CN106582533A - Amino and thiol-modified graphene/carbon nanotube composite material and preparation method therefor - Google Patents
Amino and thiol-modified graphene/carbon nanotube composite material and preparation method therefor Download PDFInfo
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- CN106582533A CN106582533A CN201710000442.XA CN201710000442A CN106582533A CN 106582533 A CN106582533 A CN 106582533A CN 201710000442 A CN201710000442 A CN 201710000442A CN 106582533 A CN106582533 A CN 106582533A
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- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
- B01J20/205—Carbon nanostructures, e.g. nanotubes, nanohorns, nanocones, nanoballs
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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Abstract
The invention discloses an amino and thiol-modified graphene/carbon nanotube composite material and a preparation method therefor. The preparation method comprises the steps of performing ultrasonic dispersion on purified carbon nanotubes in absolute ethyl alcohol, and then mixing with an absolute ethyl alcohol dispersion liquid comprising graphene oxide in an ultrasonic manner; next, performing suction filtration and drying to obtain a graphene/carbon nanotube composite material; then dispersing the composite material into a mixed solution comprising absolute ethyl alcohol, acetic acid, acetone and 3-mercaptopropyl trimethoxy silane; pumping nitrogen for protection, reacting, and then performing suction filtration, separating and drying; then dispersing into an absolute ethyl alcohol solution; and adding hydrazine under the protection of nitrogen, reacting and then washing by water and absolute ethyl alcohol, and performing vacuum drying to obtain the amino and thiol-modified graphene/carbon nanotube composite material. The composite material has nanometer dissensions and relatively large specific surface area; rapid separation of the composite material can be realized through a simple centrifuging or suction filtration operation; in addition, multiple kinds of active groups are on the surface of the composite material; and through a complexing action between the amino and thiol, heavy metal ions and organic pollutants in polluted water can be adsorbed.
Description
Technical field
The invention belongs to technical field of nano material, and in particular to mercapto and amido modified graphene/carbon nano-tube are multiple
The technology of preparing of condensation material.
Background technology
Two scientist Andre Geim of Japanese Electronic Speculum scholar Iijima S and Univ Manchester UK,
Konstantin Novoselov had found two kinds of new carbon of CNT and Graphene first respectively at 1991 and 2004
Material, this kind of new carbon is with unique space structure, excellent electric conductivity, large specific surface area, lighter mass density
And strong effect causes rapidly the extensive concern of domestic and international each field scholar and contaminant molecule between.But CNT and stone
Black alkene surface has hydrophobicity and high surface energy, and winding of easily reuniting each other is folded, and is not readily dissolved in all kinds of solvents, therefore
Greatly limit using receiving.It is in order to improve the dispersibility of two kinds of new carbons while improving its application power, general to adopt
Chemical modification and physical adsorption process.Chemical modification is due to being greatly improved its dispersibility, and completely retains its mechanics, electricity
Etc. performance, extensive concern is therefore suffered from.And the organic polymer of physical absorption surface adsorption, biomacromolecule easily come off, heat
Stability is poor.Additionally, chemical modification generally introduces one or more functional group on its surface, but it is poor to there is group introducing rate, imitates
The low shortcoming of rate, therefore if two kinds of groups being introduced on its surface can then be greatly enhanced its absorbability, improve its dispersion
Property.Based on considerations above, Graphene and CNT are prepared into into composite first, then amino and sulfur are introduced on its surface
Alcohol radical Liang Zhong functional groups, can both improve the dispersibility of material, improve its group introducing rate again, therefore cause part in recent years
Scholar notes.
Patent [CN104250005A] discloses a kind of preparation method of amination graphene aeroge and application, will oxidation
Graphene dispersing solution is uniformly mixed to get graphene oxide liquid mixture with amine water soluble compound, by graphene oxide liquid mixture
Irradiation reaction is carried out with high-energy ray irradiation under anaerobic and obtains amido modified Graphene hydrogel, lyophilization or super faced
Boundary carbon dioxide is dried and obtains final product graphene aerogel, this kind of material porous and even structure, can be used for the absorption of organic solvent.Specially
It is 340～350 DEG C in temperature using supercritical reaction kettle addition ethylenediamine that sharp [CN101774573] is disclosed a kind of, and pressure is 6
～11MPa obtains the CNT after amination, improves the introducing efficiency of nitrogen functional group.Document [Wu Lirui, a blue heart, in
Fly, aminated carbon nano tube/graphene aerogel PARA FORMALDEHYDE PRILLS(91,95) absorption research [J]. China Environmental Science. 2015,35
(11):3251-3256.] report with amido modified carbon nano tube/graphene composite and for indoor pollutant formaldehyde
Absorption research, also achieve good result.
It is more complicated to there is method of modifying in the amination reported at present, the method for Thiolation graphene/carbon nano-tube,
Introduce the shortcomings of functional group's efficiency is low, functionalization degree is not high.Additionally due to introducing functional group efficiency is low, graphite is equally existed
The shortcomings of alkene/carbon nano tube compound material surface active groups are few, absorbability is weak.
