CN106637291A - Graphene composite metal oxide electrode and preparation method and application thereof - Google Patents
Graphene composite metal oxide electrode and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a graphene composite metal oxide electrode and a preparation method and application thereof. The graphene composite metal oxide electrode comprises a titanium substrate and a composite coating positioned on the surface of the titanium substrate, wherein the composite coating is sequentially coated with a lower metal oxide layer, a graphene filled porous metal oxide layer and an upper metal oxide layer from bottom to top. The preparation method of the graphene composite metal oxide electrode is simple in process and easy to operate; the surface of the electrode is loose and porous after addition of graphene, so that the binding force between the coatings is improved; and the electrocatalytic activity is improved, and the chlorine evolution potential is lowered while the oxygen evolution potential is improved. The prepared graphene composite metal oxide electrode gives respective properties of titanium, graphene and the metal oxide layers into full play through the synergistic effect among titanium, graphene and the metal oxide layers, and is excellent in electrocatalytic activity, corrosion resistance and impact resistance, the current efficiency is improved and the service life is prolonged.
Description
Technical field
The invention belongs to electrode material field, and in particular to a kind of Graphene complex metal oxide electrode and its preparation side
Method and application.
Background technology
Metal electrode, dimensional stable anode (DSA), also known as dimensional stability electrode.From titanium as matrix
And in surface noble metal-coating oxide, there is resulting titanium-based metal oxide electrode good flexing resistance, electro-catalysis to live
Property and electrochemical stability, thus being applied to many fields, such as electroextraction is metallurgical, electroplate, prepare chlor-alkali, wastewater degradation,
Organic electro-synthesis etc..Titanium-based metal oxide electrode can be divided into Ru, Ir, Mn and Pb system electrode by oxide components classification.Now
Titanium-based metal oxide electrode manufacturing process reaches its maturity, but still cannot solve the service life of titanium-based metal oxide electrode compared with
Short shortcoming.Titanium-based metal oxide electrode failure main cause be：In electrolytic process metal oxide containing precious metals constantly dissolving and
The gas of generation makes coating constantly come off the constant impingement that coating is caused, and ultimately results in Titanium base and exposes and be passivated.Add
The characteristics of metal oxide containing precious metals high cost and big electrode later stage power consumption so that the use cost of titanium-based metal oxide electrode is very
It is high.
In sum, existing titanium-based metal oxide coating exists in mechanical property and decay resistance and a series of needs to be solved
Problem certainly.Accordingly, it would be desirable to a kind of current efficiency is high, production cost is relatively low and the electrode material that lasts a long time.
Graphene is made up of the basic structural unit phenyl ring that carbon-carbon double bond is formed, and outstanding electric property makes Graphene
It is widely used in the fields such as inductor, battery and photoelectrocatalysis.The Chinese invention patent document of Publication No. CN103526235 A
Disclose a kind of preparation method of titanium/graphene/metal oxide combination electrode：The graphene coated successively and electricity on Titanium base
Solution deposit metal oxide layers, are obtained a kind of titanium/graphene/metal oxide combination electrode.Using the compound electric of above-mentioned preparation
There are two shortcomings in pole：1st, the adhesion between Graphene and Titanium base is poor, and coating is easy to come off；2nd, graphene layer on Titanium base
Thicker, unnecessary Graphene can fly away in the electrolytic solution, affect electrolysis system.Therefore, titanium/graphene/metal oxide compound electric
The service life of pole is less than common titanium-based metal oxide electrode.
