CN106277228B - A kind of method of high catalytic activity electrode preparation and its Electrocatalysis Degradation methyl blue - Google Patents
A kind of method of high catalytic activity electrode preparation and its Electrocatalysis Degradation methyl blue Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/467—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction
- C02F1/4672—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electrooxydation
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46109—Electrodes
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46109—Electrodes
- C02F2001/46133—Electrodes characterised by the material
- C02F2001/46138—Electrodes comprising a substrate and a coating
- C02F2001/46142—Catalytic coating
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
Abstract
The invention discloses a kind of novel high catalytic activity electrode preparation and its research methods of Electrocatalysis Degradation methyl blue, belong to electro-catalysis technical field.Electrode preparation are as follows: anodizing prepares Ti/TiO2NT electrode；In matrix Ti piece and TiO2One layer of Cu is electroplated in the bottom NT, then one layer of SnO is coated on the titania nanotube prepared using the method for electro-deposition2- Ce middle layer, deposition liquid component group are divided into 18gSnCl4·5H2O and 0.7g Ce (NO3)3·6H2O, 0.1g neopelex, 2mlHCl (37%) are dissolved in the ethanol solution of 100ml, current density 20mA/cm2；It is placed on after room temperature electro-deposition 30min in 500 DEG C of Muffle furnaces and calcines 60min, obtain middle layer SnO2- Ce, Doping with Rare Earth Lanthanum PbO2The method that the preparation of surface-active layer uses DC electrodeposition, deposition liquid group are divided into 0.1~0.5M Pb (NO3)2, 0.01~0.05M La (NO3)3·6H2O and 0.04M NaF, adjusts pH value of solution=3, and current density is set as 50~100mA/cm2, 30~60min of electro-deposition at 60 DEG C.Electrode stability is good, and during methyl blue of degrading, catalytic degradation efficiency is high.
Description
Technical field
The invention belongs to electro-catalysis technical fields, more specifically to high catalytic activity Ti/Cu-TiO2NT/SnO2-
Ce/La-PbO2The method of electrode preparation and its Electrocatalysis Degradation methyl blue.
Background technique
As social industrialization degree is higher and higher, industrialization bring environmental pollution also becomes the sternness that the whole world faces and asks
Topic.Currently, chemical industry, pesticide, pharmacy and dyestuff rapid development, release in production process much to have environment and seriously pollute
Organic pollutant.Today especially so deficient in water resource, the type and quantity of industrial discharge pollutant are growing day by day, make
Limited water resource is by more serious pollution.Scientific investigations showed that multicomponent, highly concentrated is presented in these organic industrial sewages
Degree, molecular structure stabilized, it is difficult to degrade the features such as, some also have " three cause " (carcinogenic, teratogenesis, mutagenesis) effect and biological accumulation
Property, can exist for a long time in organism and environment, human health and environment are caused to seriously threaten.Reactive dark blue 194 1
Kind heteroaromatic compound is used as dyestuff use, can be used for cotton, viscose fiber dyeing, there is preferable dyeability and fastness,
Suitable for various colouring methods, it can also be used to the printing and dyeing of polyvinyl.However, the waste water containing these water-soluble reactive dye is also
One of most intractable waste water, traditional water treatment technology are not fine to these dyestuff treatment effects.
The methods of traditional physics, chemistry processing organic wastewater there are secondary pollution and it is at high cost the problems such as, so now
Research emphasis is few to secondary pollution, the simple direction of at low cost and treatment process is developed.Although bioanalysis meets this development
It is required that but by limitation due to it can only degrade biodegradable organic matter.In recent years, high-level oxidation technology was increasingly by state
Inside and outside researcher's concern, in sewage treatment field, has apparent degradation effect to the organic pollutant of difficult for biological degradation.Electrification
Learning oxidation technology is a kind of environmentally friendly high-level oxidation technology, can effective degradation biological hardly degraded organic substance, because it has
The advantages that environmentally protective, secondary pollution is few, highly-safe and easy to operate, is concerned, therefore proposes that one kind being capable of high efficiency drop
Solution dyestuff electro-catalytic process is technical problem urgently to be solved in the prior art.Ti/PbO2Electrode is as a kind of electrocatalytic oxidation
Anode material has the advantages that cheap, good conductivity, good corrosion resistance and high catalytic activity, but Ti/PbO2Electrode
It still needs further improvement with stability for activity.
Titanium-based titanium dioxide nanotube is because having biggish specific surface area, stronger mechanical strength, preferable bio-compatible
Property, to biological nontoxic, resistance to acid and alkali is good, and good chemical stability, is often introduced in PbO in recent years2It is mentioned in electrode
Its high catalytic performance.But Ti/TiO2NT is semiconductor, while matrix and TiO2Sometimes in combination with not firm between NT, its electricity is caused
Resistance is than big, electrode stability decline, so that current efficiency is not high during handling sewage, by simple electroreduction, it is conductive
Property increase rate be also not very big, by Ti matrix and and TiO2One layer of metal is electroplated between NT, to improve electrode conductivuty
And stability, SnO2Have and TiO2And PbO2Similar lattice dimensions, solid solution easy to form mention so that figure layer is closer
The service life of high electrode, and SnO2Adjustable gas evolution current potential, to effectively prevent the diffusion of nascent oxygen.But
Ti/Cu-TiO2SnO is prepared using electro-deposition techniques on NT matrix2- Ce middle layer and Doping with Rare Earth Lanthanum Ti matrix PbO2Electrode
The prior art not yet discloses, because of the Ti/TiO of prior art preparation2NT/PbO2The general specific surface area of electrode is small, and resistance is big, urges
It is not high to change activity, and electrode poor corrosion resistance, stability is not high, how to improve Ti/TiO2The electric conductivity and stability of NT, and
The SnO of uniform, size tunable the doping vario-property of special process and method preparation surface2Middle layer and rear-earth-doped through TiO2NT is repaired
Ti matrix PbO after decorations2Electrode is another technical problem urgently to be solved in the prior art.
