CN106868509A - A kind of graphene modified Lead dioxide anode modifiedby fluorine resin and preparation method thereof - Google Patents

A kind of graphene modified Lead dioxide anode modifiedby fluorine resin and preparation method thereof Download PDF

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CN106868509A
CN106868509A CN201710178144.XA CN201710178144A CN106868509A CN 106868509 A CN106868509 A CN 106868509A CN 201710178144 A CN201710178144 A CN 201710178144A CN 106868509 A CN106868509 A CN 106868509A
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graphene
pbo
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lead dioxide
fluorine resin
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CN106868509B (en
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段小月
常立民
任新
赵雪松
汤茜
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Jilin Normal University
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    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
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    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
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    • 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
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    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
    • C23C18/1204—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material inorganic material, e.g. non-oxide and non-metallic such as sulfides, nitrides based compounds
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    • C23C18/1216—Metal oxides
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    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
    • C23C18/125—Process of deposition of the inorganic material
    • C23C18/1262—Process of deposition of the inorganic material involving particles, e.g. carbon nanotubes [CNT], flakes
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    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
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    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/20—Electroplating using ultrasonics, vibrations
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    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • C02F1/46104—Devices therefor; Their operating or servicing
    • C02F1/46109—Electrodes
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    • 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

Abstract

The invention provides a kind of graphene modified Lead dioxide anode modifiedby fluorine resin and preparation method thereof, the tin-antimony oxide bottom of the electrode, α PbO2Intermediate layer and β PbO2Contain Graphene in active layer, its preparation method includes titanium plate pretreatment, the tin-antimony oxide bottom of heat deposition graphene-containing, the α PbO of bioactive coating graphene-containing2Intermediate layer, the β PbO of bioactive coating graphene-containing2Active layer.The advantage of the invention is that：The electrocatalytic oxidation activity and service life of graphene modified Lead dioxide anode modifiedby fluorine resin prepared by the present invention have raising by a relatively large margin than common Lead dioxide anode modifiedby fluorine resin, are a kind of anode materials for being suitable to Electro-catalytic Oxidation Process Organic Pollutants in Wastewater for having a development potentiality.

Description

A kind of graphene modified Lead dioxide anode modifiedby fluorine resin and preparation method thereof
Technical field
The present invention relates to a kind of graphene modified lead dioxide electrode and preparation method thereof, and use it for electrocatalytic oxidation Degraded organic pollutants, belong to water technology and electrochemical field.
Background technology
Electro-catalytic oxidation technology has that oxidability is strong, reaction rate is fast, equipment is simple, is easily manipulated, non-secondary pollution The advantages of, it is a kind of suitable poisonous, difficult for biological degradation organic wastewater water technology for the treatment of.Anode material is the core of the technology The heart, wherein lead dioxide electrode are one of most promising electrocatalytic oxidation anode materials, its catalytic oxidation activity is high, Good conductivity, corrosion resistance are strong, it is simple, cheap to prepare.But lead dioxide electrode is still suffering from current efficiency using process Low and service life needs the problems such as further improving.Therefore, in recent years, substantial amounts of scholar is devoted to entering lead dioxide electrode Row is effective modified, to improve the current efficiency and stability of lead dioxide electrode.Such as A of patent CN 102534652 are provided A kind of titanium-based mixes the preparation method of tin lead dioxide electrode, and its obtained lead dioxide electrode surface is uniform, fine and close, flawless, With larger specific surface area and electrocatalytic oxidation activity higher；The A of patent CN 101798690 provide one kind by main body lead salt What lead acetate, acidity regulator sulfamic acid, solution additive sodium fluoride, solution additive ptfe emulsion component were constituted The electroplate liquid of brown lead oxide, the smooth densification of prepared lead dioxide electrode, adhesion is good, and catalysis activity is high, long service life； The A of patent CN 103132076 provide a kind of lanthanum, the preparation method of the ti-supported lead dioxide electric pole of gadolinium codope, by lanthanum, The synergy of gadolinium codope, electrode has larger specific surface area and more active site, is conducive to the migration of pollutant, inhales Attached, desorption, can greatly improve the degradation effect to organic pollution.Therefore, rational additive can effectively improve titanium dioxide The catalysis oxidation ability and service life of lead electrode.
