CN106098405A - A kind of three-dimensional rice shape TiO2/ Graphene composite aquogel and preparation method thereof - Google Patents
A kind of three-dimensional rice shape TiO2/ Graphene composite aquogel and preparation method thereof Download PDFInfo
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- H—ELECTRICITY
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- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
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- H—ELECTRICITY
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- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
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- H—ELECTRICITY
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- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
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Abstract
The invention discloses a kind of three-dimensional rice shape TiO2/ Graphene composite aquogel and preparation method thereof, i.e. uses simple and environmentally-friendly one step hydro thermal method, with GO and TBT as raw material, sodium citrate be structure directing agent, water and ethanol be that solvent synthesizes.Prepared hydrogel structure is novel, and its macro morphology is black column, diameter about 1 2cm, high about 1 2cm；Microscopic appearance is the TiO of rice shape2Nanometer particle load is on graphene film, wherein, and TiO2Diameter of nano particles about 15 35nm, is about 30 70nm；TiO2Nanoparticle and graphene film are interweaved and reticulate structure.This TiO2Pattern and the performance of/Graphene composite aquogel are controlled, can be controlled formability and the stability of gel by the addition of regulation and control TBT and hydro-thermal time.Meanwhile, this composite aquogel not only has TiO2Nanoparticle and the respective build-in attribute of Graphene, additionally it is possible to produce novel cooperative effect.
Description
Technical field
The invention belongs to field of material synthesis technology, particularly relate to a kind of three-dimensional rice shape TiO2/ Graphene compound water congealing
Glue and preparation method thereof.
Background technology
Material with carbon element has good conductivity, specific surface area is big, chemical stability is high, and electron transfer can be provided with by carbon network
The advantages such as the path of effect, are a kind of excellent electrochemical materials.As member new in carbon family, Graphene was sent out from 2004
The very big concern of material science has been caused since Xian.But, graphite electrode have circuit easily disconnect, structure yielding
And initial capacity has the shortcomings such as loss.In order to overcome these shortcomings, by compound to inorganic nano-particle and Graphene may be
A kind of effective settling mode.TiO2, as a kind of important transition metal oxide, because its activity is high, stable, nontoxic, valency
Lattice are cheap, theoretical specific capacity advantages of higher, shown huge application potential in fields such as photocatalysis, energy storages.Such as,
Qiu et al. utilizes one step hydro thermal method to synthesize TiO2/ graphene composite material (Jingxia Qiu, Chao Lai, Yazhou
Wang.Chem.Eng.J., 2014,256,247-254), and being applied to the research of lithium battery, result confirms this composite wood
Material has higher ratio electric capacity, high rate performance and stable circulation performance.Authorization Notice No. CN 102728337 B (application number
201210188887.2) Chinese patent disclose a kind of TiO2The preparation method of/graphene composite material, specifically with
Sodium borohydride is reducing agent, and ammonium titanium fluoride is titanium source, utilizes liquid phase deposition to prepare.But, the method has following deficiency:
The TiO arrived2Pattern be nano-particle, there is no special appearance；Sodium borohydride is poisonous reducing agent, not environmentally；Preparation process ratio
More complicated.The Chinese patent of Authorization Notice No. CN 103545491 A (application number 201310441415.8) also discloses that one
TiO2The preparation method of/graphene composite material, and it is used as lithium cell cathode material.Result shows that this composite has
Good electric conductivity, bigger electrochemical lithium storage content and preferable cyclical stability.But, the post processing of this composite
Journey is complex.
At above-mentioned reported TiO2In/graphene composite material, due to strong π-π effect between the graphene film of two dimension
And Van der Waals force, easily cause irreversible gathering and accumulation, largely reduce the specific surface area of Graphene, thus limit
And TiO2The interaction of nanoparticle.
Based on problem above, some scientists begin one's study the TiO of three dimensional structure2/ graphene composite material, this is
Owing to three-dimensional nanometer material is porous network structure, specific surface area is big, mechanical strength is high, and chemical stability is good, can extensively should
For the field such as photocatalysis, electrochemistry.Such as, Zhang et al. by water heat transfer three-dimensional TiO2/ Graphene compound water congealing
Glue (Zheye Zhang, Fei Xiao, Yunlong Guo.ACS Appl.Mater.Interfaces, 2013,5 (6): 2227-
2233), and using it for the research of ultracapacitor, compared with pure Graphene hydrogel, its chemical property significantly improves.
But TiO used2Nanoparticle is P25, does not has special pattern, limits the further research of composite property.Shen
Please publication No. be that the Chinese patent literature of CN 102350335 A (application number 201110228170.1) discloses under a kind of room temperature
Preparation TiO2The method of/Graphene composite aquogel.The most at room temperature by TiO2Join the graphene oxide containing reducing agent
In aqueous solution, ultrasonic disperse obtains precursor solution；Then gained solution is at room temperature stood 8-16h, obtain product.This
Bright weak point: reduction reagent hydration hydrazine used in experimentation is poisonous, not environmentally；Pattern and performance are uncontrollable；Compound
TiO in material2Nanoparticle is prone to reunite；It is not easy to recycling when photocatalytic pollutant degradation.
Summary of the invention
It is an object of the invention to overcome the shortcoming of above method, it is provided that a kind of three-dimensional rice shape TiO2/ Graphene is combined
The preparation method of hydrogel.The TiO that microscopic appearance is rice shape of obtained composite aquogel2Nanoparticle is dispersed in graphite
On alkene sheet.In water-heat process, not only TiO2Pattern can be effectively controlled, and graphene oxide (GO) passes through high-temperature water
Thermal reduction is Graphene, environmental protection.The gel network structure finally given is novel；There is bigger specific surface area；Performance is excellent
Different；Preparation method is simple, environmental friendliness.
