CN106098405B - 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
- Publication number
- CN106098405B CN106098405B CN201610429080.1A CN201610429080A CN106098405B CN 106098405 B CN106098405 B CN 106098405B CN 201610429080 A CN201610429080 A CN 201610429080A CN 106098405 B CN106098405 B CN 106098405B
- Authority
- CN
- China
- Prior art keywords
- tio
- graphene
- tbt
- mixed solution
- composite aquogel
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
Abstract
The invention discloses a kind of three-dimensional rice shape TiO2/ graphene composite aquogel and preparation method thereof, i.e., using simple and environmentally-friendly one step hydro thermal method, using GO and TBT as raw material, sodium citrate is structure directing agent, and water and ethanol are that solvent is synthesized.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 on graphene film, wherein, TiO2The 35nm of diameter of nano particles about 15, is about 30 70nm；TiO2Nano-particle is interweaved with graphene film and reticulates structure.The TiO2The pattern and performance of/graphene composite aquogel are controllable, you can control the formability of gel and stability by regulating and controlling TBT addition and hydro-thermal time.Meanwhile the composite aquogel not only has TiO2Nano-particle and the respective build-in attribute of graphene, additionally it is possible to produce the cooperative effect of novelty.
Description
Technical field
The invention belongs to field of material synthesis technology, more particularly to a kind of three-dimensional rice shape TiO2/ graphene compound water congealing
Glue and preparation method thereof.
Background technology
Carbon material it is conductive it is good, specific surface area is big, chemical stability is high, and carbon network can to electronics shift be provided with
The advantages that path of effect, it is a kind of excellent electrochemical material.As member new in carbon family, graphene was from quilt in 2004
The very big concern of materials science field has been caused since it was found that.But there is graphite electrode circuit easily to disconnect, structure is variable
Shape and initial capacity have the shortcomings that loss.In order to overcome these shortcomings, by inorganic nano-particle with graphene is compound may
It is a kind of effective settling mode.TiO2, as a kind of important transition metal oxide, because its activity is high, stably, it is nontoxic,
Cheap, the advantages that theoretical specific capacity is high, huge application potential is shown in fields such as photocatalysis, energy stores.Example
Such as, Qiu et al. has synthesized TiO using one step hydro thermal method2/ graphene composite material (Jingxia Qiu, Chao Lai, Yazhou
Wang.Chem.Eng.J., 2014,256,247-254), and it is applied to the research of lithium battery, as a result confirms the composite wood
Material has higher specific capacitance, high rate performance and stable circulation performance.B (the application numbers of Authorization Notice No. CN 102728337
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, is made using liquid phase deposition.But the method has following deficiency：
The TiO arrived2Pattern be nano particle, without special appearance；Sodium borohydride is poisonous reducing agent, not environmentally；Preparation process ratio
It is more complicated.The A of Authorization Notice No. CN 103545491 (application number 201310441415.8) Chinese patent also discloses that one kind
TiO2The preparation method of/graphene composite material, and it is used as lithium cell cathode material.As a result show that the composite has
Good electric conductivity, larger electrochemical lithium storage content and preferable cyclical stability.But the post processing of this composite
Journey is complex.
In above-mentioned reported TiO2In/graphene composite material, because strong π-π are acted between two-dimentional graphene film
And Van der Waals force, irreversible aggregation and accumulation are easily caused, the specific surface area of graphene is largely reduced, so as to limit
And TiO2The interaction of nano-particle.
Based on problem above, some scientific workers begin one's study the TiO of three-dimensional structure2/ graphene composite material, this is
Because three-dimensional nanometer material is porous network structure, specific surface area is big, high mechanical strength, and chemical stability is good, extensively can should
For fields such as photocatalysis, electrochemistry.For example, Zhang et al. has synthesized three-dimensional TiO by hydro-thermal method2/ graphene compound water congealing
Glue (Zheye Zhang, Fei Xiao, Yunlong Guo.ACS Appl.Mater.Interfaces, 2013,5 (6):2227-
2233), and the research of ultracapacitor is used it for, compared with pure graphene hydrogel, its chemical property significantly improves.
But TiO used2Nano-particle is P25, without special pattern, limits the further research of composite property.Shen
Please publication No. be the A of CN 102350335 (application number 201110228170.1) Chinese patent literature disclose it is a kind of at room temperature
Prepare TiO2The method of/graphene composite aquogel.First at room temperature by TiO2It is added to the graphene oxide containing reducing agent
In the aqueous solution, ultrasonic disperse obtains precursor solution；Then resulting solution is stood into 8-16h at room temperature, produces product.This hair
Bright weak point：Go back original reagent hydrazine hydrate used is poisonous in experimentation, not environmentally；Pattern and performance are uncontrollable；It is compound
TiO in material2Nano-particle is easy to reunite；Recycling is not easy in photocatalytic pollutant degradation.
The content of the invention
A kind of the shortcomings that it is an object of the invention to overcome above method, there is provided three-dimensional rice shape TiO2/ graphene is compound
The preparation method of hydrogel.The microscopic appearance of obtained composite aquogel is the TiO of rice shape2Nano-particle is dispersed in graphite
On alkene piece.In water-heat process, not only TiO2Pattern can be effectively controlled, and graphene oxide (GO) passes through high-temperature water
Heat-treat as graphene, it is green.The gel network structure finally given is novel；With larger specific surface area；Performance is excellent
It is different；Preparation method is simple, environment-friendly.
To achieve 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：
With butyl titanate (TBT) for titanium source, TBT alcoholic solutions are prepared, obtained TBT alcoholic solutions are then added to GO
In the aqueous solution, sodium citrate is added to control TiO after well mixed2Oriented growth；Three have been obtained finally by hydro-thermal self assembly
Tie up rice shape TiO2/ graphene composite aquogel.
