CN110054262A - A kind of ternary modified titanium-matrix electrode, preparation method and application - Google Patents

A kind of ternary modified titanium-matrix electrode, preparation method and application Download PDF

Info

Publication number
CN110054262A
CN110054262A CN201910447920.0A CN201910447920A CN110054262A CN 110054262 A CN110054262 A CN 110054262A CN 201910447920 A CN201910447920 A CN 201910447920A CN 110054262 A CN110054262 A CN 110054262A
Authority
CN
China
Prior art keywords
electrode
ternary
titanium
solution
matrix electrode
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201910447920.0A
Other languages
Chinese (zh)
Inventor
张王兵
冷迪
赵万鑫
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Anhui University of Technology AHUT
Original Assignee
Anhui University of Technology AHUT
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Anhui University of Technology AHUT filed Critical Anhui University of Technology AHUT
Priority to CN201910447920.0A priority Critical patent/CN110054262A/en
Publication of CN110054262A publication Critical patent/CN110054262A/en
Pending legal-status Critical Current

Links

Classifications

    • 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
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/76—Treatment of water, waste water, or sewage by oxidation with halogens or compounds of halogens
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • C02F1/46104—Devices therefor; Their operating or servicing
    • C02F1/46109—Electrodes
    • C02F2001/46133—Electrodes characterised by the material
    • C02F2001/46138—Electrodes comprising a substrate and a coating
    • C02F2001/46142—Catalytic coating
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C02F2101/308—Dyes; Colorants; Fluorescent agents
    • 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
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2201/00—Apparatus for treatment of water, waste water or sewage
    • C02F2201/46—Apparatus for electrochemical processes
    • C02F2201/461—Electrolysis apparatus
    • C02F2201/46105—Details relating to the electrolytic devices
    • C02F2201/4612—Controlling or monitoring
    • C02F2201/46125—Electrical variables
    • C02F2201/4614—Current
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2201/00—Apparatus for treatment of water, waste water or sewage
    • C02F2201/46—Apparatus for electrochemical processes
    • C02F2201/461—Electrolysis apparatus
    • C02F2201/46105—Details relating to the electrolytic devices
    • C02F2201/4618—Supplying or removing reactants or electrolyte
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2305/00—Use of specific compounds during water treatment
    • C02F2305/02—Specific form of oxidant
    • C02F2305/023—Reactive oxygen species, singlet oxygen, OH radical

Landscapes

  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Water Treatment By Electricity Or Magnetism (AREA)
  • Electrodes For Compound Or Non-Metal Manufacture (AREA)

Abstract

The invention discloses a kind of preparation methods of the modified titanium-matrix electrode of ternary, include the following steps: to immerse oxalic acid solution after Titanium base is polished, 90 DEG C of water-bath acid etching 1h, and it is stand-by then to clean up preservation；Take SnCl2·2H2O is placed in container, and n-butanol, Ti (OC are then sequentially added into container4H9)4Solution, after mixing, dissolution obtains Sn/Ti coating liquid under ultrasound condition；Sn/Ti coating liquid is coated in pretreated titanium plate surface, is then dried；Titanium sheet after drying is immersed into Pb (NO3)2Solution takes out drying after impregnating 30~50s, 1~1.5h is then fired at 300~600 DEG C, is finally cooled to room temperature and obtains the modified titanium-matrix electrode of ternary, rear PbO is used for multiple times in ternary modified electrode of the invention2Active layer keeps good integrality, durable, high to the degradation efficiency of aniline dyes waste water.