The content of the invention
It is an object of the invention to provide the Graphene/carbon nanotube composite material and preparation of a kind of amino and mercapto modification
Method.
The present invention be amino and mercapto it is grapheme modified/carbon nano tube compound material and preparation method, the composite wood
Material is made up of Graphene and CNT, and one layer of thin film containing amino and thiol group is wrapped up on surface.
The preparation method of the Graphene/carbon nanotube composite material of amino and mercapto modification, its step is：
（1）CNT is distributed in mixed acid solution, is reacted 1～3 hour at 60～80 DEG C, subsequent filtration washing, 80～120
DEG C 8 ~ 12h of drying, obtains carbon pipe after purification；
（2）Native graphite is added in the concentrated sulphuric acid of mass fraction 98%, mechanical agitation is dissolved completely up to graphite, then
Add sodium nitrate and potassium permanganate temperature to be maintained at 0 ~ 10 DEG C, continue stirring 2.5 ~ 4 hours, mixture is put into into 35 DEG C of constant temperature
In water-bath, deionized water is slowly added to, mixture is put into into 20 ~ 40 points of mechanical agitation in 90 ~ 100 DEG C of water-bath subsequently
Clock, adds deionized water to be diluted to 600ml, stirs 5-15 minutes, add the hydrogen peroxide of mass fraction 30%, by product with 8000-
Solid matter after centrifugation is dispersed in 30 ~ 60 points of sonic oscillation in ethanol solution by the centrifugation of 10000r/min
Clock, is vacuum dried 12 ~ 24 hours, obtains as graphene oxide；
（3）The graphene oxide and purifying carbon nano-tube of quality such as respectively weigh respectively, each ultrasound 2 hours, then by after ultrasound
CNT after purification dropwise instill in graphene oxide, continue ultrasound 30 ~ 60 minutes, using 0.45 micron membrane filter sucking filtration,
Vacuum drying obtained graphene oxide/carbon nano tube compound material after 8 ~ 12 hours；
（4）Weigh Graphene/carbon nanotube composite material to be added to equipped with dehydrated alcohol, ultrasonic vibration 5 ~ 15 minutes is passed through
Nitrogen protects simultaneously mechanical agitation 5 minutes, adds acetic acid, 3- mercaptopropyl trimethoxysilanes, stirs 12 ~ 24 hours under room temperature, after
It is continuous to add acetone to continue stirring 6 ~ 12 hours, rinsed respectively 5 ~ 10 times using ethanol and distilled water, 60 ~ 80 DEG C of vacuum drying 8 ~ 12
Hour, obtain the Graphene/carbon nanotube composite material of mercapto modification；
（5）The Graphene/carbon nanotube composite material that mercapto is modified is added in the three-necked bottle equipped with ethanol, ultrasonic vibration
5 ~ 15 minutes, lead to nitrogen protection, add hydrazine hydrate, stirred 3 ~ 5 hours with 5000 ~ 10000r/min of rotating speed, vacuum filtration is simultaneously
Deionized water is rinsed to neutrality, and 60 ~ 80 DEG C are vacuum dried 8 ~ 12 hours, obtains the graphene/carbon of amino and mercapto modification
Nanometer tube composite materials.
Usefulness of the present invention is：（1）The present invention is by the absorption property and mercaptan of Graphene/carbon nanotube composite material
The excellent dentate of base, amino combines, and makes nano composite material have heavy metal ions in sewage, organic pollution fine
The physicochemical properties of graphene oxide, CNT, functional group three are mainly combined by captivation, are a kind of good
The carrier of good function nano granule.（2）The Graphene/carbon nanotube composite material that the present invention is obtained, CNT are interspersed in
Foster graphite alkene interlayer is tightly attached at surface of graphene oxide, increases specific surface area；Graphene/carbon nano-tube is combined
The surface of material has a large amount of mercaptos and amino group, and heavy metal ion has excellent absorption and separation process, so as to have
Beneficial to removal of heavy metal ions；The preparation method process is simple of the present invention, easy to operate and mild condition prepare product absorption and hold
Amount has greatly excellent biocompatibility.There is potential using value in fields such as biological medicine, environmental conservation.
Description of the drawings
Fig. 1 is the high resolution scanning electron microscope of specific embodiment of the invention Graphene/carbon nanotube composite material
（SEM）, Fig. 2 is the high score of the Graphene/carbon nanotube composite material of amino and mercapto modification in the specific embodiment of the invention 1
Distinguish scanning electron microscope（SEM）, Fig. 3 is the graphene/carbon nanometer of amino and mercapto modification in the specific embodiment of the invention 1
Fourier-the infrared spectrogram of pipe composite.
Specific embodiment
The present invention is the Graphene/carbon nanotube composite material and preparation method of amino and mercapto modification, described compound
Material carbon nanotube is interspersed between the lamella of graphene oxide or is tightly attached on the lamella of graphene oxide, improves
The specific surface area of composite and it is loaded with amino and mercapto group on the surface of prepared composite.