Summary of the invention
1. technical problems to be solved by the inivention
In view of the above-mentioned problems of the prior art, one of the technical problem to be solved in the present invention: how to solve matrix and
TiO2Sometimes in combination with not firm, TiO between NT2The big problem of NT resistance, and uniform using special process and method preparation surface,
Size tunable has middle layer and surface-active layer and through TiO2Ti matrix PbO after NT modification2Electrode；The invention solves
The technical issues of two: how to improve the efficiency of Electrocatalysis Degradation reactive dark blue 194.The present invention provides high catalytic activity Ti/
Cu-TiO2NT/SnO2-Ce/La-PbO2The method of electrode preparation and its Electrocatalysis Degradation reactive dark blue 194, using DC current
The method of deposition prepares Ti/Cu-TiO2NT/SnO2-Ce/La-PbO2Electrode, the method is easy to operate, improves the pure of sedimentary
Degree, density, the uniformity, and its voidage is reduced, the stability of electrode is improved, with the Ti/Cu-TiO2NT/SnO2-Ce/La-
PbO2Modified electrode is anode, handles reactive dark blue 194, the method oxygen which provides by electrocatalytic oxidation in a cell
Change the high-efficient of degradation removal reactive dark blue 194, electrode good corrosion resistance, degradation process stability is good, and degradation efficiency is than common
Lead electrode is high, and the degradation rate that the degradation rate of methyl blue reaches 99.78%, TOC reaches 99.89%, and energy consumption is significantly dropped
Low, energy consumption reduces by 30%, and degradation side reaction is few, ensure that degradation high efficiency, belongs to Green Chemistry part.
2. technical solution
In order to achieve the above objectives, technical solution provided by the invention are as follows:
A kind of high catalytic activity Ti/Cu-TiO2NT/SnO2-Ce/La-PbO2Electrode, which is characterized in that first use anodic oxygen
Change method prepares Ti/TiO2NT electrode, wherein Ti/TiO2NT electrode radius is 125nm, tube wall 12nm, by electroreduction by Ti4 +It is reduced into Ti3+, the Ti/TiO that will restore2NT electrode is anode, and Pt piece is cathode, and saturation KCl electrode is reference electrode, is put
Enter 10mMCuSO4In electroplate liquid；In matrix Ti piece and TiO2One layer of Cu is electroplated in the bottom NT, then is being prepared using the method for electro-deposition
One layer of SnO is coated on good titania nanotube2- Ce middle layer, deposition liquid component group are divided into 18gSnCl4·5H2O and 0.7g
Ce(NO3)3·6H2O, 0.1g neopelex, 2mlHCl (37%) are dissolved in the ethanol solution of 100ml, and electric current is close
Spend 20mA/cm2；It is placed on after room temperature electro-deposition 30min in 500 DEG C of Muffle furnaces and calcines 60min, obtain middle layer SnO2- Ce, rare earth
La adulterates PbO2The method that the preparation of surface-active layer uses DC electrodeposition, deposition liquid group are divided into 0.1~0.5M Pb (NO3)2,
0.01~0.05M La (NO3)3·6H2O and 0.04M NaF, adjusts pH value of solution=2, and current density is set as 50~100mA/cm2,
30~60min of electro-deposition at 60 DEG C.
As a further improvement of the present invention, the specific steps prepared are as follows:
Step 1:
It selects pure titanium metal as titanium sheet, titanium sheet is successively used to three kinds of 600 mesh, 1000 mesh and 2000 mesh different sizes first
Sand paper polish, the then successively supersound washing 10min in dehydrated alcohol, acetone, deionized water by the titanium sheet polished,
Place into ethylene glycol, polishing treatment 10min in the mixed solution of hydrofluoric acid and secondary distilled water, and cleaned with deionized water dry
Only, in which: the volume ratio of hydrofluoric acid, ethylene glycol and secondary distilled water is 1:3:10；
Step 2:
Titania nanotube is prepared using anodizing, is at room temperature 0.5%NH in mass fraction4F and 2V%H2O
Ethylene glycol electrolyte in, anode is made with titanium sheet, Cu piece makees cathode and carries out anodic oxidation, oxidation voltage 60V, oxidization time
7h, oxidation process carry out magnetic agitation always, and soaked in absolute ethyl alcohol sample 2h, dehydrated alcohol ultrasonic cleaning are used after oxidation
10min makes annealing treatment under air atmosphere, 500 DEG C of annealing temperature, keeps the temperature 2h, and heating-cooling speed is all 2 DEG C/min, can be made half
Diameter is 125nm, the Ti/TiO of tube wall 12nm2NT electrode；
Step 3:
The Ti/TiO that step 2 is prepared2NT electrode is saturated KCl electrode as ginseng as anode as cathode, Pt piece
Than electrode, it is put into 1molL-1(NH4)2SO4In solution under -1.5V reductase 12 0s, Ti4+It is reduced into Ti3+；By what is restored
Ti/TiO2NT electrode is anode, and Pt piece is cathode, and saturation KCl electrode is reference electrode, is put into 10mMCuSO4In electroplate liquid；?
Matrix Ti piece and TiO2One layer of Cu is electroplated in the bottom NT.