Description

A kind of ternary modified titanium-matrix electrode, preparation method and application
Technical field
The invention belongs to electrode fabrication field more particularly to a kind of ternary modified titanium-matrix electrode, preparation method and answer With.
Background technique
China is DYE PRODUCTION big country, in recent years textile dyestuff rapid industrial development, and the various DYE PRODUCTIONs in China are total at present Amount accounts for the 60% of whole world dyestuff yield up to 900,000 tons.Wherein, aniline dyes due to its lovely luster, answer by good water solubility With it is simple the advantages that and be widely used in printing and dyeing industry.During producing aniline dyes, nitrification, condensation, diazotising, The techniques such as coupling can generate waste liquid, and a large amount of suspended matter, ammonia nitrogen class intermediate are contained in these waste liquids.Therefore, aniline dyes Chroma in waste water is big, COD high, not easy to handle.
Technology using Electrode treatment waste water includes handling waste water using high boron-doped diamond electrode ink, (high using AOP Grade oxidation processes) technology is degraded or decomposing organic pollutant, and the COD (chemical oxygen consumption (COC)) for reducing waste water has good Effect.However due to that can generate amount of heat when electrode works, electrode base material has temperature difference and expand with diamond film is Number is different, and the diamond film for causing electrode to show is easy to produce crackle during the work time, leads to electrode damage.Additionally, due to benzene The degradation of amine dyestuff has its particularity, therefore existing electrode is lower for the degradation rate of aniline dyes waste water.
Summary of the invention
Technical problem to be solved by the present invention lies in: existing electrode is easy to damage in aniline degradation class waste water from dyestuff, drops Solution rate is lower, provides a kind of ternary modified titanium-matrix electrode, preparation method and application.
The present invention is that solution above-mentioned technical problem, a kind of modified titanium-based of ternary of the invention are electric by the following technical programs The preparation method of pole, includes the following steps:
(1) pre-processing titanium matrix:
Pickling solution is immersed after Titanium base is polished, 90 DEG C of water-bath acid etching 1h take out cleaning, are placed in preservation liquid and save；
(2) Sn/Ti coating liquid is prepared:
Take SnCl2·2H2O is placed in container, and n-butanol, Ti (OC are then sequentially added into container4H9)4Solution, mixing After uniformly, dissolved under ultrasound condition；
The SnCl2·2H2O, n-butanol total in Sn/Ti coating liquid, Ti (OC4H9)4Mass ratio be (0.4~ 1.4):3:0.2；
(3) Sn/Ti intermediate oxide layer is prepared:
Sn/Ti coating liquid is coated in pretreated Titanium base surface, is then dried, repetitive coatings, baking step 3~ 5 times, obtain Sn/Ti intermediate oxide layer；
(4) PbO is prepared2Active layer:
Pb (NO is impregnated on Sn/Ti intermediate oxide layer surface3)2Then solution is dried, calcines, is cooled to room temperature, repeat Above-mentioned steps 3~5 times, prepare PbO2Active layer obtains the modified titanium-matrix electrode of ternary.
It in the step (1), is successively polished with the sand paper of 360 mesh, 600 mesh Titanium base, pickling solution is that quality is dense The oxalic acid solution that degree is 8% saves the oxalic acid solution that liquid is 2%.
In the step (2), Ti (OC4H9)4The concentration of solution is 0.2g/mL, and solvent is n-butanol.
In the step (3), Sn/Ti coating liquid is dried using infrared lamp.
In the step (4), Pb (NO3)2Solution concentration is 0.03~0.09mol/L, 30~50s of soaking time, and use is red Outer lamp is to Pb (NO3)2Solution is dried, and 300~600 DEG C of calcination temperature, 1~1.5h of calcination time.
A kind of modified titanium-matrix electrode of ternary that the preparation method by the modified titanium-matrix electrode of ternary is prepared, including titanium-based Body, middle layer, active layer, the intermediate layer material include Sn/Ti oxide, and the active layer substance includes PbO2, the Sn/ Ti oxide includes SnO, SnO2、TiO2。
A kind of electro-oxidation processes using the modified titanium-matrix electrode processing aniline dyes waste water of ternary, use the ternary Modified titanium-matrix electrode establishes reaction member, and the anode of the reaction member is the modified titanium-matrix electrode of ternary, and cathode is graphite electrode.
The current density of the electro-oxidation processes is 10~30mA/cm2, supporting electrolyte Na2SO4With the mixing of NaCl The contact area of solution, the electrode and waste water is 3~5cm2, electrode spacing is 1~2.5cm, the graphite electrode and ternary Modified titanium-matrix electrode specification is identical.
The Na2SO40.3~0.9g/L of concentration of solution, 1~5g/L of concentration of NaCl solution.
The aniline dyes waste water includes methyl orange dye waste water, rhdamine B waste water, methylene blue dye wastewater One or more of combination.
The electro-oxidation processes generate oxidizer containing chlorine, and the aniline dyes in the waste water are made in the oxidizer containing chlorine Rudimentary organic matter is degraded under.
The degradation rate of the aniline dyes is 69.8~98.8%.
The working principle of aniline dyes R in the electro-oxidation processes degrading waste water is as follows:
Under current field condition, PbO2Active layer is catalyzed the OH that the water in waste water generates free state:
H2O→·OH+H++e-,
R+·OH→CO2+H2O,
When OH is more in waste water, OH, which can be generated, to be buried in oblivion:
2·OH→H2O+1/2O2,
Under electric field action, when in waste water there are when chlorine, PbO2Active layer catalysis chlorine reacted with OH generation Cl, HClO、ClO-Equal oxidants:
2Cl-→Cl2+ 2e-,
Cl2+·OH→HClO+Cl-,
OH, Cl, HClO, ClO of generation-Equal oxidants have very strong oxidation, aoxidize in aniline dyes Aniline structure generates degradable organic matter.By taking methyl orange as an example, the reaction mechanism is as follows for Strong oxdiative group and dye molecule:
In the preparation method of ternary modified electrode of the invention, the PbO of preparation2Active layer is not only urged in electro-oxidation process Change hydroxyl radical free radical to generate, is further catalyzed chlorine and generates Cl, HClO, ClO-Equal oxidizer containing chlorines, oxidizer containing chlorine is to benzene The degradation rate of amine dyestuff is higher than other oxidants, facilitates the degradation to aniline dyes waste water；Calcining preparation PbO2Activity In the reaction of layer, Titanium base and PbO2There are temperature differences for active layer, and the coefficient of expansion of the two is different, is easy to produce active layer Crackle, therefore it is PbO that Sn/Ti intermediate oxide layer, which is arranged,2Active layer provides protection, and avoiding cracking leads to electrode damage.