For achieving the above object, the present invention adopts the following technical scheme that
The present invention provides a kind of three-dimensional rice shape TiO2The preparation method of/Graphene composite aquogel, comprises the following steps:
It is titanium source with butyl titanate (TBT), prepares TBT alcoholic solution, then prepared TBT alcoholic solution is joined GO water
In solution, add sodium citrate after mix homogeneously to control TiO2Oriented growth；Three-dimensional has been obtained finally by hydro-thermal self assembly
Rice shape TiO2/ Graphene composite aquogel.
Although above-mentioned steps is not particularly limited concrete conditional parameter, but the inventive concept that the present invention provides is:
Use simple and environmentally-friendly one step hydro thermal method, with GO and TBT as raw material, sodium citrate be structure directing agent, water and ethanol be solvent
Synthesize, obtained the TiO of specific morphology by this inventive concept2/ Graphene composite aquogel, for the TiO of other pattern2/
The preparation of Graphene composite aquogel provides a kind of new synthesis thinking.
In the present invention, the preparation of GO can use multiple method of the prior art, selects a kind of modification therein here
Hummers method is prepared.The more important thing is, in the present invention, Graphene is obtained by the method for thermal reduction, is not required to add reduction
Agent, environmental protection.Its preparation method comprises the following steps:
1. by 1-3g graphite powder, 10-30mL concentrated sulphuric acid, 1-3g K2S2O8, 1-3g P2O5It is added sequentially in beaker, ultrasonic
5-10min, is placed in water-bath, is heated to 75～85 DEG C (preferably 80 DEG C), stirs 4-8h, is cooled to room temperature；
2. by step product 500-1000mL distilled water diluting 1., stand overnight；
3. the diluent that step is 2. obtained is carried out sucking filtration, form filter cake, overnight natural drying；
4. the filter cake that 3. step obtains is scraped in container, add 100-150mL concentrated sulphuric acid, ultrasonic 0.5-1h；
5. under ice bath, the solution after ultrasonic is slowly added to 5-15g potassium permanganate, controls temperature and be less than 20 DEG C, stirring
4-6h, is then to slowly warm up to 35-50 DEG C, stirs and is incubated 8-10h；
The most then in solution, it is slowly added to 100-300mL deionized water, under room temperature, stirs 1.5～2.5h (preferably 2h)；
Continuously add 500-700mL deionized water, stir 1.5～2.5h (preferably 2h)；
7. 10-30mL hydrogen peroxide it is subsequently added, it is thus achieved that jonquilleous acid GO aqueous solution, stirring 0.5-1h rear chamber is gentle and quiet
Put；
8. the supernatant of 7. gained solution is outwelled, use HCl/water solution (its concentration preferred 1mol L-1) washing remove residual
Remaining metal ion, is centrifuged ultrasonic through washing repeatedly the most again, obtains close to neutral GO aqueous solution, through lyophilization
Obtaining the GO of lamellar, it is standby that powder is made in grinding.
The mixed solution that TBT alcoholic solution is TBT and ethanol in the present invention, concrete operation method is: TBT is added drop-wise to nothing
In water-ethanol, after stirring, form mixed solution A.Note: the reaction temperature of alcoholysis process is 30-40 DEG C.Described TBT and ethanol
Volume ratio is: (0.16-0.76): (3-10).
In the present invention, GO aqueous solution adds ammonia and is mixed to form mixed solution B.Concrete operation is: by ultrasonic stripping
Preparation GO aqueous solution, is subsequently added ammonia, stirs, obtain mixed solution B.Wherein, the concentration of GO aqueous solution is 1.5-
3mg/mL, ultrasonic time is 0.5-2h.
Wherein, described TBT is (0.16-0.76) with the volume of ammonia: (0.5-1).
In the present invention, described mixed solution A is joined in described mixed solution B, mix homogeneously, be subsequently added into citric acid
Sodium, stirring forms mixed solution C, and wherein, the volume ratio of described mixed solution A and mixed solution B is (3-10): (15-30).
Described whipping temp is 30-40 DEG C, and mixing time is 2-4h (preferably 3h).
Preferably operating procedure is: under conditions of being stirred continuously, be added dropwise to obtained by described mixed solution A
In mixed solution B.The purpose of this operating procedure is to enable GO to be combined with titanium source carrying out evenly.
Described TBT is (0.16-0.76) mL:(0.05-0.15 with the addition ratio of sodium citrate) g.
In the present invention, the concrete operation step of hydro-thermal self assembly is: described mixed solution C transferred in politef
Lining autoclave in, reactor is tightened and puts into baking oven, carry out hydrothermal treatment consists, after reactor is naturally cooled to room
Temperature, i.e. obtains three-dimensional rice shape TiO2/ Graphene composite aquogel.Wherein, hydrothermal temperature 160-180 DEG C, the hydro-thermal time is 6-
24h, optimum condition is: 180 DEG C of insulation 12h.
The present invention utilizes the Hummers method of improvement to prepare GO, and with TBT for titanium source, sodium citrate is structure directing agent, logical
Cross hydro-thermal method and prepare three-dimensional TiO2/ Graphene composite aquogel.The feature of this composite aquogel is: macro morphology is diameter 1-
The black column of 2cm, high 1-2cm；Microscopic appearance is rice shape TiO2Nanoparticle uniform load is on graphene film, and stone
It is interweaved between ink alkene sheet and reticulates structure, wherein TiO2A diameter of 15-35nm of nanoparticle, a length of 30-70nm.
