CN106241779B - A kind of preparation method of CNT graphene oxide hybrid three-dimensional material - Google Patents
A kind of preparation method of CNT graphene oxide hybrid three-dimensional material Download PDFInfo
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Abstract
The invention belongs to field of nanometer material technology, and in particular to a kind of preparation method of CNT graphene oxide hybrid three-dimensional material.The present invention is the surfactant properties using graphene oxide, graphene oxide and CNT are assembled into amphipathic controllable Pickering system stabilizers, self assembling process driving force formation oil-in-water emulsion systems are used as using oil phase and the reduction of aqueous phase interface free energy, the nano-sized carbon hybrid materials that CNT and graphene oxide are assembled into are coated on oil droplets, after freeze-dried and removal oil phase, obtain the CNT graphene oxide hybrid materials of full carbon structure, the features of graphene oxide and CNT are remained simultaneously, with adjustable electric conductivity, thermal conductivity and three-dimensional macro morphology, preparation technology is easy, it is with low cost.
Description
Technical field
The invention belongs to field of nanometer material technology, and in particular to a kind of CNT-graphene oxide hybrid three-dimensional material
Preparation method.
Background technology
There is huge specific surface area, excellent mechanical property by the nano-carbon material of representative of CNT and graphene
With conductive, heat conductivility, received much attention in recent years in electronic information, novel energy, biology and field of functional materials.Typically recognize
For material property fundamentally depends on its internal microstructure, is that it has using the fundamental starting point of nano-carbon material
Have bysp 2Hybridized orbit formation from threshold pi bond, chemical vapor deposition widely used at present（CVD）Method produce CNT and
Graphene, on the one hand with more completesp 2Atomic structure of carbon, thus with preferably conductive, heat conductivility relatively.It is another
Aspect, high temperature, the use of metallic catalyst and graphene migration problem have impact on the promotion and application of nano-carbon material.Nanometer
The development of carbon composite faces following three aspects problem：（1）Because a peacekeeping two-dimensional structure of CNT and graphene is led
The function anisotropy of cause；（2）High length-diameter ratio（Transverse and longitudinal ratio）And stronger π-π interactions make nano-carbon material easily produce
Reunite and pile up, it is serious to restrict giving full play to for nano-carbon material performance；（3）The CNT and graphene tool of CVD production
There is very strong hydrophobicity and resulting chemical inertness.
Graphene oxide is the Graphene derivative obtained using chemical peeling, in preparation process, oxidation processes
In graphenic surface, substantial amounts of hydroxyl, epoxy radicals and carboxyl isopolarity group are especially introduced at edge, part is formedsp 3
Hydbridized carbon atoms, and not oxidized region remain in that it is hydrophobicsp 2Hydbridized carbon atoms structure, therefore graphene oxide is in guarantor
While staying graphene flexibility two-dimensional structure, the attribute of polymer, colloid and surfactant is had concurrently.By graphene oxide and carbon
Nanotube, which is assembled into three-dimensional manometer carbon hybrid structure, has huge specific surface area, overcomes one-dimensional CNT and two-dimentional stone
Anisotropy of the black alkene in terms of 26S Proteasome Structure and Function, fundamentally solves nano-carbon material aggregation in use and heap
Block problem.Particularly CNT-graphene oxide hybrid materials be applicable thermal reduction and make the characteristics of electronation its structure and
Performance has very big regulation and control space.At present, the method for manufacture CNT-graphene oxide hybrid materials mainly has following two
Kind：（1）CNT-graphene hybrid materials are successively grown on base material using two step CVDs of different catalysts, this
The method of kind can cause hybrid materials internal residual metallic catalyst and strong-hydrophobicity, and follow-up transition process inevitably influences
Nano-sized carbon hybrid structure and performance；（2）CNT and graphene oxide in aqueous phase direct-assembling into aeroge, CNT
π-π interactions are only existed between graphene oxide, the self-maintaining of this full carbon aerogels still needs further raising.
Pickering emulsions refer to solids self-assemble in two-phase liquid surface and stablize the multiphase body at the interface
System, CNT disclosed by the invention-graphene oxide hybrid materials make use of CNT and graphene oxide to exist
Pickering system oil-water two-phase interfaces self assembling processes, obtain a kind of high self-maintaining three-dimensional full carbon nano hybrid structure,
The fields such as Industrial Catalysis, electrochemical capacitor, thermal interfacial material and phase-change material have vast potential for future development.