Amino and mercapto it is grapheme modified/carbon nano tube compound material, be made up of Graphene and CNT, surface
One layer of thin film containing amino and thiol group of parcel.
The preparation method of the Graphene/carbon nanotube composite material of amino and mercapto modification, its step is：
（1）CNT is distributed in mixed acid solution, is reacted 1～3 hour at 60～80 DEG C, subsequent filtration washing, 80～
120 DEG C of 8 ~ 12h of drying, obtain carbon pipe after purification；
（2）Native graphite is added in the concentrated sulphuric acid of mass fraction 98%, mechanical agitation is dissolved completely up to graphite, then
Add sodium nitrate and potassium permanganate temperature to be maintained at 0 ~ 10 DEG C, continue stirring 2.5 ~ 4 hours, mixture is put into into 35 DEG C of constant temperature
In water-bath, deionized water is slowly added to, mixture is put into into 20 ~ 40 points of mechanical agitation in 90 ~ 100 DEG C of water-bath subsequently
Clock, adds deionized water to be diluted to 600ml, stirs 5-15 minutes, add the hydrogen peroxide of mass fraction 30%, by product with 8000-
Solid matter after centrifugation is dispersed in 30 ~ 60 points of sonic oscillation in ethanol solution by the centrifugation of 10000r/min
Clock, is vacuum dried 12 ~ 24 hours, obtains as graphene oxide；
（3）The graphene oxide and purifying carbon nano-tube of quality such as respectively weigh respectively, each ultrasound 2 hours, then by after ultrasound
CNT after purification dropwise instill in graphene oxide, continue ultrasound 30 ~ 60 minutes, using 0.45 micron membrane filter sucking filtration,
Vacuum drying obtained graphene oxide/carbon nano tube compound material after 8 ~ 12 hours；
（4）Weigh Graphene/carbon nanotube composite material to be added to equipped with dehydrated alcohol, ultrasonic vibration 5 ~ 15 minutes is passed through
Nitrogen protects simultaneously mechanical agitation 5 minutes, adds acetic acid, 3- mercaptopropyl trimethoxysilanes, stirs 12 ~ 24 hours under room temperature, after
It is continuous to add acetone to continue stirring 6 ~ 12 hours, rinsed respectively 5 ~ 10 times using ethanol and distilled water, 60 ~ 80 DEG C of vacuum drying 8 ~ 12
Hour, obtain the Graphene/carbon nanotube composite material of mercapto modification；
（5）The Graphene/carbon nanotube composite material that mercapto is modified is added in the three-necked bottle equipped with ethanol, ultrasonic vibration
5 ~ 15 minutes, lead to nitrogen protection, add hydrazine hydrate, stirred 3 ~ 5 hours with 5000 ~ 10000r/min of rotating speed, vacuum filtration is simultaneously
Deionized water is rinsed to neutrality, and 60 ~ 80 DEG C are vacuum dried 8 ~ 12 hours, obtains the graphene/carbon of amino and mercapto modification
Nanometer tube composite materials.
In made as described above method, the CNT is many walls or SWCN.
In made as described above method, the mixed acid solution is concentrated sulphuric acid and concentrated nitric acid composition, concentrated sulphuric acid and concentrated nitric acid
Volume ratio is 3:1.
In made as described above method, the purifying carbon nano-tube and graphene oxide mass ratio are 2:1.
In made as described above method, the mass ratio of concentrated sulphuric acid and native graphite is 50:1-80:1；Sodium nitrate and natural stone
The mass ratio of ink is 1:2-2:1.
In made as described above method, the mass ratio of potassium permanganate and native graphite is 3:1-6:1.
In made as described above method, the volume ratio of hydrogen peroxide and concentrated sulphuric acid is 1:2-1:4.
In made as described above method, the Graphene/carbon nanotube composite material and 3- mercaptopropyl trimethoxysilanes
Rate of charge be approximately (0.4 ~ 2) × 103。
In made as described above method, the throwing of the Graphene/carbon nanotube composite material and hydrazine of the mercapto modification
Material ratio about 20～30.