The invention has the beneficial effects as follows:
(1) present invention utilizes sodium citrate as structure directing agent, synthesized three-dimensional TiO2/ Graphene composite aquogel
Pattern be rice shape TiO2Nanometer particle load on graphene film, wherein TiO2The diameter of nanoparticle is about 15-35nm,
It is about 30-70nm.
(2) the three-dimensional TiO prepared by the present invention2In/Graphene composite aquogel, GO is gone back under high-temperature water heat condition
Former, it is not required to add poisonous reducing agent, environmental protection；Rice shape TiO2Particle good dispersion, the most significantly reunites, and this is of value to
Reduce the interfacial resistance in charge transfer process, get ready for further application.
(3) the three-dimensional TiO prepared by the present invention2In/Graphene composite aquogel, TiO2Controlled with the ratio of Graphene, enter
And the physicochemical property of composite aquogel is capable of optimization.
(4) the three-dimensional TiO prepared by the present invention2/ Graphene composite aquogel has bigger specific surface area, three constructed
Dimension network structure can shorten diffusion and the migration path of electrolyte ion in charge and discharge process, is of value to electric transmission, and then
Improve the application in electrochemical field.
(5) three-dimensional TiO prepared by the present invention2/ Graphene composite aquogel not only has TiO2The most intrinsic with Graphene
Attribute, additionally it is possible to producing novel cooperative effect, compared with pure Graphene hydrogel, composite aquogel is at the electric current of 0.2A/g
Than electric capacity up to 332.6F/g under density.
(6) synthesis condition of the present invention is gentle, and raw material is cheap and easy to get, and technological operation is simple and easy to implement, for other pattern
TiO2The preparation of/Graphene composite aquogel provides a kind of new synthesis thinking.
The present invention combines sol-gal process and hydro-thermal method, by the water-soluble liquid-phase mixing of the alcoholic solution of TBT Yu Graphene, success
It is prepared for three-dimensional Detitanium-ore-type TiO2/ Graphene composite aquogel.The TiO of rice shape2Nanometer particle load on graphene film,
And the most significantly assemble.This TiO2Pattern and the performance of/Graphene composite aquogel are controlled, can be by regulation and control TBT and GO
The interpolation when hydro-thermal time control formability and the stability of gel, and along with the increase of Graphene content, pluralgel
Pattern and physicochemical property all present certain regularity.
Accompanying drawing explanation
Fig. 1 is the three-dimensional rice shape TiO of the embodiment of the present invention 32The digital photograph of/Graphene composite aquogel；
Fig. 2 is GO and TiO2The transmission electron microscope picture (TEM) of/Graphene composite aquogel, wherein, a be the TEM of GO, b be real
Execute the TiO of example 3 preparation2The TEM of/Graphene composite aquogel, c are rice shape TiO in pluralgel2The HRTEM of particle, d are big
Rice shape TiO2The electronogram of particle；
Fig. 3 is the TiO of the embodiment of the present invention 3 preparation2The field of aeroge formed by the composite aquogel lyophilization of/Graphene
Launch scanning electron microscope (SEM) photograph (FESEM)；
Fig. 4 is GO, pure Graphene hydrogel and TiO2The x-ray diffraction pattern (XRD) of/Graphene composite aquogel, its
In, a is the XRD figure of GO, and b is the XRD figure of pure Graphene hydrogel, and c is the TiO of embodiment 3 preparation2/ Graphene hydrogel
XRD figure；
Fig. 5 is pure Graphene hydrogel and TiO2The cyclic voltammetry curve figure (CV) of/Graphene composite aquogel, its
In, a is the CV figure of pure Graphene hydrogel, and b is the TiO of embodiment 3 preparation2The CV figure of/Graphene composite aquogel；
Fig. 6 is pure Graphene hydrogel and TiO2The constant current charge-discharge figure (GCD) of/Graphene composite aquogel, its
In, a is the GCD figure of pure Graphene hydrogel, and b is the TiO of embodiment 3 preparation2The GCD figure of/Graphene hydrogel.
Detailed description of the invention
Below in conjunction with embodiment and accompanying drawing, the present invention is further described.
Embodiment 1
(1) GO aqueous solution is prepared
By 3g graphite powder, 30mL concentrated sulphuric acid, 3g K2S2O8, 3g P2O5It is added sequentially in beaker, ultrasonic 5min, is placed in water
Bath, is heated to 80 DEG C of stirring 6h, is cooled to room temperature；Use 1000mL distilled water diluting, stand overnight；The diluent of gained is entered
Row sucking filtration, forms filter cake, overnight natural drying；Filter cake spoon is scraped in small beaker, adds 150mL concentrated sulphuric acid, stirring, surpass
Sound 1h；Under ice bath, the solution after ultrasonic is slowly added to 15g potassium permanganate, controls temperature and be less than 20 DEG C, stir 4h, then
It is to slowly warm up to 40 DEG C, stirs and be incubated 8h；Then in solution, it is slowly added to 300mL deionized water, under room temperature, stirs 2h；Continue
The continuous 700mL deionized water that adds, stirring 2h；It is subsequently added 20mL hydrogen peroxide, it is thus achieved that jonquilleous acid GO aqueous solution, stirring
Stand after 0.5h；The supernatant of gained solution is outwelled, uses 1mol L-1The washing of HCl/water solution remove remaining metal ion,
Eventually pass washing repeatedly and be centrifuged ultrasonic, obtain close to neutral GO aqueous solution；Lamellar is finally given by lyophilization
GO, it is standby that powder is made in grinding.