The content of the invention
The problem of existing for prior art, the present invention provides a kind of CNT-graphene oxide hybrid three-dimensional material
Preparation method, it is therefore an objective to using graphene oxide surfactant properties, graphene oxide is assembled into CNT
For amphipathic controllable Pickering system stabilizers, driven using oil phase and the reduction of aqueous phase interface free energy as self assembling process
Power formation oil-in-water emulsion systems, the nano-sized carbon hybrid materials that CNT and graphene oxide are assembled into are coated on oil droplet table
After face, freeze-dried and removal oil phase, CNT-graphene oxide hybrid materials of full carbon structure are obtained, are retained simultaneously
The features of graphene oxide and CNT, with adjustable electric conductivity, thermal conductivity and three-dimensional macro morphology, prepare work
Skill is easy, with low cost.
Realize that the technical scheme of the object of the invention is followed the steps below：
（1）By graphene oxide in water ultrasonic disperse 30 ~ 60 minutes, obtain graphene oxide dispersion；
（2）CNT is added to step（1）In gained graphene oxide dispersion, ultrasonic disperse is obtained after 2 ~ 3 hours
To CNT-graphene oxide dispersion, it is 2-6 to add acid regulation dispersion pH value；
（3）Using hydrophobic organic compound as oil phase, it is added into step（2）Gained CNT-graphene oxide point
Granular media system, is warming up to 45 ~ 50oC, ultrasonic disperse 4 ~ 6 hours obtains the stable oil-in-water type of CNT-graphene oxide
Pickering emulsions；
（4）By step（3）The stable oil-in-water type Pickering emulsions of gained CNT-graphene oxide are cooled to room
Temperature, after being handled 12 ~ 14 hours through liquid-nitrogen freeze drying, obtains by the organic matter oil droplet of CNT-graphene oxide cladding, goes
Except the organic matter as oil phase, preliminary CNT-graphene oxide hybrid materials are obtained；
（5）Using thermal reduction or chemical reduction method to step（4）Preliminary CNT-the graphene oxide of gained mixes material
Material is reduced, and obtains the controllable CNT-graphene oxide hybrid materials of surface nature, electric conductivity, heat conductivility.
Wherein, step（1）A diameter of 20 μm -100 μm of described graphene oxide, the concentration of graphene oxide dispersion
For 0.1mg/ml-4mg/ml.
Step（2）Described CNT is that surface carboxyl groups are carbon nano-tube modified, surface amino groups are carbon nano-tube modified or table
Face hydroxyl modified CNT, it is single wall, double-walled or multi-walled carbon nanotube.
Step（2）Described graphene oxide and the weight ratio of CNT are 3 ~ 1:1
Step（2）Described acid is hydrochloric acid or acetic acid.
Step（3）Described hydrophobic organic compound is chloroform, carbon tetrachloride, toluene or benzyl chloride；When described hydrophobicity
When organic matter is chloroform, carbon tetrachloride or toluene, step（4）Described in removal as the organic matter of oil phase method be vacuum
Dry；When described hydrophobic organic compound is benzyl chloride, step（4）Described in removal as the organic matter of oil phase method
To be dried in vacuo after being washed 4 times using ethanol as solvent.
Step（5）The reduction temperature of described thermal reduction method is 200-800 oC, the recovery time is 0.5-4 hours.
Step（5）Described chemical reduction method is that, using sodium borohydride, hydrazine hydrate as reducing agent, the reduction reaction time is
0.5-8 hours, reduction temperature was 25oC-80 oC。
Compared with prior art, the features of the present invention and beneficial effect are：
（1）The present invention is, using the amphipathic of graphene oxide, to make CNT dispersed in water, mutual by π-π
Effect and oil-water interfaces free energy reduce driving CNT and graphene oxide is self-assembled into as with well self-maintaining three
Tie up nano-sized carbon hybrid materials.
（2）CNT-graphene oxide hybrid materials had both had the polar active group of graphene oxide, had carbon again
The structure and high length-diameter ratio of nanotube（As shown in Figure 1）, thus with high-specific surface area, the highly conductive, capacity of heat transmission.