Although above-mentioned steps are not particularly limited specific conditional parameter, inventive concept provided by the invention is：
Using simple and environmentally-friendly one step hydro thermal method, using GO and TBT as raw material, sodium citrate is structure directing agent, and water and ethanol are solvent
Synthesized, the TiO of specific morphology has been obtained by the inventive concept2/ graphene composite aquogel, it is the TiO of other patterns2/
The preparation of graphene composite aquogel provides a kind of new synthesis thinking.
GO preparation can use a variety of methods of the prior art in the present invention, select a kind of modification therein here
It is prepared by Hummers methods.Importantly, graphene is obtained by the method for thermal reduction in the present invention, it is not required to add reduction
Agent, it is green.Its preparation method comprises the following steps：
1. by 1-3g graphite powders, the 10-30mL concentrated sulfuric acids, 1-3g K2S2O8, 1-3g P2O5It is added sequentially in beaker, ultrasound
5-10min, water-bath is placed in, be heated to 75~85 DEG C (preferably 80 DEG C), stirred 4-8h, be cooled to room temperature；
2. by the step 500-1000mL distilled water dilutings of product 1., stand overnight；
3. to step, 2. resulting dilution filters, and forms filter cake, spontaneously dries overnight；
4. 3. filter cake that step is obtained is scraped in container, the 100-150mL concentrated sulfuric acids, ultrasonic 0.5-1h are added；
5. under ice bath, 5-15g potassium permanganate is slowly added into the solution after ultrasound, control temperature is less than 20 DEG C, stirring
4-6h, 35-50 DEG C is then to slowly warm up to, stirs and be incubated 8-10h；
6. being then slowly added to 100-300mL deionized waters into solution, 1.5~2.5h (preferably 2h) is stirred under normal temperature；
Continuously add 500-700mL deionized waters, 1.5~2.5h of stirring (preferably 2h)；
7. then adding 10-30mL hydrogen peroxide, the acid GO aqueous solution of glassy yellow is obtained, room temperature is quiet after stirring 0.5-1h
Put；
8. the supernatant of 7. resulting solution is outwelled, HCl/water solution (the preferred 1mol L of its concentration are used-1) washing remove it is residual
Remaining metal ion, finally obtain approaching the neutral GO aqueous solution, by freeze-drying by washing centrifugation ultrasound repeatedly again
The GO of sheet is obtained, it is standby that powder is made in grinding.
TBT alcoholic solutions in the present invention are TBT and the mixed solution of ethanol, and concrete operation method is：TBT is added drop-wise to nothing
In water-ethanol, mixed solution A is formed after stirring.Pay attention to：The reaction temperature of alcoholysis process is 30-40 DEG C.The TBT and ethanol
Volume ratio be：(0.16-0.76):(3-10).
In the present invention, the GO aqueous solution adds ammoniacal liquor and is mixed to form mixed solution B.Specifically operating is：Peeled off by ultrasound
The GO aqueous solution is prepared, ammoniacal liquor is then added, stirs, obtain mixed solution B.Wherein, the concentration of the GO aqueous solution is 1.5-
3mg/mL, ultrasonic time 0.5-2h.
Wherein, the volume of the TBT and ammoniacal liquor are (0.16-0.76):(0.5-1).
In the present invention, the mixed solution A is added in the mixed solution B, is well mixed, is subsequently added into citric acid
Sodium, stirring form mixed solution C, wherein, the mixed solution A and mixed solution B volume ratio are (3-10):(15-
30).The 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, the mixed solution A is added dropwise to obtained
In mixed solution B.The purpose of this operating procedure is in order that GO can be compound with the carry out of titanium source evenly.
The addition ratio of the TBT and sodium citrate are (0.16-0.76) mL:(0.05-0.15)g.
In the present invention, the concrete operation step of hydro-thermal self assembly is：The mixed solution C is transferred in polytetrafluoroethylene (PTFE)
In the autoclave of lining, reactor is tightened and is put into baking oven, carry out hydro-thermal process, after reactor naturally cooled into room
Temperature, that is, obtain three-dimensional rice shape TiO2/ graphene composite aquogel.Wherein, 160-180 DEG C of hydrothermal temperature, hydro-thermal time are 6-
24h, optimum condition are：180 DEG C of insulation 12h.
The present invention prepares GO using improved Hummers methods, and using TBT as titanium source, sodium citrate is structure directing agent, leads to
Cross hydro-thermal method and prepare three-dimensional TiO2/ graphene composite aquogel.The characteristics of composite aquogel is：Macro morphology is diameter 1-
2cm, high 1-2cm black column；Microscopic appearance is rice shape TiO2Nano-particle uniform load is on graphene film, and stone
It is interweaved between black alkene piece and reticulates structure, wherein TiO2A diameter of 15-35nm of nano-particle, a length of 30-70nm.
The beneficial effects of the invention are as follows：
(1) present invention is used as structure directing agent, synthesized three-dimensional TiO by the use of sodium citrate2/ graphene composite aquogel
Pattern be rice shape TiO2Nanometer particle load is on graphene film, wherein TiO2The diameter of nano-particle 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 hydrothermal condition
Original, it is not required to add poisonous reducing agent, it is green；Rice shape TiO2Particle good dispersion, does not reunite significantly, and this is beneficial to
Reduce the interfacial resistance in charge transfer process, got ready for further application.
(3) the three-dimensional TiO prepared by the present invention2In/graphene composite aquogel, TiO2It is controllable with the ratio of graphene, enter
And the physicochemical property of composite aquogel can realize optimization.