(2) the three-dimensional rice shape TiO of synthesis2/ Graphene composite aquogel
At 40 DEG C, 0.16mL TBT is slowly dropped in 5mL dehydrated alcohol, after stirring, forms mixed solution A；By super
Sound, stirring prepare the GO aqueous solution of 2mg/mL, are subsequently added 0.5mL ammonia, stir, obtain mixed solution B；To mix molten
Liquid A is slowly added in mixed solution B, is subsequently added 0.08g sodium citrate, continues stirring 3h and forms mixed solution C；Will mixing
Solution C is transferred in teflon-lined autoclave, is tightened by autoclave and puts in baking oven, 180 DEG C of conditions
Lower insulation 12h, naturally cools to room temperature by autoclave after hydro-thermal reaction, obtains black columnar object；The column that will obtain
The impurity of remnants is removed in thing washing several times, i.e. obtains three-dimensional TiO2/ Graphene composite aquogel.
Embodiment 2
(1) GO aqueous solution is prepared
By 3g graphite powder, 30mL concentrated sulphuric acid, 3g K2S2O8, 3g P2O5It is added sequentially in beaker, ultrasonic 5min, is placed in water
Bath, is heated to 80 DEG C of stirring 6h, is cooled to room temperature；Use 1000mL distilled water diluting, stand overnight；The diluent of gained is entered
Row sucking filtration, forms filter cake, overnight natural drying；Filter cake spoon is scraped in small beaker, adds 150mL concentrated sulphuric acid, stirring, surpass
Sound 1h；Under ice bath, the solution after ultrasonic is slowly added to 15g potassium permanganate, controls temperature and be less than 20 DEG C, stir 4h, then
It is to slowly warm up to 40 DEG C, stirs and be incubated 8h；Then in solution, it is slowly added to 300mL deionized water, under room temperature, stirs 2h；Continue
The continuous 700mL deionized water that adds, stirring 2h；It is subsequently added 20mL hydrogen peroxide, it is thus achieved that jonquilleous acid GO aqueous solution, stirring
Stand after 0.5h；The supernatant of gained solution is outwelled, uses 1mol L-1The washing of HCl/water solution remove remaining metal ion,
Eventually pass washing repeatedly and be centrifuged ultrasonic, obtain close to neutral GO aqueous solution；Lamellar is finally given by lyophilization
GO, it is standby that powder is made in grinding.
(2) the three-dimensional rice shape TiO of synthesis2/ Graphene composite aquogel
At 40 DEG C, 0.23mL TBT is slowly dropped in 5mL dehydrated alcohol, after stirring, forms mixed solution A；By super
Sound, stirring prepare the GO aqueous solution of 2mg/mL, are subsequently added 0.5mL ammonia, stir, obtain mixed solution B；To mix molten
Liquid A is slowly added in mixed solution B, is subsequently added 0.08g sodium citrate, continues stirring 3h and forms mixed solution C；Will mixing
Solution C is transferred in teflon-lined autoclave, is tightened by autoclave and puts in baking oven, 180 DEG C of conditions
Lower insulation 12h, naturally cools to room temperature by autoclave after hydro-thermal reaction, obtains black columnar object；The column that will obtain
The impurity of remnants is removed in thing washing several times, i.e. obtains three-dimensional TiO2/ Graphene composite aquogel.
Embodiment 3
(1) GO aqueous solution is prepared
By 3g graphite powder, 30mL concentrated sulphuric acid, 3g K2S2O8, 3g P2O5It is added sequentially in beaker, ultrasonic 5min, is placed in water
Bath, is heated to 80 DEG C of stirring 6h, is cooled to room temperature；Use 1000mL distilled water diluting, stand overnight；The diluent of gained is entered
Row sucking filtration, forms filter cake, overnight natural drying；Filter cake spoon is scraped in small beaker, adds 150mL concentrated sulphuric acid, stirring, surpass
Sound 1h；Under ice bath, the solution after ultrasonic is slowly added to 15g potassium permanganate, controls temperature and be less than 20 DEG C, stir 4h, then
It is to slowly warm up to 40 DEG C, stirs and be incubated 8h；Then in solution, it is slowly added to 300mL deionized water, under room temperature, stirs 2h；Continue
The continuous 700mL deionized water that adds, stirring 2h；It is subsequently added 20mL hydrogen peroxide, it is thus achieved that jonquilleous acid GO aqueous solution, stirring
Stand after 0.5h；The supernatant of gained solution is outwelled, uses 1mol L-1The washing of HCl/water solution remove remaining metal ion,
Eventually pass washing repeatedly and be centrifuged ultrasonic, obtain close to neutral GO aqueous solution；Lamellar is finally given by lyophilization
GO, it is standby that powder is made in grinding.
(2) the three-dimensional rice shape TiO of synthesis2/ Graphene composite aquogel
At 40 DEG C, 0.30mL TBT is slowly dropped in 5mL dehydrated alcohol, after stirring, forms mixed solution A；By super
Sound, stirring prepare the GO aqueous solution of 2mg/mL, are subsequently added 0.5mL ammonia, stir, obtain mixed solution B；To mix molten
Liquid A is slowly added in mixed solution B, is subsequently added 0.08g sodium citrate, continues stirring 3h and forms mixed solution C；Will mixing
Solution C is transferred in teflon-lined autoclave, is tightened by autoclave and puts in baking oven, 180 DEG C of conditions
Lower insulation 12h, naturally cools to room temperature by autoclave after hydro-thermal reaction, obtains black columnar object；The column that will obtain
The impurity of remnants is removed in thing washing several times, i.e. obtains three-dimensional TiO2/ Graphene composite aquogel.
As shown in Fig. 1,2,3 and 4, the macro morphology of the Graphene hydrogel that the present embodiment 3 prepares is black column, directly
Footpath is about 1-2cm, high about 1-2cm；Microscopic appearance is rice shape TiO2Nanoparticle is uniformly dispersed on graphene film, its
Middle TiO2Nanoparticle is Detitanium-ore-type, and diameter is about 15-35nm, long about 30-70nm；After hydrogel cool-drying becomes aeroge
Present three-dimensional porous network structure.From Fig. 5 and 6 it can be seen that compared with pure Graphene hydrogel, the present embodiment 3 synthesizes
Composite aquogel show more superior chemical property.