Step 4: coating one layer of SnO on the titania nanotube prepared using the method for electro-deposition2Among-Ce
Layer, deposition liquid component group are divided into 18gSnCl4·5H2O and 0.7g Ce (NO3)3·6H2O, 0.1g neopelex,
2mlHCl (37%) is dissolved in the ethanol solution of 100ml, current density 20mA/cm2；500 are placed on after room temperature electro-deposition 30min
60min is calcined in DEG C Muffle furnace, obtains middle layer SnO2- Ce, temperature rate are all 5 DEG C/min；
Step 5: by the modified electrode deposition surface active layer of the coating middle layer of step 4 preparation, rare earth Pr doping
PbO2The method that the preparation of surface-active layer uses DC electrodeposition, deposition liquid group are divided into 0.1~0.5M Pb (NO3)2, 0.01~
0.05M La(NO3)3·6H2O and 0.04M NaF, adjusts pH value of solution=2, and current density is set as 50~100mA/cm2, in 60 DEG C
30~60min of lower deposition prepares Ti/Cu-TiO2NT/SnO2-Ce/La-PbO2Electrode.
As a further improvement of the present invention, the Ti/TiO that will have been restored in preparation method step 32NT electrode is anode,
Pt piece is cathode, and saturation KCl electrode is reference electrode, is put into 10mMCuSO4In electroplate liquid；In matrix Ti piece and TiO2The bottom NT
One layer of Cu is electroplated.
As a further improvement of the present invention, the method in preparation method step 4 using electro-deposition is in the dioxy prepared
Change and coats one layer of SnO on titanium nanotube2- Ce middle layer, deposition liquid component group are divided into 18gSnCl4·5H2O and 0.7g Ce
(NO3)3·6H2O, 0.1g neopelex, 2mlHCl (37%) are dissolved in the ethanol solution of 100ml, current density
20mA/cm2；It is placed on after room temperature electro-deposition 30min in 500 DEG C of Muffle furnaces and calcines 60min, obtain middle layer SnO2- Ce, heating and cooling
Rate is all 5 DEG C/min；
High catalytic activity Ti/Cu-TiO of the invention2NT/SnO2-Ce/La-PbO2Electrode preparation and its Electrocatalysis Degradation first
The method of base indigo plant, the steps include:
1) high catalytic activity Ti/Cu-TiO, is prepared2NT/SnO2-Ce/La-PbO2Electrode first uses anodizing to prepare
Ti/TiO2NT electrode, wherein Ti/TiO2NT electrode radius is 125nm, tube wall 12nm, Ti4+It is reduced into Ti3+；It will reduction
Good Ti/TiO2NT electrode is anode, and Pt piece is cathode, and saturation KCl electrode is reference electrode, is put into 10mMCuSO4Electroplate liquid
In；In matrix Ti piece and TiO2One layer of Cu is electroplated in the bottom NT, then uses the method for electro-deposition in the nano titania prepared
One layer of SnO is coated on pipe2- Ce middle layer, deposition liquid component group are divided into 18gSnCl4·5H2O and 0.7g Ce (NO3)3·6H2O,
0.1g neopelex, 2mlHCl (37%) are dissolved in the ethanol solution of 100ml, current density 20mA/cm2；Often
It is placed on after warm electro-deposition 30min in 500 DEG C of Muffle furnaces and calcines 60min, obtain middle layer SnO2- Ce, Doping with Rare Earth Lanthanum PbO2Surface
The method that the preparation of active layer uses DC electrodeposition, deposition liquid group are divided into 0.1~0.5M Pb (NO3)2, 0.01~0.05M La
(NO3)3·6H2O and 0.04M NaF, adjusts pH value of solution=2, and current density is set as 50~100mA/cm2, the electro-deposition at 60 DEG C
30~60min.
2), Electrocatalysis Degradation reactive dark blue 194
The modification Ti/Cu-TiO that will be prepared in step 12NT/SnO2-Ce/La-PbO2Electrode is made as anode, copper electrode
For cathode, using constant voltage supply, 25 DEG C of temperature, current density 70mA/cm2, degradation solution are as follows: 50mg/L reactive dark blue 194+
0.5mol/LNa2SO4。
As a further improvement of the present invention, high catalytic activity Ti/Cu-TiO is prepared in step 1)2NT/SnO2-Ce/La-
PbO2The specific steps of electrode are as follows:
Step 1:
It selects pure titanium metal as titanium sheet, titanium sheet is successively used to three kinds of 600 mesh, 1000 mesh and 2000 mesh different sizes first
Sand paper polish, the then successively supersound washing 10min in dehydrated alcohol, acetone, deionized water by the titanium sheet polished,
Place into ethylene glycol, polishing treatment 10min in the mixed solution of hydrofluoric acid and secondary distilled water, and cleaned with deionized water dry
Only, in which: the volume ratio of hydrofluoric acid, ethylene glycol and secondary distilled water is 1:3:10；
Step 2:
Titania nanotube is prepared using anodizing, is at room temperature 0.5%NH in mass fraction4F and 2V%H2O
Ethylene glycol electrolyte in, anode is made with titanium sheet, Cu piece makees cathode and carries out anodic oxidation, oxidation voltage 60V, oxidization time
7h, oxidation process carry out magnetic agitation always, and soaked in absolute ethyl alcohol sample 2h, dehydrated alcohol ultrasonic cleaning are used after oxidation
10min makes annealing treatment under air atmosphere, 500 DEG C of annealing temperature, keeps the temperature 2h, and heating-cooling speed is all 2 DEG C/min, can be made half
Diameter is 125nm, the Ti/TiO of tube wall 12nm2NT electrode；
Step 3:
The Ti/TiO that step 2 is prepared2NT electrode is saturated KCl electrode as ginseng as anode as cathode, Pt piece
Than electrode, it is put into 1molL-1(NH4)2SO4In solution under -1.5V reductase 12 0s, Ti4+It is reduced into Ti3+；By what is restored
Ti/TiO2NT electrode is anode, and Pt piece is cathode, and saturation KCl electrode is reference electrode, is put into 10mMCuSO4In electroplate liquid；?
