CN104891567B - Tubulose TiO2The preparation method of/redox graphene composite - Google Patents
Tubulose TiO2The preparation method of/redox graphene composite Download PDFInfo
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Abstract
The invention discloses a kind of tubulose TiO2The preparation method of/redox graphene composite, first with TiOSO4It is soft template as titanium source, Pluronic type block copolymer (P123), in ethanol ethylene glycol mixed solution, synthesized tubulose TiO2；Then graphene oxide is synthesized with improved Hummers method；Finally, at high temperature, with tubulose TiO2It is raw material with graphene oxide, tubulose TiO is prepared for using hydro-thermal method self assembly2/ redox graphene composite.The method is preparing tubulose TiO2During/redox graphene composite, it is not added with reducing agent, graphene oxide adopts high temperature hydrothermal reduction, environmental protection.And the addition of graphene oxide is to TiO2Pattern does not make significant difference, TiO2Tubular morphology can effectively be kept, by adjusting TiO2The tubulose TiO of different proportion can be prepared with the ratio of graphene oxide2/ redox graphene composite.
Description
Technical field
The present invention relates to tubulose TiO2The preparation method of/redox graphene composite, belongs to inorganic semiconductor material
Material preparation field.
Background technology
TiO2Because the chemical physical property that it is nontoxic, chemical stability is good and excellent is applied to multiple fields, such as：Light is urged
Change, sensing, ultracapacitor and solaode etc..Graphene be by carbon atom tightly packed formed there is hexagonal structure
Unit two-dimension plane structure, has the advantages that specific surface area is big, electron mobility is high and good conductivity.But TiO2Electric conductivity
Poor, Graphene and TiO2Recombination energy increases its electric conductivity, specific surface area and capacitance, promotes dividing of its electron-hole pair
From.Existing TiO2The preparation method of/graphene composite material, the composite obtaining mostly is graphene-supported TiO2Granule, and
TiO2Pattern uncontrollable, easily reunite；And need to add the reducing agents such as hydrazine hydrate during graphene oxide reduction, this
Class reducing agent is not only poisonous but also big to environmental hazard.
For example, yang etc. is prepared for TiO using sol-gel process and hydro-thermal method2/ graphene composite material, wherein TiO2Receive
Rice grain is reunited seriously, bad dispersibility (Min-Quan Yang, Nan Zhang, and Yi-Jun Xu.ACS
Appl.Mater.Interfaces,2013,5,1156-1164).Application publication number CN 103936065 A (application number
201410119700.2) Chinese patent literature disclose a kind of TiO2With the preparation method of graphene composite nano material, lead to
Cross tert-butylamine and graphene oxide is reduced to Graphene, add titanium source that TiO is obtained2With graphene composite nano material, wherein TiO2
Pattern be nano-particle.And add tert-butylamine larger to environmental hazard in preparation process.Application publication number CN
The Chinese patent literature of 102527366 A (application number 201210008265.7) discloses a kind of titanium dioxide nanotube graphene
Mixing photocatalyst and preparation method, with TiO2For titanium source, composite is prepared using hydro-thermal method, its preparation process needs repeatedly
Washing, step is more.The pattern of composite covers TiO for Graphene2Nanotube.Authorization Notice No. CN 102496700 B
The Chinese patent literature of (application number 201110429717.4) disclose a kind of graphene-titanium dioxide nanotube composite material and
Preparation method, with P25 or anatase TiO2For titanium source, composite is prepared using hydro-thermal method, its preparation process needs repeatedly to wash
Wash, relatively complicated.The pattern of composite is graphene-supported TiO2Nanotube.
Content of the invention
It is an object of the invention to provide a kind of tubulose TiO2The preparation method of/redox graphene composite, the party
The pattern of the composite that method is prepared coats tubulose TiO for redox graphene2, TiO2Pattern can effectively control,
And adopt high temperature hydrothermal reduction to replace reducing agent, environmental protection in preparation process.
For reaching above-mentioned purpose, the technical scheme that the present invention takes is：
A kind of tubulose TiO2The preparation method of/redox graphene composite, first with TiOSO4As titanium source, gather
Oxygen ethylene-polyoxypropylene polyoxyethylene triblock copolymer (P123) is soft template, molten in ethanol-glycol-ether mixing
A length of 4-12 μm has been synthesized, wall thickness is 100-300nm and caliber is 0.5-1.5 μm of tubulose TiO in liquid2；At 110-150 DEG C,
With tubulose TiO2It is raw material with graphene oxide, tubulose TiO is prepared for using hydro-thermal method self assembly2/ redox graphene is combined
Material.