（3）CNT-graphene oxide hybrid materials have full carbon structure, and its performance can be by controlling graphene oxide
Size, it is adjusted with CNT ratio and consumption and reducing degree.
（4）Equipment is simple needed for of the invention, with low cost, and technological operation is convenient.
Brief description of the drawings
Fig. 1 is the infrared spectrum of the CNT-graphene oxide hybrid three-dimensional material prepared in the embodiment of the present invention 1
Figure；
Fig. 2 is the XRD spectrum of the CNT-graphene oxide hybrid three-dimensional material prepared in the embodiment of the present invention 1；
Fig. 3 is the optical photograph of the CNT-graphene oxide hybrid three-dimensional material prepared in the embodiment of the present invention 1.
Embodiment
Following examples are that the present invention is further illustrated, chloroform, carbon tetrachloride, toluene and the benzyl used in embodiment
Base chlorine is commercial products.
The surface carboxyl groups that are used in the embodiment of the present invention are carbon nano-tube modified, surface amino groups are carbon nano-tube modified and surface hydroxyl
Carbon nano-tube modified base is commercial products, wherein, single-walled nanotube specific surface area>140m2/ g, the ratio surface of double-walled nanotubes
Product>350m2/ g, the specific surface area of multi-walled carbon nanotube>500m2/g；A diameter of 20 μm of the graphene oxide that the present embodiment is used-
100μm。
The ultrasonic field working frequency used in the embodiment of the present invention is 45kHz, and power is 100W.
Embodiment 1
The preparation method of the CNT of the present embodiment-graphene oxide hybrid three-dimensional material is followed the steps below：
（1）By 2g graphene oxides in 2000ml water ultrasonic disperse 30 minutes, obtain 1mg/ml graphene oxides disperse
Liquid；
（2）1g carboxyl modified CNTs are added to step（1）In gained graphene oxide dispersion, ultrasonic disperse 2
After hour, CNT-graphene oxide dispersion is obtained, it is 2-6 to add hydrochloric acid regulation dispersion pH value；
（3）Using toluene as oil phase, it is added into step（2）Gained CNT-graphene oxide dispersion, rises
Temperature is to 45 oC, ultrasonic disperse 4 hours obtains the stable oil-in-water type Pickering of carboxyl modified CNT-graphene oxide
Emulsion；
（4）By step（3）The stable oil-in-water type Pickering breasts of gained carboxyl modified CNT-graphene oxide
Liquid is cooled to room temperature, after being handled 14 hours through liquid-nitrogen freeze drying, obtains by the organic matter oil of CNT-graphene oxide cladding
Drop, removes the organic matter as oil phase, obtains preliminary carboxyl modified CNT-graphene oxide hybrid materials；
（5）Using thermal reduction method to step（4）The preliminary carboxyl modified CNT-graphene oxide hybrid materials of gained
Reduced, obtain the controllable carboxyl modified CNT-graphene oxide of surface nature, electric conductivity, heat conductivility and mix
Material, its electrical conductivity is 0.1Sm-1, specific surface area is 3.5m2g-1, thermal conductivity is 4.6Wm-1K-1；Its infrared spectrogram such as Fig. 1 institutes
Show, as can be seen from Figure 1 gained carboxyl modified CNT-active functional group in graphene oxide hybrid materials surface；Its
XRD was as shown in Fig. 2 CNT-graphene oxide hybrid materials both had in 2 θ=25.9 as can be seen from Figure 2oConduction
Graphite-structure, and in 2 θ=21.5oForm new structure, thus the hybrid materials have high-specific surface area, it is highly conductive, lead
Heat energy power；Its optical photograph is as shown in figure 3, it has hybrid three-dimensional structure.