Matrix Ti piece and TiO2One layer of Cu is electroplated in the bottom NT.
Step 4: coating one layer of SnO on the titania nanotube prepared using the method for electro-deposition2Among-Ce
Layer, deposition liquid component group are divided into 18gSnCl4·5H2O and 0.7g Ce (NO3)3·6H2O, 0.1g neopelex,
2mlHCl (37%) is dissolved in the ethanol solution of 100ml, current density 20mA/cm2；500 are placed on after room temperature electro-deposition 30min
60min is calcined in DEG C Muffle furnace, obtains middle layer SnO2- Ce, temperature rate are all 5 DEG C/min；
Step 5: by the modified electrode deposition surface active layer of the coating middle layer of step 4 preparation, rare earth Pr doping
PbO2The method that the preparation of surface-active layer uses DC electrodeposition, deposition liquid group are divided into 0.1~0.5M Pb (NO3)2, 0.01~
0.05M La(NO3)3·6H2O and 0.04M NaF, adjusts pH value of solution=2, and current density is set as 50~100mA/cm2, in 60 DEG C
30~60min of lower deposition prepares Ti/Cu-TiO2NT/SnO2-Ce/La-PbO2Electrode.
As a further improvement of the present invention, the Ti/TiO that will have been restored in preparation method step 32NT electrode is anode,
Pt piece is cathode, and saturation KCl electrode is reference electrode, is put into 10mMCuSO4In electroplate liquid；In matrix Ti piece and TiO2The bottom NT
One layer of Cu is electroplated.
As a further improvement of the present invention, the method in preparation method step 4 using electro-deposition is in the dioxy prepared
Change and coats one layer of SnO on titanium nanotube2- Ce middle layer, deposition liquid component group are divided into 18gSnCl4·5H2O and 0.7g Ce
(NO3)3·6H2O, 0.1g neopelex, 2mlHCl (37%) are dissolved in the ethanol solution of 100ml, current density
20mA/cm2；It is placed on after room temperature electro-deposition 30min in 500 DEG C of Muffle furnaces and calcines 60min, obtain middle layer SnO2- Ce, heating and cooling
Rate is all 5 DEG C/min.
3. beneficial effect
Using technical solution provided by the invention, compared with existing well-known technique, there is following remarkable result:
(1) a kind of high catalytic activity Ti/Cu-TiO2NT/SnO2-Ce/La-PbO2 electrode of the invention, using anodic oxygen
The method of change prepares TiO2NT on titanium sheet matrix, and compared to titanium sheet, specific surface area is significantly increased, and provides more depositions
Point.
(2) a kind of high catalytic activity Ti/Cu-TiO2NT/SnO2-Ce/La-PbO2 electrode of the invention, by the way that Cu is electroplated,
It solves between matrix and TiO2NT sometimes in combination with not firm, the big problem of TiO2NT resistance.
(3) a kind of high catalytic activity Ti/Cu-TiO2NT/SnO2-Ce/La-PbO2 electrode of the invention, using electro-deposition
Method one layer of SnO2-Ce middle layer is coated on the titania nanotube prepared so that coating is even closer, improve electricity
The service life of pole.
(4) high catalytic activity Ti/Cu-TiO2NT/SnO2-Ce/La-PbO2 electrode of the invention preparation and its electro-catalysis drop
The method for solving reactive dark blue 194, electrode prepares that simple, easy to operate, equipment is easy to get, process flow is simple, cost of investment is low, this
High-efficient, the electrode good corrosion resistance for the method oxidative degradation removal reactive dark blue 194 that invention provides, degradation process stability
Good, degradation efficiency is higher than common lead electrode, and the degradation rate that the degradation rate of reactive dark blue 194 reaches 99.78%, TOC reaches
99.89%, energy consumption is significantly reduced, and energy consumption reduces by 30%, and degradation side reaction is few, be ensure that degradation high efficiency, is belonged to
Green Chemistry part.
Specific embodiment
To further appreciate that the contents of the present invention, the present invention will be further described with reference to the examples below.
To further appreciate that the contents of the present invention, the present invention is described in detail in conjunction with the embodiments.