The ternary modified electrode of this method preparation includes Titanium base, Sn/Ti intermediate oxide layer, PbO2Active layer, it is intermediate Layer provides protection for active layer, durable, after being used for multiple times, PbO2Active layer keeps good integrality, durability It is high；In electro-oxidation processes, PbO2Active layer catalysis generates hydroxyl radical free radical, Cl, HClO, ClO-Equal oxidizer containing chlorines, to benzene Amine waste water from dyestuff has extremely strong specific aim, and degradation efficiency is high；NaCl is not only the supporting electrolyte in electrochemical reaction, also Reactant is provided for the generation reaction of oxidizer containing chlorine.
The present invention has the advantage that rear PbO is used for multiple times in ternary modified electrode of the invention compared with prior art2Activity Layer keeps good integrality, durable, high to the degradation efficiency of aniline dyes waste water.
Detailed description of the invention
Fig. 1 is the modified titanium-matrix electrode structural schematic diagram of ternary,
1,5- electrode connection points, 2-PbO2Active layer, 3- Titanium base, 4-Sn/Ti intermediate oxide layer；
Fig. 2 is the SEM figure of active layer before and after the use of A2 electrode；
Fig. 3 is active layer SEM figure before and after the use of B2 electrode；
Fig. 4 is active layer SEM figure before and after the use of C3 electrode；
Fig. 5 is the electrode use front and back active layer SEM figure of D2；
Fig. 6 is active layer SEM figure before and after the use of E2 electrode；
Fig. 7 is the impedance characterization result of each preference electrode in Examples 1 to 5；
Fig. 8 is titanium-based surface distribution situation of each element in ternary modified electrode,
1-Ti, 2-Sn, 3-Pb, 4-O.
Specific embodiment
It elaborates below to the embodiment of the present invention, the present embodiment carries out under the premise of the technical scheme of the present invention Implement, the detailed implementation method and specific operation process are given, but protection scope of the present invention is not limited to following implementation Example.
Embodiment 1
As shown in Figure 1, the modified titanium-matrix electrode of ternary manufactured in the present embodiment include Titanium base, Sn/Ti intermediate oxide layer, PbO2Active layer, it is different from Ti mass ratio according to Sn in Sn/Ti coating liquid, prepare respectively three ternary modified electrode sample A1, A2, A3, the corresponding Sn and Ti mass ratio of the Sn/Ti intermediate oxide layer of A1, A2, A3 are shown in Table 1, and preparation process is as follows:
(1) Titanium base is pre-processed:
Titanium base has successively been polishing to metallic luster with 360 mesh and 600 mesh sand paper, Titanium base is then immersed 8% In oxalic acid solution, rough grey pitted skin, no metallic luster, by acid etching is presented in 90 DEG C of water-bath acid etching 1h, Titanium base surface Good Titanium base takes out, and is put into 2% oxalic acid solution and is saved for use after cleaning up；
(2) Sn/Ti coating liquid is prepared:
The SnCl of 0.52g, 0.87g, 1.21g are accurately weighed in assay balance2·2H2O is respectively put into the plastics of 4 4mL In centrifuge tube, n-butanol solvent is then added to 3mL, is eventually adding the Ti (OC that concentration is 0.2g/mL4H9)4Solution is to 4mL.It is suitable After concussion, being put into ultrasonic machine dissolves it sufficiently；
(3) Sn/Ti intermediate oxide layer is prepared:
SnCl is coated on pretreated Titanium base surface2·2H2O and Ti (OC4H9)4The different Sn/Ti coating liquid of mass ratio, It is dried, is repeated the above steps 3 times using infrared lamp after coating uniformly, prepare Sn/Ti intermediate oxide layer；
(4) PbO is prepared2Active layer:
0.03mol/L Pb (NO is impregnated on Sn/Ti intermediate oxide layer surface3)2Solution takes out after 30s, and utilization is infrared Lamp drying, is then placed in 300 DEG C of baking ovens and fires 1h, be finally cooled to room temperature, repeat the above steps 3 times, prepares PbO2Activity The modified titanium-matrix electrode of ternary is made in layer.
The Sn/Ti intermediate oxide layer preparation process table of table 1 sample A1, A2, A3
It the use of A1, A2, A3 electrode difference concentration for the treatment of is 100mg/L containing methyl orange, methylene blue, three kinds of rhodamine B The simulated wastewater 250mL of dyestuff, the technological parameter of electroxidation are as follows: current density 10mA/cm2, contact of the electrode with waste water Area is 3cm2, electrode spacing 1cm, electrolysis time 40min, Na2SO4Concentration 0.3g/L, NaCl concentration 1g/L.
After treatment, using the absorbance of 722 type spectrophotometer measurement simulated wastewaters, comparison electrolysis front and back simulation is useless The absorbance of water calculates the modified titanium-matrix electrode of ternary of preparation to the degradation rate of three kinds of dyestuffs, the results are shown in Table 4.As shown in Table 4, As SnCl in Sn/Ti coating liquid2·2H2SnO when O concentration increases, in electrode Sn/Ti intermediate oxide layer2Content increases, electricity Electrode resistance increases, and oxidation efficiency reduces, and works as SnCl2·2H2O and Ti (OC4H9)4When mass ratio is 3:1, to the degradation efficiency of dyestuff Preferably 98%.
Fig. 2 is the SEM figure of active layer before and after the use of preference A2 electrode, and left figure is the SEM figure before use, and right figure is processing SEM schemes after waste water 18h, uses rear PbO2Active layer keeps good integrality.
Embodiment 2
The present embodiment is according to the Pb (NO of dipping3)2Solution concentration is different, prepare respectively three ternary modified electrode sample B1, B2, B3, sample B1, B2, B3 and Pb (NO3)2Solution concentration corresponding relationship is shown in Table 2, and preparation process is as follows:
(1) Titanium base is pre-processed:
Titanium base has successively been polishing to metallic luster with 360 mesh and 600 mesh sand paper, Titanium base is then immersed 8% In oxalic acid solution, rough grey pitted skin, no metallic luster, by acid etching is presented in 90 DEG C of water-bath acid etching 1h, Titanium base surface Good Titanium base takes out, and is put into 2% oxalic acid solution and is saved for use after cleaning up；