(4) the three-dimensional TiO prepared by the present invention2/ graphene composite aquogel has larger specific surface area, three constructed
Dimension network structure can shorten the diffusion of electrolyte ion and migration path in charge and discharge process, be beneficial 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 TiO2It is each intrinsic with graphene
Attribute, additionally it is possible to produce the cooperative effect of novelty, compared with pure graphene hydrogel, electricity of the composite aquogel in 0.2A/g
Specific capacitance is up to 332.6F/g under current 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, is other patterns
TiO2The preparation of/graphene composite aquogel provides a kind of new synthesis thinking.
The present invention combines sol-gal process and hydro-thermal method, and the aqueous solution of TBT alcoholic solution and graphene is mixed, 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 do not assemble significantly.The TiO2The pattern and performance of/graphene composite aquogel are controllable, you can by regulating and controlling TBT and GO
Addition when the hydro-thermal time controls the formability of gel and stability, and with the increase of graphene content, plural gel
Pattern and physicochemical property show certain regularity.
Brief description of the drawings
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 is GO TEM, and b is
TiO prepared by embodiment 32The TEM of/graphene composite aquogel, c are rice shape TiO in plural gel2The HRTEM of particle, d are
Rice shape TiO2The electron diffraction diagram of particle；
Fig. 3 is TiO prepared by the embodiment of the present invention 32The field of aeroge formed by the freeze-drying of/graphene composite aquogel
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 GO XRD, and b is the XRD of pure graphene hydrogel, and c is TiO prepared by embodiment 32/ graphene hydrogel
XRD；
Fig. 5 is pure graphene hydrogel and TiO2The cyclic voltammetry curve figure (CV) of/graphene composite aquogel, its
In, a is that the CV of pure graphene hydrogel schemes, and b is TiO prepared by embodiment 32The CV figures 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 that the GCD of pure graphene hydrogel schemes, and b is TiO prepared by embodiment 32The GCD figures of/graphene hydrogel.
Embodiment
With reference to embodiment and accompanying drawing, the present invention is further described.
Embodiment 1
(1) the GO aqueous solution is prepared
By 3g graphite powders, the 30mL concentrated sulfuric acids, 3g K2S2O8, 3g P2O5It is added sequentially in beaker, ultrasonic 5min, is placed in water
Bath, 80 DEG C of stirring 6h are heated to, are cooled to room temperature；With 1000mL distilled water dilutings, stand overnight；The dilution of gained is entered
Row filters, and forms filter cake, spontaneously dries overnight；Filter cake is scraped in small beaker with spoon, adds the 150 mL concentrated sulfuric acids, is stirred,
Ultrasonic 1h；Under ice bath, 15g potassium permanganate is slowly added into the solution after ultrasound, control temperature is less than 20 DEG C, stirs 4h, so
After be to slowly warm up to 40 DEG C, stirring and insulation 8h；Then 300mL deionized waters are slowly added into solution, are stirred under normal temperature
2h；700mL deionized waters are continuously added, stir 2h；20mL hydrogen peroxide is then added, obtains the acid GO aqueous solution of glassy yellow,
Stood after stirring 0.5h；The supernatant of resulting solution is outwelled, with 1mol L-1The washing of HCl/water solution remove remaining metal
Ion, finally by washing centrifugation ultrasound repeatedly, obtain approaching the neutral GO aqueous solution；Piece is finally given by freeze-drying
The GO of shape, it is standby that powder is made in grinding.
(2) three-dimensional rice shape TiO is synthesized2/ graphene composite aquogel
At 40 DEG C, 0.16mL TBT are slowly dropped in 5mL absolute ethyl alcohols, mixed solution A is formed after stirring；By super
Sound, stirring prepare the 2mg/mL GO aqueous solution, then add 0.5mL ammoniacal liquor, stir, obtain mixed solution B；It will mix molten
Liquid A is slowly added into mixed solution B, then adds 0.08g sodium citrates, continues to stir 3h formation mixed solution Cs；Will be mixed
Close solution C to be transferred in the autoclave of polytetrafluoroethyllining lining, autoclave is tightened and is put into baking oven, 180 DEG C of bars
It is incubated 12h under part, autoclave is naturally cooled into room temperature after hydro-thermal reaction, obtains black columnar object；The post that will be obtained
The washing of shape thing removes remnants impurity several times, that is, obtains three-dimensional TiO2/ graphene composite aquogel.
Embodiment 2
(1) the GO aqueous solution is prepared
By 3g graphite powders, the 30mL concentrated sulfuric acids, 3g K2S2O8, 3g P2O5It is added sequentially in beaker, ultrasonic 5min, is placed in water
Bath, 80 DEG C of stirring 6h are heated to, are cooled to room temperature；With 1000mL distilled water dilutings, stand overnight；The dilution of gained is entered
Row filters, and forms filter cake, spontaneously dries overnight；Filter cake is scraped in small beaker with spoon, adds the 150 mL concentrated sulfuric acids, is stirred,
Ultrasonic 1h；Under ice bath, 15g potassium permanganate is slowly added into the solution after ultrasound, control temperature is less than 20 DEG C, stirs 4h, so
After be to slowly warm up to 40 DEG C, stirring and insulation 8h；Then 300mL deionized waters are slowly added into solution, are stirred under normal temperature
2h；700mL deionized waters are continuously added, stir 2h；20mL hydrogen peroxide is then added, obtains the acid GO aqueous solution of glassy yellow,
Stood after stirring 0.5h；The supernatant of resulting solution is outwelled, with 1mol L-1The washing of HCl/water solution remove remaining metal
Ion, finally by washing centrifugation ultrasound repeatedly, obtain approaching the neutral GO aqueous solution；Piece is finally given by freeze-drying
The GO of shape, it is standby that powder is made in grinding.
