CN106241779A - 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 PDF

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CN106241779A
CN106241779A CN201610569907.9A CN201610569907A CN106241779A CN 106241779 A CN106241779 A CN 106241779A CN 201610569907 A CN201610569907 A CN 201610569907A CN 106241779 A CN106241779 A CN 106241779A
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graphene oxide
cnt
dimensional
hybrid
oil
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CN106241779B (en
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王柏臣
刘永娜
李俊杰
高禹
李伟
马克明
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沈阳航空航天大学
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    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2204/00Structure or properties of graphene
    • C01B2204/20Graphene characterized by its properties
    • C01B2204/32Size or surface area
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    • C01P2002/70Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00Crystal-structural characteristics
    • C01P2002/80Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
    • C01P2002/82Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by IR- or Raman-data

Abstract

The invention belongs to field of nanometer material technology, be specifically related to the preparation method of a kind of CNT graphene oxide hybrid three-dimensional material.The present invention is to utilize the surfactant properties of graphene oxide, graphene oxide and CNT are assembled into amphipathic controlled Pickering system stabilizers, reduce using oil phase and aqueous phase interface free energy and form oil-in-water emulsion systems as self assembling process driving force, the nano-sized carbon hybrid materials that CNT and graphene oxide are assembled into are coated on oil droplets, freeze-dried and remove after oil phase, obtain the CNT graphene oxide hybrid materials of full carbon structure, remain the features of graphene oxide and CNT simultaneously, there is adjustable electric conductivity, heat conductivity and three-dimensional macro morphology, preparation technology is easy, with low cost.

Description

A kind of preparation method of CNT-graphene oxide hybrid three-dimensional material
Technical field
The invention belongs to field of nanometer material technology, be specifically related to a kind of CNT-graphene oxide hybrid three-dimensional material Preparation method.
Background technology
With CNT and Graphene, the nano-carbon material as representative has huge specific surface area, excellent mechanical property With conduction, heat conductivility, receive much attention in electronic information, novel energy, biology and field of functional materials in recent years.Typically recognize For, material property fundamentally depends on its internal microstructure, utilizes the fundamental starting point of nano-carbon material to be that it has Have by sp2Hybrid orbital formed from threshold π key, the most widely used chemical gaseous phase deposition (CVD) method produce CNT and Graphene, on the one hand has the most complete sp2Atomic structure of carbon, thus there is the most preferably conduction, heat conductivility.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 aspect problems: (1) leads due to a peacekeeping two-dimensional structure of CNT and Graphene The function anisotropy caused;(2) high length-diameter ratio (transverse and longitudinal ratio) and stronger π-π interact and make nano-carbon material easily produce Reunite and pile up, giving full play to of serious restriction nano-carbon material performance;(3) CVD produces CNT and Graphene have There are the strongest hydrophobicity and consequent chemical inertness.
Graphene oxide is the Graphene derivative using chemical peeling to obtain, in preparation process, oxidation processes At graphenic surface, especially introduce substantial amounts of hydroxyl, epoxy radicals and carboxyl isopolarity group, forming part sp at edge3 Hydbridized carbon atoms, and not oxidized region remains in that hydrophobic sp2Hydbridized carbon atoms structure, therefore graphene oxide is being protected While staying Graphene flexibility two-dimensional structure, have the attribute of polymer, colloid and surfactant concurrently.By graphene oxide and carbon Nanotube is assembled into three-dimensional manometer carbon hybrid structure and has huge specific surface area, overcomes one-dimensional CNT and two dimension stone Ink alkene anisotropy in terms of 26S Proteasome Structure and Function, fundamentally solves nano-carbon material gathering in use and heap Block problem.Particularly the feature of the reduction of CNT-graphene oxide hybrid materials applied heat and electronation make its structure and Performance has the biggest regulation and control space.At present, the method manufacturing CNT-graphene oxide hybrid materials mainly has following two Kind: (1) uses two step CVD of different catalysts successively to grow CNT-Graphene hybrid materials on base material, this The method of kind can cause hybrid materials internal residual metallic catalyst and strong-hydrophobicity, and follow-up transition process inevitably affects Nano-sized carbon hybrid structure and performance;(2) CNT becomes aeroge, CNT with graphene oxide direct-assembling in aqueous phase And between graphene oxide, only existing π-π interaction, self-maintaining still the needing of this full carbon aerogels is improved further.
Pickering emulsion refers to that solids self-assemble is in biphase liquid surface the heterogeneous body of stablizing this 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 process, it is thus achieved that 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.