Embodiment 1：
The pretreatment of step 1, CNT：
By 1g original multi-walled carbon nano-tubes（It is prepared by chemical vapour deposition technique）It is distributed to 30ml concentrated sulphuric acids and 10ml concentrated nitric acids
In mixed acid solution, stirring reaction 3 hours at 60 DEG C are washed to neutrality with distillation, standby after 80 DEG C of vacuum drying 12 hours；
The preparation of step 2, graphene oxide：
The natural crystalline flake graphites of 2g are taken with electronic balance；Graduated cylinder is measured in the three-necked bottle that the concentrated sulphuric acid of 50ml pours 1000ml into, cold
But between 0 ~ 5 DEG C, load weighted 2g graphite is added in 50ml concentrated sulphuric acids, 0 ~ 5 DEG C of stirring is cooled to using ice-water bath straight
It is completely dissolved to graphite, adds 1g sodium nitrates and 6g potassium permanganate to be stirred vigorously simultaneously with certain speed, make the temperature of mixture
Degree is maintained at less than 10 DEG C and continues stirring 2.5 hours；Remove ice-water bath to be put in 35 DEG C of thermostat water bath, be slowly added to 95ml
Warm deionized water is stirred 30 minutes；Three-necked bottle is put into into stirring reaction 25 minutes in 90 DEG C of water-bath, going for warm is added
Ionized water is diluted to 280ml, and stirring added 20ml, 30% hydrogen peroxide after 5 minutes（Color is changed into golden yellow）Insulation 5 minutes, will
Product is poured in centrifuge tube and is washed with the centrifugation of 8000r/min, with barium chloride detection until in supernatant sulfate radical-free from
Son is present；Solid matter after centrifugation is put into ultrasound in ethanol solution to be vacuum dried 24 hours after 30 minutes；
The preparation of step 3, Graphene/carbon nanotube composite material：
0.1g graphene oxides are taken respectively and purifying carbon nano-tube is added separately in the three-necked bottle equipped with 100ml ethanol, respectively
Ultrasound 2 hours；Carbon pipe is dropwise instilled in graphene oxide under ultrasonication, completion of dropping continues ultrasound 30 minutes；With
0.45 micron membrane filter sucking filtration, vacuum drying grind after 8 hours and obtain graphene oxide/carbon nano tube compound material；
The preparation of step 4, thiolating Graphene/carbon nanotube composite material：
Take during 0.2g composites are added to the three-necked bottle equipped with 75ml dehydrated alcohol and shake 5 minutes, lead to nitrogen mechanical agitation 5
Add 0.5ml acetic acid, 0.1mlMPTs after minute.Stir 24 hours under room temperature；To in three-necked bottle, 25ml acetone is added to continue stirring 6 little
When, sucking filtration is neutral with alcohol rinse to washing liquid simultaneously, and 60 DEG C are vacuum dried 12 hours；
Step 5, amination, the preparation of thiolating Graphene/carbon nanotube composite material：
Composite obtained by taking 0.1g previous steps is put in the three-necked bottle equipped with 50ml ethanol and is shaken 5 minutes, leads to nitrogen machine
Tool stirring drains air in bottle for 5 minutes, adds 3.75ml hydrazine hydrates, room temperature water-bath 3 hours；Sucking filtration is simultaneously with alcohol rinse to washing
Liquid is neutrality, and 60 DEG C are vacuum dried 12 hours.
Embodiment 2：
The pretreatment of step 1, CNT：
By 2g original multi-walled carbon nano-tubes（It is prepared by chemical vapour deposition technique）It is distributed to 60ml concentrated sulphuric acids and 20ml concentrated nitric acids
In mixed acid solution, stirring reaction 3 hours at 60 DEG C are washed to neutrality with distillation, standby after 80 DEG C of vacuum drying 12 hours；
The preparation of step 2, graphene oxide：
The natural crystalline flake graphites of 4g are taken with electronic balance；Graduated cylinder is measured in the three-necked bottle that the concentrated sulphuric acid of 92ml pours 1000ml into, cold
But between 0 ~ 5 DEG C, load weighted 4g graphite is added in 92ml concentrated sulphuric acids, 0 ~ 5 DEG C of stirring is cooled to using ice-water bath straight
It is completely dissolved to graphite, adds 2g sodium nitrates and 12g potassium permanganate to be stirred vigorously simultaneously with certain speed, make the temperature of mixture
Degree is maintained at less than 10 DEG C and continues stirring 2.5 hours；Remove ice-water bath to be put in 35 DEG C of thermostat water bath, be slowly added to
184ml warm deionized waters are stirred 30 minutes；Three-necked bottle is put into into stirring reaction 25 minutes in 90 DEG C of water-bath, warm is added
Deionized water be diluted to 560ml, stirring added 40ml, 30% hydrogen peroxide after 5 minutes（Color is changed into golden yellow）5 points of insulation
Clock, product is poured in centrifuge tube and is washed with the centrifugation of 10000r/min, with barium chloride detection until without sulfur in supernatant
Acid ion is present；Solid matter after centrifugation is put into ultrasound in ethanol solution to be vacuum dried 24 hours after 30 minutes；
The preparation of step 3, Graphene/carbon nanotube composite material：
0.2g graphene oxides are taken respectively and purifying carbon nano-tube is added separately in the three-necked bottle equipped with 100ml ethanol, respectively
Ultrasound 2 hours；Carbon pipe is dropwise instilled in graphene oxide under ultrasonication, completion of dropping continues ultrasound 30 minutes；With
0.45 micron membrane filter sucking filtration, vacuum drying grind after 8 hours and obtain graphene oxide/carbon nano tube compound material；
The preparation of step 4, thiolating Graphene/carbon nanotube composite material：
Take during 0.4g composites are added to the three-necked bottle equipped with 150ml dehydrated alcohol and shake 5 minutes, lead to nitrogen mechanical agitation
Add 1ml acetic acid, 0.2mlMPTs after 5 minutes.Stir 24 hours under room temperature；To in three-necked bottle, 50ml acetone is added to continue stirring 6 little
When, sucking filtration is neutral with alcohol rinse to washing liquid simultaneously, and 60 DEG C are vacuum dried 12 hours；
Step 5, amination, the preparation of thiolating Graphene/carbon nanotube composite material：
Composite obtained by taking 0.2g previous steps is put in the three-necked bottle equipped with 20ml ethanol and is shaken 5 minutes, leads to nitrogen machine
Tool stirring drains air in bottle for 5 minutes, adds 7.5ml hydrazine hydrates, room temperature water-bath 3 hours；Sucking filtration is simultaneously with alcohol rinse to washing
Liquid is neutrality, and 60 DEG C are vacuum dried 12 hours.