(2) Sn/Ti coating liquid is prepared:
The SnCl of 0.87g is accurately weighed in assay balance2·2H2O is put into the plastic centrifuge tube of 4mL, is then added just Butanol solvent is eventually adding the Ti (OC that concentration is 0.2g/mL to 3mL4H9)4To 4mL.After appropriate concussion, being put into ultrasonic machine makes It is sufficiently dissolved；
(3) Sn/Ti intermediate oxide layer is prepared:
SnCl is coated on pretreated Titanium base surface2·2H2O and Ti (OC4H9)4The Sn/Ti that mass ratio is 4.4:1 is coated Liquid is dried after coating uniformly using infrared lamp, repetitive coatings baking step 5 times, and Sn/Ti intermediate oxide layer is prepared；
(4) PbO is prepared2Active layer:
Various concentration Pb (NO is impregnated on Sn/Ti intermediate oxide layer surface3)2Solution takes out after impregnating 40s, and utilization is infrared Lamp drying, is then placed in 450 DEG C of baking ovens and fires 1.2h, is finally cooled to room temperature, repeats above step 3 times, prepares PbO2It is living Property layer, obtain the modified titanium-matrix electrode of ternary.
Other embodiments are the same as embodiment 1.
It the use of electrode B 1, B2, B3 difference concentration for the treatment of is 100mg/L containing methyl orange, methylene blue, three kinds of rhodamine B The simulated wastewater 250mL of dyestuff the results are shown in Table 4 to the degradation rate of three kinds of dyestuffs.As seen from the results in Table 4, nitric acid lead concentration changes Becoming influences less dyestuff degradation rate, but lead oxide is used as catalyst in degradation reaction, accelerates hydroxyl free in electrolytic process The generation of base, if electrode surface active layer does not aoxidize lead finish, the degradation rate of dyestuff is very slow.
Fig. 3 is active layer SEM figure before and after the use of preference B2 electrode, and left figure is to be schemed using preceding SEM, and right figure is processing waste water SEM schemes after 18h, uses rear PbO2Active layer keeps good integrality.
2 sample B1, B2, B3 and Pb (NO of table3)2Solution concentration corresponds to table
Sample label Pb(NO3)2Solution concentration/mol/L
B1 0
B2 0.03
B3 0.07
Embodiment 3
The present embodiment is different according to the calcination temperature for preparing Sn/Ti intermediate oxide layer, and it is modified to prepare three ternarys respectively Electrode sample C1, C2, C3, sample C1, C2, C3 and calcination temperature corresponding relationship are shown in Table 3, and preparation process is as follows:
(1) Titanium base is pre-processed:
Titanium base has successively been polishing to metallic luster with 360 mesh and 600 mesh sand paper, Titanium base is then immersed 8% In oxalic acid solution, rough grey pitted skin, no metallic luster, by acid etching is presented in 90 DEG C of water-bath acid etching 1h, Titanium base surface Good Titanium base takes out, and is put into 2% oxalic acid solution and is saved for use after cleaning up；
(2) Sn/Ti coating liquid is prepared:
The SnCl of 0.87g is accurately weighed in assay balance2·2H2O is put into the plastic centrifuge tube of 4mL, is then added just Butanol solvent is eventually adding the Ti (OC that concentration is 0.2g/mL to 3mL4H9)4To 4mL.After appropriate concussion, being put into ultrasonic machine makes It is sufficiently dissolved；
(3) Sn/Ti intermediate oxide layer is prepared:
SnCl is coated on pretreated Titanium base surface2·2H2O and Ti (OC4H9)4The Sn/Ti that mass ratio is 4.4:1 is coated Liquid is dried using infrared lamp after coating uniformly, is repeated the above steps 3 times, and Sn/Ti intermediate oxide layer is prepared；
(4) PbO is prepared2Active layer:
0.09mol/LPb (NO is impregnated on Sn/Ti intermediate oxide layer surface3)2Solution takes out after 50s, and utilization is infrared Lamp drying, then fires 1.5h under certain temperature, is finally cooled to room temperature, repeats above step 5 times, prepares PbO2Active layer, Obtain the modified titanium-matrix electrode of ternary.
Other embodiments are the same as embodiment 1.
Using electrode C1, C2, C3 concentration for the treatment of be 100mg/L containing methyl orange, methylene blue, rhdamine B mould Quasi- waste water 250mL, the results are shown in Table 4 to the degradation rate of three kinds of dyestuffs.
Fig. 4 is active layer SEM figure before and after the use of preference C3 electrode, and left figure is to be schemed using preceding SEM, and right figure is processing waste water SEM schemes after 18h, uses rear PbO2Active layer keeps good integrality.
Table 3 sample C1, C2, C3 and calcination temperature corresponding relationship
Sample label Calcination temperature/DEG C
C1 350
C2 400
C3 500
Embodiment 4
The present embodiment prepares the modified titanium-matrix electrode of ternary, and preparation process is as follows:
(1) Titanium base is pre-processed:
Titanium base has successively been polishing to metallic luster with 360 mesh and 600 mesh sand paper, Titanium base is then immersed 8% In oxalic acid solution, rough grey pitted skin, no metallic luster, by acid etching is presented in 90 DEG C of water-bath acid etching 1h, Titanium base surface Good Titanium base takes out, and is put into 2% oxalic acid solution and is saved for use after cleaning up；
(2) Sn/Ti coating liquid is prepared:
The SnCl of 1.18g is accurately weighed in assay balance2·2H2O is put into the plastic centrifuge tube of 4mL, is then added just Butanol solvent is eventually adding the Ti (OC that concentration is 0.2g/mL to 3mL4H9)4To 4mL.After appropriate concussion, being put into ultrasonic machine makes It is sufficiently dissolved；
(3) Sn/Ti intermediate oxide layer is prepared:
SnCl is coated on pretreated Titanium base surface2·2H2O and Ti (OC4H9)4The Sn/Ti that mass ratio is 6:1 is coated Liquid is dried using infrared lamp after coating uniformly, is repeated the above steps 3 times, and Sn/Ti intermediate oxide layer is prepared；
(4) PbO is prepared2Active layer:
0.05mol/L Pb (NO is impregnated on Sn/Ti intermediate oxide layer surface3)2Solution takes out after 45s, and utilization is infrared Lamp drying, is then placed in 300 DEG C of baking ovens and fires 1h, and last room temperature is cooling, repeats above step 3 times, prepares PbO2Active layer, Obtain the modified titanium-matrix electrode of ternary.
Other embodiments are the same as embodiment 1.
It is useless to the simulation containing methyl orange, methylene blue, rhdamine B that concentration is 100mg/L using the electrode of preparation Water 250mL carries out electroxidation processing, wherein in electro-oxidation processes, Na2SO4Concentration be 0g/L, processing result be labeled as D1, Na2SO4Concentration be 0.4g/L, processing result be labeled as D2, Na2SO4Concentration be 0.8g/L, processing result be labeled as D3, it is right The degradation rate of three kinds of dyestuffs the results are shown in Table 4, be known by table 4, and aniline dyes belong to nonconducting organic matter, and supporting electrolyte has Nothing has a significant impact to treatment effect.
