The clearance of enanthic acid is more than 99%.
Comparative example 1: this comparative example is derived from reported in literature (efficient electrochemical oxidation of
perfluorooctanoate using a ti/sno2-sb-bianode.environmental science&
Technology, 2011,45 (7): 2973-2979).This report is passed through in traditional ti/sno2Bismuth is mixed, to increase on-sb electrode
Electrode life is used for the perfluorochemical degraded in water body, and the presoma that electrode preparation adopts includes sncl4、sbcl3And bicl3,
By sol-gel process prepares coating liquid, subsequently coating high temperature sintering preparation target coating electrode, this ti/ on Titanium base
sno2- sb-bi electrode life reaches 20h, is ti/sno prepared by it2One times of-sb electrode, Electrooxidation degradation 25ml 50mg/l's
Pfoa solution, the pfoa clearance of electrolysis 3h is 89.9%.
And the present invention is only using a kind of presoma of tin halides, such as snf4Or sncl4, that is, achieve ti/sno2The synchronization of electrode
Doping halogen, obtains the anode material of efficient degradation perfluorochemical, and required reagent is simple, and technique is convenient, and can fast electric
The pfoa of 50ml100mg/l can be removed more than 99.9% by the pfoa in oxidative degradation water body, 30min, and its clearance is obvious
Higher than this comparative example, wherein ti/sno2The life-span of-f electrode is also more than the ti/sno of this comparative example2- sb-bi electrode is high.
Comparative example 2: this comparative example is derived from reported in literature (highly efficient and mild
electrochemical mineralization of long-chain perfluorocarboxylic acids (c9-
c10)by ti/sno2-sb-ce,ti/sno2-sb/ce-pbo2,and ti/bdd electrodes.environmental
Science＆technology, 2013,47:13039-13046).This report technology for preparing electrode is complicated, and electrode preparation adopts
Presoma includes sncl4、sbcl3With ce (no3)3, prepare binary doped after sol-gel process and coating high temperature sintering
Ti/sno2- sb-ce electrode, as the ti/sno preparing ternary doping2-sb/ce-pbo2During electrode, also to pass through electro-deposition work
Skill is in ti/sno2Pbo is loaded on-sb-ce electrode2, both is in ti/sno2The electrode degrading that developed on electrode base is complete
During fluorine n-nonanoic acid (pfna), the degradation rate of the pfna electrolysis 3h of 100mg/l is 95.8% and 97.1% respectively.
And electrode coating raw material of the present invention is simple, only using snf4Etc. a kind of presoma of tin halides, in coated electrode preparation
During realize fluorine (halogen) element doping, degraded 100mg/l pfna when, electrolysis 30min achieve that its more than 99% degraded
Efficiency.In addition, this comparative example non-inspecting electrode life-span.
Comparative example 3: this comparative example is derived from reported in literature (fabrication of novel sno2-sb,carbon
aerogel electrode for ultrasonic electrochemical oxidation of
perfluorooctanoate with high catalytic efficiency.applied catalysis b:
environmental,2013,136-137:278-286).This report electrode adopts sncl4、sbcl3Gather with tristyryl phenol
Oxygen vinyl Ether is dissolved in dehydrated alcohol as presoma, above loads in charcoal-aero gel (ca) and high temperature burns under nitrogen environmental protection
Knot, prepares ca/sno2- sb electrode, 20ma/cm2The pfoa of lower degraded 100mg/l, electrolysis its clearance of 5h, less than 50%, increases
After the supersonic synergetic effect of 50w 33khz, the pfoa degradation efficiency of electrolysis 5h brings up to 91.3%.Even so, with this
Bright comparison, the relative complex preparation technology of this comparative example and longer degradation time, and increase the high energy consumption that ultrasonic field is brought
Deng so that the present invention has more advantage.
In sum, prepared ti/sno2The organic dirt of perfluor that electrode is representative for Electrooxidation degradation perfluoro caprylic acid
Dye thing, when its initial concentration is 100mg/l, electric current density 20ma/cm2The clearance of lower electrolysis 30min, pfoa up to 80% with
On.Especially prepared ti/sno2- f electrode, the clearance of pfoa up to more than 99.9%, defluorinate rate more than 70%, and
Its electrode performance is stable, and the conversion life-span can exceed 400h, compared with ti/sno2The electrodes such as-sb substantially possess longer electrode life.