Summary of the invention
The problem existed 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 utilize the surfactant properties of graphene oxide, graphene oxide be assembled into CNT For amphipathic controlled Pickering system stabilizers, reduce using oil phase and aqueous phase interface free energy and drive as self assembling process Power forms oil-in-water emulsion systems, and the nano-sized carbon hybrid materials that CNT and graphene oxide are assembled into are coated on oil droplet table Face, freeze-dried and remove after oil phase, it is thus achieved that the CNT-graphene oxide hybrid materials of full carbon structure, retain simultaneously The features of graphene oxide and CNT, has adjustable electric conductivity, heat conductivity and three-dimensional macro morphology, prepares work Skill is easy, with low cost.
The technical scheme realizing the object of the invention follows the steps below:
(1) by graphene oxide ultrasonic disperse 30~60 minutes in water, graphene oxide dispersion is obtained;
(2) CNT is joined in step (1) gained graphene oxide dispersion, ultrasonic disperse 2~after 3 hours, Obtaining CNT-graphene oxide dispersion, adding acid regulation dispersion pH value is 2-6;
(3) using hydrophobic organic compound as oil phase, it is added into step (2) gained CNT-graphene oxide dividing Prose style free from parallelism system, is warming up to 45~50 DEG C, and ultrasonic disperse 4~6 hours obtain the oil-in-water type that CNT-graphene oxide is stable Pickering emulsion;
(4) water stable for step (3) gained CNT-graphene oxide is protected oil type Pickering emulsion and be cooled to room Temperature, after liquid-nitrogen freeze drying processes 12~14 hours, it is thus achieved that by the Organic substance oil droplet of CNT-graphene oxide cladding, Remove the Organic substance as oil phase, obtain preliminary CNT-graphene oxide hybrid materials;
(5) thermal reduction or chemical reduction method CNT-graphene oxide preliminary to step (4) gained is used to mix material Material reduces, it is thus achieved that CNT-graphene oxide hybrid materials that surface nature, electric conductivity, heat conductivility are controlled.
Wherein, a diameter of 20 μm-100 μm of the graphene oxide described in step (1), the concentration of graphene oxide dispersion For 0.1mg/ml-4mg/ml.
CNT described in step (2) is that surface carboxyl groups is carbon nano-tube modified, surface amino groups is carbon nano-tube modified or table Face hydroxyl modified CNT, it is single wall, double-walled or multi-walled carbon nano-tubes.
Graphene oxide described in step (2) is 3~1:1 with the weight ratio of CNT
Acid described in step (2) is hydrochloric acid or acetic acid.
Hydrophobic organic compound described in step (3) is chloroform, carbon tetrachloride, toluene or benzyl chloride;When described hydrophobicity When Organic substance is chloroform, carbon tetrachloride or toluene, the organic method as oil phase of removing described in step (4) is vacuum It is dried;When described hydrophobic organic compound is benzyl chloride, the removal described in step (4) is as the organic method of oil phase For using ethanol to be vacuum dried after washing 4 times as solvent.
The reduction temperature of the thermal reduction method described in step (5) is 200-800 DEG C, and the recovery time is 0.5-4 hour.
Chemical reduction method described in step (5) is 0.5-8 hour, reduction temperature was 25 DEG C-80 DEG C.
Compared with prior art, the feature of the present invention and providing the benefit that:
(1) present invention is utilize graphene oxide amphipathic, makes 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 having the most self-maintaining three Dimension nano-sized carbon hybrid materials.
(2) CNT-graphene oxide hybrid materials had both had the polar active group of graphene oxide, had again carbon The structure of nanotube and high length-diameter ratio (as shown in Figure 1), thus there is high-specific surface area, high connductivity, the capacity of heat transmission.
(3) CNT-graphene oxide hybrid materials have full carbon structure, and its performance can be by controlling graphene oxide Size and CNT ratio and consumption and reducing degree are adjusted.
(4) equipment needed thereby of the present invention is simple, with low cost, and technological operation is convenient.
Accompanying drawing explanation
Fig. 1 is the infrared spectrum of the CNT-graphene oxide hybrid three-dimensional material of preparation in the embodiment of the present invention 1 Figure;
Fig. 2 is the XRD figure spectrum of the CNT-graphene oxide hybrid three-dimensional material of preparation in the embodiment of the present invention 1;
Fig. 3 is the optical photograph of the CNT-graphene oxide hybrid three-dimensional material of preparation in the embodiment of the present invention 1.
Detailed description of the invention
Following example are to further illustrate the present invention, chloroform, carbon tetrachloride, toluene and the benzyl used in embodiment Base chlorine is commercial products.