Embodiment 1
Prepared by the high catalytic activity Ti/TiO2NT/SnO2-Y/Pr-PbO2 electrode of the present embodiment and its Electrocatalysis Degradation is living
The method of property dark blue 194, specific steps are as follows:
Step 1:
It selects pure titanium metal as titanium sheet, titanium sheet is successively used to three kinds of 600 mesh, 1000 mesh and 2000 mesh different sizes first
Sand paper polish, the then successively supersound washing 10min in dehydrated alcohol, acetone, deionized water by the titanium sheet polished,
Place into ethylene glycol, polishing treatment 10min in the mixed solution of hydrofluoric acid and secondary distilled water, and cleaned with deionized water dry
Only, in which: the volume ratio of hydrofluoric acid, ethylene glycol and secondary distilled water is 1:3:10；
Step 2:
Titania nanotube is prepared using anodizing, is at room temperature 0.5%NH4F and 2V%H2O in mass fraction
Ethylene glycol electrolyte in, anode is made with titanium sheet, Cu piece makees cathode and carries out anodic oxidation, oxidation voltage 60V, oxidization time
7h, oxidation process carry out magnetic agitation always, and soaked in absolute ethyl alcohol sample 2h, dehydrated alcohol ultrasonic cleaning are used after oxidation
10min makes annealing treatment under air atmosphere, 500 DEG C of annealing temperature, keeps the temperature 2h, and heating-cooling speed is all 2 DEG C/min, can be made half
Diameter is 125nm, the Ti/TiO2NT electrode of tube wall 12nm；
Step 3:
The Ti/TiO2NT electrode that step 2 is prepared is saturated KCl electrode as ginseng as anode as cathode, Pt piece
Than electrode, it is put into 1molL-1 (NH4) 2SO4 solution the reductase 12 0s under -1.5V, Ti4+ is reduced into Ti3+；It will restore
Ti/TiO2NT electrode be anode, Pt piece be cathode, saturation KCl electrode be reference electrode, be put into 10mMCuSO4 electroplate liquid；
One layer of Cu is electroplated in matrix Ti piece and the bottom TiO2NT.
Step 4: being coated among one layer of SnO2-Ce on the titania nanotube prepared using the method for electro-deposition
Layer, deposition liquid component group are divided into 18gSnCl45H2O and 0.7gCe (NO3) 36H2O, 0.1g neopelex,
2mlHCl (37%) is dissolved in the ethanol solution of 100ml, current density 20mA/cm2；500 are placed on after room temperature electro-deposition 30min
60min is calcined in DEG C Muffle furnace, obtains middle layer SnO2-Ce, temperature rate is all 5 DEG C/min；
Step 5: by the modified electrode deposition surface active layer of the coating middle layer of step 4 preparation, rare earth Pr doping
The method that the preparation of PbO2 surface-active layer uses DC electrodeposition, deposition liquid group are divided into 0.3M Pb (NO3) 2,0.01M La
(NO3) 36H2O and 0.04MNaF adjusts pH value of solution=2, and current density is set as 50mA/cm2, and 50min system is deposited at 60 DEG C
Standby Ti/Cu-TiO2NT/SnO2-Ce/La-PbO2 electrode；
Step 6: the electrode that step 5 has been modified, as anode, copper electrode is permanent using the constant current of HYL-A type as cathode
Voltage source, 25 DEG C of temperature, current density 70mA/cm2, degradation solution are as follows: 50mg/L reactive dark blue 194,0.5mol/LNa2SO4, electricity
Current utilization efficiency is up to 92.5% in solution preocess, and the degradation rate that the degradation rate of reactive dark blue 194 reaches 99.6%, TOC reaches
99.5%.
Embodiment 2
The high catalytic activity Ti/Cu-TiO2NT/SnO2-Ce/La-PbO2 electrode of the present embodiment prepares and its electro-catalysis drop
Solve reactive dark blue 194 method, process substantially with embodiment 1, the difference is that: Step 1:
It selects pure titanium metal as titanium sheet, titanium sheet is successively used to three kinds of 600 mesh, 1000 mesh and 2000 mesh different sizes first
Sand paper polish, the then successively supersound washing 10min in dehydrated alcohol, acetone, deionized water by the titanium sheet polished,
Place into ethylene glycol, polishing treatment 10min in the mixed solution of hydrofluoric acid and secondary distilled water, and cleaned with deionized water dry
Only, in which: the volume ratio of hydrofluoric acid, ethylene glycol and secondary distilled water is 1:3:10；
Step 2:
Titania nanotube is prepared using anodizing, is at room temperature 0.5%NH4F and 2V%H2O in mass fraction
Ethylene glycol electrolyte in, anode is made with titanium sheet, Cu piece makees cathode and carries out anodic oxidation, oxidation voltage 60V, oxidization time
7h, oxidation process carry out magnetic agitation always, and soaked in absolute ethyl alcohol sample 2h, dehydrated alcohol ultrasonic cleaning are used after oxidation
10min makes annealing treatment under air atmosphere, 500 DEG C of annealing temperature, keeps the temperature 2h, and heating-cooling speed is all 2 DEG C/min, can be made half
Diameter is 125nm, the Ti/TiO2NT electrode of tube wall 12nm；
Step 3:
The Ti/TiO2NT electrode that step 2 is prepared is saturated KCl electrode as ginseng as anode as cathode, Pt piece
Than electrode, it is put into 1molL-1 (NH4) 2SO4 solution the reductase 12 0s under -1.5V, Ti4+ is reduced into Ti3+；It will restore
Ti/TiO2NT electrode be anode, Pt piece be cathode, saturation KCl electrode be reference electrode, be put into 10mMCuSO4 electroplate liquid；
One layer of Cu is electroplated in matrix Ti piece and the bottom TiO2NT.