Embodiment 4
(1) GO aqueous solution is prepared
By 3g graphite powder, 30mL concentrated sulphuric acid, 3g K2S2O8, 3g P2O5It is added sequentially in beaker, ultrasonic 5min, is placed in water
Bath, is heated to 80 DEG C of stirring 6h, is cooled to room temperature；Use 1000mL distilled water diluting, stand overnight；The diluent of gained is entered
Row sucking filtration, forms filter cake, overnight natural drying；Filter cake spoon is scraped in small beaker, adds 150mL concentrated sulphuric acid, stirring, surpass
Sound 1h；Under ice bath, the solution after ultrasonic is slowly added to 15g potassium permanganate, controls temperature and be less than 20 DEG C, stir 4h, then
It is to slowly warm up to 40 DEG C, stirs and be incubated 8h；Then in solution, it is slowly added to 300mL deionized water, under room temperature, stirs 2h；Continue
The continuous 700mL deionized water that adds, stirring 2h；It is subsequently added 20mL hydrogen peroxide, it is thus achieved that jonquilleous acid GO aqueous solution, stirring
Stand after 0.5h；The supernatant of gained solution is outwelled, uses 1mol L-1The washing of HCl/water solution remove remaining metal ion,
Eventually pass washing repeatedly and be centrifuged ultrasonic, obtain close to neutral GO aqueous solution；Lamellar is finally given by lyophilization
GO, it is standby that powder is made in grinding.
(2) the three-dimensional rice shape TiO of synthesis2/ Graphene composite aquogel
At 40 DEG C, 0.56mL TBT is slowly dropped in 5mL dehydrated alcohol, after stirring, forms mixed solution A；By super
Sound, stirring prepare the GO aqueous solution of 2mg/mL, are subsequently added 0.5mL ammonia, stir, obtain mixed solution B；To mix molten
Liquid A is slowly added in mixed solution B, is subsequently added 0.08g sodium citrate, continues stirring 3h and forms mixed solution C；Will mixing
Solution C is transferred in teflon-lined autoclave, is tightened by autoclave and puts in baking oven, 180 DEG C of conditions
Lower insulation 12h, naturally cools to room temperature by autoclave after hydro-thermal reaction, obtains black columnar object；The column that will obtain
The impurity of remnants is removed in thing washing several times, i.e. obtains three-dimensional TiO2/ Graphene composite aquogel.
Embodiment 5
(1) GO aqueous solution is prepared
By 3g graphite powder, 30mL concentrated sulphuric acid, 3g K2S2O8, 3g P2O5It is added sequentially in beaker, ultrasonic 5min, is placed in water
Bath, is heated to 80 DEG C of stirring 6h, is cooled to room temperature；Use 1000mL distilled water diluting, stand overnight；The diluent of gained is entered
Row sucking filtration, forms filter cake, overnight natural drying；Filter cake spoon is scraped in small beaker, adds 150mL concentrated sulphuric acid, stirring, surpass
Sound 1h；Under ice bath, the solution after ultrasonic is slowly added to 15g potassium permanganate, controls temperature and be less than 20 DEG C, stir 4h, then
It is to slowly warm up to 40 DEG C, stirs and be incubated 8h；Then in solution, it is slowly added to 300mL deionized water, under room temperature, stirs 2h；Continue
The continuous 700mL deionized water that adds, stirring 2h；It is subsequently added 20mL hydrogen peroxide, it is thus achieved that jonquilleous acid GO aqueous solution, stirring
Stand after 0.5h；The supernatant of gained solution is outwelled, uses 1mol L-1The washing of HCl/water solution remove remaining metal ion,
Eventually pass washing repeatedly and be centrifuged ultrasonic, obtain close to neutral GO aqueous solution；Lamellar is finally given by lyophilization
GO, it is standby that powder is made in grinding.
(2) the three-dimensional rice shape TiO of synthesis2/ Graphene composite aquogel
At 40 DEG C, 0.76mL TBT is slowly dropped in 5mL dehydrated alcohol, after stirring, forms mixed solution A；By super
Sound, stirring prepare the GO aqueous solution of 2mg/mL, are subsequently added 0.5mL ammonia, stir, obtain mixed solution B；To mix molten
Liquid A is slowly added in mixed solution B, is subsequently added 0.08g sodium citrate, continues stirring 3h and forms mixed solution C；Will mixing
Solution C is transferred in teflon-lined autoclave, is tightened by autoclave and puts in baking oven, 180 DEG C of conditions
Lower insulation 12h, naturally cools to room temperature by autoclave after hydro-thermal reaction, obtains black columnar object；The column that will obtain
The impurity of remnants is removed in thing washing several times, i.e. obtains three-dimensional TiO2/ Graphene composite aquogel.