In the method, the TiO that the first step obtains2Pattern is tubulose, and in the recombination process of second step, TiO2Pattern
Will not because of with the compound of redox graphene and change, control TiO in composite such that it is able to effective2Shape
Looks.During second step prepares composite, the method using high temperature hydrothermal reduction obtains redox graphene, is not required to
Add reducing agent, environmental protection.The tubulose TiO that the method obtains2The pattern of/redox graphene composite is oxygen reduction
Graphite alkene coats tubulose TiO2.
Specifically include following steps：
(1) solvent-thermal method prepares tubulose TiO2
1. P123 is dissolved in ethanol-glycol-ether mixed solution, stirs to clear solution under room temperature；
2. by TiOSO4It is added to step 1. in the clear solution of gained, stirring 2-48h obtains suspension；
3. the suspension that 2. step is prepared is transferred in autoclave, under the conditions of 110-150 DEG C, is incubated 12-48h,
After hydrothermal treatment consists, autoclave is cooled to room temperature, is precipitated thing；
4. after the precipitate centrifugation 3. step being obtained, washing, centrifugation, be dried, 450-500 DEG C after grinding at calcine
3-6h obtains tubulose TiO2, tubulose TiO2A length of 4-12 μm, wall thickness is 100-300nm, and caliber is 0.5-1.5 μm；
(2) prepare tubulose TiO2/ redox graphene composite
1. by tubulose TiO2It is dispersed in water, ultrasonic, obtain tubulose TiO2Dispersion liquid；Wherein, described tubulose TiO2And steaming
The adding proportion of distilled water is：(0.0500-0.2000)g：20mL
2. graphene oxide powder is dispersed in water, ultrasonic, obtain the dispersion liquid of graphene oxide；Wherein, described oxygen
Graphite alkene with the adding proportion of water is：(0.0025-0.0400)g：10mL；
3. by step, dispersion liquid 2. adds in step dispersion liquid 1. under agitation, ultrasonic agitation 2-6h；
4. mixed dispersion liquid is transferred in autoclave, is incubated 12-48h, hydrothermal treatment consists under the conditions of 110-150 DEG C
Afterwards autoclave is cooled to room temperature, is precipitated thing；
5. after the precipitate obtaining centrifugation, will wash, be centrifuged, be dried, after grinding, obtain tubulose TiO2/ reduction-oxidation
(redox graphene is coated on tubulose TiO to graphene composite material2Surface).
In step (1), raw materials used TiOSO4, P123, ethanol, ether and ethylene glycol mol ratio be 1：0.00552-
0.02758：54.622-109.243：15.340-36.680：28.659-57.319, it is preferably in a proportion of 1：0.00552：
71.008：19.942：37.257.
In step (1), the molecular weight of described P123 is 4000～7000g/moL, preferably 5800g/moL.
Step (1) 2. in, optimum reacting time be 12h.
Step (1) 3. in, hydrothermal condition be preferably 110 DEG C insulation 24h.
Step (1) 4. in, calcination condition be preferably 500 DEG C at calcine 4h.
Step (2) 2. in, the preparation method of graphene oxide powder is as follows：
By graphite powder, concentrated sulphuric acid and K2S2O8Mixing, stirring, ultrasonic, 80 DEG C of stirring 6-8h；The product obtaining is done
Dry, add concentrated sulphuric acid and phosphoric acid after being dried, stirring, ultrasonic；Solution cooling after will be ultrasonic, is subsequently adding potassium permanganate, continues
Stirring 4-6h, then heats to 35 DEG C, stirring insulation 8-12h；It is subsequently adding water, reaction 2-3h is stirred at room temperature；It is eventually adding double
Oxygen water, through washing, separate, ultrasonic and be dried to obtain graphene oxide.
Concrete preparation process is as follows：
1. by 2-5g graphite powder, 30-80ml concentrated sulphuric acid, 2-5g K2S2O8It is added sequentially in beaker, stirring, ultrasonic 5-30
Minute, put into water-bath, be heated to 80 DEG C of stirring 6-8h；
2. by step product distilled water diluting 1. to 1000ml, then sucking filtration, drying at room temperature 8-12h；
3. the filter cake that 2. step obtains is added in beaker, adds 120-200ml concentrated sulphuric acid, 20-50ml phosphoric acid, stir,
Ultrasonic 1-2h；
4. the solution after will be ultrasonic is placed in ice bath, cools down 0.5-1h, is added slowly with stirring 12-30g potassium permanganate,
Control temperature to be less than 5 DEG C, continue stirring 4-6h, then heat to 35 DEG C, stirring insulation 8-12h；5. and then in solution slowly
Add 150-300ml distilled water, reaction 2-3h is stirred at room temperature；
6. it is eventually adding 16-40ml hydrogen peroxide, stirs 0.5-2h, through washing repeatedly, centrifugation, ultrasonic, obtain PH ≈ 7
Graphene oxide solution, through being dried to obtain graphene oxide.