Step 4: being coated among one layer of SnO2-Ce on the titania nanotube prepared using the method for electro-deposition
Layer, deposition liquid component group are divided into 18gSnCl45H2O and 0.7gCe (NO3) 36H2O, 0.1g neopelex,
2mlHCl (37%) is dissolved in the ethanol solution of 100ml, current density 20mA/cm2；500 are placed on after room temperature electro-deposition 30min
60min is calcined in DEG C Muffle furnace, obtains middle layer SnO2-Ce, temperature rate is all 5 DEG C/min；
Step 5: by the modified electrode deposition surface active layer of the coating middle layer of step 4 preparation, rare earth Pr doping
The method that the preparation of PbO2 surface-active layer uses DC electrodeposition, deposition liquid group are divided into 0.5M Pb (NO3) 2,0.05M La
(NO3) 36H2O and 0.04MNaF, adjusts pH value of solution=3, and current density is set as 100mA/cm2, deposits 40min at 60 DEG C
Prepare Ti/Cu-TiO2NT/SnO2-Ce/La-PbO2 electrode；
Step 6: the electrode that step 5 has been modified, as anode, copper electrode is permanent using the constant current of HYL-A type as cathode
Voltage source, 25 DEG C of temperature, current density 70mA/cm2, degradation solution are as follows: 50mg/L reactive dark blue 194,0.5mol/LNa2SO4, electricity
Current utilization efficiency is up to 93.4% in solution preocess, and the degradation rate that the degradation rate of reactive dark blue 194 reaches 99.7%, TOC reaches
99.8%.
A kind of high catalytic activity Ti/TiO2NT/SnO2-Y/Pr-PbO2 electrode of the present embodiment invention, middle layer SnO2 tool
Have and improves the use longevity of electrode so that figure layer is closer with lattice dimensions similar in TiO2 and PbO2, solid solution easy to form
Life, and the adjustable gas evolution current potential of SnO2, to effectively prevent the diffusion of nascent oxygen.By dilute in surface-active layer
The doping of native Pr makes the lattice dilatation of PbO2, and particle becomes smaller, and specific surface increases, and improves more electronics transfer active sites, solves
It has determined the uppity problem of its granule-morphology in the prior art, compared with pure PbO2, electro-catalysis position increases, and increased activity is
Being modified using Ti/Cu-TiO2NT/SnO2-Ce/La-PbO2 in a kind of electrode embodiment 1~2 of the high catalytic efficiency of high activity
The method that electrode electrocatalytic oxidation handles methyl blue, using the high activity Ti/Cu-TiO2NT/SnO2- of homemade doping vario-property
Ce/La-PbO2 modified electrode is as anode, and electrode should not inactivate in degradation process, electrode good corrosion resistance, electrolytic process selection
Property it is good, electrolysis side reaction is few, and degradation efficiency is high, and reaction condition is mild, does not need plus catalyst, easy to operate, equipment is easy to get,
Process flow is simple, cost of investment is low, and preparation is green, pollution-free with degradation process.Remove high-efficient, the electrode corrosion resistant of methyl blue
Corrosion is good, and degradation process stability is good, and degradation efficiency is higher than common lead electrode, and the degradation rate of reactive dark blue 194 reaches
The degradation rate of 99.78%, TOC reach 99.89%, energy consumption is significantly reduced, and energy consumption reduces by 30%.
Schematically the present invention and embodiments thereof are described above, description is not limiting, in embodiment
Shown in be also one of embodiments of the present invention, actual structure is not limited to this.So if this field it is common
Technical staff is enlightened by it, without departing from the spirit of the invention, is not inventively designed and the technical side
The similar frame mode of case and embodiment, are within the scope of protection of the invention.
Claims (10)
1. a kind of high catalytic activity Ti/Cu-TiO2NT/SnO2-Ce/La-PbO2Electrode, which is characterized in that first use anodic oxidation
Method prepares Ti/TiO2NT electrode, wherein Ti/TiO2NT electrode radius is 125nm, tube wall 12nm, by electroreduction by Ti4+
It is reduced into Ti3+, the Ti/TiO that will restore2NT electrode is anode, and Pt piece is cathode, and saturation KCl electrode is reference electrode, is put into
10mMCuSO4In electroplate liquid；In matrix Ti piece and TiO2One layer of Cu is electroplated in the bottom NT, then is being prepared using the method for electro-deposition
Titania nanotube on coat one layer of SnO2- Ce middle layer, deposition liquid group are divided into 18gSnCl4·5H2O and 0.7g Ce
(NO3)3·6H2The HCl of O, 0.1g neopelex, 2ml37% is dissolved in the ethanol solution of 100ml, current density
20mA/cm2；It is placed on after room temperature electro-deposition 30min in 500 DEG C of Muffle furnaces and calcines 60min, obtain middle layer SnO2- Ce, rare earth La
Adulterate PbO2The method that the preparation of surface-active layer uses DC electrodeposition, deposition liquid group are divided into 0.1~0.5M Pb (NO3)2,
0.01~0.05M La (NO3)3·6H2O and 0.04M NaF, adjusts pH value of solution=2, and current density is set as 50~100mA/cm2,
30~60min of electro-deposition at 60 DEG C.