Embodiment 6
(1) GO aqueous solution is prepared
By 3g graphite powder, 30mL concentrated sulphuric acid, 3g K2S2O8, 3g P2O5It is added sequentially in beaker, ultrasonic 5min, is placed in water
Bath, is heated to 80 DEG C of stirring 6h, is cooled to room temperature；Use 1000mL distilled water diluting, stand overnight；The diluent of gained is entered
Row sucking filtration, forms filter cake, overnight natural drying；Filter cake spoon is scraped in small beaker, adds 150mL concentrated sulphuric acid, stirring, surpass
Sound 1h；Under ice bath, the solution after ultrasonic is slowly added to 15g potassium permanganate, controls temperature and be less than 20 DEG C, stir 4h, then
It is to slowly warm up to 40 DEG C, stirs and be incubated 8h；Then in solution, it is slowly added to 300mL deionized water, under room temperature, stirs 2h；Continue
The continuous 700mL deionized water that adds, stirring 2h；It is subsequently added 20mL hydrogen peroxide, it is thus achieved that jonquilleous acid GO aqueous solution, stirring
Stand after 0.5h；The supernatant of gained solution is outwelled, uses 1mol L-1The washing of HCl/water solution remove remaining metal ion,
Eventually pass washing repeatedly and be centrifuged ultrasonic, obtain close to neutral GO aqueous solution；Lamellar is finally given by lyophilization
GO, it is standby that powder is made in grinding.
(2) the three-dimensional rice shape TiO of synthesis2/ Graphene composite aquogel
At 40 DEG C, 0.30mL TBT is slowly dropped in 5mL dehydrated alcohol, after stirring, forms mixed solution A；By super
Sound, stirring prepare the GO aqueous solution of 2mg/mL, are subsequently added 0.5mL ammonia, stir, obtain mixed solution B；To mix molten
Liquid A is slowly added in mixed solution B, is subsequently added 0.08g sodium citrate, continues stirring 3h and forms mixed solution C；Will mixing
Solution C is transferred in teflon-lined autoclave, is tightened by autoclave and puts in baking oven, 180 DEG C of conditions
Lower insulation 6h, naturally cools to room temperature by autoclave after hydro-thermal reaction, obtains black columnar object；The column that will obtain
The impurity of remnants is removed in washing several times, i.e. obtains three-dimensional TiO2/ Graphene composite aquogel.
Embodiment 7
(1) GO aqueous solution is prepared
By 3g graphite powder, 30mL concentrated sulphuric acid, 3g K2S2O8, 3g P2O5It is added sequentially in beaker, ultrasonic 5min, is placed in water
Bath, is heated to 80 DEG C of stirring 6h, is cooled to room temperature；Use 1000mL distilled water diluting, stand overnight；The diluent of gained is entered
Row sucking filtration, forms filter cake, overnight natural drying；Filter cake spoon is scraped in small beaker, adds 150mL concentrated sulphuric acid, stirring, surpass
Sound 1h；Under ice bath, the solution after ultrasonic is slowly added to 15g potassium permanganate, controls temperature and be less than 20 DEG C, stir 4h, then
It is to slowly warm up to 40 DEG C, stirs and be incubated 8h；Then in solution, it is slowly added to 300mL deionized water, under room temperature, stirs 2h；Continue
The continuous 700mL deionized water that adds, stirring 2h；It is subsequently added 20mL hydrogen peroxide, it is thus achieved that jonquilleous acid GO aqueous solution, stirring
Stand after 0.5h；The supernatant of gained solution is outwelled, uses 1mol L-1The washing of HCl/water solution remove remaining metal ion,
Eventually pass washing repeatedly and be centrifuged ultrasonic, obtain close to neutral GO aqueous solution；Lamellar is finally given by lyophilization
GO, it is standby that powder is made in grinding.
(2) the three-dimensional rice shape TiO of synthesis2/ Graphene composite aquogel
At 40 DEG C, 0.30mL TBT is slowly dropped in 5mL dehydrated alcohol, after stirring, forms mixed solution A；By super
Sound, stirring prepare the GO aqueous solution of 2mg/mL, are subsequently added 0.5mL ammonia, stir, obtain mixed solution B；To mix molten
Liquid A is slowly added in mixed solution B, is subsequently added 0.08g sodium citrate, continues stirring 3h and forms mixed solution C；Will mixing
Solution C is transferred in teflon-lined autoclave, is tightened by autoclave and puts in baking oven, 180 DEG C of conditions
Lower insulation 18h, naturally cools to room temperature by autoclave after hydro-thermal reaction, obtains black columnar object；The column that will obtain
The impurity of remnants is removed in thing washing several times, i.e. obtains three-dimensional TiO2/ Graphene composite aquogel.
Embodiment 8
(1) GO aqueous solution is prepared
By 3g graphite powder, 30mL concentrated sulphuric acid, 3g K2S2O8, 3g P2O5It is added sequentially in beaker, ultrasonic 5min, is placed in water
Bath, is heated to 80 DEG C of stirring 6h, is cooled to room temperature；Use 1000mL distilled water diluting, stand overnight；The diluent of gained is entered
Row sucking filtration, forms filter cake, overnight natural drying；Filter cake spoon is scraped in small beaker, adds 150mL concentrated sulphuric acid, stirring, surpass
Sound 1h；Under ice bath, the solution after ultrasonic is slowly added to 15g potassium permanganate, controls temperature and be less than 20 DEG C, stir 4h, then
It is to slowly warm up to 40 DEG C, stirs and be incubated 8h；Then in solution, it is slowly added to 300mL deionized water, under room temperature, stirs 2h；Continue
The continuous 700mL deionized water that adds, stirring 2h；It is subsequently added 20mL hydrogen peroxide, it is thus achieved that jonquilleous acid GO aqueous solution, stirring
Stand after 0.5h；The supernatant of gained solution is outwelled, uses 1mol L-1The washing of HCl/water solution remove remaining metal ion,
Eventually pass washing repeatedly and be centrifuged ultrasonic, obtain close to neutral GO aqueous solution；Lamellar is finally given by lyophilization
GO, it is standby that powder is made in grinding.