Graphene is made up of the basic structural unit phenyl ring that carbon-carbon double bond is formed, and outstanding electric property makes Graphene
It is widely used in the fields such as inductor, battery and photoelectrocatalysis.Additionally, Graphene is in mechanical strength, chemical stability and impervious
The performance such as saturating is also very excellent.The present invention is compound as electrode coating using Graphene and metal oxide, can fully send out
Wave the advantage of its composite construction.Graphene metal composite oxide coating has the advantage that：(1) porosity for making coating surface is carried
Height, increases the real table area of coating, while the adhesion between each coating of metal oxides is higher；(2) Graphene machinery is strong
Degree, makes coating in combination more firmly, slows down coming off for coating；(3) Graphene has good anti-permeability, can effectively prevent oxygen molecule
With Titanium base directly contact and cause passivation；(4) add Graphene to improve the segregation phenomena of Ru, Ir oxide, make coating table
The active component in face is improved.The electrode material provides new technological approaches to prepare high life metal oxide electrode.
The content of the invention
The purpose of the present invention is a kind of new Graphene complex metal oxide electrode of exploitation, and the electrode has electro-catalysis
The advantages of property good, corrosion-resistant and long service life.
A kind of Graphene complex metal oxide electrode, including Titanium base and the composite coating positioned at Titanium base surface, institute
State composite coating and be sequentially coated with lower metal oxide layer, Graphene filling porous metal oxide layer and upper metal from the bottom to top
Oxide skin(coating).
The present invention adds Graphene to improve the electric conductivity and impact resistance of coating, appropriate graphite in composite coating
Alkene can strengthen the adhesion in coating between metal oxide, be corroded using the corrosion resistance and anti-permeability barrier coat of Graphene
With Titanium base passivation, while playing the chemical property of Graphene, the electrode is set to have electrocatalysis good, corrosion-resistant and use the longevity
The advantages of ordering long.
Graphene filling porous metal oxide layer is made up of Graphene and metal oxide, with loose structure and
Graphene is filled with duct.
The coated weight of the composite coating is 5～50g/m2。
The upper metal oxide layer is consistent with lower metal oxide composition of layer, containing in Ru, Ir, Sn and Ti oxide
One or more.
It is 0.5～5mm, twine that the Titanium base is the plate thickness of the plate or net of titanium or titanium alloy, the titanium or titanium alloy
A diameter of 0.1～2mm.
The titanium alloy is the titanium alloy trade mark TA2 or TA4.
The preparation method of above-mentioned Graphene complex metal oxide electrode, including：
(1) Titanium base is pre-processed with sandblasting and etching；
(2) preparing metal oxide precursor liquid solution, the metal oxide precursor solution is coated in step (1)
On pretreated Titanium base, 5～30min is aoxidized in 400～600 DEG C, obtain Titanium base/metal oxide composite；
(3) oxidation of the metal containing Graphene suspended particulate is coated on the Titanium base/metal oxide composite
Thing precursor solution, with 400～600 DEG C of 5～30min of sintering after 50～120 DEG C of 2～20min of drying, obtains titanium/metal oxygen
Compound/porous metal oxide combination electrode；
(4) titanium/metal oxide/porous metal oxide combination electrode is immersed in graphene suspension, is surpassed
Sound stirs 10～20min, and the titanium/metal oxide/porous metal oxide combination electrode of Graphene filling is obtained after being dried；
(5) repeat step (3)～(4) 5～15 times, last repeat step (2) coats layer of metal oxide, and in 400
～600 DEG C of 1～2h of sintering, finally obtain the Graphene complex metal oxide electrode.
In step (2), the preparation of the metal oxide precursor solution includes：It is mixed with the n-butanol containing metal ion
Conjunction solution is presoma, is diluted with watery hydrochloric acid or n-butanol so that the total concentration of metal ion is 0.1～2.0mol/L, is stirred
Uniformly, the metal oxide precursor solution is obtained.The metallic atom is one or more in Ru, Ir, Sn and Ti.
In step (3), in the metal oxide precursor solution containing Graphene suspended particulate, Graphene suspension
Grain concentration is 0.5～15g/L, and the total concentration of correspondence metal ion is 0.1～2.0mol/L.
In step (3), by high temperature sintering, applying after the Graphene oxidation not combined with metal oxide crystal in coating
Loose structure is formed in layer, the surface area of electrode is improved.