2. a kind of high catalytic activity Ti/Cu-TiO according to claim 12NT/SnO2-Ce/La-PbO2Electrode, preparation
Specific steps are as follows:
Step 1:
It selects pure titanium metal as titanium sheet, titanium sheet is successively used to the sand of 600 mesh, 1000 mesh and 2,000 three kinds of different sizes of mesh first
Paper is polished, then the successively supersound washing 10min in dehydrated alcohol, acetone, deionized water by the titanium sheet polished, then is put
Enter ethylene glycol, polishing treatment 10min in the mixed solution of hydrofluoric acid and secondary distilled water, and cleaned up with deionized water,
In: the volume ratio of hydrofluoric acid, ethylene glycol and secondary distilled water is 1:3:10；
Step 2:
Titania nanotube is prepared using anodizing, is at room temperature 0.5%NH in mass fraction4F and volume fraction are
2%H2In the ethylene glycol electrolyte of O, anode is made with titanium sheet, Cu piece makees cathode and carries out anodic oxidation, oxidation voltage 60V, oxidation
Time 7h,
Oxidation process carries out magnetic agitation always, and soaked in absolute ethyl alcohol sample 2h, dehydrated alcohol ultrasonic cleaning are used after oxidation
10min,
It is made annealing treatment under air atmosphere, 500 DEG C of annealing temperature, keeps the temperature 2h, heating-cooling speed is all 2 DEG C/min, and radius can be made
For 125nm, the Ti/TiO of tube wall 12nm2NT electrode；
Step 3:
The Ti/TiO that step 2 is prepared2NT electrode is saturated KCl electrode as reference electricity as anode as cathode, Pt piece
Pole is put into 1molL-1(NH4)2SO4In solution under -1.5V reductase 12 0s, Ti4+It is reduced into Ti3+；The Ti/ that will have been restored
TiO2NT electrode is anode, and Pt piece is cathode, and saturation KCl electrode is reference electrode, is put into 10mMCuSO4In electroplate liquid；In matrix
Ti piece and TiO2One layer of Cu is electroplated in the bottom NT；
Step 4: coating one layer of SnO on the titania nanotube prepared using the method for electro-deposition2- Ce middle layer is sunk
Hydrops group is divided into 18gSnCl4·5H2O and 0.7g Ce (NO3)3·6H2O, 0.1g neopelex, the HCl of 2ml37%
It is dissolved in the ethanol solution of 100ml, current density 20mA/cm2；It is placed in 500 DEG C of Muffle furnaces and forges after room temperature electro-deposition 30min
60min is burnt, middle layer SnO is obtained2- Ce, temperature rate are all 5 DEG C/min；
Step 5: by the modified electrode deposition surface active layer of the coating middle layer of step 4 preparation, Doping with Rare Earth Lanthanum PbO2Surface
The method that the preparation of active layer uses DC electrodeposition, deposition liquid group are divided into 0.1~0.5M Pb (NO3)2, 0.01~0.05MLa
(NO3)3·6H2O and 0.04M NaF, adjusts pH value of solution=2, and current density is set as 50~100mA/cm2, 30 are deposited at 60 DEG C
~60min prepares Ti/Cu-TiO2NT/SnO2-Ce/La-PbO2Electrode.
3. a kind of high catalytic activity Ti/Cu-TiO according to claim 22NT/SnO2-Ce/La-PbO2Electrode, feature
Be: pure titanium metal uses TA in preparation method step 11The pure titanium metal of type, purity 99.9%.
4. a kind of high catalytic activity Ti/Cu-TiO according to claim 32NT/SnO2-Ce/La-PbO2Electrode, feature
It is: the Ti/TiO that will have been restored in preparation method step 32NT electrode is anode, and Pt piece is cathode, and saturation KCl electrode is ginseng
Than electrode, it is put into 10mMCuSO4In electroplate liquid；In matrix Ti piece and TiO2One layer of Cu is electroplated in the bottom NT.
5. a kind of high catalytic activity Ti/Cu-TiO according to claim 42NT/SnO2-Ce/La-PbO2Electrode, feature
It is: one layer of SnO is coated on the titania nanotube prepared using the method for electro-deposition in preparation method step 42-
Ce middle layer, deposition liquid group are divided into 18gSnCl4·5H2O and 0.7g Ce (NO3)3·6H2O, 0.1g neopelex,
2ml37%HCl is dissolved in the ethanol solution of 100ml, current density 20mA/cm2；500 DEG C are placed on after room temperature electro-deposition 30min
60min is calcined in Muffle furnace, obtains middle layer SnO2- Ce, temperature rate are all 5 DEG C/min.
6. a kind of high catalytic activity Ti/Cu-TiO2NT/SnO2-Ce/La-PbO2The side of electrode Electrocatalysis Degradation reactive dark blue 194
Method the steps include:
1) high catalytic activity Ti/Cu-TiO2NT/SnO2-Ce/La-PbO2 electrode is prepared
Ti/TiO is first prepared using anodizing2NT electrode, wherein Ti/TiO2NT electrode radius is 125nm, and tube wall is
12nm, by electroreduction by Ti4+It is reduced into Ti3+, the Ti/TiO that will restore2NT electrode is anode, and Pt piece is cathode, saturation
KCl electrode is reference electrode, is put into 10mMCuSO4In electroplate liquid；In matrix Ti piece and TiO2One layer of Cu is electroplated in the bottom NT, then adopts
One layer of SnO is coated on the titania nanotube prepared with the method for electro-deposition2- Ce middle layer, deposition liquid group are divided into
18gSnCl4·5H2O and 0.7gCe (NO3)3·6H2The HCl of O, 0.1g neopelex, 2ml37% is dissolved in 100ml
Ethanol solution in, current density 20mA/cm2；It is placed on after room temperature electro-deposition 30min in 500 DEG C of Muffle furnaces and calcines 60min, obtained
To middle layer SnO2- Ce, Doping with Rare Earth Lanthanum PbO2The method that the preparation of surface-active layer uses DC electrodeposition, deposits liquid component
For 0.1~0.5MPb (NO3)2, 0.01~0.05MLa (NO3)3·6H2O and 0.04MNaF adjusts pH value of solution=3, current density
It is set as 50~100mA/cm2, 30~60min of electro-deposition prepares Ti/Cu-TiO at 60 DEG C2NT/SnO2-Ce/L a-PbO2Electricity
Pole；
2) Electrocatalysis Degradation reactive dark blue 194；
3) using the modification Ti/Cu-TiO2NT/SnO2-Ce/La-PbO2 electrode prepared in step 1 as anode, copper electrode conduct
Cathode, using constant voltage supply, 25 DEG C of temperature, current density 70mA/cm2, degradation solution are as follows: 50mg/L reactive dark blue 194+
0.5mol/LNa2SO4 adjusts pH value of solution=6.