Active layer SEM figure before and after the electrode use that Fig. 5 is preference D2, left figure are to be schemed using preceding SEM, and right figure is that processing is useless SEM schemes after water 18h, uses rear PbO2Active layer keeps good integrality.
Embodiment 5:
The present embodiment prepares the modified titanium-matrix electrode of ternary, and preparation process is as follows:
(1) Titanium base is pre-processed:
Titanium base has successively been polishing to metallic luster with 360 mesh and 600 mesh sand paper, Titanium base is then immersed 8% In oxalic acid solution, rough grey pitted skin, no metallic luster, by acid etching is presented in 90 DEG C of water-bath acid etching 1h, Titanium base surface Good Titanium base takes out, and is put into 2% oxalic acid solution and is saved for use after cleaning up；
(2) Sn/Ti coating liquid is prepared:
The SnCl of 1.18g is accurately weighed in assay balance2·2H2O is put into the plastic centrifuge tube of 4mL, is then added just Butanol solvent is eventually adding the Ti (OC that concentration is 0.2g/mL to 3mL4H9)4To 4mL.After appropriate concussion, being put into ultrasonic machine makes It is sufficiently dissolved；
(3) Sn/Ti intermediate oxide layer is prepared:
SnCl is coated on pretreated Titanium base surface2·2H2O and Ti (OC4H9)4The Sn/Ti that mass ratio is 6:1 is coated Liquid is dried using infrared lamp after coating uniformly, is repeated the above steps 3 times, and Sn/Ti intermediate oxide layer is prepared；
(4) PbO is prepared2Active layer:
0.05mol/L Pb (NO is impregnated on Sn/Ti intermediate oxide layer surface3)2Solution takes out after 45s, and utilization is infrared Lamp drying, is then placed in 300 DEG C of baking ovens and fires 1h, and last room temperature is cooling, repeats above step 3 times, prepares PbO2Active layer, Obtain the modified titanium-matrix electrode of ternary.
It is useless to the simulation containing methyl orange, methylene blue, rhdamine B that concentration is 100mg/L using the electrode of preparation Water 250mL carries out electroxidation processing, the results are shown in Table 4 to the degradation rate of three kinds of dyestuffs, wherein in electro-oxidation processes, the concentration of NaCl For 0g/L, processing result is labeled as E1, and the concentration of NaCl is 3g/L, and processing result is labeled as E2, and the concentration of NaCl is 6g/L, place Reason result queue be E3, as seen from the results in Table 4, the electrolyte without NaCl although have degradation effect but degradation rate obviously compared with Slowly, the electric conductivity of solution not only can be improved in NaCl, also has catalysis, reaction rate can be greatly improved, so Cl-? It is played a crucial role during dyestuff electrolysis and degradation.
Other embodiments are the same as embodiment 1.
Fig. 6 is active layer SEM figure before and after the use of preference E2 electrode, and left figure is to be schemed using preceding SEM, and right figure is processing waste water SEM schemes after 18h, uses rear PbO2Active layer keeps good integrality.
Fig. 7 is the impedance characterization of each preference electrode in Examples 1 to 5 as a result, it is found that when in Sn/Ti coating liquid SnCl2·2H2When O concentration increases, electrode resistance also be will increase.The SnO of electrode middle layer2When content increases, electrode resistance increases Greatly, oxidation efficiency reduces.But pass through active layer SEM figure before and after comparison electrode use, it is known that as the SnO of electrode middle layer2Content When increase, the electrode surface active layer amount of falling off is reduced, and crack is relatively small, so SnO2Electrode can be effectively protected, extend Electrode life.
Fig. 8 is titanium-based surface distribution situation of each element in ternary modified electrode, and left figure is each element in titanium-based surface point Cloth situation, right table are mass ratio shared by each element.
Embodiment 6:
Choose the waste water generated during A2 Electrode treatment Shanghai DYE PRODUCTION company production methylene blue dye, dyestuff The initial content of COD (COD) is 3240mg/L in waste water, and initial chroma is 310 times, and (suspended solid is named suspension to SS Object) initial content be 330mg/L, in addition to the electroxidation time, other technological parameters of electroxidation are same as Example 1.
After electroxidation handles 50min, coloration reduces by 98.00%, and the COD content of waste water increases 33.00%, SS and reduces 21.00%；After handling 7h, coloration reduces by 99.50%, and the COD content of waste water is 96mg/L, and SS is completely removed, so this hair The ternary modified electrode of bright preparation is preferable by electro-oxidation processes processing aniline dyes waste water effect.
The coloration of the present embodiment is measured according to the cuvette colorimetric method of GB11903-89, and COD is according to GB11914-89 Potassium dichromate feedback method be measured, SS is measured according to the gravimetric method of GB11901-89.
Degradation rate result of the 4 ternary modified electrode of table to dyestuff
Embodiment 7:
Choose what the big type dye Co., Ltd production rhodamine B dyestuff in A2 Electrode treatment Zhejiang generated in the process Waste water, the initial content of COD is 6540mg/L in waste water from dyestuff, and initial chroma is 240 times, and SS initial content is 620mg/L.It removes Outside the electroxidation time, the technological parameter of electroxidation is same as Example 1.
After electroxidation handles 75min, coloration is reduced to 97.00%, and the COD content of waste water increases 44.30%, SS and reduces 13%；After handling 12h, it is 110mg/L that the coloration of waste water, which reduces by 98.00%, COD content, and SS is completely removed, so of the invention The ternary modified electrode of preparation is preferable by electro-oxidation processes processing aniline dyes waste water effect.
The coloration of the present embodiment is measured according to the cuvette colorimetric method of GB11903-89, and COD is according to GB11914-89 Potassium dichromate feedback method be measured, SS is measured according to the gravimetric method of GB11901-89.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention Made any modifications, equivalent replacements, and improvements etc., should all be included in the protection scope of the present invention within mind and principle.