In step (4), in the presence of ultrasonic agitation, graphene suspension is penetrated into the hole of coating, play protection
The conductive effect of electrode and enhancing.Preferably, Graphene concentration of suspended particles is 0.5～15g/L
Present invention also offers a kind of application of above-mentioned Graphene complex metal oxide electrode in waste water from dyestuff is processed.
It is a further object to provide a kind of above-mentioned Graphene complex metal oxide electrode is in chlor-alkali production
Application.
Compared with prior art, the invention has the advantages that：
(1) the two-dimension periodic honeycomb lattice structure that Graphene is made up of carbon hexatomic ring, its carbon skeleton is highly stable, by force
Degree is high and is difficult to be corroded.Improve the adhesion and coating morphology of metal oxide interlayer by introducing graphene layer,
Alleviate Titanium base oxidation using the anti-permeability of Graphene, and then extend the service life of titanium-based metal oxide electrode.
(2) technology for preparing electrode is simple, easy to operate, and the analysis chlorine of electrode is made after metal oxide interlayer adds Graphene
Current potential is reduced and oxygen evolution potential is improved, improve current efficiency with its as chlorine industry electrode material, and without graphite
The titanium-based metal oxide electrode of alkene is compared, and the oxygen content for generating chlorine declines 1%～3%, and single ton of caustic soda energy consumption declines 3%～
8%, with certain energy-saving effect.
(3) after the metal oxide precursor solution of graphene coated suspended particulate, electrode surface Ru and Ir containing measuring
To raising, the utilization rate for making precious metal element rises, and the electrode production cost under equal performance is further reduced.
Description of the drawings
Fig. 1 is the structural representation of Graphene complex metal oxide electrode of the present invention；
Fig. 2 is the surface shape of titanium/metal oxide/porous metal oxide combination electrode prepared by the embodiment of the present invention 1
Looks figure；
Fig. 3 is the surface topography map of the compound Ru-Ir-Sn metal oxide electrodes of Graphene prepared by the embodiment of the present invention 1.
Specific embodiment
Further illustrate the flesh and blood of the present invention with specific embodiments and the drawings below, but present disclosure is not limited
In this.
The structural representation of Graphene complex metal oxide electrode of the present invention is as shown in Figure 1.
Embodiment 1
The compound Ru-Ir-Sn metal oxide electrodes of Graphene manufactured in the present embodiment, including Titanium base and positioned at Titanium base
The composite coating on surface, the composite coating is sequentially coated with from the bottom to top lower metal oxide layer, Graphene filling porous gold
Category oxide skin(coating) and upper metal oxide layer.
Concrete preparation method includes：
(1) from the technical grade titanium plate that the titanium alloy trade mark is TA2, thickness is 2mm, the rectangle of 80 × 20 × 2mm is cut into,
Sandblasting is carried out, surface is etched and cleaned with oxalic acid, remove the oxide layer on surface；
(2) with RuCl3·xH2O、H2IrCl6And SnCl4·5H2The n-butanol mixed solution of O is presoma, wherein Ru, Ir
It is 17 with the mol ratio of Sn：23：60, diluted with n-butanol so that the total concentration of metal ion is 0.6mol/L, is stirred,
Obtain metal oxide precursor solution；By the RuCl of identical mol ratio3·xH2O、H2IrCl6And SnCl4·5H2O, with 4g/L's
Graphene suspension dissolves, and concentration of metal ions keeps 0.6mol/L constant, obtains the metal oxygen containing Graphene suspended particulate
Compound precursor solution；
(3) gained metal oxide precursor solution is coated uniformly on pretreated Titanium base, is put into Muffle furnace
It is interior, 15min is aoxidized at 420 DEG C, obtain Titanium base/Ru-Ir-Sn coating composite materials；
(4) metal oxygen containing Graphene suspended particulate is coated on the Titanium base/Ru-Ir-Sn coating composite materials
Compound precursor solution, is dried after 10min with 420 DEG C of sintering 15min in 120 DEG C, obtains titanium/metal oxide/porous metals
Oxide combination electrode, its surface topography is as shown in Fig. 2 it can be seen that the titanium/metal oxide/porous metals
Oxide combination electrode defines loose structure；
(5) titanium/metal oxide/porous metal oxide combination electrode is immersed in the graphene suspension of 4g/L
In, ultrasonic agitation 10min obtains the titanium/metal oxide/porous metal oxide combination electrode of Graphene filling after being dried；
(6) repeat step (4)～(5) 15 times, last repeat step (3) coats layer of metal oxide, and in 420 DEG C of burnings
Knot 2h, finally obtains the compound Ru-Ir-Sn metal oxide electrodes of the Graphene.