(2) the three-dimensional rice shape TiO of synthesis2/ Graphene composite aquogel
At 40 DEG C, 0.30mL TBT is slowly dropped in 5mL dehydrated alcohol, after stirring, forms mixed solution A；By super
Sound, stirring prepare the GO aqueous solution of 2mg/mL, are subsequently added 0.5mL ammonia, stir, obtain mixed solution B；To mix molten
Liquid A is slowly added in mixed solution B, is subsequently added 0.08g sodium citrate, continues stirring 3h and forms mixed solution C；Will mixing
Solution C is transferred in teflon-lined autoclave, is tightened by autoclave and puts in baking oven, 180 DEG C of conditions
Lower insulation 24h, naturally cools to room temperature by autoclave after hydro-thermal reaction, obtains black columnar object；The column that will obtain
The impurity of remnants is removed in thing washing several times, i.e. obtains three-dimensional TiO2/ Graphene composite aquogel.
Embodiment 9
(1) GO aqueous solution is prepared
By 3g graphite powder, 30mL concentrated sulphuric acid, 3g K2S2O8, 3g P2O5It is added sequentially in beaker, ultrasonic 5min, is placed in water
Bath, is heated to 80 DEG C of stirring 6h, is cooled to room temperature；Use 1000mL distilled water diluting, stand overnight；The diluent of gained is entered
Row sucking filtration, forms filter cake, overnight natural drying；Filter cake spoon is scraped in small beaker, adds 150mL concentrated sulphuric acid, stirring, surpass
Sound 1h；Under ice bath, the solution after ultrasonic is slowly added to 15g potassium permanganate, controls temperature and be less than 20 DEG C, stir 4h, then
It is to slowly warm up to 40 DEG C, stirs and be incubated 8h；Then in solution, it is slowly added to 300mL deionized water, under room temperature, stirs 2h；Continue
The continuous 700mL deionized water that adds, stirring 2h；It is subsequently added 20mL hydrogen peroxide, it is thus achieved that jonquilleous acid GO aqueous solution, stirring
Stand after 0.5h；The supernatant of gained solution is outwelled, uses 1mol L-1The washing of HCl/water solution remove remaining metal ion,
Eventually pass washing repeatedly and be centrifuged ultrasonic, obtain close to neutral GO aqueous solution；Lamellar is finally given by lyophilization
GO, it is standby that powder is made in grinding.
(2) the three-dimensional rice shape TiO of synthesis2/ Graphene composite aquogel
At 30 DEG C, 0.30mL TBT is slowly dropped in 3mL dehydrated alcohol, after stirring, forms mixed solution A；By super
Sound, stirring prepare the GO aqueous solution of 1.5mg/mL, are subsequently added 0.8mL ammonia, stir, obtain mixed solution B；Will mixing
Solution A is slowly added in mixed solution B, is subsequently added 0.05g sodium citrate, continues stirring 2h and forms mixed solution C；Will be mixed
Close solution C and transfer in teflon-lined autoclave, autoclave is tightened and puts in baking oven, 170 DEG C of bars
It is incubated 12h under part, after hydro-thermal reaction, autoclave is naturally cooled to room temperature, obtain black columnar object；The post that will obtain
The impurity of remnants is removed in the washing of shape thing several times, i.e. obtains three-dimensional TiO2/ Graphene composite aquogel.
Embodiment 10
(1) GO aqueous solution is prepared
By 3g graphite powder, 30mL concentrated sulphuric acid, 3g K2S2O8, 3g P2O5It is added sequentially in beaker, ultrasonic 5min, is placed in water
Bath, is heated to 80 DEG C of stirring 6h, is cooled to room temperature；Use 1000mL distilled water diluting, stand overnight；The diluent of gained is entered
Row sucking filtration, forms filter cake, overnight natural drying；Filter cake spoon is scraped in small beaker, adds 150mL concentrated sulphuric acid, stirring, surpass
Sound 1h；Under ice bath, the solution after ultrasonic is slowly added to 15g potassium permanganate, controls temperature and be less than 20 DEG C, stir 4h, then
It is to slowly warm up to 40 DEG C, stirs and be incubated 8h；Then in solution, it is slowly added to 300mL deionized water, under room temperature, stirs 2h；Continue
The continuous 700mL deionized water that adds, stirring 2h；It is subsequently added 20mL hydrogen peroxide, it is thus achieved that jonquilleous acid GO aqueous solution, stirring
Stand after 0.5h；The supernatant of gained solution is outwelled, uses 1mol L-1The washing of HCl/water solution remove remaining metal ion,
Eventually pass washing repeatedly and be centrifuged ultrasonic, obtain close to neutral GO aqueous solution；Lamellar is finally given by lyophilization
GO, it is standby that powder is made in grinding.
(2) the three-dimensional rice shape TiO of synthesis2/ Graphene composite aquogel
At 35 DEG C, 0.30mL TBT is slowly dropped in 10mL dehydrated alcohol, after stirring, forms mixed solution A；Pass through
The GO aqueous solution of 3mg/mL is prepared in ultrasonic, stirring, is subsequently added 1mL ammonia, stirs, obtains mixed solution B；To mix molten
Liquid A is slowly added in mixed solution B, is subsequently added 0.15g sodium citrate, continues stirring 4h and forms mixed solution C；Will mixing
Solution C is transferred in teflon-lined autoclave, is tightened by autoclave and puts in baking oven, 160 DEG C of conditions
Lower insulation 12h, naturally cools to room temperature by autoclave after hydro-thermal reaction, obtains black columnar object；The column that will obtain
The impurity of remnants is removed in thing washing several times, i.e. obtains three-dimensional TiO2/ Graphene composite aquogel.
Hydrogel prepared by embodiment 1-2 and 4-10, it is the poorest that its both macro and micro pattern and embodiment 3 there is no
Different, it is the TiO of rice shape2Particle load is on graphene film.Wherein, rice shape TiO2The diameter of particle is about 15-35nm,
Long about 30-70nm.