Claims (10)

1. a kind of preparation method of the modified titanium-matrix electrode of ternary, which comprises the steps of:
(1) pre-processing titanium matrix:
Pickling solution is immersed after Titanium base is polished, 90 DEG C of acid etching 1h take out cleaning, are placed in preservation liquid and save；
(2) Sn/Ti coating liquid is prepared:
Take SnCl2·2H2O is placed in container, and n-butanol, Ti (OC are then sequentially added into container4H9)4Solution is uniformly mixed Afterwards, it is dissolved under ultrasound condition；
The SnCl2·2H2O, n-butanol total in Sn/Ti coating liquid, Ti (OC4H9)4Mass ratio be (0.4~1.4): 3: 0.2；
(3) Sn/Ti intermediate oxide layer is prepared:
Sn/Ti coating liquid is coated in pretreated Titanium base surface, is then dried, repetitive coatings, baking step 3~5 times, Obtain Sn/Ti intermediate oxide layer；
(4) PbO is prepared2Active layer:
Pb (NO is impregnated on Sn/Ti intermediate oxide layer surface3)2Then solution is dried, calcines, is cooled to room temperature, repeat above-mentioned Step 3~5 time prepare PbO2Active layer obtains the modified titanium-matrix electrode of ternary.
2. a kind of preparation method of the modified titanium-matrix electrode of ternary according to claim 1, which is characterized in that the step (1) it in, is successively polished with the sand paper of 360 mesh, 600 mesh Titanium base, pickling solution is that the oxalic acid that mass concentration is 8% is molten Liquid saves the oxalic acid solution that liquid is 2%；
In the step (2), Ti (OC4H9)4The concentration of solution is 0.2g/mL.
3. a kind of preparation method of the modified titanium-matrix electrode of ternary according to claim 1, which is characterized in that the step (3) in, Sn/Ti coating liquid is dried using infrared lamp.
4. a kind of preparation method of the modified titanium-matrix electrode of ternary according to claim 1, which is characterized in that the step (4) in, Pb (NO3)2Solution concentration is 0.03~0.09mol/L, 30~50s of soaking time, using infrared lamp to Pb (NO3)2It is molten Liquid is dried, and 300~600 DEG C of calcination temperature, 1~1.5h of calcination time.
5. a kind of ternary that the preparation method by the modified titanium-matrix electrode of the described in any item ternarys of Claims 1 to 4 is prepared Modified titanium-matrix electrode, which is characterized in that including Titanium base, middle layer, active layer, the intermediate layer material includes Sn/Ti oxidation Object, the active layer substance includes PbO2。
6. a kind of electro-oxidation processes using the modified titanium-matrix electrode processing aniline dyes waste water of ternary described in claim 5, It is characterized in that, establishing reaction member using the modified titanium-matrix electrode of the ternary, the anode of the reaction member changes for ternary Property titanium-matrix electrode, cathode is graphite electrode.
7. electro-oxidation processes according to claim 6, which is characterized in that the current density of the electro-oxidation processes be 10~ 30mA/cm2, supporting electrolyte Na2SO4With the mixed solution of NaCl, the contact area of the electrode and waste water is 3~5cm2, Electrode spacing is 1~2.5cm, and the graphite electrode is identical as the modified titanium-matrix electrode specification of ternary.
8. electro-oxidation processes according to claim 7, which is characterized in that the Na2SO4The concentration 0.3 of solution~ 0.9g/L, 1~5g/L of concentration of NaCl solution.
9. electro-oxidation processes according to claim 6, which is characterized in that the aniline dyes waste water includes methyl orange dye Expect the combination of one or more of waste water, rhdamine B waste water, methylene blue dye wastewater.
10. electro-oxidation processes according to claim 6, which is characterized in that the electro-oxidation processes generate oxidizer containing chlorine, Aniline dyes in the waste water are degraded to rudimentary organic matter under oxidizer containing chlorine effect, the aniline dyes Degradation rate is 69.8~98.8%.
CN201910447920.0A 2019-05-27 2019-05-27 A kind of ternary modified titanium-matrix electrode, preparation method and application Pending CN110054262A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201910447920.0A CN110054262A (en) 2019-05-27 2019-05-27 A kind of ternary modified titanium-matrix electrode, preparation method and application