In Graphene complex metal oxide electrode manufactured in the present embodiment, the coated weight of composite coating is 10g/m2, table
Face shape appearance figure is as shown in Figure 3.
Comparative example 1
Compared with Example 1, the metal oxide precursor for being free from Graphene of coating in step (4) is differed only in
Solution and omission step (5), finally obtain Ru-Ir-Sn metal oxide electrodes.
Ru-Ir- prepared by the compound Ru-Ir-Sn metal oxide electrodes of Graphene prepared by embodiment 1 and comparative example 1
Sn metal oxide electrodes respectively in saturated aqueous common salt and 0.25mol/L sulfuric acid solutions, with 3000A/m2Current density is carried out
Analysis chlorine and oxygen evolution potential test, while being that, with 20000A/m2 current densities, titanium plate is entered as negative electrode in 0.5mol/L sulfuric acid solutions
Row reinforcing life is tested, and the comparing result of two kinds of electrodes is as shown in table 1, from table 1 it follows that graphite prepared by embodiment 1
The Ru-Ir-Sn metal oxide electrodes that the compound Ru-Ir-Sn metal oxide electrodes of alkene are prepared with comparative example 1 are compared, analysis chlorine electricity
Position declines 0.064V, and oxygen evolution potential rises 0.072V, and reinforcing life improves 182.9%.
Table 1
Embodiment 2
Graphene complex metal oxide electrode net manufactured in the present embodiment, including Titanium base and positioned at Titanium base surface
Composite coating, the composite coating is sequentially coated with from the bottom to top lower metal oxide layer, Graphene filling porous metals oxidation
Nitride layer and upper metal oxide layer.Concrete preparation method includes：
(1) from the technical grade titanium plate that the titanium alloy trade mark is TA2, thickness is 2mm, the rectangle of 80 × 20 × 2mm is cut into,
Sandblasting is carried out, surface is etched and cleaned with oxalic acid, remove the oxide layer on surface；
(2) with RuCl3·xH2O、H2IrCl6、SnCl4·5H2The n-butanol mixed solution of O and butyl titanate is forerunner
The mol ratio of body, wherein Ru, Ir, Sn and Ti is 36：4：20：40, diluted with watery hydrochloric acid so that the total concentration of metal ion is
1.6mol/L, stirs, and obtains metal oxide precursor solution；By the RuCl of identical mol ratio3·xH2O、H2IrCl6、
SnCl4·5H2O and butyl titanate, are dissolved with the graphene suspension of 10g/L, and concentration of metal ions keeps 1.6mol/L not
Become, obtain the metal oxide precursor solution containing Graphene suspended particulate；
(3) gained metal oxide precursor solution is coated uniformly on pretreated Titanium base, is put into Muffle furnace
It is interior, 15min is aoxidized at 480 DEG C, obtain Titanium base/Ru-Ir-Sn-Ti coating composite materials；
(4) oxidation of the metal containing Graphene suspended particulate is coated on the Titanium base/metal oxide composite
Thing precursor solution, is dried after 10min with 480 DEG C of sintering 15min in 120 DEG C, obtains titanium/metal oxide/porous metals oxygen
Compound combination electrode；
(5) Graphene that the titanium/metal oxide/porous metal oxide combination electrode is immersed in 10g/L is suspended
In liquid, ultrasonic agitation 10min obtains the titanium/metal oxide/porous metal oxide compound electric of Graphene filling after being dried
Pole；
(6) repeat step (4)～(5) 15 times, last repeat step (3) coats layer of metal oxide, and in 480 DEG C of burnings
Knot 2h, finally obtains the compound Ru-Ir-Sn-Ti metal oxide electrodes of the Graphene.