Embodiment 2
The preparation method of the CNT of the present embodiment-graphene oxide hybrid three-dimensional material is followed the steps below：
（1）By 2g graphene oxides in 2000ml water ultrasonic disperse 60 minutes, obtain 1mg/ml graphene oxides disperse
Liquid；
（2）1g hydroxyl modified CNTs are added to step（1）In gained graphene oxide dispersion, ultrasonic disperse 3
After hour, hydroxyl modified CNT-graphene oxide dispersion is obtained, it is 2-6 to add acetic acid regulation dispersion pH value；
（3）Using chloroform as oil phase, it is added into step（2）Gained CNT-graphene oxide dispersion, rises
Temperature is to 50 oC, ultrasonic disperse 6 hours obtains the stable oil-in-water type Pickering of hydroxyl modified CNT-graphene oxide
Emulsion；
（4）By step（3）The stable oil-in-water type Pickering breasts of gained hydroxyl modified CNT-graphene oxide
Liquid is cooled to room temperature, after being handled 12 hours through liquid-nitrogen freeze drying, obtains by hydroxyl modified CNT-graphene oxide cladding
Organic matter oil droplet, removes the organic matter as oil phase, obtains preliminary hydroxyl modified CNT-graphene oxide hybrid materials；
（5）Using chemical reduction method to step（4）The preliminary hydroxyl modified CNT-graphene oxide of gained mixes material
Material is reduced, and is obtained the controllable hydroxyl modified CNT-graphene oxide of surface nature, electric conductivity, heat conductivility and is mixed
Miscellaneous material, its electrical conductivity is 3.2Sm-1, specific surface area is 7.1m2g-1, thermal conductivity is 2.6Wm-1K-1
Embodiment 3
The preparation method of the CNT of the present embodiment-graphene oxide hybrid three-dimensional material is followed the steps below：
（1）By 1.5g graphene oxides in 2000ml water ultrasonic disperse 45 minutes, obtain 0.75mg/ml graphene oxides
Dispersion liquid；
（2）The amido modified CNTs of 0.5g are added to step（1）In gained graphene oxide dispersion, ultrasonic disperse
After 2 hours, amido modified CNT-graphene oxide dispersion is obtained, it is 2- to add hydrochloric acid regulation dispersion pH value
6；
（3）Using carbon tetrachloride as oil phase, it is added into step（2）Gained CNT-graphene oxide dispersion
System, is warming up to 48 oC, ultrasonic disperse 5 hours obtains the stable oil-in-water type of amido modified CNT-graphene oxide
Pickering emulsions；
（4）By step（3）The stable oil-in-water type Pickering breasts of the amido modified CNT of gained-graphene oxide
Liquid is cooled to room temperature, after being handled 13 hours through liquid-nitrogen freeze drying, obtains by amido modified CNT-graphene oxide cladding
Organic matter oil droplet, removes the organic matter as oil phase, obtains preliminary amido modified CNT-graphene oxide hybrid materials；
（5）Using thermal reduction method to step（4）The preliminary amido modified CNT-graphene oxide hybrid materials of gained
Reduced, obtain the controllable amido modified CNT-graphene oxide of surface nature, electric conductivity, heat conductivility and mix
Material, its electrical conductivity is 0.38Sm-1, specific surface area is 2.5m2g-1, thermal conductivity is 6.1Wm-1K-1
Embodiment 4
The preparation method of the CNT of the present embodiment-graphene oxide hybrid three-dimensional material is followed the steps below：
（1）By 2g graphene oxides in 2000ml water ultrasonic disperse 30 minutes, obtain 1mg/ml graphene oxides disperse
Liquid；
（2）2g carboxyl modified CNTs are added to step（1）In gained graphene oxide dispersion, ultrasonic disperse 2
After hour, carboxyl modified CNT-graphene oxide dispersion is obtained, it is 2-6 to add acetic acid regulation dispersion pH value；
（3）Using benzyl chloride as oil phase, it is added into step（2）Gained CNT-graphene oxide dispersion,
It is warming up to 45 oC, ultrasonic disperse 4 hours obtains the stable oil-in-water type of carboxyl modified CNT-graphene oxide
Pickering emulsions；
（4）By step（3）The stable oil-in-water type Pickering breasts of gained carboxyl modified CNT-graphene oxide
Liquid is cooled to room temperature, after being handled 14 hours through liquid-nitrogen freeze drying, obtains by carboxyl modified CNT-graphene oxide cladding
Organic matter oil droplet, removes the organic matter as oil phase, obtains preliminary carboxyl modified CNT-graphene oxide hybrid materials；