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201910447920.0A CN110054262A (en) 2019-05-27 2019-05-27 A kind of ternary modified titanium-matrix electrode, preparation method and application

Publications (1)

Publication Number Publication Date
CN110054262A true CN110054262A (en) 2019-07-26

Family

ID=67324700

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201910447920.0A Pending CN110054262A (en) 2019-05-27 2019-05-27 A kind of ternary modified titanium-matrix electrode, preparation method and application

Country Status (1)

Country Link
CN (1) CN110054262A (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2024027076A1 (en) * 2022-08-04 2024-02-08 上海纳米技术及应用国家工程研究中心有限公司 Preparation method for flexible polyimide/titanium mesh film composite electrode material, product and use thereof

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3296680A (en) * 1963-09-26 1967-01-10 British Nylon Spinners Ltd Apparatus for treating and advancing filamentary material
JPH02294494A (en) * 1989-05-10 1990-12-05 Japan Carlit Co Ltd:The Anode for generating oxygen
CN1850643A (en) * 2006-05-26 2006-10-25 南京大学 Method for degrading aminobenzene or/and nitrobenzene in waste water by electrolytic process
CN101417831A (en) * 2008-11-11 2009-04-29 北京师范大学 Novel ti-supported lead dioxide electric pole and preparation method thereof
CN102534652A (en) * 2011-12-28 2012-07-04 南京理工大学 Preparation method for titanium base tin-doped lead dioxide electrode
JP2012251195A (en) * 2011-06-02 2012-12-20 Japan Carlit Co Ltd:The Electrode for use in electrolysis, and method of producing the same
CN103014755A (en) * 2012-12-20 2013-04-03 西安交通大学 Fabrication method of long-life titanium base electrode
CN106745526A (en) * 2016-11-17 2017-05-31 河北智生环保科技有限公司 A kind of preparation method and applications of titania modified lead dioxide electrode
CN106868509A (en) * 2017-03-23 2017-06-20 吉林师范大学 A kind of graphene modified Lead dioxide anode modifiedby fluorine resin and preparation method thereof