Step (2) 3. in, described mixing ultrasonic agitation time is 2h.
Step (2) 4. in, hydrothermal condition be preferably 110 DEG C insulation 24h.
The present invention is with TiOSO4For titanium source, surfactant P123 is soft template, using the solvent-thermal method of mixed solvent
Prepare tubulose TiO2, graphene oxide is prepared with improved Hummers method, then adopts hydro-thermal method that tubulose TiO is obtained2/ also
Former graphene oxide composite material.
The invention has the advantages that：
1st, the tubulose TiO that the present invention is obtained2/ redox graphene composite, tubulose TiO2Long about 4-12 μm, wall
Thick about 100-300nm, caliber is about 0.5-1.5 μm, and redox graphene is coated on tubulose TiO2Surface.
2nd, the present invention prepares tubulose TiO using two-step method2/ redox graphene composite, graphene oxide and TiO2
Ratio controlled；And TiO2Pattern will not change because of the addition of redox graphene, for the TiO of other patterns2/
Redox graphene composite provides reference.
3rd, the present invention prepares tubulose TiO2During/redox graphene composite, graphene oxide is in high temperature hydro-thermal bar
Reduce under part, be not required to add reducing agent, environmental protection.
Brief description
Fig. 1 is the tubulose TiO of preparation2And tubulose TiO2The transmission electron microscope picture (TEM) of/redox graphene composite,
Wherein a is tubulose TiO2TEM, b be embodiment 1 preparation tubulose TiO2The TEM of/redox graphene composite；
Fig. 2 is the tubulose TiO of preparation2And tubulose TiO2The field emission scanning electron microscope figure of/redox graphene composite
(FESEM), wherein a is tubulose TiO2FESEM, b be embodiment 1 preparation tubulose TiO2/ redox graphene composite
FESEM；
Fig. 3 is the tubulose TiO of preparation2, graphene oxide and tubulose TiO2The X- of/redox graphene composite penetrates
Ray diffraction diagram (XRD), wherein a is the XRD of graphene oxide；B is tubulose TiO2XRD；C is the tubulose of embodiment 1 preparation
TiO2The XRD of/redox graphene composite.
Specific embodiment
Further illustrate with reference to specific embodiment.
Embodiment 1
(1) prepare tubulose TiO2Take 0.1000g P123 in beaker, add 13ml ethanol, 6.5ml ethylene glycol, 6.5ml
Ether, stirs 1h under room temperature；Add 0.5000g TiOSO4, stir 12h and obtain suspension；Suspension is transferred to polytetrafluoroethyl-ne
In the autoclave of alkene liner, autoclave is tightened and puts in baking oven, be incubated 24h, hydrothermal treatment consists under the conditions of 110 DEG C
Afterwards autoclave is naturally cooled to room temperature, be precipitated thing；After the precipitate obtaining centrifugation, washed using ethanol
Wash, be centrifuged, being dried, at grinding latter 500 DEG C, calcining 4h obtains tubulose TiO2.
(2) prepare graphene oxide by 3g graphite powder, 30ml concentrated sulphuric acid, 3g K2S2O8It is added sequentially in beaker, stirring,
Ultrasonic 5 minutes, put into water-bath, be heated to 80 DEG C of stirring 6h；It is slowly added to distilled water diluting to 1000ml, then sucking filtration, room
Warm dried overnight；The filter cake obtaining is added in beaker, adds 150ml concentrated sulphuric acid, 20ml phosphoric acid, stirring, ultrasonic 1h；Will be ultrasonic
Solution afterwards is placed in ice bath, cools down 0.5h, is added slowly with stirring 18g potassium permanganate, controls temperature to be less than 5 DEG C, continues
Stirring 4h, then heats to 35 DEG C, stirring insulation 8h；Then it is slowly added into 250ml distilled water in solution, reaction is stirred at room temperature
2h；It is eventually adding 24ml hydrogen peroxide, stirs 0.5h, through washing repeatedly, centrifugation, ultrasonic, obtain the graphene oxide of pH ≈ 7
Solution, through being dried to obtain graphene oxide.