（5）Using chemical reduction method to step（4）The preliminary carboxyl modified CNT-graphene oxide of gained mixes material
Material is reduced, and is obtained the controllable carboxyl modified CNT-graphene oxide of surface nature, electric conductivity, heat conductivility and is mixed
Miscellaneous material, its electrical conductivity is 0.75Sm-1, specific surface area is 1.9m2g-1, thermal conductivity is 7.6Wm-1K-1。
Claims (8)
1. the preparation method of a kind of CNT-graphene oxide hybrid three-dimensional material, it is characterised in that enter according to following steps
OK：
（1）By graphene oxide in water ultrasonic disperse 30 ~ 60 minutes, obtain graphene oxide dispersion；
（2）CNT is added to step（1）In gained graphene oxide dispersion, ultrasonic disperse obtains carbon after 2 ~ 3 hours
Nanotube-graphene oxide dispersion, it is 2-6 to add acid regulation dispersion pH value；
（3）Using hydrophobic organic compound as oil phase, it is added into step（2）Gained CNT-graphene oxide dispersion
System, is warming up to 45 ~ 50oC, ultrasonic disperse 4 ~ 6 hours obtains the stable oil-in-water type of CNT-graphene oxide
Pickering emulsions；
（4）By step（3）The stable oil-in-water type Pickering emulsions of gained CNT-graphene oxide are cooled to room temperature, pass through
After liquid-nitrogen freeze drying is handled 12 ~ 14 hours, obtain by the organic matter oil droplet of CNT-graphene oxide cladding, remove and make
For the organic matter of oil phase, preliminary CNT-graphene oxide hybrid materials are obtained；
（5）Using thermal reduction or chemical reduction method to step（4）The preliminary CNT of gained-graphene oxide hybrid materials enter
Row reduction, obtains the controllable CNT-graphene oxide hybrid materials of surface nature, electric conductivity, heat conductivility.
2. a kind of preparation method of CNT according to claim 1-graphene oxide hybrid three-dimensional material, its feature
It is step（1）A diameter of 20-100 μm of described graphene oxide, the concentration of graphene oxide dispersion is 0.1mg/mL
-4mg/mL 。
3. a kind of preparation method of CNT according to claim 1-graphene oxide hybrid three-dimensional material, its feature
It is step（2）Described CNT is that surface carboxyl groups are carbon nano-tube modified, surface amino groups are carbon nano-tube modified or surface hydroxyl
Base is carbon nano-tube modified, and it is single wall, double-walled or multi-walled carbon nanotube.
4. a kind of preparation method of CNT according to claim 1-graphene oxide hybrid three-dimensional material, its feature
It is step（2）Described graphene oxide and the weight ratio of CNT are 3 ~ 1:1.
5. a kind of preparation method of CNT according to claim 1-graphene oxide hybrid three-dimensional material, its feature
It is step（2）Described acid is hydrochloric acid or acetic acid.
6. a kind of preparation method of CNT according to claim 1-graphene oxide hybrid three-dimensional material, its feature
It is step（3）Described hydrophobic organic compound is chloroform, carbon tetrachloride, toluene or benzyl chloride；When described hydrophobicity is organic
When thing is chloroform, carbon tetrachloride or toluene, step（4）Described in removal it is dry for vacuum as the method for the organic matter of oil phase
It is dry；When described hydrophobic organic compound is benzyl chloride, step（4）Described in removal as the method for the organic matter of oil phase be
It is dried in vacuo after being washed 4 times using ethanol as solvent.
7. a kind of preparation method of CNT according to claim 1-graphene oxide hybrid three-dimensional material, its feature
It is step（5）The reduction temperature of described thermal reduction method is 200-800 DEG C, and the recovery time is 0.5-4 hours.
8. a kind of preparation method of CNT according to claim 1-graphene oxide hybrid three-dimensional material, its feature
It is step（5）Described chemical reduction method is that the reduction reaction time is 0.5- using sodium borohydride, hydrazine hydrate as reducing agent
8 hours, reduction temperature was 25 DEG C -80 DEG C.
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| CN114539981A (en) * | 2020-11-27 | 2022-05-27 | 中国科学院苏州纳米技术与纳米仿生研究所南昌研究院 | Graphene/carbon nanotube composite low-temperature phase change material, preparation method and application |
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