Graphene, SP2The hexatomic ring honeycomb-like network structural material that hydbridized carbon atoms are constituted, not only with chemically stable high Property, and with remarkable electricity, optics, calorifics and mechanical property, resistance to mass tranfer can be reduced as the composite of electrode, The conductive path of uniqueness can be also provided for the fast transfer of electric charge and conduction.Therefore, it is proposed that Graphene is incorporated into dioxy In each film layer of change lead electrode, to improve the electrocatalytic oxidation activity of electrode and the service life of electrode.
The content of the invention
The purpose of the present invention is：A kind of graphene modified Lead dioxide anode modifiedby fluorine resin and preparation method thereof is provided, and is utilized The electrode Electro-catalytic Oxidation Process organic pollutants, obtained graphene modified Lead dioxide anode modifiedby fluorine resin has electro-catalysis Oxidation activity is high, long service life, simple preparation method the advantages of.
The object of the present invention is achieved like this, and the graphene modified Lead dioxide anode modifiedby fluorine resin includes：
Titanium base；
The tin-antimony oxide bottom of graphene-containing of the heat deposition on Titanium base；
α-the PbO of graphene-containing of the bioactive coating on tin-antimony oxide bottom2Intermediate layer；
Bioactive coating is in α-PbO2β-the PbO of the graphene-containing on intermediate layer2Active layer.
The preparation method of described graphene modified lead dioxide electrode is comprised the following steps：
1., the pretreatment of Titanium base：Titanium base is polished successively until silver is presented with the sand paper of 120 mesh, 600 mesh and 1200 mesh first White metal gloss；Ultrasonically treated 10 minutes during the Titanium base polished is sequentially placed into acetone and deionized water again, titanium is removed The greasy dirt of plate surface and other impurity；Then the Titanium base after will be ultrasonically treated is immersed in oxalic acid etching liquid in 80 DEG C ~ micro-boiling Under conditions of etch 2 hours, be placed in after taking-up oxalic acid preserve liquid in preserve.
Described oxalic acid etching liquid is that 150 grams of oxalic acid are dissolved in 1 liter of deionized water, and heating stirring is to dissolving preparation Into；It is that 10 grams of oxalic acid are dissolved in 1 liter of deionized water that described oxalic acid preserves liquid, and stirring to dissolving is formulated.
2., the preparation of the tin-antimony oxide bottom of graphene-containing：Coating liquid containing Graphene is coated on 1. middle treatment On Titanium base surface afterwards, dried 10 minutes at 120 DEG C in the electrically heated drying cabinet, then the Titanium base of drying is placed in Muffle furnace It is calcined 10 minutes at 300 DEG C, is so repeated 10 times, the roasting time in Muffle furnace is 1 hour for the last time, is naturally cooled to Room temperature.
3., the α-PbO containing Graphene2The preparation in intermediate layer：The tin antimony oxygen with graphene-containing that 2. step is prepared The Titanium base of compound bottom is plated as negative electrode as anode, the stainless steel plate of homalographic in 100 milliliters of alkalescence containing Graphene Bioactive coating α-PbO in liquid2Intermediate layer, electrode spacing is 3cm, and the current density of electro-deposition is 3mA/cm2, depositing temperature is 40 DEG C, sedimentation time is 0.5 ~ 2 hour, there is ultrasonic wave added in deposition process, and supersonic frequency is 40kHz, 100 ~ 600W of power.Acoustic-electric After deposition terminates, it is washed with deionized water net.
4., the β-PbO containing Graphene2The preparation of active layer：By step 3. in the obtained α-PbO containing Graphene2In The Titanium base of interbed as anode, the stainless steel plate of homalographic as negative electrode, in 100 milliliters of acidic baths for being mixed with Graphene Bioactive coating β-PbO2Active layer, electrode spacing is 3cm, and the current density of electro-deposition is 15mA/cm2, depositing temperature is 65 DEG C, Sedimentation time is 0.5 ~ 2 hour, and plating solution volume is 100 milliliters, there is ultrasonic wave added in electrodeposition process, and supersonic frequency is 40kHz, 100 ~ 600W of power.After bioactive coating terminates, it is washed with deionized water net.
Step 2. described in coating liquid be that 20 grams of butters of tin and 2 grams of trichloride antimonies are added to 13 milliliters of mass concentrations In 37% concentrated hydrochloric acid and 87 milliliters of isopropanol mixed liquors, to stir to after being completely dissolved, 0.05 ~ 0.3 gram of Graphene, stirring are added Uniform and ultrasound is formulated for 30 minutes.
Step 3. described in the alkali plating solution for being mixed with Graphene be that PbO and NaOH are added in deionized water, Heating stirring is completely dissolved to PbO, after naturally cooling to room temperature, adds Graphene, stir and ultrasound prepare within 30 minutes and Into.The each component content of plating solution is the mol/Ls of PbO 0.1, the mol/L of NaOH 3.5,0.5 ~ 5.0 g/l of Graphene.
The 4. described acidic bath for being mixed with Graphene of step is that plumbi nitras, sodium fluoride are added in salpeter solution, is stirred Mix to after being completely dissolved, add Graphene, stir and ultrasonic 30 minutes made, each component content is Graphene in plating solution 0.5 ~ 5.0 g/l, the mol/L of plumbi nitras 0.5, the mol/L of nitric acid 1.0, the mol/L of sodium fluoride 0.05.
Step 2., 3., the preparation method of 4. described Graphene be：Graphite paper is cleaned with absolute ethyl alcohol, deionized water, is put Enter in baking oven and dried 1 hour at 60 DEG C.It is electrolysed under constant voltage using DC voltage-stabilizing constant-current switch power source, is made with graphite paper It is the electrode of negative and positive two, 100 milliliters of mass concentrations are that the ammonium persulfate solution of 0.4 % is electrolyte, and two electrode spacings are 2cm, electricity It is 20V to press.After switching on power, a large amount of bubbles are had on anode graphite paper and is produced, while it is observed that graphite paper generation is swollen Swollen and have floccule (Graphene) to come off, the color of electrolyte is changed into light yellow.Floccule and deionized water mixture are carried out Ultrasound is simultaneously cleaned, repeated washing 3 times with centrifugal process, and to remove the ammonium persulfate of residual, Graphene is collected in drying afterwards.
The present invention has following features：
（1）The tin-antimony oxide bottom of the graphene modified Lead dioxide anode modifiedby fluorine resin prepared by the present invention, α-PbO2Intermediate layer With β-PbO2Contain Graphene in active layer, improve the electric conductivity of film layer, improve transfer velocity of the electric charge in film layer.
（2）The present invention is preparing the α-PbO of graphene-containing2Intermediate layer and the β-PbO of graphene-containing2During active layer Bioactive coating technology is employed, Graphene degree of scatter in the plating solution is effectively increased, it is preparation process is simple, cheap.
（3）Graphene modified Lead dioxide anode modifiedby fluorine resin Electro-catalytic Oxidation Process phenol prepared by the present invention, in solution Phenol clearance improves 25.98% than common Lead dioxide anode modifiedby fluorine resin, and service life is up to common Lead dioxide anode modifiedby fluorine resin 2.6 times.
（4）Difficult for biological degradation organic contamination in graphene modified Lead dioxide anode modifiedby fluorine resin degradation water prepared by the present invention Thing, effect substantially, convenient management, being adapted as the processing method of organic wastewater, be independently operated, also can be used as the preceding place of bioanalysis Reason technology is used with other technical tie-ups.