(3) prepare tubulose TiO2The tubulose TiO that 0.0500g is prepared by/redox graphene composite2Add
In 20ml distilled water, ultrasonic, stir 1h, obtain tubulose TiO2Dispersion liquid；The graphene oxide powder that 0.0025g is prepared
Add in 10ml distilled water, ultrasonic, stir 1h, obtain the dispersion liquid of graphene oxide；By graphene oxide dispersion in stirring
Lower addition tubulose TiO2In dispersion liquid, ultrasonic agitation 2h；Mixed dispersion liquid is transferred to teflon-lined reaction under high pressure
In kettle, autoclave is tightened and puts in baking oven, be incubated 24h under the conditions of 110 DEG C, by autoclave after hydrothermal treatment consists
Naturally cool to room temperature, be precipitated thing；After the precipitate obtaining centrifugation, using washing with alcohol, centrifugation, it is dried, grinds
Tubulose TiO is obtained after mill2/ redox graphene composite.
As shown in Figure 1,2 and 3, the tubulose TiO that the present embodiment 1 is obtained2/ redox graphene composite, tubulose TiO2
Long about 4-12 μm, wall thickness is about 100-300nm, and caliber is about 0.5-1.5 μm, and redox graphene is coated on tubulose TiO2
Surface.Fig. 1 a, 2a are TiO2Tubulose, Fig. 1 b, 2b are tubulose TiO2/ redox graphene composite, can from figure
Go out, after composite reduction graphene oxide, TiO2Remain in that tubulose, do not change.Therefore, redox graphene
Addition can't change TiO2Pattern.
Embodiment 2
(1) prepare tubulose TiO2Take 0.1000g P123 in beaker, add 13ml ethanol, 6.5ml ethylene glycol, 6.5ml
Ether, stirs 1h under room temperature；Add 0.5000g TiOSO4, stir 12h and obtain suspension；Suspension is transferred to polytetrafluoroethyl-ne
In the autoclave of alkene liner, autoclave is tightened and puts in baking oven, be incubated 24h, hydrothermal treatment consists under the conditions of 110 DEG C
Afterwards autoclave is naturally cooled to room temperature, be precipitated thing；After the precipitate obtaining centrifugation, washed using ethanol
Wash, be centrifuged, being dried, at grinding latter 500 DEG C, calcining 4h obtains tubulose TiO2.
(2) prepare graphene oxide by 3g graphite powder, 30ml concentrated sulphuric acid, 3g K2S2O8It is added sequentially in beaker, stirring,
Ultrasonic 5 minutes, put into water-bath, be heated to 80 DEG C of stirring 6h；It is slowly added to distilled water diluting to 1000ml, then sucking filtration, room
Warm dried overnight；The filter cake obtaining is added in beaker, adds 150ml concentrated sulphuric acid, 20ml phosphoric acid, stirring, ultrasonic 1h；Will be ultrasonic
Solution afterwards is placed in ice bath, cools down 0.5h, is added slowly with stirring 18g potassium permanganate, controls temperature to be less than 5 DEG C, continues
Stirring 4h, then heats to 35 DEG C, stirring insulation 8h；Then it is slowly added into 250ml distilled water in solution, reaction is stirred at room temperature
2h；It is eventually adding 24ml hydrogen peroxide, stirs 0.5h, through washing repeatedly, centrifugation, ultrasonic, obtain the graphene oxide of pH ≈ 7
Solution, through being dried to obtain graphene oxide.
(3) prepare tubulose TiO2The tubulose TiO that 0.0500g is prepared by/redox graphene composite2Add
In 20ml distilled water, ultrasonic, stir 1h, obtain tubulose TiO2Dispersion liquid；The graphene oxide powder that 0.0050g is prepared
Add in 10ml distilled water, ultrasonic, stir 1h, obtain the dispersion liquid of graphene oxide；By graphene oxide dispersion in stirring
Lower addition tubulose TiO2In dispersion liquid, ultrasonic agitation 2h；Mixed dispersion liquid is transferred to teflon-lined reaction under high pressure
In kettle, autoclave is tightened and puts in baking oven, under the conditions of 110 DEG C, be incubated 24h, after hydrothermal treatment consists by autoclave certainly
So it is cooled to room temperature, be precipitated thing；After the precipitate obtaining centrifugation, using washing with alcohol, centrifugation, it is dried, grinds
After obtain tubulose TiO2/ redox graphene composite.