(2) three-dimensional rice shape TiO is synthesized2/ graphene composite aquogel
At 40 DEG C, 0.23mL TBT are slowly dropped in 5mL absolute ethyl alcohols, mixed solution A is formed after stirring；By super
Sound, stirring prepare the 2mg/mL GO aqueous solution, then add 0.5mL ammoniacal liquor, stir, obtain mixed solution B；It will mix molten
Liquid A is slowly added into mixed solution B, then adds 0.08g sodium citrates, continues to stir 3h formation mixed solution Cs；Will be mixed
Close solution C to be transferred in the autoclave of polytetrafluoroethyllining lining, autoclave is tightened and is put into baking oven, 180 DEG C of bars
It is incubated 12h under part, autoclave is naturally cooled into room temperature after hydro-thermal reaction, obtains black columnar object；The post that will be obtained
The washing of shape thing removes remnants impurity several times, that is, obtains three-dimensional TiO2/ graphene composite aquogel.
Embodiment 3
(1) the GO aqueous solution is prepared
By 3g graphite powders, the 30mL concentrated sulfuric acids, 3g K2S2O8, 3g P2O5It is added sequentially in beaker, ultrasonic 5min, is placed in water
Bath, 80 DEG C of stirring 6h are heated to, are cooled to room temperature；With 1000mL distilled water dilutings, stand overnight；The dilution of gained is entered
Row filters, and forms filter cake, spontaneously dries overnight；Filter cake is scraped in small beaker with spoon, adds the 150 mL concentrated sulfuric acids, is stirred,
Ultrasonic 1h；Under ice bath, 15g potassium permanganate is slowly added into the solution after ultrasound, control temperature is less than 20 DEG C, stirs 4h, so
After be to slowly warm up to 40 DEG C, stirring and insulation 8h；Then 300mL deionized waters are slowly added into solution, are stirred under normal temperature
2h；700mL deionized waters are continuously added, stir 2h；20mL hydrogen peroxide is then added, obtains the acid GO aqueous solution of glassy yellow,
Stood after stirring 0.5h；The supernatant of resulting solution is outwelled, with 1mol L-1The washing of HCl/water solution remove remaining metal
Ion, finally by washing centrifugation ultrasound repeatedly, obtain approaching the neutral GO aqueous solution；Piece is finally given by freeze-drying
The GO of shape, it is standby that powder is made in grinding.
(2) three-dimensional rice shape TiO is synthesized2/ graphene composite aquogel
At 40 DEG C, 0.30mL TBT are slowly dropped in 5mL absolute ethyl alcohols, mixed solution A is formed after stirring；By super
Sound, stirring prepare the 2mg/mL GO aqueous solution, then add 0.5mL ammoniacal liquor, stir, obtain mixed solution B；It will mix molten
Liquid A is slowly added into mixed solution B, then adds 0.08g sodium citrates, continues to stir 3h formation mixed solution Cs；Will be mixed
Close solution C to be transferred in the autoclave of polytetrafluoroethyllining lining, autoclave is tightened and is put into baking oven, 180 DEG C of bars
It is incubated 12h under part, autoclave is naturally cooled into room temperature after hydro-thermal reaction, obtains black columnar object；The post that will be obtained
The washing of shape thing removes remnants impurity several times, that is, obtains three-dimensional TiO2/ graphene composite aquogel.
As shown in Fig. 1,2,3 and 4, the macro morphology of graphene hydrogel made from the present embodiment 3 is black column, directly
Footpath is about 1-2cm, and height is about 1-2cm；Microscopic appearance is rice shape TiO2Nano-particle is uniformly dispersed on graphene film, its
Middle TiO2Nano-particle is Detitanium-ore-type, and diameter is about 15-35nm, and long is about 30-70nm；Hydrogel cool-drying is into after aeroge
Show three-dimensional porous network structure.From Fig. 5 and 6 as can be seen that compared with pure graphene hydrogel, the present embodiment 3 synthesizes
Composite aquogel show more superior chemical property.
Embodiment 4
(1) the GO aqueous solution is prepared
By 3g graphite powders, the 30mL concentrated sulfuric acids, 3g K2S2O8, 3g P2O5It is added sequentially in beaker, ultrasonic 5min, is placed in water
Bath, 80 DEG C of stirring 6h are heated to, are cooled to room temperature；With 1000mL distilled water dilutings, stand overnight；The dilution of gained is entered
Row filters, and forms filter cake, spontaneously dries overnight；Filter cake is scraped in small beaker with spoon, adds the 150 mL concentrated sulfuric acids, is stirred,
Ultrasonic 1h；Under ice bath, 15g potassium permanganate is slowly added into the solution after ultrasound, control temperature is less than 20 DEG C, stirs 4h, so
After be to slowly warm up to 40 DEG C, stirring and insulation 8h；Then 300mL deionized waters are slowly added into solution, are stirred under normal temperature
2h；700mL deionized waters are continuously added, stir 2h；20mL hydrogen peroxide is then added, obtains the acid GO aqueous solution of glassy yellow,
Stood after stirring 0.5h；The supernatant of resulting solution is outwelled, with 1mol L-1The washing of HCl/water solution remove remaining metal
Ion, finally by washing centrifugation ultrasound repeatedly, obtain approaching the neutral GO aqueous solution；Piece is finally given by freeze-drying
The GO of shape, it is standby that powder is made in grinding.
(2) three-dimensional rice shape TiO is synthesized2/ graphene composite aquogel
At 40 DEG C, 0.56mL TBT are slowly dropped in 5mL absolute ethyl alcohols, mixed solution A is formed after stirring；By super
Sound, stirring prepare the 2mg/mL GO aqueous solution, then add 0.5mL ammoniacal liquor, stir, obtain mixed solution B；It will mix molten
Liquid A is slowly added into mixed solution B, then adds 0.08g sodium citrates, continues to stir 3h formation mixed solution Cs；Will be mixed
Close solution C to be transferred in the autoclave of polytetrafluoroethyllining lining, autoclave is tightened and is put into baking oven, 180 DEG C of bars
It is incubated 12h under part, autoclave is naturally cooled into room temperature after hydro-thermal reaction, obtains black columnar object；The post that will be obtained
The washing of shape thing removes remnants impurity several times, that is, obtains three-dimensional TiO2/ graphene composite aquogel.