In Graphene complex metal oxide electrode manufactured in the present embodiment, the coated weight of composite coating is 30g/m2。
Comparative example 2
Compared with Example 2, the metal oxide precursor for being free from Graphene of coating in step (4) is differed only in
Solution and omission step (5), finally obtain Ru-Ir-Sn-Ti metal oxide electrodes.
Ru- prepared by the compound Ru-Ir-Sn-Ti metal oxide electrodes of Graphene prepared by embodiment 2 and comparative example 2
Ir-Sn-Ti metal oxide electrodes respectively in saturated aqueous common salt and 0.25mol/L sulfuric acid solutions, with 3000A/m2Electric current is close
Degree carry out analyse chlorine and oxygen evolution potential test, while 0.5mol/L sulfuric acid solutions be using 20000A/m2 current densities titanium plate as
Negative electrode carries out reinforcing life test, and the comparing result of two kinds of electrodes is as shown in table 2, from Table 2, it can be seen that prepared by embodiment 2
The Ru-Ir-Sn-Ti metal oxide electrodes that prepare with comparative example 2 of the compound Ru-Ir-Sn-Ti metal oxide electrodes of Graphene
Compare, analysis chlorine declines 0.193V, and analysis chlorine oxygen evolution potential difference is extended to 0.338V, but reinforcing life is reduced to 28h.
Table 2
Embodiment 3
The compound Ru-Ir-Sn metal oxide electrodes of Graphene manufactured in the present embodiment, including Titanium base and positioned at Titanium base
The composite coating on surface, the composite coating is sequentially coated with from the bottom to top lower metal oxide layer, Graphene filling porous gold
Category oxide skin(coating) and upper metal oxide layer.Concrete preparation method includes：
(1) from the technical grade titanium plate that the titanium alloy trade mark is TA2, thickness is 2mm, the rectangle of 80 × 20 × 2mm is cut into,
Sandblasting is carried out, surface is etched and cleaned with oxalic acid, remove the oxide layer on surface；
(2) with RuCl3·xH2O、H2IrCl6And SnCl4·5H2The n-butanol mixed solution of O is presoma, wherein Ru, Ir
It is 17 with the mol ratio of Sn：23：60, diluted with n-butanol so that the total concentration of metal ion is 0.6mol/L, is stirred,
Obtain metal oxide precursor solution；By the RuCl of identical mol ratio3·xH2O、H2IrCl6And SnCl4·5H2O, with 4g/L's
Graphene suspension dissolves, and concentration of metal ions keeps 0.6mol/L constant, obtains the metal oxygen containing Graphene suspended particulate
Compound precursor solution；
(3) gained metal oxide precursor solution is coated uniformly on pretreated Titanium base, is put into Muffle furnace
It is interior, 15min is aoxidized at 450 DEG C Jing after 120 DEG C of dryings, obtain Titanium base/Ru-Ir-Sn coating composite materials；
(4) metal oxygen containing Graphene suspended particulate is coated on the Titanium base/Ru-Ir-Sn coating composite materials
Compound precursor solution, is dried after 10min with 450 DEG C of sintering 15min in 120 DEG C, obtains titanium/metal oxide/porous metals
Oxide combination electrode；
(5) titanium/metal oxide/porous metal oxide combination electrode is immersed in the graphene suspension of 4g/L
In, ultrasonic agitation 10min obtains the titanium/metal oxide/porous metal oxide combination electrode of Graphene filling after being dried；
(6) repeat step (4)～(5) 10 times, last repeat step (3) coats layer of metal oxide, and in 450 DEG C of burnings
Knot 2h, finally obtains the compound Ru-Ir-Sn metal oxide electrodes of the Graphene.