Embodiment 3
(1) prepare tubulose TiO2Take 0.1000g P123 in beaker, add 13ml ethanol, 6.5ml ethylene glycol, 6.5ml
Ether, stirs 1h under room temperature；Add 0.5000g TiOSO4, stir 12h and obtain suspension；Suspension is transferred to polytetrafluoroethyl-ne
In the autoclave of alkene liner, autoclave is tightened and puts in baking oven, be incubated 24h under the conditions of 110 DEG C, at hydro-thermal
After reason, autoclave is naturally cooled to room temperature, be precipitated thing；After the precipitate obtaining centrifugation, washed using ethanol
Wash, be centrifuged, being dried, at grinding latter 500 DEG C, calcining 4h obtains tubulose TiO2.
(2) prepare graphene oxide by 3g graphite powder, 30ml concentrated sulphuric acid, 3g K2S2O8It is added sequentially in beaker, stirring,
Ultrasonic 5 minutes, put into water-bath, be heated to 80 DEG C of stirring 6h；It is slowly added to distilled water diluting to 1000ml, then sucking filtration, room
Warm dried overnight；The filter cake obtaining is added in beaker, adds 150ml concentrated sulphuric acid, 20ml phosphoric acid, stirring, ultrasonic 1h；Will be ultrasonic
Solution afterwards is placed in ice bath, cools down 0.5h, is added slowly with stirring 18g potassium permanganate, controls temperature to be less than 5 DEG C, continues
Stirring 4h, then heats to 35 DEG C, stirring insulation 8h；Then it is slowly added into 250ml distilled water in solution, reaction is stirred at room temperature
2h；It is eventually adding 24ml hydrogen peroxide, stirs 0.5h, through washing repeatedly, centrifugation, ultrasonic, obtain the graphene oxide of pH ≈ 7
Solution, through being dried to obtain graphene oxide.
(3) prepare tubulose TiO2The tubulose TiO that 0.0500g is prepared by/redox graphene composite2Add
In 20ml distilled water, ultrasonic, stir 1h, obtain tubulose TiO2Dispersion liquid；The graphene oxide powder that 0.0075g is prepared
Add in 10ml distilled water, ultrasonic, stir 1h, obtain the dispersion liquid of graphene oxide；By graphene oxide dispersion in stirring
Lower addition tubulose TiO2In dispersion liquid, ultrasonic agitation 2h；Mixed dispersion liquid is transferred to teflon-lined reaction under high pressure
In kettle, autoclave is tightened and puts in baking oven, under the conditions of 110 DEG C, be incubated 24h, after hydrothermal treatment consists by autoclave certainly
So it is cooled to room temperature, be precipitated thing；After the precipitate obtaining centrifugation, using washing with alcohol, centrifugation, it is dried, grinds
After obtain tubulose TiO2/ redox graphene composite.
Embodiment 4
(1) prepare tubulose TiO2Take 0.1000g P123 in beaker, add 13ml ethanol, 6.5ml ethylene glycol, 6.5ml
Ether, stirs 1h under room temperature；Add 0.5000g TiOSO4, stir 12h and obtain suspension；Suspension is transferred to polytetrafluoroethyl-ne
In the autoclave of alkene liner, autoclave is tightened and puts in baking oven, be incubated 24h, hydrothermal treatment consists under the conditions of 110 DEG C
Afterwards autoclave is naturally cooled to room temperature, be precipitated thing；After the precipitate obtaining centrifugation, washed using ethanol
Wash, be centrifuged, being dried, at grinding latter 500 DEG C, calcining 4h obtains tubulose TiO2.
(2) prepare graphene oxide by 3g graphite powder, 30ml concentrated sulphuric acid, 3g K2S2O8It is added sequentially in beaker, stirring,
Ultrasonic 5 minutes, put into water-bath, be heated to 80 DEG C of stirring 6h；It is slowly added to distilled water diluting to 1000ml, then sucking filtration, room
Warm dried overnight；The filter cake obtaining is added in beaker, adds 150ml concentrated sulphuric acid, 20ml phosphoric acid, stirring, ultrasonic 1h；Will be ultrasonic
Solution afterwards is placed in ice bath, cools down 0.5h, is added slowly with stirring 18g potassium permanganate, controls temperature to be less than 5 DEG C, continues
Stirring 4h, then heats to 35 DEG C, stirring insulation 8h；Then it is slowly added into 250ml distilled water in solution, reaction is stirred at room temperature
2h；It is eventually adding 24ml hydrogen peroxide, stirs 0.5h, through washing repeatedly, centrifugation, ultrasonic, obtain the graphene oxide of pH ≈ 7
Solution, through being dried to obtain graphene oxide.