Embodiment 5
(1) the GO aqueous solution is prepared
By 3g graphite powders, the 30mL concentrated sulfuric acids, 3g K2S2O8, 3g P2O5It is added sequentially in beaker, ultrasonic 5min, is placed in water
Bath, 80 DEG C of stirring 6h are heated to, are cooled to room temperature；With 1000mL distilled water dilutings, stand overnight；The dilution of gained is entered
Row filters, and forms filter cake, spontaneously dries overnight；Filter cake is scraped in small beaker with spoon, adds the 150 mL concentrated sulfuric acids, is stirred,
Ultrasonic 1h；Under ice bath, 15g potassium permanganate is slowly added into the solution after ultrasound, control temperature is less than 20 DEG C, stirs 4h, so
After be to slowly warm up to 40 DEG C, stirring and insulation 8h；Then 300mL deionized waters are slowly added into solution, are stirred under normal temperature
2h；700mL deionized waters are continuously added, stir 2h；20mL hydrogen peroxide is then added, obtains the acid GO aqueous solution of glassy yellow,
Stood after stirring 0.5h；The supernatant of resulting solution is outwelled, with 1mol L-1The washing of HCl/water solution remove remaining metal
Ion, finally by washing centrifugation ultrasound repeatedly, obtain approaching the neutral GO aqueous solution；Piece is finally given by freeze-drying
The GO of shape, it is standby that powder is made in grinding.
(2) three-dimensional rice shape TiO is synthesized2/ graphene composite aquogel
At 40 DEG C, 0.76mL TBT are slowly dropped in 5mL absolute ethyl alcohols, mixed solution A is formed after stirring；By super
Sound, stirring prepare the 2mg/mL GO aqueous solution, then add 0.5mL ammoniacal liquor, stir, obtain mixed solution B；It will mix molten
Liquid A is slowly added into mixed solution B, then adds 0.08g sodium citrates, continues to stir 3h formation mixed solution Cs；Will be mixed
Close solution C to be transferred in the autoclave of polytetrafluoroethyllining lining, autoclave is tightened and is put into baking oven, 180 DEG C of bars
It is incubated 12h under part, autoclave is naturally cooled into room temperature after hydro-thermal reaction, obtains black columnar object；The post that will be obtained
The washing of shape thing removes remnants impurity several times, that is, obtains three-dimensional TiO2/ graphene composite aquogel.
Embodiment 6
(1) the GO aqueous solution is prepared
By 3g graphite powders, the 30mL concentrated sulfuric acids, 3g K2S2O8, 3g P2O5It is added sequentially in beaker, ultrasonic 5min, is placed in water
Bath, 80 DEG C of stirring 6h are heated to, are cooled to room temperature；With 1000mL distilled water dilutings, stand overnight；The dilution of gained is entered
Row filters, and forms filter cake, spontaneously dries overnight；Filter cake is scraped in small beaker with spoon, adds the 150 mL concentrated sulfuric acids, is stirred,
Ultrasonic 1h；Under ice bath, 15g potassium permanganate is slowly added into the solution after ultrasound, control temperature is less than 20 DEG C, stirs 4h, so
After be to slowly warm up to 40 DEG C, stirring and insulation 8h；Then 300mL deionized waters are slowly added into solution, are stirred under normal temperature
2h；700mL deionized waters are continuously added, stir 2h；20mL hydrogen peroxide is then added, obtains the acid GO aqueous solution of glassy yellow,
Stood after stirring 0.5h；The supernatant of resulting solution is outwelled, with 1mol L-1The washing of HCl/water solution remove remaining metal
Ion, finally by washing centrifugation ultrasound repeatedly, obtain approaching the neutral GO aqueous solution；Piece is finally given by freeze-drying
The GO of shape, it is standby that powder is made in grinding.
(2) three-dimensional rice shape TiO is synthesized2/ graphene composite aquogel
At 40 DEG C, 0.30mL TBT are slowly dropped in 5mL absolute ethyl alcohols, mixed solution A is formed after stirring；By super
Sound, stirring prepare the 2mg/mL GO aqueous solution, then add 0.5mL ammoniacal liquor, stir, obtain mixed solution B；It will mix molten
Liquid A is slowly added into mixed solution B, then adds 0.08g sodium citrates, continues to stir 3h formation mixed solution Cs；Will be mixed
Close solution C to be transferred in the autoclave of polytetrafluoroethyllining lining, autoclave is tightened and is put into baking oven, 180 DEG C of bars
It is incubated 6h under part, autoclave is naturally cooled into room temperature after hydro-thermal reaction, obtains black columnar object；The column that will be obtained
Thing washing removes remnants impurity several times, that is, obtains three-dimensional TiO2/ graphene composite aquogel.
Embodiment 7
(1) the GO aqueous solution is prepared
By 3g graphite powders, the 30mL concentrated sulfuric acids, 3g K2S2O8, 3g P2O5It is added sequentially in beaker, ultrasonic 5min, is placed in water
Bath, 80 DEG C of stirring 6h are heated to, are cooled to room temperature；With 1000mL distilled water dilutings, stand overnight；The dilution of gained is entered
Row filters, and forms filter cake, spontaneously dries overnight；Filter cake is scraped in small beaker with spoon, adds the 150 mL concentrated sulfuric acids, is stirred,
Ultrasonic 1h；Under ice bath, 15g potassium permanganate is slowly added into the solution after ultrasound, control temperature is less than 20 DEG C, stirs 4h, so
After be to slowly warm up to 40 DEG C, stirring and insulation 8h；Then 300mL deionized waters are slowly added into solution, are stirred under normal temperature
2h；700mL deionized waters are continuously added, stir 2h；20mL hydrogen peroxide is then added, obtains the acid GO aqueous solution of glassy yellow,
Stood after stirring 0.5h；The supernatant of resulting solution is outwelled, with 1mol L-1The washing of HCl/water solution remove remaining metal
Ion, finally by washing centrifugation ultrasound repeatedly, obtain approaching the neutral GO aqueous solution；Piece is finally given by freeze-drying
The GO of shape, it is standby that powder is made in grinding.