The surface carboxyl groups used in the embodiment of the present invention is carbon nano-tube modified, surface amino groups is carbon nano-tube modified and surface hydroxyl Base is carbon nano-tube modified is commercial products, wherein, single-walled nanotube specific surface area > 140m2/ g, the specific surface of double-walled nanotubes Long-pending > 350m2/ g, the specific surface area of multi-walled carbon nano-tubes > 500m2/g;A diameter of 20 μm of graphene oxide that the present embodiment uses- 100μm。
The ultrasonic field operating 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 follows the steps below:
(1) by 2g graphene oxide ultrasonic disperse 30 minutes in 2000ml water, the dispersion of 1mg/ml graphene oxide is obtained Liquid;
(2) 1g carboxyl modified CNT is joined in step (1) gained graphene oxide dispersion, ultrasonic disperse 2 After hour, obtaining CNT-graphene oxide dispersion, adding hydrochloric acid regulation dispersion pH value is 2-6;
(3) using toluene as oil phase, it is added into step (2) gained CNT-graphene oxide dispersion, rises Warm to 45 DEG C, ultrasonic disperse 4 hours, obtain oil-in-water type Pickering that carboxyl modified CNT-graphene oxide is stable Emulsion;
(4) water stable for step (3) gained carboxyl modified CNT-graphene oxide is protected oil type Pickering breast Liquid is cooled to room temperature, after liquid-nitrogen freeze drying processes 14 hours, it is thus achieved that by the Organic substance of CNT-graphene oxide cladding Oil droplet, removes the Organic substance as oil phase, obtains preliminary carboxyl modified CNT-graphene oxide hybrid materials;
(5) use thermal reduction method to step (4) gained preliminary carboxyl modified CNT-graphene oxide hybrid materials Reduce, it is thus achieved that the controlled carboxyl modified CNT-graphene oxide of surface nature, electric conductivity, heat conductivility mixes 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 institute Show, as can be seen from Figure 1 gained carboxyl modified CNT-active functional group in graphene oxide hybrid materials surface;Its XRD figure as in figure 2 it is shown, as can be seen from Figure 2 CNT-graphene oxide hybrid materials both there is leading in 2 θ=25.9 ° Electro-graphitic structure, defines again new structure in 2 θ=21.5 °, the most described hybrid materials have high-specific surface area, high connductivity, The capacity of heat transmission;Its optical photograph is as it is shown on 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 follows the steps below:
(1) by 2g graphene oxide ultrasonic disperse 60 minutes in 2000ml water, the dispersion of 1mg/ml graphene oxide is obtained Liquid;
(2) 1g hydroxyl modified CNT is joined in step (1) gained graphene oxide dispersion, ultrasonic disperse 3 After hour, obtaining hydroxyl modified CNT-graphene oxide dispersion, adding acetic acid regulation dispersion pH value is 2-6;
(3) using chloroform as oil phase, it is added into step (2) gained CNT-graphene oxide dispersion, rises Warm to 50 DEG C, ultrasonic disperse 6 hours, obtain oil-in-water type Pickering that hydroxyl modified CNT-graphene oxide is stable Emulsion;
(4) water stable for step (3) gained hydroxyl modified CNT-graphene oxide is protected oil type Pickering breast Liquid is cooled to room temperature, after liquid-nitrogen freeze drying processes 12 hours, it is thus achieved that by hydroxyl modified CNT-graphene oxide cladding Organic substance oil droplet, removes the Organic substance as oil phase, obtains preliminary hydroxyl modified CNT-graphene oxide hybrid materials;
(5) use chemical reduction method that step (4) gained preliminary hydroxyl modified CNT-graphene oxide is mixed material Material reduces, it is thus achieved that the controlled hydroxyl modified CNT-graphene oxide of surface nature, electric conductivity, heat conductivility mixes 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 follows the steps below:
(1) by 1.5g graphene oxide ultrasonic disperse 45 minutes in 2000ml water, 0.75mg/ml graphene oxide is obtained Dispersion liquid;
(2) amido modified for 0.5g CNT is joined in step (1) gained graphene oxide dispersion, ultrasonic disperse After 2 hours, obtaining amido modified CNT-graphene oxide dispersion, adding hydrochloric acid regulation dispersion pH value is 2- 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 DEG C, and ultrasonic disperse 5 hours obtains the oil-in-water type that amido modified CNT-graphene oxide is stable Pickering emulsion;
(4) water stable for amido modified for step (3) gained CNT-graphene oxide is protected oil type Pickering breast Liquid is cooled to room temperature, after liquid-nitrogen freeze drying processes 13 hours, it is thus achieved that by amido modified CNT-graphene oxide cladding Organic substance oil droplet, removes the Organic substance as oil phase, obtains preliminary amido modified CNT-graphene oxide hybrid materials;
(5) thermal reduction method amido modified CNT-graphene oxide hybrid materials preliminary to step (4) gained are used Reduce, it is thus achieved that the controlled amido modified CNT-graphene oxide of surface nature, electric conductivity, heat conductivility mixes 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 follows the steps below:
(1) by 2g graphene oxide ultrasonic disperse 30 minutes in 2000ml water, the dispersion of 1mg/ml graphene oxide is obtained Liquid;
(2) 2g carboxyl modified CNT is joined in step (1) gained graphene oxide dispersion, ultrasonic disperse 2 After hour, obtaining carboxyl modified CNT-graphene oxide dispersion, adding acetic acid regulation dispersion pH value is 2-6;
(3) using benzyl chloride as oil phase, it is added into step (2) gained CNT-graphene oxide dispersion, It is warming up to 45 DEG C, ultrasonic disperse 4 hours, obtain the oil-in-water type that carboxyl modified CNT-graphene oxide is stable Pickering emulsion;
(4) water stable for step (3) gained carboxyl modified CNT-graphene oxide is protected oil type Pickering breast Liquid is cooled to room temperature, after liquid-nitrogen freeze drying processes 14 hours, it is thus achieved that by carboxyl modified CNT-graphene oxide cladding Organic substance oil droplet, removes the Organic substance as oil phase, obtains preliminary carboxyl modified CNT-graphene oxide hybrid materials;
(5) use chemical reduction method that step (4) gained preliminary carboxyl modified CNT-graphene oxide is mixed material Material reduces, it is thus achieved that the controlled carboxyl modified CNT-graphene oxide of surface nature, electric conductivity, heat conductivility mixes 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 CNT-graphene oxide hybrid three-dimensional material, it is characterised in that enter according to following steps OK:
(1) by graphene oxide ultrasonic disperse 30 ~ 60 minutes in water, graphene oxide dispersion is obtained;
(2) being joined by CNT in step (1) gained graphene oxide dispersion, ultrasonic disperse, after 2 ~ 3 hours, obtains carbon Nanotube-graphene oxide dispersion, adding acid regulation dispersion pH value is 2-6;
(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, obtain the oil-in-water type that CNT-graphene oxide is stable Pickering emulsion;
(4) water stable for step (3) gained CNT-graphene oxide is protected oil type Pickering emulsion and be cooled to room temperature, warp After liquid-nitrogen freeze drying processes 12 ~ 14 hours, it is thus achieved that by the Organic substance oil droplet of CNT-graphene oxide cladding, remove and make For the Organic substance of oil phase, obtain preliminary CNT-graphene oxide hybrid materials;
(5) thermal reduction or chemical reduction method CNT preliminary to step (4) gained-graphene oxide hybrid materials are used to enter Row reduction, it is thus achieved that CNT-graphene oxide hybrid materials that surface nature, electric conductivity, heat conductivility are controlled.
The preparation method of a kind of CNT the most according to claim 1-graphene oxide hybrid three-dimensional material, its feature Being a diameter of 20-100 μm of graphene oxide described in step (1), the concentration of graphene oxide dispersion is 0.1mg/ ml-4mg/ml。
The preparation method of a kind of CNT the most according to claim 1-graphene oxide hybrid three-dimensional material, its feature It is that the CNT described in step (2) is that surface carboxyl groups is carbon nano-tube modified, surface amino groups is carbon nano-tube modified or surface hydroxyl Base is carbon nano-tube modified, and it is single wall, double-walled or multi-walled carbon nano-tubes.
The preparation method of a kind of CNT the most according to claim 1-graphene oxide hybrid three-dimensional material, its feature It is that graphene oxide described in step (2) is 3 ~ 1:1 with the weight ratio of CNT.
The preparation method of a kind of CNT the most according to claim 1-graphene oxide hybrid three-dimensional material, its feature It is that the acid described in step (2) is hydrochloric acid or acetic acid.
The preparation method of a kind of CNT the most according to claim 1-graphene oxide hybrid three-dimensional material, its feature It is that the hydrophobic organic compound described in step (3) is chloroform, carbon tetrachloride, toluene or benzyl chloride;When described hydrophobicity is organic When thing is chloroform, carbon tetrachloride or toluene, the organic method as oil phase of removing described in step (4) is that vacuum is done Dry;When described hydrophobic organic compound is benzyl chloride, the organic method as oil phase of removing described in step (4) is Ethanol is used to be vacuum dried after washing 4 times as solvent.
The preparation method of a kind of CNT the most according to claim 1-graphene oxide hybrid three-dimensional material, its feature The reduction temperature being the thermal reduction method described in step (5) is 200-800 oC, the recovery time is 0.5-4 hour.
The preparation method of a kind of CNT the most according to claim 1-graphene oxide hybrid three-dimensional material, its feature It is that the chemical reduction method described in step (5) is that the reduction reaction time is 0.5-using sodium borohydride, hydrazine hydrate as reducing agent 8 hours, reduction temperature was 25oC-80℃。
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