Brief description of the drawings
Fig. 1 is the structural representation of graphene modified Lead dioxide anode modifiedby fluorine resin of the present invention.
Fig. 2 is the scanning electron microscope (SEM) photograph of common Lead dioxide anode modifiedby fluorine resin.
Fig. 3 is the scanning electron microscope (SEM) photograph of graphene modified Lead dioxide anode modifiedby fluorine resin of the present invention.
Fig. 4 is the scanning electron microscope (SEM) photograph of top layer graphene modified Lead dioxide anode modifiedby fluorine resin.
Fig. 5 is graphene modified Lead dioxide anode modifiedby fluorine resin of the present invention, the fluorine-containing titanium dioxide of top layer graphene modified The clearance change curve of lead electrode and common Lead dioxide anode modifiedby fluorine resin Electro-catalytic Oxidation Process phenol.
Fig. 6 is graphene modified Lead dioxide anode modifiedby fluorine resin of the present invention, the fluorine-containing titanium dioxide of top layer graphene modified The accelerating lifetime testing curve map of lead electrode and common Lead dioxide anode modifiedby fluorine resin in sulfuric acid solution.
Specific embodiment
For the ease of the comparing of product of the present invention, we are prepared for common Lead dioxide anode modifiedby fluorine resin, specific preparation method It is as follows：
（1）Successively with 120 mesh, 600 mesh and 1200 mesh sand papering Titanium bases（30 millimeters × 50 millimeters × 0.8 millimeter）, until Titanium base is presented silvery white metallic luster, ultrasonically treated 10 points during the Titanium base polished is sequentially placed into acetone and deionized water Clock, removes the greasy dirt and other impurity of matrix surface；Then the Titanium base after will be ultrasonically treated is immersed in oxalic acid etching liquid（Grass Acid etch liquid is that 150 grams of oxalic acid are dissolved in 1 liter of deionized water, and heating stirring to dissolving is formulated）In 80 DEG C ~ micro-boiling condition Lower etching 2 hours, is placed in oxalic acid and preserves liquid after taking-up（It is that 10 grams of oxalic acid are dissolved in 1 liter of deionized water that oxalic acid preserves liquid, stirring It is formulated to being completely dissolved）Middle preservation.
（2）Coating liquid is made during butter of tin and trichloride antimony are dissolved in into concentrated hydrochloric acid and isopropyl alcohol mixture（Coating liquid It is that 20 grams of butters of tin and 2 grams of trichloride antimonies are added into 13 milliliters of mass concentrations is that 37% concentrated hydrochloric acid and 87 milliliters of isopropanols are mixed Close in solution, stirring is formulated to being completely dissolved）, by step（1）In be stored in oxalic acid preserve liquid in Titanium base take out, profit Surface is cleaned with deionized water, coating liquid is coated on clean Titanium base, dry 10 points in the electrically heated drying cabinet at 120 DEG C Clock, then the Titanium base after drying is placed in Muffle furnace roasting 10 minutes at 300 DEG C, so it is repeated 10 times, for the last time in horse Not the roasting time in stove is 1 hour, naturally cools to room temperature, obtains the Titanium base with tin-antimony oxide bottom.
（3）By step（2）Prepare the Titanium base with tin-antimony oxide bottom as anode, with the stainless steel of homalographic Plate as negative electrode, in 100 milliliters of alkali plating solutions dissolved with 0.1 mol/L PbO and 3.5 mol/L NaOH electro-deposition α- PbO2Intermediate layer, the current density of electro-deposition is 3mA/cm2, depositing temperature is 40 DEG C, and sedimentation time is 1 hour.Use deionized water After cleaning, obtain with α-PbO2The Titanium base in intermediate layer.
（4）By step（3）Prepare with α-PbO2The Titanium base in intermediate layer is made as anode, the stainless steel plate of homalographic It is negative electrode, in 100 milliliters of acid platings containing 0.5 mol/L plumbi nitras, 0.05 mol/L sodium fluoride and 1 mol/L nitric acid Electro-deposition β-PbO in liquid2Surface-active layer, electro-deposition current density is 15mA/cm2, depositing temperature is 65 DEG C, and sedimentation time is 1 Hour, the common Lead dioxide anode modifiedby fluorine resin for being prepared, as shown in Figure 2：As can be seen from Fig., common fluorine-containing titanium dioxide Lead electrode is piled up by a large amount of pyramid brown lead oxide crystal grains and formed.
It is anode to use the common Lead dioxide anode modifiedby fluorine resin for preparing, and the stainless steel plate of homalographic is negative electrode, electrode Spacing is 1 centimetre, Electrocatalytic Oxidation of Phenol in Water, and the concentration of phenol is 50 mg/litres, and the sodium sulphate of 0.05 mol/L is propped up Electrolyte is held, the volume of solution is 200 milliliters, and electrocatalytic oxidation current density is 30mA/cm2, temperature is 30 DEG C, degradation process Phenol clearance curve such as accompanying drawing 5, the clearance of phenol is 72.26% after reacting 120 minutes.
It is anode with the common Lead dioxide anode modifiedby fluorine resin for preparing, platinum electrode is negative electrode, in the sulfuric acid of 1 mol/L In solution, 1A/cm2Current density under, measure accelerated aging curve such as accompanying drawing 6, the reinforcing of common Lead dioxide anode modifiedby fluorine resin Life-span is about 51 hours.
The specific embodiment for preparing product of the present invention is as follows：
Embodiment 1：
As shown in Figure 1：The structure of graphene modified Lead dioxide anode modifiedby fluorine resin of the invention includes：
Titanium base 1；
The tin-antimony oxide bottom 2 of graphene-containing of the heat deposition on Titanium base；
α-the PbO of graphene-containing of the bioactive coating on bottom 22Intermediate layer 3；
β-the PbO of graphene-containing of the bioactive coating on intermediate layer 32Active layer 4.
Preparation method is as follows：
（1）Graphite paper is cleaned with absolute ethyl alcohol, deionized water, is put into baking oven and is dried 1 hour at 60 DEG C.It is permanent using DC voltage-stabilizing Current switching power supply is electrolysed under constant voltage, and using graphite paper as the electrode of negative and positive two, 100 milliliters of mass concentrations are 0.4% mistake Ammonium sulfate is electrolyte, and two electrode spacings are 2cm, and voltage is 20 V.After switching on power, had on anode graphite paper big Amount bubble is produced, while it is observed that graphite paper is expanded and has floccule（Graphene）Come off, the color of electrolyte becomes For light yellow.Floccule and deionized water mixture are carried out into ultrasound and is cleaned with centrifugal process, repeated washing 3 times, to remove The ammonium persulfate of residual is removed, Graphene is collected in drying afterwards.
（2）Successively with 120 mesh, 600 mesh and 1200 mesh sand papering Titanium bases（30 millimeters × 50 millimeters × 0.8 millimeter）, Until Titanium base is presented silvery white metallic luster, it is ultrasonically treated during the Titanium base polished is sequentially placed into acetone and deionized water 10 minutes, remove the greasy dirt and other impurity of matrix surface；Then the Titanium base after will be ultrasonically treated is immersed in oxalic acid etching liquid In（Oxalic acid etching liquid is that 150 grams of oxalic acid are dissolved in 1 liter of deionized water, and heating stirring is formulated to being completely dissolved）At 80 DEG C Etched 2 hours under the conditions of ~ micro-boiling, oxalic acid is placed in after taking-up and preserves liquid（It is that 10 grams of oxalic acid are dissolved in into 1 liter of deionization that oxalic acid preserves liquid In water, stirring is formulated to being completely dissolved）Middle preservation.
（3）It is that 37% concentrated hydrochloric acid and 87 milliliters are different that 20 grams of butters of tin and 2 grams of trichloride antimonies are dissolved in into 13 milliliters of mass concentrations In propyl alcohol mixed solution, 0.1 gram of Graphene is added, stirred and ultrasonic 30 minutes, coating liquid is made, by step（2）Middle guarantor There is the Titanium base taking-up that oxalic acid is preserved in liquid, surface is cleaned using deionized water, coating liquid is evenly applied to clean titanium On matrix, dried 10 minutes at 120 DEG C in the electrically heated drying cabinet, then the Titanium base after drying is placed in Muffle furnace at 300 DEG C Roasting 10 minutes, is so repeated 10 times, and the roasting time in Muffle furnace is 1 hour for the last time, naturally cools to room temperature, is obtained To the Titanium base of the tin-antimony oxide bottom with graphene-containing.
（4）0.1 gram of Graphene is added to 100 milliliters dissolved with 0.1 mol/L PbO and 3.5 mol/L NaOH In solution, stir and ultrasonic 30 minutes, be made the alkali plating solution for being mixed with Graphene.By step（3）Prepare with containing stone The Titanium base of the tin-antimony oxide bottom of black alkene, using the stainless steel plate of homalographic as negative electrode, is plated as anode in above-mentioned alkalescence Bioactive coating α-PbO in liquid2Intermediate layer, electrode spacing is 3cm, and the current density of electro-deposition is 3mA/cm2, depositing temperature is 40 DEG C, sedimentation time is 1 hour, there is ultrasonic wave added in electrodeposition process, and supersonic frequency is 40kHz, power 200W.Bioactive coating knot It is washed with deionized water after beam only, obtains the α-PbO with graphene-containing2The Titanium base in intermediate layer.
（5）0.1 gram of Graphene is added to 100 milliliters dissolved with 0.5 mol/L plumbi nitras, 0.05 mol/L sodium fluoride In 1 mol/L salpeter solution, stir and ultrasonic 30 minutes, be made the acidic bath for being mixed with Graphene.By step（4）System Standby α-the PbO with graphene-containing2The Titanium base in intermediate layer as anode, the stainless steel plate of homalographic as negative electrode, upper State bioactive coating β-PbO in acidic bath2Surface-active layer, electro-deposition current density is 15mA/cm2, depositing temperature is 65 DEG C, Sedimentation time is 1 hour, there is ultrasonic wave added in electrodeposition process, and supersonic frequency is 40kHz, and power 200W, bioactive coating terminates After be washed with deionized water net, obtain graphene modified Lead dioxide anode modifiedby fluorine resin, as shown in Figure 3：From the figure 3, it may be seen that prepare The surfacing of graphene modified Lead dioxide anode modifiedby fluorine resin, densification, β-PbO2Crystal grain size is significantly less than common fluorine-containing two Lead dioxide electrode.
It is anode to use the graphene modified Lead dioxide anode modifiedby fluorine resin for preparing, and the stainless steel plate of homalographic is the moon Pole, Electrocatalytic Oxidation of Phenol in Water, the concentration of phenol is 50 mg/litres, and the sodium sulphate of 0.05 mol/L does supporting electrolyte, The volume of solution is 200 milliliters, and electrode spacing is 1 centimetre, and electrocatalytic oxidation current density is 30mA/cm2, temperature is 30 DEG C, Degradation process phenol clearance curve such as accompanying drawing 5, the clearance of phenol is 91.03% after reacting 120 minutes, than common by fluorine-containing two Lead dioxide electrode improves 25.98%.
It is anode with the graphene modified Lead dioxide anode modifiedby fluorine resin for preparing, platinum electrode is negative electrode, in 1 mol/L Sulfuric acid solution in, 1A/cm2Current density under, measure accelerated aging curve such as accompanying drawing 6, the fluorine-containing titanium dioxide of graphene modified Lead electrode reinforcing life is about 134 hours, is 2.6 times of common Lead dioxide anode modifiedby fluorine resin.
Embodiment 2：
The preparation method of electrode is with embodiment 1.
Except that α-the PbO of bioactive coating graphene-containing2Intermediate layer and the β-PbO of graphene-containing2The plating solution of active layer The concentration of middle Graphene is 0.5 g/l, obtains graphene modified Lead dioxide anode modifiedby fluorine resin.
It is anode to use the graphene modified Lead dioxide anode modifiedby fluorine resin for preparing, and the stainless steel plate of homalographic is the moon Pole, electrode spacing is 1 centimetre, Electrocatalytic Oxidation of Phenol in Water, and the concentration of phenol is 50 mg/litres, the sulfuric acid of 0.05 mol/L Sodium does supporting electrolyte, and the volume of solution is 200 milliliters, and electrode spacing is 1 centimetre, and electrocatalytic oxidation current density is 30mA/ cm2, temperature is 30 DEG C, and the clearance of phenol is 86.55% after reacting 120 minutes.
It is anode with the graphene modified Lead dioxide anode modifiedby fluorine resin for preparing, platinum electrode is negative electrode, in 1 mol/L Sulfuric acid solution in, 1A/cm2Current density under, the reinforcing life for measuring electrode is about 95 hours, is common fluorine-containing titanium dioxide 1.86 times of lead electrode.
At present, common lead dioxide electrode method of modifying is that active material is entrained in into β-PbO2In surface-active layer, therefore We are prepared for only in β-PbO2The Lead dioxide anode modifiedby fluorine resin of doped graphene in surface-active layer（Referred to hereinafter as top layer Graphene Modification Lead dioxide anode modifiedby fluorine resin）, for being compared with graphene modified lead dioxide electrode obtained in the embodiment of the present invention 1 Research.
The preparation process of top layer graphene modified Lead dioxide anode modifiedby fluorine resin contains with graphene modified in the embodiment of the present invention 1 Fluorodioxy lead electrode is identical, the difference is that in tin-antimony oxide intermediate layer and α-PbO2Without Graphene in the preparation process of intermediate layer Add, α-PbO2Also without ultrasonic wave added in the preparation process of intermediate layer.Gained top layer graphene modified Lead dioxide anode modifiedby fluorine resin, such as Shown in accompanying drawing 4：Understood compared with accompanying drawing 3, the flatness on the top layer graphene modified Lead dioxide anode modifiedby fluorine resin surface of preparation It is poor compared with graphene modified lead dioxide electrode in the embodiment of the present invention 1 with compactness, and crystal grain is uneven.
It is anode to use the top layer graphene modified Lead dioxide anode modifiedby fluorine resin for preparing, and the stainless steel plate of homalographic is Negative electrode, electrode spacing is 1 centimetre, Electrocatalytic Oxidation of Phenol in Water, and the concentration of phenol is 50 mg/litres, the sulphur of 0.05 mol/L Sour sodium does supporting electrolyte, and the volume of solution is 200 milliliters, and electrode spacing is 1 centimetre, and electrocatalytic oxidation current density is 30mA/cm2, temperature is 30 DEG C, degradation process phenol clearance curve such as accompanying drawing 5, and the clearance of phenol is after reacting 120 minutes 82.11%, hence it is evident that less than the clearance of graphene modified Lead dioxide anode modifiedby fluorine resin Pyrogentisinic Acid in the embodiment of the present invention 1 （91.03%）.
It is anode with the top layer graphene modified Lead dioxide anode modifiedby fluorine resin for preparing, platinum electrode is negative electrode, is rubbed in 1 You/liter sulfuric acid solution in, 1A/cm2Current density under, measure accelerated aging curve such as accompanying drawing 6, top layer graphene modified contains Fluorodioxy lead electrode reinforcing life is about 78 hours, is 1.53 times of common Lead dioxide anode modifiedby fluorine resin, and the present invention is implemented Graphene modified Lead dioxide anode modifiedby fluorine resin reinforcing life is about 134 hours in example 1, is common Lead dioxide anode modifiedby fluorine resin 2.6 times.

Claims (5)

1. a kind of graphene modified Lead dioxide anode modifiedby fluorine resin, the electrode includes Titanium base, tin-antimony oxide bottom, α-PbO2In Interbed and β-PbO2Active layer, it is characterised in that：The tin-antimony oxide bottom of the electrode, α-PbO2Intermediate layer and β-PbO2Activity Contain Graphene in layer.
2. a kind of preparation method of graphene modified Lead dioxide anode modifiedby fluorine resin, it is characterised in that：Comprise the following steps：
（1）The pretreatment of Titanium base；
（2）The tin-antimony oxide bottom of heat deposition graphene-containing：Coating liquid containing Graphene is evenly applied to step（1）In advance On Titanium base surface after treatment, dried 10 minutes at 120 DEG C in the electrically heated drying cabinet, then the Titanium base of drying is placed in Muffle It is calcined 10 minutes at 300 DEG C in stove, is so repeated 10 times, the roasting time in Muffle furnace is 1 hour for the last time, naturally cold But to room temperature；
（3）α-the PbO of bioactive coating graphene-containing2Intermediate layer：By step（2）The electrode of preparation as anode, homalographic it is stainless Steel plate as negative electrode, bioactive coating α-PbO in being mixed with the alkali plating solution of Graphene at 100 milliliters2Intermediate layer, electrode spacing is 3cm, the current density of electro-deposition is 3mA/cm2, depositing temperature is 40 DEG C, and sedimentation time is 0.5-2 hours, is had in deposition process Ultrasonic wave added, supersonic frequency is 40kHz, and power is 100 ~ 600W；After bioactive coating terminates, it is washed with deionized water net；
（4）β-the PbO of bioactive coating graphene-containing2Active layer：By step（3）The electrode of preparation as anode, homalographic it is stainless Steel plate as negative electrode, bioactive coating β-PbO in being mixed with the acidic bath of Graphene at 100 milliliters2Active layer, electrode spacing is 3cm, the current density of electro-deposition is 15mA/cm2, depositing temperature is 65 DEG C, and sedimentation time is 0.5-2 hours, and plating solution volume is 100 milliliters, there is ultrasonic wave added in electrodeposition process, supersonic frequency is 40kHz, and power is 100 ~ 600W；After bioactive coating terminates, It is washed with deionized water net.
3. the preparation method of a kind of graphene modified Lead dioxide anode modifiedby fluorine resin according to claim 2, it is characterised in that： Step（2）Described in the coating liquid containing Graphene be that 20 grams of butters of tin and 2 grams of trichloride antimonies are added to 13 milliliters of matter Amount concentration adds 0.05 ~ 0.3 gram of graphite in 37% concentrated hydrochloric acid and 87 milliliters of isopropanol mixed liquors, to stir to after being completely dissolved Alkene, stir and ultrasound be formulated within 30 minutes.
4. the preparation method of a kind of graphene modified Lead dioxide anode modifiedby fluorine resin according to claim 2, it is characterised in that： Step（3）The described alkali plating solution for being mixed with Graphene is that PbO and NaOH are added in deionized water, and heating stirring is extremely PbO is completely dissolved, and after naturally cooling to room temperature, adds Graphene, stirs and ultrasound is formulated for 30 minutes；Plating solution it is each Constituent content is the mol/Ls of PbO 0.1, the mol/L of NaOH 3.5,0.5 ~ 5.0 g/l of Graphene.
5. the preparation method of a kind of graphene modified Lead dioxide anode modifiedby fluorine resin according to claim 2, it is characterised in that： Step（4）The described acidic bath for being mixed with Graphene is that plumbi nitras, sodium fluoride are added in salpeter solution, and stirring is to complete After dissolving, add Graphene, stir and ultrasound 30 minutes it is made, in plating solution each component content be 0.5 ~ 5.0 gram of Graphene/ Liter, the mol/L of plumbi nitras 0.5, the mol/L of nitric acid 1.0, the mol/L of sodium fluoride 0.05.
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