(3) prepare tubulose TiO2The tubulose TiO that 0.0500g is prepared by/redox graphene composite2Add
In 20ml distilled water, ultrasonic, stir 1h, obtain tubulose TiO2Dispersion liquid；The graphene oxide powder that 0.0100g is prepared
End adds in 10ml distilled water, ultrasonic, stirs 1h, obtains the dispersion liquid of graphene oxide；Graphene oxide dispersion is being stirred
Mix lower addition tubulose TiO2In dispersion liquid, ultrasonic agitation 2h；Mixed dispersion liquid is transferred to teflon-lined high pressure anti-
Answer in kettle, autoclave is tightened and puts in baking oven, be incubated 24h under the conditions of 110 DEG C, by autoclave after hydrothermal treatment consists
Naturally cool to room temperature, be precipitated thing；After the precipitate obtaining centrifugation, using washing with alcohol, centrifugation, it is dried, grinds
Tubulose TiO is obtained after mill2/ redox graphene composite.
Embodiment 5
(1) prepare tubulose TiO2Take 0.2000g P123 in beaker, add 13ml ethanol, 6.5ml ethylene glycol, 6.5ml
Ether, stirs 1h under room temperature；Add 0.5000g TiOSO4, stir 2h and obtain suspension；Suspension is transferred to polytetrafluoroethyl-ne
In the autoclave of alkene liner, autoclave is tightened and puts in baking oven, be incubated 12h, hydrothermal treatment consists under the conditions of 110 DEG C
Afterwards autoclave is naturally cooled to room temperature, be precipitated thing；After the precipitate obtaining centrifugation, washed using ethanol
Wash, be centrifuged, being dried, at grinding latter 450 DEG C, calcining 6h obtains tubulose TiO2.
(2) prepare graphene oxide by 3g graphite powder, 30ml concentrated sulphuric acid, 3g K2S2O8It is added sequentially in beaker, stirring,
Ultrasonic 5 minutes, put into water-bath, be heated to 80 DEG C of stirring 6h；It is slowly added to distilled water diluting to 1000ml, then sucking filtration, room
Warm dried overnight；The filter cake obtaining is added in beaker, adds 150ml concentrated sulphuric acid, 20ml phosphoric acid, stirring, ultrasonic 1h；Will be ultrasonic
Solution afterwards is placed in ice bath, cools down 0.5h, is added slowly with stirring 18g potassium permanganate, controls temperature to be less than 5 DEG C, continues
Stirring 4h, then heats to 35 DEG C, stirring insulation 8h；Then it is slowly added into 250ml distilled water in solution, reaction is stirred at room temperature
2h；It is eventually adding 24ml hydrogen peroxide, stirs 0.5h, through washing repeatedly, centrifugation, ultrasonic, obtain the graphene oxide of pH ≈ 7
Solution, through being dried to obtain graphene oxide.
(3) prepare tubulose TiO2The tubulose TiO that 0.0500g is prepared by/redox graphene composite2Add
In 20ml distilled water, ultrasonic, stir 1h, obtain tubulose TiO2Dispersion liquid；The graphene oxide powder that 0.0025g is prepared
Add in 10ml distilled water, ultrasonic, stir 1h, obtain the dispersion liquid of graphene oxide；By graphene oxide dispersion in stirring
Lower addition tubulose TiO2In dispersion liquid, ultrasonic agitation 2h；Mixed dispersion liquid is transferred to teflon-lined reaction under high pressure
In kettle, autoclave is tightened and puts in baking oven, under the conditions of 110 DEG C, be incubated 12h, after hydrothermal treatment consists by autoclave certainly
So it is cooled to room temperature, be precipitated thing；After the precipitate obtaining centrifugation, using washing with alcohol, centrifugation, it is dried, grinds
After obtain tubulose TiO2/ redox graphene composite.
Embodiment 6
(1) prepare tubulose TiO2Take 0.1000g P123 in beaker, add 13ml ethanol, 6.5ml ethylene glycol, 6.5ml
Ether, stirs 1h under room temperature；Add 0.5000g TiOSO4, stir 48h and obtain suspension；Suspension is transferred to polytetrafluoroethyl-ne
In the autoclave of alkene liner, autoclave is tightened and puts in baking oven, be incubated 48h, hydrothermal treatment consists under the conditions of 150 DEG C
Afterwards autoclave is naturally cooled to room temperature, be precipitated thing；After the precipitate obtaining centrifugation, washed using ethanol
Wash, be centrifuged, being dried, at grinding latter 500 DEG C, calcining 3h obtains tubulose TiO2.