It should be appreciated that the application of the present invention is not limited to above-mentioned citing, for those of ordinary skills, can
To be improved according to the above description or to convert, all these modifications and variations all should belong to the guarantor of claims of the present invention
Shield scope.
Claims (9)
1. a kind of ti/sno for degrading perfluorinated Organic substance2The preparation method of electrode is it is characterised in that comprise the following steps:
The preparation of sol-gel liquid: mix after citric acid and alcohols heating, obtain acid alcohol solution；By tin halides pressed powder
It is added in acid alcohol solution, heated and stirred, obtain sol-gel liquid；
The preparation of coated electrode: titanio material is immersed lifting coating in sol-gel, takes out post-drying, then high temperature sintering, and
Lifting coating is repeated on titanio material, dries and high temperature sintering more than 20 times；
Wherein, alcohols: citric acid: the mol ratio of tin halides is 140～160:20～30:7～15；
The preparation process of sol-gel liquid particularly as follows:
Citric acid and alcohols are heated to mixing after 50～80 DEG C, stirring is until citric acid is completely dissolved；Do not stop stirring acid alcohol molten
Liquid is simultaneously heated to 85～98 DEG C, and tin halides pressed powder is added in acid alcohol solution, and stirs 10 under the conditions of 90～98 DEG C
～40min.
2. ti/sno according to claim 12The preparation method of electrode is it is characterised in that the preparation process of coated electrode
In, the temperature of drying is 120 DEG C～160 DEG C, and the time of drying is 5～15min；The temperature of high temperature sintering is 450 DEG C～550
DEG C, the time of high temperature sintering is 5～15min.
3. ti/sno according to claim 22The preparation method of electrode is it is characterised in that the preparation process of coated electrode
In, further comprising the steps of after high temperature sintering the last time:
It is maintained at sintering 1～2h in 450 DEG C～550 DEG C environment.
4. ti/sno according to claim 12The preparation method of electrode is it is characterised in that comprise the following steps:
Pretreatment to titanio material: by titanio material through sand papering, alkali liquor oil removing and oxalic acid oxide film dissolving.
5. ti/sno according to claim 12The preparation method of electrode is it is characterised in that the pretreatment to titanio material is concrete
For:
First with sand paper, titanium substrate surface is polished；Put into alkali cleaning oil removing in naoh solution；Put in ultrasonic cleaner and use
Distilled water cleans；Put into and in Herba Houttuyniae acid solution, remove surface film oxide；After the titanio timber-used distilled water flushing processing, put into ultrasonic
Cleaned with distilled water in ripple washer, then be placed in 1～3% oxalic acid solution and save backup.
6. ti/sno according to claim 12The preparation method of electrode is it is characterised in that titanio material is titanium plate material, web material
Or bar；Described alcohols is ethylene glycol, ethanol or diethylene glycol；Described tin halides are stannic fluoride, stannic chloride, Tin tetrabromide. or iodate
Stannum.
7. a kind of ti/sno2Electrode is it is characterised in that described ti/sno2Electrode is using as described in claim 1～6 any one
Ti/sno2The preparation method of electrode prepares.
8. a kind of ti/sno as claimed in claim 72The application of electrode is it is characterised in that by described ti/sno2Electrode is used for
Perfluorochemical in Electrooxidation degradation aqueous phase, specifically includes following steps:
With described ti/sno2Electrode is set to anode, with titanio material as negative electrode, adds supporting electrolyte, using constant current mode, electricity
Perfluorochemical in oxidative degradation aqueous phase.
9. ti/sno according to claim 82The application of electrode is it is characterised in that current density range is set to 5ma/
cm2～25ma/cm2, described supporting electrolyte is naclo4、nacl、nano3Or na2so4.
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| CN109772295B (en) * | 2019-03-11 | 2020-09-08 | 中南大学 | Bismuth tungstate modified antimony-doped tin dioxide composite photoelectric catalytic electrode, preparation method and application |
| CN110844976A (en) * | 2019-10-15 | 2020-02-28 | 许嘉琦 | Preparation method of antimony-doped tin dioxide aerogel-titanium electrode |
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