Embodiment 11
A kind of ultracapacitor, its electrode material uses three-dimensional TiO in embodiment 32/ Graphene composite aquogel, passes through
Verification experimental verification, this ultracapacitor has good application in electrochemical field.
The present invention is with GO and TBT as raw material, and sodium citrate is structure directing agent, uses simple and environmentally-friendly hydro-thermal method, a step
The three-dimensional rice shape TiO of synthesis2/ Graphene composite aquogel.Gel is regulated and controled by the addition and hydro-thermal time changing TBT
Formability and stability.Utilize the advantage of three-dimensional net structure simultaneously, the composite aquogel of preparation is applied to ultracapacitor
Research, result shows TiO2/ Graphene composite aquogel has high ratio electric capacity, and the circulation that superior high rate performance is become reconciled is steady
Qualitative energy.
Although the detailed description of the invention of the present invention is described by the above-mentioned accompanying drawing that combines, but not the present invention is protected model
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 various amendments or deformation that creative work can make still within protection scope of the present invention.
Claims (10)
1. a three-dimensional rice shape TiO2The preparation method of/Graphene composite aquogel, is characterized in that, comprises the following steps:
It is titanium source with butyl titanate (TBT), prepares TBT alcoholic solution；Then prepared TBT alcoholic solution is joined GO aqueous solution
In, add sodium citrate after mix homogeneously to control TiO2Oriented growth；Three-dimensional rice has been obtained finally by hydro-thermal self assembly
Shape TiO2/ Graphene composite aquogel.
2. preparation method as claimed in claim 1, is characterized in that: described TBT alcoholic solution is the mixed solution of TBT and ethanol,
Concrete operation method is: be added drop-wise in dehydrated alcohol by TBT, forms mixed solution A after stirring.
3. preparation method as claimed in claim 2, is characterized in that: described TBT with the volume ratio of ethanol is: (0.16-0.76):
(3-10)。
4. preparation method as claimed in claim 1, is characterized in that: graphene oxide water solution adds ammonia and is mixed to form mixing
Solution B；Wherein, the concentration of GO aqueous solution is 1.5-3mg/mL；Preferably, described TBT is (0.16-with the volume of ammonia
0.76):(0.5-1)。
5. preparation method as claimed in claim 2, is characterized in that: described mixed solution A joined described in claim 4
In mixed solution B, mix homogeneously, be subsequently added into sodium citrate, stirring forms mixed solution C, wherein, described mixed solution A and
The volume ratio of mixed solution B is (3-10): (15-30).
6. preparation method as claimed in claim 1, is characterized in that: carry out mix and blend, described stirring after adding sodium citrate
Temperature is 30-40 DEG C, and mixing time is 2-4h.
7. preparation method as claimed in claim 1, is characterized in that: described TBT with the addition ratio of sodium citrate is
(0.16-0.76)mL:(0.05-0.15)g。
8. preparation method as claimed in claim 1, is characterized in that: described hydrothermal condition: hydrothermal temperature 160-180 DEG C, hydro-thermal
Time is 6-24h, it is preferred that 180 DEG C of insulation 12h.
9. use the three-dimensional rice shape TiO that the method according to any one of claim 1～8 prepares2/ Graphene Compound Water
Gel.
10. hydrogel as claimed in claim 9, is characterized in that: the macro morphology of this composite aquogel is diameter 1-2cm, high
The black column of 1-2cm；Microscopic appearance is rice shape TiO2Nanoparticle uniform load is on graphene film, and graphene film
Between be interweaved and reticulate structure, wherein TiO2A diameter of 15-35nm of nanoparticle, a length of 30-70nm.
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| CN106582518A (en) * | 2016-11-17 | 2017-04-26 | 南京大学 | Graphene-TiO2 nanotube hydrogel, preparation method, and application thereof |
| CN106824065A (en) * | 2016-12-29 | 2017-06-13 | 贵州科学院 | The graphene-based TiO of humic acid in a kind of removal rural potable water2Nano composite material and preparation method thereof |
| CN107445150A (en) * | 2017-07-13 | 2017-12-08 | 华北电力大学 | A kind of preparation method of multifunctional graphite vinyl aeroge |
| CN114464760A (en) * | 2022-02-10 | 2022-05-10 | 合肥福纳科技有限公司 | Electron transport layer material and preparation method thereof, semiconductor device and preparation method thereof |
| CN115975442A (en) * | 2022-12-16 | 2023-04-18 | 哈尔滨端赛科技有限公司 | TiO 2 2 Graphene water-based fluorocarbon paint and preparation method thereof |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106582518A (en) * | 2016-11-17 | 2017-04-26 | 南京大学 | Graphene-TiO2 nanotube hydrogel, preparation method, and application thereof |
| CN106824065A (en) * | 2016-12-29 | 2017-06-13 | 贵州科学院 | The graphene-based TiO of humic acid in a kind of removal rural potable water2Nano composite material and preparation method thereof |
| CN107445150A (en) * | 2017-07-13 | 2017-12-08 | 华北电力大学 | A kind of preparation method of multifunctional graphite vinyl aeroge |
| CN114464760A (en) * | 2022-02-10 | 2022-05-10 | 合肥福纳科技有限公司 | Electron transport layer material and preparation method thereof, semiconductor device and preparation method thereof |
| CN114464760B (en) * | 2022-02-10 | 2024-03-26 | 合肥福纳科技有限公司 | Electron transport layer material, semiconductor device and preparation method of electron transport layer material and semiconductor device |
| CN115975442A (en) * | 2022-12-16 | 2023-04-18 | 哈尔滨端赛科技有限公司 | TiO 2 2 Graphene water-based fluorocarbon paint and preparation method thereof |
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