7. a kind of high catalytic activity Ti/Cu-TiO according to claim 62NT/SnO2-Ce/La-PbO2Electrode electro-catalysis
The method of degrading activity dark blue 194, it is characterised in that: high catalytic activity Ti/Cu-TiO2NT/SnO2-Ce/ is prepared in step 1)
The specific steps of La-PbO2 electrode are as follows:
Step 1:
It selects pure titanium metal as titanium sheet, titanium sheet is successively used to the sand of 600 mesh, 1000 mesh and 2,000 three kinds of different sizes of mesh first
Paper is polished, then the successively supersound washing 10min in dehydrated alcohol, acetone, deionized water by the titanium sheet polished, then is put
Enter ethylene glycol, polishing treatment 10min in the mixed solution of hydrofluoric acid and secondary distilled water, and cleaned up with deionized water,
In: the volume ratio of hydrofluoric acid, ethylene glycol and secondary distilled water is 1:3:10；
Step 2:
Titania nanotube is prepared using anodizing, is at room temperature 0.5%NH in mass fraction4F and volume fraction are
2%H2In the ethylene glycol electrolyte of O, anode is made with titanium sheet, Cu piece makees cathode and carries out anodic oxidation, oxidation voltage 60V, oxidation
Time 7h,
Oxidation process carries out magnetic agitation always, and soaked in absolute ethyl alcohol sample 2h, dehydrated alcohol ultrasonic cleaning are used after oxidation
10min,
It is made annealing treatment under air atmosphere, 500 DEG C of annealing temperature, keeps the temperature 2h, heating-cooling speed is all 2 DEG C/min, and radius can be made
For 125nm, the Ti/TiO of tube wall 12nm2NT electrode；
Step 3:
The Ti/TiO that step 2 is prepared2NT electrode is saturated KCl electrode as reference electricity as anode as cathode, Pt piece
Pole is put into 1molL-1(NH4)2SO4In solution under -1.5V reductase 12 0s, Ti4+It is reduced into Ti3+；The Ti/ that will have been restored
TiO2NT electrode is anode, and Pt piece is cathode, and saturation KCl electrode is reference electrode, is put into 10mMCuSO4In electroplate liquid；In matrix
Ti piece and TiO2One layer of Cu is electroplated in the bottom NT；
Step 4: coating one layer of SnO on the titania nanotube prepared using the method for electro-deposition2- Ce middle layer is sunk
Hydrops group is divided into 18gSnCl4·5H2O and 0.7gCe (NO3)3·6H2O, 0.1g neopelex, the HCl of 2ml37%
It is dissolved in the ethanol solution of 100ml, current density 20mA/cm2；It is placed in 500 DEG C of Muffle furnaces and forges after room temperature electro-deposition 30min
60min is burnt, middle layer SnO is obtained2- Ce, temperature rate are all 5 DEG C/min；
Step 5: by the modified electrode deposition surface active layer of the coating middle layer of step 4 preparation, Doping with Rare Earth Lanthanum PbO2Surface
The method that the preparation of active layer uses DC electrodeposition, deposition liquid group are divided into 0.1~0.5M Pb (NO3)2, 0.01~0.05MLa
(NO3)3·6H2O and 0.04M NaF, adjusts pH value of solution=2, and current density is set as 50~100mA/cm2, 30 are deposited at 60 DEG C
~60min prepares Ti/Cu-TiO2NT/SnO2-Ce/La-PbO2Electrode.
8. a kind of high catalytic activity Ti/Cu-TiO according to claim 72NT/SnO2-Ce/La-PbO2Electrode electro-catalysis
The method of degrading activity dark blue 194, it is characterised in that: pure titanium metal uses TA in preparation method step 11The pure titanium metal of type,
Its purity is 99.9%.
9. a kind of high catalytic activity Ti/Cu-TiO according to claim 82NT/SnO2-Ce/La-PbO2Electrode electro-catalysis
The method of degrading activity dark blue 194, it is characterised in that: the Ti/TiO that will have been restored in preparation method step 32NT electrode is sun
Pole, Pt piece are cathode, and saturation KCl electrode is reference electrode, are put into 10mMCuSO4In electroplate liquid；In matrix Ti piece and TiO2The bottom NT
One layer of Cu is electroplated in portion.
10. a kind of high catalytic activity Ti/Cu-TiO according to claim 92NT/SnO2-Ce/La-PbO2Electrode electro-catalysis
The method of degrading activity dark blue 194, it is characterised in that: the method in preparation method step 4 using electro-deposition is in two prepared
One layer of SnO is coated on titanium oxide nanotubes2- Ce middle layer, deposition liquid group are divided into 18gSnCl4·5H2O and 0.7g Ce (NO3)3·
6H2The HCl of O, 0.1g neopelex, 2ml37% is dissolved in the ethanol solution of 100ml, current density 20mA/
cm2；It is placed on after room temperature electro-deposition 30min in 500 DEG C of Muffle furnaces and calcines 60min, obtain middle layer SnO2- Ce, temperature rate is all
For 5 DEG C/min.
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| CN105195161A (en) * | 2015-09-30 | 2015-12-30 | 淮南师范学院 | Ti/TiO2NT/Yb-Fe2O3-PbO2 electrode and method for degrading paraquat through electro-catalysis |
| 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 |
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| 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 |
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