(2) prepare graphene oxide by 3g graphite powder, 30ml concentrated sulphuric acid, 3g K2S2O8It is added sequentially in beaker, stirring,
Ultrasonic 30 minutes, put into water-bath, be heated to 80 DEG C of stirring 8h；It is slowly added to distilled water diluting to 1000ml, then sucking filtration, room
Warm dried overnight；The filter cake obtaining is added in beaker, adds 150ml concentrated sulphuric acid, 20ml phosphoric acid, stirring, ultrasonic 2h；Will be ultrasonic
Solution afterwards is placed in ice bath, cools down 1h, is added slowly with stirring 18g potassium permanganate, controls temperature to be less than 5 DEG C, continues to stir
Mix 6h, then heat to 35 DEG C, stirring insulation 12h；Then it is slowly added into 250ml distilled water in solution, reaction is stirred at room temperature
3h；It is eventually adding 24ml hydrogen peroxide, stirs 2h, through washing repeatedly, centrifugation, ultrasonic, the graphene oxide obtaining pH ≈ 7 is molten
Liquid, through being dried to obtain graphene oxide.
(3) prepare tubulose TiO2The tubulose TiO that 0.0500g is prepared by/redox graphene composite2Add
In 20ml distilled water, ultrasonic, stir 1h, obtain tubulose TiO2Dispersion liquid；The graphene oxide powder that 0.0050g is prepared
Add in 10ml distilled water, ultrasonic, stir 6h, obtain the dispersion liquid of graphene oxide；By graphene oxide dispersion in stirring
Lower addition tubulose TiO2In dispersion liquid, ultrasonic agitation 2h；Mixed dispersion liquid is transferred to teflon-lined reaction under high pressure
In kettle, autoclave is tightened and puts in baking oven, under the conditions of 150 DEG C, be incubated 48h, after hydrothermal treatment consists by autoclave certainly
So it is cooled to room temperature, be precipitated thing；After the precipitate obtaining centrifugation, using washing with alcohol, centrifugation, it is dried, grinds
After obtain tubulose TiO2/ redox graphene composite.
The molecular weight of the P123 that embodiment 1～6 uses is 5800g/moL.
The tubulose TiO that embodiment 2～6 is obtained2The knot of/redox graphene composite, its pattern and embodiment 1
Really, have no significant difference.Wherein, tubulose TiO2Long about 4-12 μm, wall thickness is about 100-300nm, and caliber is about 0.5-1.5 μ
M, redox graphene is coated on tubulose TiO2Surface forms composite.
Tubulose TiO is prepared using two-step method2/ redox graphene composite, graphene oxide and TiO2Ratio can
Control；And TiO2Pattern will not change because of the addition of redox graphene, for the TiO of other patterns2/ reduction-oxidation
Graphene composite material provides reference.
Although the above-mentioned accompanying drawing that combines is described to the specific embodiment of the present invention, not model is protected to the present invention
The restriction enclosed, one of ordinary skill in the art should be understood that on the basis of technical scheme, and those skilled in the art are not
Need to pay the various modifications that creative work can make or deformation still within protection scope of the present invention.