(2) three-dimensional rice shape TiO is synthesized2/ graphene composite aquogel
At 40 DEG C, 0.30mL TBT are slowly dropped in 5mL absolute ethyl alcohols, mixed solution A is formed after stirring；By super
Sound, stirring prepare the 2mg/mL GO aqueous solution, then add 0.5mL ammoniacal liquor, stir, obtain mixed solution B；It will mix molten
Liquid A is slowly added into mixed solution B, then adds 0.08g sodium citrates, continues to stir 3h formation mixed solution Cs；Will be mixed
Close solution C to be transferred in the autoclave of polytetrafluoroethyllining lining, autoclave is tightened and is put into baking oven, 180 DEG C of bars
It is incubated 18h under part, autoclave is naturally cooled into room temperature after hydro-thermal reaction, obtains black columnar object；The post that will be obtained
The washing of shape thing removes remnants impurity several times, that is, obtains three-dimensional TiO2/ graphene composite aquogel.
Embodiment 8
(1) the GO aqueous solution is prepared
By 3g graphite powders, the 30mL concentrated sulfuric acids, 3g K2S2O8, 3g P2O5It is added sequentially in beaker, ultrasonic 5min, is placed in water
Bath, 80 DEG C of stirring 6h are heated to, are cooled to room temperature；With 1000mL distilled water dilutings, stand overnight；The dilution of gained is entered
Row filters, and forms filter cake, spontaneously dries overnight；Filter cake is scraped in small beaker with spoon, adds the 150 mL concentrated sulfuric acids, is stirred,
Ultrasonic 1h；Under ice bath, 15g potassium permanganate is slowly added into the solution after ultrasound, control temperature is less than 20 DEG C, stirs 4h, so
After be to slowly warm up to 40 DEG C, stirring and insulation 8h；Then 300mL deionized waters are slowly added into solution, are stirred under normal temperature
2h；700mL deionized waters are continuously added, stir 2h；20mL hydrogen peroxide is then added, obtains the acid GO aqueous solution of glassy yellow,
Stood after stirring 0.5h；The supernatant of resulting solution is outwelled, with 1mol L-1The washing of HCl/water solution remove remaining metal
Ion, finally by washing centrifugation ultrasound repeatedly, obtain approaching the neutral GO aqueous solution；Piece is finally given by freeze-drying
The GO of shape, it is standby that powder is made in grinding.
(2) three-dimensional rice shape TiO is synthesized2/ graphene composite aquogel
At 40 DEG C, 0.30mL TBT are slowly dropped in 5mL absolute ethyl alcohols, mixed solution A is formed after stirring；By super
Sound, stirring prepare the 2mg/mL GO aqueous solution, then add 0.5mL ammoniacal liquor, stir, obtain mixed solution B；It will mix molten
Liquid A is slowly added into mixed solution B, then adds 0.08g sodium citrates, continues to stir 3h formation mixed solution Cs；Will be mixed
Close solution C to be transferred in the autoclave of polytetrafluoroethyllining lining, autoclave is tightened and is put into baking oven, 180 DEG C of bars
It is incubated 24h under part, autoclave is naturally cooled into room temperature after hydro-thermal reaction, obtains black columnar object；The post that will be obtained
The washing of shape thing removes remnants impurity several times, that is, obtains three-dimensional TiO2/ graphene composite aquogel.
Embodiment 9
(1) the GO aqueous solution is prepared
By 3g graphite powders, the 30mL concentrated sulfuric acids, 3g K2S2O8, 3g P2O5It is added sequentially in beaker, ultrasonic 5min, is placed in water
Bath, 80 DEG C of stirring 6h are heated to, are cooled to room temperature；With 1000mL distilled water dilutings, stand overnight；The dilution of gained is entered
Row filters, and forms filter cake, spontaneously dries overnight；Filter cake is scraped in small beaker with spoon, adds the 150 mL concentrated sulfuric acids, is stirred,
Ultrasonic 1h；Under ice bath, 15g potassium permanganate is slowly added into the solution after ultrasound, control temperature is less than 20 DEG C, stirs 4h, so
After be to slowly warm up to 40 DEG C, stirring and insulation 8h；Then 300mL deionized waters are slowly added into solution, are stirred under normal temperature
2h；700mL deionized waters are continuously added, stir 2h；20mL hydrogen peroxide is then added, obtains the acid GO aqueous solution of glassy yellow,
Stood after stirring 0.5h；The supernatant of resulting solution is outwelled, with 1mol L-1The washing of HCl/water solution remove remaining metal
Ion, finally by washing centrifugation ultrasound repeatedly, obtain approaching the neutral GO aqueous solution；Piece is finally given by freeze-drying
The GO of shape, it is standby that powder is made in grinding.