In Graphene complex metal oxide electrode manufactured in the present embodiment, the coated weight of composite coating is 10g/m2。
Comparative example 3
Compared with Example 3, the metal oxide precursor for being free from Graphene of coating in step (4) is differed only in
Solution and omission step (5), finally obtain Ru-Ir-Sn metal oxide electrodes.
The Ru-Ir- that the compound Ru-Ir-Sn metal oxide electrodes of Graphene prepared by embodiment 3 are prepared with comparative example 3
Cationic Red X-GRL dye wastewater of the Sn metal oxide electrodes to concentration for 1000mg/L carries out Electrochemical Decolorization reality
Test, current density is 1000A/m2, titanium plate is used as negative electrode, and the comparing result of two kinds of electrodes is as shown in table 3.Can from table 3
Go out, the Ru-Ir-Sn metal oxygens that the compound Ru-Ir-Sn metal oxide electrodes of Graphene prepared by embodiment 3 are prepared with comparative example 3
Compound electrode is compared, and tank voltage rises 0.1V, and Jing after 10min electrolysis, dyestuff clearance improves about 40%.
Table 3
Comparative example 4
The compound Ru-Ir-Sn metal oxide electrodes of Graphene prepared by this comparative example#, including Titanium base and positioned at titanium-based
The composite coating in body surface face, the composite coating is sequentially coated with from the bottom to top Graphene filling porous metal oxide layer and upper
Metal oxide layer.
Concrete preparation method includes：
(1) from the technical grade titanium plate that the titanium alloy trade mark is TA2, thickness is 2mm, the rectangle of 80 × 20 × 2mm is cut into,
Sandblasting is carried out, surface is etched and cleaned with oxalic acid, remove the oxide layer on surface；
(2) with RuCl3·xH2O、H2IrCl6And SnCl4·5H2The n-butanol mixed solution of O is presoma, wherein Ru, Ir
It is 17 with the mol ratio of Sn：23：60, diluted with n-butanol so that the total concentration of metal ion is 0.6mol/L, is stirred,
Obtain metal oxide precursor solution；By the RuCl of identical mol ratio3·xH2O、H2IrCl6And SnCl4·5H2O, with 4g/L's
Graphene suspension dissolves, and concentration of metal ions keeps 0.6mol/L constant, obtains the metal oxygen containing Graphene suspended particulate
Compound precursor solution；
(3) by gained the metal oxide precursor solution containing Graphene suspended particulate be coated uniformly on it is pretreated
On Titanium base, it is dried after 10min in 120 DEG C with 480 DEG C of sintering 15min, obtains Titanium base/porous metal oxide compound electric
Pole；
(4) Titanium base/porous metal oxide combination electrode is immersed in the graphene suspension of 4g/L, ultrasound
Stirring 10min, obtains the titanium/porous metal oxide combination electrode of Graphene filling after being dried；
(5) repeat step (3)～(4) 15 times, finally coat layer of metal oxide precursor liquid solution, and in 480 DEG C of burnings
Knot 2h, finally obtains the compound Ru-Ir-Sn metal oxide electrodes of the Graphene#。
In Graphene complex metal oxide electrode prepared by this comparative example, the coated weight of composite coating is 10g/m2。
Graphene prepared by the compound Ru-Ir-Sn metal oxide electrodes of Graphene prepared by embodiment 1 and comparative example 4
Compound Ru-Ir-Sn metal oxide electrodes#Respectively in saturated aqueous common salt and 0.25mol/L sulfuric acid solutions, with 3000A/m2Electricity
Current density carries out analysing chlorine and oxygen evolution potential test, while being with 20000A/m2 current densities, titanium plate in 0.5mol/L sulfuric acid solutions
Reinforcing life test is carried out as negative electrode, the comparing result of two kinds of electrodes is as shown in table 4, as can be seen from Table 4, comparative example 4
The compound Ru-Ir-Sn metal oxide electrodes of the Graphene of preparation#With the compound Ru-Ir-Sn metals of Graphene prepared by embodiment 1
Oxide electrode is compared, and chlorine evolution potential declines 0.079V, and oxygen evolution potential declines 0.034V, but reinforcing life foreshortens to 9.5h.
Table 4
Above example is elaborated to the specific embodiment of the present invention, but the present invention is not limited to above-mentioned reality
Mode is applied, can be so that various changes can be made on the premise of without departing from present inventive concept.
Claims (10)
1. a kind of Graphene complex metal oxide electrode, including Titanium base and the composite coating positioned at Titanium base surface, it is special
Levy and be, the composite coating is sequentially coated with from the bottom to top lower metal oxide layer, Graphene filling porous metal oxide
Layer and upper metal oxide layer.
2. Graphene complex metal oxide electrode according to claim 1, it is characterised in that the Graphene filling is more
Mesoporous metal oxide skin(coating) is made up of Graphene and metal oxide, and Graphene is filled with loose structure and in duct.
3. Graphene complex metal oxide electrode according to claim 1, it is characterised in that the painting of the composite coating
The amount of covering is 5～50g/m2。
4. Graphene complex metal oxide electrode according to claim 1, it is characterised in that the upper metal oxide
Layer is consistent with lower metal oxide composition of layer, containing one or more in Ru, Ir, Sn and Ti oxide.
5. Graphene complex metal oxide electrode according to claim 1, it is characterised in that the Titanium base be titanium or
The plate thickness of the plate or net of titanium alloy, the titanium or titanium alloy is 0.5～5mm, mesh wire diameter is 0.1～2mm.
6. a kind of preparation method of the Graphene complex metal oxide electrode according to any one of Claims 1 to 5, it is special
Levy and be, including：
(1) Titanium base is pre-processed with sandblasting and etching；
(2) preparing metal oxide precursor liquid solution, is coated on Jing in step (1) pre- by the metal oxide precursor solution
On the Titanium base of process, 5～30min is aoxidized in 400～600 DEG C, obtain Titanium base/metal oxide composite；
(3) before coating the metal oxide containing Graphene suspended particulate on the Titanium base/metal oxide composite
Drive liquid solution, after 50～120 DEG C of 2～20min of drying with 400～600 DEG C sintering 5～30min, obtain titanium/metal oxide/
Porous metal oxide combination electrode；
(4) titanium/metal oxide/porous metal oxide combination electrode is immersed in graphene suspension, ultrasound is stirred
10～20min is mixed, the titanium/metal oxide/porous metal oxide combination electrode of Graphene filling is obtained after being dried；
(5) repeat step (3)～(4) 5～15 times, last repeat step (2) coats layer of metal oxide, and in 400～600
DEG C sintering 1～2h, finally obtain the Graphene complex metal oxide electrode.
7. the preparation method of Graphene complex metal oxide electrode according to claim 6, it is characterised in that the gold
In category oxide precursor liquid solution, the total concentration of metal ion is 0.1～2.0mol/L.
8. the preparation method of Graphene complex metal oxide electrode according to claim 6, it is characterised in that step
(3) in, in the metal oxide precursor solution containing Graphene suspended particulate, Graphene concentration of suspended particles is 0.5
～15g/L, the total concentration of correspondence metal ion is 0.1～2.0mol/L.
9. a kind of Graphene complex metal oxide electrode according to any one of Claims 1 to 5 is processing waste water from dyestuff
In application.
10. a kind of Graphene complex metal oxide electrode according to any one of Claims 1 to 5 is in chlor-alkali production
Using.
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