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3296680A (en) * 1963-09-26 1967-01-10 British Nylon Spinners Ltd Apparatus for treating and advancing filamentary material
JPH02294494A (en) * 1989-05-10 1990-12-05 Japan Carlit Co Ltd:The Anode for generating oxygen
CN1850643A (en) * 2006-05-26 2006-10-25 南京大学 Method for degrading aminobenzene or/and nitrobenzene in waste water by electrolytic process
CN101417831A (en) * 2008-11-11 2009-04-29 北京师范大学 Novel ti-supported lead dioxide electric pole and preparation method thereof
JP2012251195A (en) * 2011-06-02 2012-12-20 Japan Carlit Co Ltd:The Electrode for use in electrolysis, and method of producing the same
CN102534652A (en) * 2011-12-28 2012-07-04 南京理工大学 Preparation method for titanium base tin-doped lead dioxide electrode
CN103014755A (en) * 2012-12-20 2013-04-03 西安交通大学 Fabrication method of long-life titanium base electrode
CN106745526A (en) * 2016-11-17 2017-05-31 河北智生环保科技有限公司 A kind of preparation method and applications of titania modified lead dioxide electrode
CN106868509A (en) * 2017-03-23 2017-06-20 吉林师范大学 A kind of graphene modified Lead dioxide anode modifiedby fluorine resin and preparation method thereof

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
孔海申: "钛基二氧化铅电极（Ti/PbO2）稳定性的若干基础问题研究", 《中国博士学位论文全文数据库 工程科技I辑》 *
陈延禧: "《电解工程》", 31 August 1993, 天津科学技术出版社 *
韩顺昌等: "《金属腐蚀显微组织图谱》", 3 November 2008, 国防工业出版社 *
黄永昌等: "锡锑中间层在钛基二氧化铅电极中作用机理探讨", 《上海交通大学学报》 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2024027076A1 (en) * 2022-08-04 2024-02-08 上海纳米技术及应用国家工程研究中心有限公司 Preparation method for flexible polyimide/titanium mesh film composite electrode material, product and use thereof

Similar Documents

Publication Publication Date Title
WO2021159555A1 (en) Electrocatalytic fenton oxidation-electrochemical oxidation coupled process and device for efficient treatment of chemical industry wastewater
Xiong et al. An experimental investigation of chemical oxygen demand removal from the wastewater containing oxalic acid using three-phase three-dimensional electrode reactor
Morsi et al. Electrochemical degradation of some organic dyes by electrochemical oxidation on a Pb/PbO2 electrode
CN111470673B (en) Double-oxidation device and method for advanced treatment of electroplating wastewater
CN104047020B (en) A kind of titanio mixes polyvinylidene fluoride anode of lead dioxide and preparation thereof and application
CN106277229B (en) A kind of method of modified electrode electrocatalytic oxidation processing organic pollutant Atrazine
CN101245469A (en) Method for manufacturing titanium base lead dioxide electrode capable of controlling coating granularity
CN111285446A (en) Pd/NiCo2O4/Ni foam composite electrode and preparation method and application thereof
CN104876305A (en) Preparation method of copper-doped coated electrode for treating printing and dyeing wastewater
CN113690455B (en) Long-life anode electrode material and preparation method thereof
Jeong et al. Electrochemical oxidation of industrial wastewater with the tube type electrolysis module system
Soni et al. Decolourization and mineralization of Reactive black-5 with transition metal oxide coated electrodes by electrochemical oxidation
CN108017120A (en) A kind of method using Novel anode electrocatalytic oxidation processing phenol organic wastewater
CN110354851A (en) A kind of method of nanotube-shaped titania-tin oxide-ruthenium-oxide composite coating catalytic degradation organic pollutant
CN101230467A (en) Titanium-based manganese-iridium composite oxide coating anode and preparation method thereof
CN108054390A (en) A kind of method of modifying of efficiently and effectively graphite felt for vanadium cell
CN110054262A (en) A kind of ternary modified titanium-matrix electrode, preparation method and application
CN107653447B (en) A kind of mineral carbon load stannic oxide electrode and preparation method
CN108328703A (en) The application that titanium-based titanium dioxide nanotube deposits the preparation of tin antimony fluoride electrode and its degrades to chromium fog inhibitor in chromium-electroplating waste water
Sáez et al. Lead dioxide film sonoelectrodeposition in acidic media: Preparation and performance of stable practical anodes
CN107459234A (en) A kind of three-dimensional class electricity Fenton processing tetracycline water treatment system and method
CN104846357B (en) A kind of preparation method of metal oxides coating of anode
Abu Ghalwa et al. Electrochemical degradation of acid green dye in aqueous wastewater dyestuff solutions using a lead oxide coated titanium electrode
CN104005047B (en) Novel mixed metal oxide electrode for low-temperature sea water electrolysis antifouling
CN105217743B (en) The method that electrocatalytic oxidation handles methanol and formaldehyde industrial wastewater

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
RJ01 Rejection of invention patent application after publication

Application publication date: 20190726

RJ01 Rejection of invention patent application after publication