(2) three-dimensional rice shape TiO is synthesized2/ graphene composite aquogel
At 30 DEG C, 0.30mL TBT are slowly dropped in 3mL absolute ethyl alcohols, mixed solution A is formed after stirring；By super
Sound, stirring prepare the 1.5mg/mL GO aqueous solution, then add 0.8mL ammoniacal liquor, stir, obtain mixed solution B；Will mixing
Solution A is slowly added into mixed solution B, then adds 0.05g sodium citrates, continues to stir 2h formation mixed solution Cs；Will
Mixed solution C is transferred in the autoclave of polytetrafluoroethyllining lining, and autoclave is tightened and is put into baking oven, 170 DEG C
Under the conditions of be incubated 12h, autoclave is naturally cooled into room temperature after hydro-thermal reaction, obtains black columnar object；By what is obtained
Column washing removes remnants impurity several times, that is, obtains three-dimensional TiO2/ graphene composite aquogel.
Embodiment 10
(1) the GO aqueous solution is prepared
By 3g graphite powders, the 30mL concentrated sulfuric acids, 3g K2S2O8, 3g P2O5It is added sequentially in beaker, ultrasonic 5min, is placed in water
Bath, 80 DEG C of stirring 6h are heated to, are cooled to room temperature；With 1000mL distilled water dilutings, stand overnight；The dilution of gained is entered
Row filters, and forms filter cake, spontaneously dries overnight；Filter cake is scraped in small beaker with spoon, adds the 150 mL concentrated sulfuric acids, is stirred,
Ultrasonic 1h；Under ice bath, 15g potassium permanganate is slowly added into the solution after ultrasound, control temperature is less than 20 DEG C, stirs 4h, so
After be to slowly warm up to 40 DEG C, stirring and insulation 8h；Then 300mL deionized waters are slowly added into solution, are stirred under normal temperature
2h；700mL deionized waters are continuously added, stir 2h；20mL hydrogen peroxide is then added, obtains the acid GO aqueous solution of glassy yellow,
Stood after stirring 0.5h；The supernatant of resulting solution is outwelled, with 1mol L-1The washing of HCl/water solution remove remaining metal
Ion, finally by washing centrifugation ultrasound repeatedly, obtain approaching the neutral GO aqueous solution；Piece is finally given by freeze-drying
The GO of shape, it is standby that powder is made in grinding.
(2) three-dimensional rice shape TiO is synthesized2/ graphene composite aquogel
At 35 DEG C, 0.30mL TBT are slowly dropped in 10mL absolute ethyl alcohols, mixed solution A is formed after stirring；Pass through
Ultrasound, stirring prepare the 3mg/mL GO aqueous solution, then add 1mL ammoniacal liquor, stir, obtain mixed solution B；It will mix molten
Liquid A is slowly added into mixed solution B, then adds 0.15g sodium citrates, continues to stir 4h formation mixed solution Cs；Will be mixed
Close solution C to be transferred in the autoclave of polytetrafluoroethyllining lining, autoclave is tightened and is put into baking oven, 160 DEG C of bars
It is incubated 12h under part, autoclave is naturally cooled into room temperature after hydro-thermal reaction, obtains black columnar object；The post that will be obtained
The washing of shape thing removes remnants impurity several times, that is, obtains three-dimensional TiO2/ graphene composite aquogel.
Hydrogel prepared by embodiment 1-2 and 4-10, its both macro and micro pattern and embodiment 3 have no obvious poor
It is different, it is the TiO of rice shape2Particle is supported on graphene film.Wherein, rice shape TiO2The diameter of particle is about 15-35nm,
Long is about 30-70nm.
Embodiment 11
A kind of ultracapacitor, its electrode material use three-dimensional TiO in embodiment 32/ graphene composite aquogel, pass through
Verification experimental verification, the ultracapacitor have good application in electrochemical field.
The present invention is using GO and TBT as raw material, and sodium citrate is structure directing agent, using simple and environmentally-friendly hydro-thermal method, a step
Synthesize three-dimensional rice shape TiO2/ graphene composite aquogel.Regulate and control gel by changing TBT addition and hydro-thermal time
Formability and stability.Simultaneously using the advantage of three-dimensional net structure, the composite aquogel of preparation is applied to ultracapacitor
Research, the results showed that TiO2/ graphene composite aquogel has a high specific capacitance, and the circulation that superior high rate performance is become reconciled is steady
Qualitative energy.
Although above-mentioned the embodiment of the present invention is described with reference to accompanying drawing, model not is protected to the present invention
The limitation enclosed, one of ordinary skill in the art should be understood that on the basis of technical scheme those skilled in the art are not
Need to pay various modifications or deformation that creative work can make still within protection scope of the present invention.
Claims (7)
- A kind of 1. three-dimensional rice shape TiO2The preparation method of/graphene composite aquogel, it is characterized in that, comprise the following steps：With butyl titanate（TBT）For titanium source, TBT alcoholic solutions are prepared；The TBT alcoholic solutions are the mixed solution of TBT and ethanol, Concrete operation method is：TBT is added drop-wise in absolute ethyl alcohol, mixed solution A is formed after stirring；Then obtained TBT alcoholic solutions are added in the GO aqueous solution, sodium citrate is added to control TiO after well mixed2Orientation Growth；Graphene oxide water solution adds ammoniacal liquor and is mixed to form mixed solution B；Wherein, the concentration of the GO aqueous solution is 1.5-3 mg/ mL；The volume of the TBT and ammoniacal liquor are (0.16-0.76):(0.5-1)；The addition ratio of the TBT and sodium citrate is (0.16-0.76) mL:(0.05-0.15) g；Three-dimensional rice shape TiO has been obtained finally by hydro-thermal self assembly2/ graphene composite aquogel, wherein, hydrothermal temperature 160- 180 °C, the hydro-thermal time is 6-24 h；The macro morphology of obtained composite aquogel is diameter 1-2 cm, high 1-2 cm black Column；Microscopic appearance is rice shape TiO2Nano-particle uniform load is mutually handed on graphene film between graphene film It is made into network structure, wherein TiO2A diameter of 15-35 nm of nano-particle, a length of 30-70 nm.