Claims (9)
1. a kind of tubulose TiO2The preparation method of/redox graphene composite, is characterized in that：First with TiOSO4As
Titanium source, polyoxyethylene-poly-oxypropylene polyoxyethylene triblock copolymer (P123) are soft template, in ethanol-glycol-ether
A length of 4-12 μm has been synthesized, wall thickness is 100-300nm and caliber is 0.5-1.5 μm of tubulose TiO in mixed solution2；In 110-150
At DEG C, with tubulose TiO2It is raw material with graphene oxide, tubulose TiO is prepared for using hydro-thermal method self assembly2/ reduction-oxidation graphite
Alkene composite；Specifically include following steps：
(1) solvent-thermal method prepares tubulose TiO2
1. P123 is dissolved in ethanol-glycol-ether mixed solution, stirs to clear solution under room temperature；
2. by TiOSO4It is added in the clear solution of step (1) gained, stirring 2-48h obtains suspension；
3. the suspension that 2. step is prepared is transferred in autoclave, be incubated 12-48h, hydro-thermal under the conditions of 110-150 DEG C
After process, autoclave is cooled to room temperature, is precipitated thing；
Wherein, raw materials used TiOSO4, P123, ethanol, ether and ethylene glycol mol ratio be 1：0.00552-0.02758：
54.622-109.243：15.340-36.680：28.659-57.319；
4. after the precipitate centrifugation 3. step being obtained, washing, centrifugation, be dried, 450-500 DEG C after grinding at calcine 3-6h
Obtain tubulose TiO2；
(2) prepare tubulose TiO2/ redox graphene composite
1. by tubulose TiO2It is dispersed in water, ultrasonic, obtain tubulose TiO2Dispersion liquid；Wherein, described tubulose TiO2And distilled water
Adding proportion be：(0.0500-0.2000)g：20mL
2. graphene oxide powder is dispersed in water, ultrasonic, obtain the dispersion liquid of graphene oxide；Wherein, described oxidation stone
Black alkene with the adding proportion of water is：(0.0025-0.0400)g：10mL；
3. by step, dispersion liquid 2. adds in step dispersion liquid 1. under agitation, ultrasonic agitation 2-6h；
4. mixed dispersion liquid is transferred in autoclave, under the conditions of 110-150 DEG C, is incubated 12-48h, will after hydrothermal treatment consists
Autoclave is cooled to room temperature, is precipitated thing；
5. after the precipitate obtaining centrifugation, will wash, be centrifuged, be dried, after grinding, obtain tubulose TiO2/ reduction-oxidation graphite
Alkene composite.
2. preparation method as claimed in claim 1, is characterized in that：Raw materials used TiOSO4, P123, ethanol, ether and ethylene glycol
Mol ratio be 1：0.00552：71.008：19.942：37.257.
3. preparation method as claimed in claim 1, is characterized in that：Step (1) 2. in, optimum reacting time be 12h.
4. preparation method as claimed in claim 1, is characterized in that：Step (1) 3. in, hydrothermal condition be preferably 110 DEG C insulation
24h.
5. preparation method as claimed in claim 1, is characterized in that：Step (1) 4. in, calcination condition be preferably 500 DEG C at forge
Burn 4h.
6. preparation method as claimed in claim 1, is characterized in that：Step (2) 2. in, the preparation method of graphene oxide powder
As follows：
By graphite powder, concentrated sulphuric acid and K2S2O8Mixing, stirring, ultrasonic, 80 DEG C of stirring 6-8h；The product obtaining is dried, does
Concentrated sulphuric acid and phosphoric acid is added after dry, stirring, ultrasonic；Solution cooling after will be ultrasonic, is subsequently adding potassium permanganate, continues stirring 4-
6h, then heats to 35 DEG C, stirring insulation 8-12h；It is subsequently adding water, reaction 2-3h is stirred at room temperature；It is eventually adding hydrogen peroxide, warp
Cross washing, separation, ultrasonic and be dried to obtain graphene oxide.
7. preparation method as claimed in claim 6, is characterized in that：Specifically include following steps：
1. by 2-5g graphite powder, 30-80ml concentrated sulphuric acid, 2-5g K2S2O8It is added sequentially in beaker, stirring, ultrasonic 5-30 divides
Clock, puts into water-bath, is heated to 80 DEG C of stirring 6-8h；
2. by step product distilled water diluting 1. to 1000ml, then sucking filtration, drying at room temperature 8-12h；
3. the filter cake that 2. step obtains is added in beaker, add 120-200ml concentrated sulphuric acid, 20-50ml phosphoric acid, stir, ultrasonic
1-2h；
4. the solution after will be ultrasonic is placed in ice bath, cools down 0.5-1h, is added slowly with stirring 12-30g potassium permanganate, controls
Temperature is less than 5 DEG C, continues stirring 4-6h, then heats to 35 DEG C, stirring insulation 8-12h；
5. and then it is slowly added into 150-300ml distilled water in solution, reaction 2-3h is stirred at room temperature；
6. it is eventually adding 16-40ml hydrogen peroxide, stirs 0.5-2h, through washing repeatedly, centrifugation, ultrasonic, obtain the oxygen of PH ≈ 7
Graphite alkene solution, through being dried to obtain graphene oxide.
8. preparation method as claimed in claim 1, is characterized in that：Step (2) 3. in, the described mixing ultrasonic agitation time is
2h.
9. preparation method as claimed in claim 1, is characterized in that：Step (2) 4. in, hydrothermal condition be 110 DEG C insulation 24h.
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