As shown in Figure 1 and Figure 2, CNT is attached or is interspersed in graphenic surface and interlayer, and composite material surface has one
Layer film.Shown in Fig. 3, there is Si-N keys in infrared spectrogram proves amino grafting on mercapto, and-NH is present proves amino
Exist, Si-C keys prove that 3- mercaptopropyl trimethoxysilanes are carried on composite material surface.
Embodiment 3：
The pretreatment of step 1, CNT：
By 0.5g original multi-walled carbon nano-tubes（It is prepared by chemical vapour deposition technique）It is distributed to 15ml concentrated sulphuric acids and 5ml concentrated nitric acids
In mixed acid solution, stirring reaction 3 hours at 60 DEG C are washed to neutrality with distillation, standby after 80 DEG C of vacuum drying 12 hours；
The preparation of step 2, graphene oxide：
The natural crystalline flake graphites of 2.5g are taken with electronic balance；Graduated cylinder is measured in the three-necked bottle that the concentrated sulphuric acid of 60ml pours 1000ml into,
Be cooled between 0 ~ 5 DEG C, load weighted 2.5g graphite is added in 60ml concentrated sulphuric acids, 0 ~ 5 DEG C is cooled to using ice-water bath and is stirred
Mix up to graphite and be completely dissolved, add 1.5g sodium nitrates and 9g potassium permanganate to be stirred vigorously simultaneously with certain speed, make mixing
The temperature of thing is maintained at less than 10 DEG C and continues stirring 2.5 hours；Remove ice-water bath to be put in 35 DEG C of thermostat water bath, it is slow to add
Enter 120ml warm deionized waters to stir 30 minutes；Three-necked bottle is put into into stirring reaction 25 minutes in 90 DEG C of water-bath, temperature is added
The deionized water of heat is diluted to 350ml, and stirring added 30ml, 30% hydrogen peroxide after 5 minutes（Color is changed into golden yellow）Insulation 5
Minute, product is poured in centrifuge tube and is washed with the centrifugation of 9000r/min, with barium chloride detection until without sulfur in supernatant
Acid ion is present；Solid matter after centrifugation is put into ultrasound in ethanol solution to be vacuum dried 24 hours after 30 minutes；
The preparation of step 3, Graphene/carbon nanotube composite material：
0.2g graphene oxides are taken respectively and purifying carbon nano-tube is added separately in the three-necked bottle equipped with 100ml dehydrated alcohol,
It is ultrasonic 2 hours respectively；Carbon pipe is dropwise instilled in graphene oxide under ultrasonication, completion of dropping continues ultrasound 30 minutes；
With 0.45 micron membrane filter sucking filtration, grind after being vacuum dried 8 hours and obtain graphene oxide/carbon nano tube compound material；
The preparation of step 4, thiolating Graphene/carbon nanotube composite material：
Take during 0.4g composites are added to the three-necked bottle equipped with 150ml dehydrated alcohol and shake 5 minutes, lead to nitrogen mechanical agitation
Add 1ml acetic acid, 0.2mlMPTs after 5 minutes.Stir 24 hours under room temperature；To in three-necked bottle, 50ml acetone is added to continue stirring 6 little
When, sucking filtration is neutral with alcohol rinse to washing liquid simultaneously, and 60 DEG C are vacuum dried 12 hours；
Step 5, amination, the preparation of thiolating Graphene/carbon nanotube composite material：
Composite obtained by taking 0.2g previous steps is put in the three-necked bottle equipped with 10ml ethanol and is shaken 5 minutes, leads to nitrogen machine
Tool stirring drains air in bottle for 5 minutes, adds 7.5ml hydrazine hydrates, room temperature water-bath 3 hours；Sucking filtration is simultaneously with alcohol rinse to washing
Liquid is neutrality, and 60 DEG C are vacuum dried 12 hours.
Embodiment 4：
The pretreatment of step 1, CNT：
By 4g original multi-walled carbon nano-tubes（It is prepared by chemical vapour deposition technique）It is distributed to 120ml concentrated sulphuric acids and 40ml concentrated nitric acids
In mixed acid solution, stirring reaction 3 hours at 60 DEG C are washed to neutrality with distillation, standby after 80 DEG C of vacuum drying 12 hours；
The preparation of step 2, graphene oxide：
The natural crystalline flake graphites of 6g are taken with electronic balance；Graduated cylinder is measured in the three-necked bottle that the concentrated sulphuric acid of 138ml pours 1000ml into, cold
But between 0 ~ 5 DEG C, load weighted 6g graphite is added in 138ml concentrated sulphuric acids, 0 ~ 5 DEG C of stirring is cooled to using ice-water bath straight
It is completely dissolved to graphite, adds 3g sodium nitrates and 18g potassium permanganate to be stirred vigorously simultaneously with certain speed, make the temperature of mixture
Degree is maintained at less than 10 DEG C and continues stirring 2.5 hours；Remove ice-water bath to be put in 35 DEG C of thermostat water bath, be slowly added to
250ml warm deionized waters are stirred 30 minutes；Three-necked bottle is put into into stirring reaction 25 minutes in 90 DEG C of water-bath, warm is added
Deionized water be diluted to 840ml, stirring added 60ml, 30% hydrogen peroxide after 5 minutes（Color is changed into golden yellow）5 points of insulation
Clock, product is poured in centrifuge tube and is washed with the centrifugation of 8000r/min, with barium chloride detection until without sulphuric acid in supernatant
Radical ion is present；Solid matter after centrifugation is put into ultrasound in ethanol solution to be vacuum dried 24 hours after 30 minutes；
The preparation of step 3, Graphene/carbon nanotube composite material：
0.4g graphene oxides are taken respectively and purifying carbon nano-tube is added separately in the three-necked bottle equipped with 100ml dehydrated alcohol,
It is ultrasonic 2.5 hours respectively；Carbon pipe is dropwise instilled in graphene oxide under ultrasonication, completion of dropping continues 30 points of ultrasound
Clock；With 0.45 micron membrane filter sucking filtration, grind after being vacuum dried 8 hours and obtain graphene oxide/carbon nano tube compound material；
The preparation of step 4, thiolating Graphene/carbon nanotube composite material：
Take during 0.5g composites are added to the three-necked bottle equipped with 75ml dehydrated alcohol and shake 5 minutes, lead to nitrogen mechanical agitation 5
Add 1.5ml acetic acid, 0.5mlMPTs after minute.Stir 24 hours under room temperature；To in three-necked bottle, add 62.5ml acetone to continue stirring 6
Hour, sucking filtration is neutral with alcohol rinse to washing liquid simultaneously, and 60 DEG C are vacuum dried 12 hours；
Step 5, amination, the preparation of thiolating Graphene/carbon nanotube composite material：
Composite obtained by taking 0.4g previous steps is put in the three-necked bottle equipped with 20ml ethanol and is shaken 5 minutes, leads to nitrogen machine
Tool stirring drains air in bottle for 5 minutes, adds 15ml hydrazine hydrates, room temperature water-bath 3 hours；Sucking filtration is simultaneously with alcohol rinse to washing liquid
For neutrality, 60 DEG C are vacuum dried 12 hours.
Embodiment 5：
The pretreatment of step 1, CNT：
By 0.2g original multi-walled carbon nano-tubes（It is prepared by chemical vapour deposition technique）It is distributed to 15ml concentrated sulphuric acids and 5ml concentrated nitric acids
In mixed acid solution, stirring reaction 3 hours at 60 DEG C are washed to neutrality with distillation, standby after 80 DEG C of vacuum drying 12 hours；
The preparation of step 2, graphene oxide：
The natural crystalline flake graphites of 1g are taken with electronic balance；Graduated cylinder is measured in the three-necked bottle that the concentrated sulphuric acid of 25ml pours 1000ml into, cold
But between 0 ~ 5 DEG C, load weighted 1g graphite is added in 25ml concentrated sulphuric acids, 0 ~ 5 DEG C of stirring is cooled to using ice-water bath straight
It is completely dissolved to graphite, adds 0.5g sodium nitrates and 3g potassium permanganate to be stirred vigorously simultaneously with certain speed, make mixture
Temperature is maintained at less than 10 DEG C and continues stirring 2.5 hours；Remove ice-water bath to be put in 35 DEG C of thermostat water bath, be slowly added to
50ml warm deionized waters are stirred 30 minutes；Three-necked bottle is put into into stirring reaction 25 minutes in 90 DEG C of water-bath, warm is added
Deionized water be diluted to 140ml, stirring added 10ml, 30% hydrogen peroxide after 5 minutes（Color is changed into golden yellow）5 points of insulation
Clock, product is poured in centrifuge tube and is washed with the centrifugation of 10000r/min, with barium chloride detection until without sulfur in supernatant
Acid ion is present；Solid matter after centrifugation is put into ultrasound in ethanol solution to be vacuum dried 24 hours after 30 minutes；
The preparation of step 3, Graphene/carbon nanotube composite material：
0.2g graphene oxides are taken respectively and purifying carbon nano-tube is added separately in the three-necked bottle equipped with 100ml dehydrated alcohol,
It is ultrasonic 2 hours respectively；Carbon pipe is dropwise instilled in graphene oxide under ultrasonication, completion of dropping continues ultrasound 30 minutes；
With 0.45 micron membrane filter sucking filtration, grind after being vacuum dried 8 hours and obtain graphene oxide/carbon nano tube compound material；
The preparation of step 4, thiolating Graphene/carbon nanotube composite material：
Take during 1g composites are added to the three-necked bottle equipped with 75ml dehydrated alcohol and shake 5 minutes, lead to 5 points of nitrogen mechanical agitation
Zhong Houjia 2.5ml acetic acid, 0.5mlMPTs.Stir 24 hours under room temperature；To in three-necked bottle, 125ml acetone is added to continue stirring 6 little
When, sucking filtration is neutral with alcohol rinse to washing liquid simultaneously, and 60 DEG C are vacuum dried 12 hours；
Step 5, amination, the preparation of thiolating Graphene/carbon nanotube composite material：
Composite obtained by taking 1g previous steps is put in the three-necked bottle equipped with 50ml ethanol and is shaken 5 minutes, leads to nitrogen machinery
Stirring drains air in bottle for 5 minutes, adds 40ml hydrazine hydrates, room temperature water-bath 3 hours；Sucking filtration with alcohol rinse to washing liquid is simultaneously
Neutrality, 60 DEG C are vacuum dried 12 hours.
Embodiment 6：
The pretreatment of step 1, CNT：
By 3g original multi-walled carbon nano-tubes（It is prepared by chemical vapour deposition technique）It is distributed to 90ml concentrated sulphuric acids and 30ml concentrated nitric acids
In mixed acid solution, stirring reaction 3 hours at 60 DEG C are washed to neutrality with distillation, standby after 80 DEG C of vacuum drying 12 hours；
The preparation of step 2, graphene oxide：
The natural crystalline flake graphites of 5g are taken with electronic balance；Graduated cylinder is measured in the three-necked bottle that the concentrated sulphuric acid of 120ml pours 1000ml into, cold
But between 0 ~ 5 DEG C, load weighted 5g graphite is added in 120ml concentrated sulphuric acids, 0 ~ 5 DEG C of stirring is cooled to using ice-water bath straight
It is completely dissolved to graphite, adds 2.5g sodium nitrates and 15g potassium permanganate to be stirred vigorously simultaneously with certain speed, make mixture
Temperature is maintained at less than 10 DEG C and continues stirring 2.5 hours；Remove ice-water bath to be put in 35 DEG C of thermostat water bath, be slowly added to
230ml warm deionized waters are stirred 30 minutes；Three-necked bottle is put into into stirring reaction 25 minutes in 90 DEG C of water-bath, warm is added
Deionized water be diluted to 700ml, stirring added 50ml, 30% hydrogen peroxide after 5 minutes（Color is changed into golden yellow）5 points of insulation
Clock, product is poured in centrifuge tube and is washed with the centrifugation of 8000r/min, with barium chloride detection until without sulphuric acid in supernatant
Radical ion is present；Solid matter after centrifugation is put into ultrasound in ethanol solution to be vacuum dried 24 hours after 30 minutes；
The preparation of step 3, Graphene/carbon nanotube composite material：
1g graphene oxides are taken respectively and purifying carbon nano-tube is added separately in the three-necked bottle equipped with 100ml dehydrated alcohol, point
It is not ultrasonic 2 hours；Carbon pipe is dropwise instilled in graphene oxide under ultrasonication, completion of dropping continues ultrasound 30 minutes；With
0.45 micron membrane filter sucking filtration, vacuum drying grind after 8 hours and obtain graphene oxide/carbon nano tube compound material；
The preparation of step 4, thiolating Graphene/carbon nanotube composite material：
Take during 0.8g composites are added to the three-necked bottle equipped with 150ml dehydrated alcohol and shake 5 minutes, lead to nitrogen mechanical agitation
Add 2ml acetic acid, 0.4mlMPTs after 5 minutes.Stir 24 hours under room temperature；To in three-necked bottle, 100ml acetone is added to continue stirring 6 little
When, sucking filtration is neutral with alcohol rinse to washing liquid simultaneously, and 60 DEG C are vacuum dried 12 hours；
Step 5, amination, the preparation of thiolating Graphene/carbon nanotube composite material：
Composite obtained by taking 0.8g previous steps is put in the three-necked bottle equipped with 40ml ethanol and is shaken 5 minutes, leads to nitrogen machine
Tool stirring drains air in bottle for 5 minutes, adds 30ml hydrazine hydrates, room temperature water-bath 3 hours；Sucking filtration is simultaneously with alcohol rinse to washing liquid
For neutrality, 60 DEG C are vacuum dried 12 hours.
Claims (10)
1. amino and mercapto it is grapheme modified/carbon nano tube compound material, it is characterised in that the composite is by graphite
Alkene and CNT composition, one layer of thin film containing amino and thiol group is wrapped up on surface.
2. amino described in claim 1 and the Graphene/carbon nanotube composite material preparation method of mercapto modification, its feature
It is that its step is：
（1）CNT is distributed in mixed acid solution, is reacted 1～3 hour at 60～80 DEG C, subsequent filtration washing, 80～
120 DEG C of 8 ~ 12h of drying, obtain carbon pipe after purification；
（2）Native graphite is added in the concentrated sulphuric acid of mass fraction 98%, mechanical agitation is dissolved completely up to graphite, then
Add sodium nitrate and potassium permanganate temperature to be maintained at 0 ~ 10 DEG C, continue stirring 2.5 ~ 4 hours, mixture is put into into 35 DEG C of constant temperature
In water-bath, deionized water is slowly added to, mixture is put into into 20 ~ 40 points of mechanical agitation in 90 ~ 100 DEG C of water-bath subsequently
Clock, adds deionized water to be diluted to 600ml, stirs 5-15 minutes, add the hydrogen peroxide of mass fraction 30%, by product with 8000-
Solid matter after centrifugation is dispersed in 30 ~ 60 points of sonic oscillation in ethanol solution by the centrifugation of 10000r/min
Clock, is vacuum dried 12 ~ 24 hours, obtains as graphene oxide；
（3）The graphene oxide and purifying carbon nano-tube of quality such as respectively weigh respectively, each ultrasound 2 hours, then by after ultrasound
CNT after purification dropwise instill in graphene oxide, continue ultrasound 30 ~ 60 minutes, using 0.45 micron membrane filter sucking filtration,
Vacuum drying obtained graphene oxide/carbon nano tube compound material after 8 ~ 12 hours；
（4）Weigh Graphene/carbon nanotube composite material to be added to equipped with dehydrated alcohol, ultrasonic vibration 5 ~ 15 minutes is passed through
Nitrogen protects simultaneously mechanical agitation 5 minutes, adds acetic acid, 3- mercaptopropyl trimethoxysilanes, stirs 12 ~ 24 hours under room temperature, after
It is continuous to add acetone to continue stirring 6 ~ 12 hours, rinsed respectively 5 ~ 10 times using ethanol and distilled water, 60 ~ 80 DEG C of vacuum drying 8 ~ 12
Hour, obtain the Graphene/carbon nanotube composite material of mercapto modification；
（5）The Graphene/carbon nanotube composite material that mercapto is modified is added in the three-necked bottle equipped with ethanol, ultrasonic vibration
5 ~ 15 minutes, lead to nitrogen protection, add hydrazine hydrate, stirred 3 ~ 5 hours with 5000 ~ 10000r/min of rotating speed, vacuum filtration is simultaneously
Deionized water is rinsed to neutrality, and 60 ~ 80 DEG C are vacuum dried 8 ~ 12 hours, obtains the graphene/carbon of amino and mercapto modification
Nanometer tube composite materials.
3. the Graphene/carbon nanotube composite material preparation method that amino according to claim 2 and mercapto are modified, its
It is characterised by：The CNT is many walls or SWCN.
4. the Graphene/carbon nanotube composite material preparation method that amino according to claim 2 and mercapto are modified, its
It is characterised by：The mixed acid solution is that concentrated sulphuric acid and concentrated nitric acid are constituted, and the volume ratio of concentrated sulphuric acid and concentrated nitric acid is 3:1.
5. the Graphene/carbon nanotube composite material preparation method that amino according to claim 2 and mercapto are modified, its
It is characterised by：The purifying carbon nano-tube and graphene oxide mass ratio are 2:1.
6. the Graphene/carbon nanotube composite material preparation method that amino according to claim 2 and mercapto are modified, its
It is characterised by：The mass ratio of concentrated sulphuric acid and native graphite is 50:1-80:1；The mass ratio of sodium nitrate and native graphite is 1:2-2:
1。
7. the Graphene/carbon nanotube composite material preparation method that amino according to claim 2 and mercapto are modified, its
It is characterised by：The mass ratio of potassium permanganate and native graphite is 3:1-6:1.
8. the Graphene/carbon nanotube composite material preparation method that amino according to claim 2 and mercapto are modified, its
It is characterised by：The volume ratio of hydrogen peroxide and concentrated sulphuric acid is 1:2-1:4.
9. the Graphene/carbon nanotube composite material preparation method that amino according to claim 2 and mercapto are modified, its
It is characterised by：The rate of charge of the Graphene/carbon nanotube composite material and 3- mercaptopropyl trimethoxysilanes is approximately (0.4 ~ 2)
×103。
10. the Graphene/carbon nanotube composite material preparation method that amino according to claim 2 and mercapto are modified,
It is characterized in that：The Graphene/carbon nanotube composite material of mercapto modification is about 20～30 with the rate of charge of hydrazine.
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