- 2. preparation method as claimed in claim 1, it is characterized in that：The volume ratio of the TBT and ethanol is：(0.16-0.76): (3-10)。
- 3. preparation method as claimed in claim 1, it is characterized in that：The mixed solution A is added to described mixed solution B In, it is well mixed, is subsequently added into sodium citrate, stirring forms mixed solution C, wherein, the mixed solution A and mixed solution B Volume ratio be (3-10):(15-30).
- 4. preparation method as claimed in claim 1, it is characterized in that：Mixed after adding sodium citrate, the stirring Temperature is 30-40 °C, and mixing time is 2-4 h.
- 5. preparation method as claimed in claim 1, it is characterized in that：The hydrothermal condition：Hydrothermal temperature is 180 °C, hydro-thermal Time is 12 h.
- 6. the three-dimensional rice shape TiO being prepared using the method any one of claim 1 ~ 52/ graphene compound water congealing Glue.
- 7. hydrogel as claimed in claim 6, it is characterized in that：The macro morphology of the composite aquogel is diameter 1-2 cm, high 1-2 cm black column；Microscopic appearance is rice shape TiO2Nano-particle uniform load is on graphene film, and graphene It is interweaved between piece and reticulates structure, wherein TiO2A diameter of 15-35 nm of nano-particle, a length of 30-70 nm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610429080.1A CN106098405B (en) | 2016-06-14 | 2016-06-14 | A kind of three-dimensional rice shape TiO2/ graphene composite aquogel and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610429080.1A CN106098405B (en) | 2016-06-14 | 2016-06-14 | A kind of three-dimensional rice shape TiO2/ graphene composite aquogel and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106098405A CN106098405A (en) | 2016-11-09 |
| CN106098405B true CN106098405B (en) | 2017-12-26 |
Family
ID=57235683
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610429080.1A Active CN106098405B (en) | 2016-06-14 | 2016-06-14 | A kind of three-dimensional rice shape TiO2/ graphene composite aquogel and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106098405B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| 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 |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2743232A4 (en) * | 2011-08-08 | 2015-11-25 | Ajinomoto Kk | Porous structure and method for producing same |
| CN102706853A (en) * | 2012-06-05 | 2012-10-03 | 湖南大学 | Raman reinforced substrate material, preparation and application methods thereof |
-
2016
- 2016-06-14 CN CN201610429080.1A patent/CN106098405B/en active Active
Non-Patent Citations (1)
| Title |
|---|
| Eco-friendly one-pot synthesis of ultradispersed TiO2 nanocrystals/graphene nanocomposites with high photocatalytic activity for dye degradation;Penghui Shao etc;《J. Mater. Chem. A》;20151231;第3卷;全文 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106098405A (en) | 2016-11-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106098405B (en) | A kind of three-dimensional rice shape TiO2/ graphene composite aquogel and preparation method thereof | |
| Ghasemi et al. | Sonochemical-assisted synthesis of nano-structured lead dioxide | |
| CN104810509B (en) | Ferroso-ferric oxide/graphene three dimensional composite structure and its preparation method and application | |
| CN105895384B (en) | A kind of graphene/ultra micro cobaltosic oxide Particles dispersed electrode material preparation method | |
| CN105363483A (en) | Preparation method of titanium dioxide nanowire/two-dimensional layered titanium carbide composite material | |
| CN105428633A (en) | Method for preparing titanium niobate mesoporous microspheres | |
| CN105914358A (en) | Preparation method of yolk-eggshell structured nitrogen-doped carbon-coated Fe3O4@SnO2 magnetic nanometer box | |
| CN106450265A (en) | In-situ nitrogen-doped carbon coated lithium titanate composite electrode material and preparation method thereof | |
| CN108288703A (en) | A kind of preparation method and applications of graphene coated fluorine doped lithium titanate nano wire | |
| CN105118691B (en) | Nickel foam supports ferrous sub-micron tube electrode material of cobalt acid and preparation method thereof | |
| CN106252651A (en) | A kind of lithium ion battery porous composite negative pole material and preparation method thereof | |
| CN107123794A (en) | A kind of preparation method of carbon coating manganese monoxide/N doping redox graphene lithium ion battery negative material | |
| CN107808958A (en) | Preparation method of ferroso-ferric oxide/nitrogen-doped graphene composite and products thereof and application | |
| CN113353917B (en) | Controllable preparation method of self-supporting two-dimensional mesoporous nano material | |
| CN104577049A (en) | Hierarchical pore structure silicon-based negative electrode material for lithium battery and preparation method of hierarchical pore structure silicon-based negative electrode material | |
| CN104891567A (en) | Preparing method of tubular TiO2/reduced graphene oxide composite | |
| CN106450241A (en) | Titanium nitride/carbon nitride/graphene oxide composite nano-material and preparation method thereof | |
| CN110350170A (en) | A kind of preparation method of lithium titanate/graphene composite material | |
| CN110247072A (en) | NiFe-LDH@CNT nano material and preparation method thereof | |
| Nie et al. | Using Prussian blue as a self-sacrificial template to construct MnO/MnFe2O4 microcubes as anodes for lithium-ion batteries | |
| CN105869907A (en) | Preparation method of carbon-nitrogen-codoped NiFe2O4-Ni nanocomposite material with cubic structure | |
| Dong et al. | Assembly of flexible nanohelix films: stress–exporting insights into the electrochemical performance of lithium–ion batteries | |
| CN106356523A (en) | Preparation method of titanium dioxide sodium-ion battery cathode material and product thereof | |
| CN111704732B (en) | Metal organic framework loaded graphene microspheres and preparation method and application thereof | |
| CN108666546A (en) | A kind of lithium cell cathode material and preparation method of layered nano-graphene |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant |