CN106672943B - A kind of magnetic carbon nano-tube and preparation method thereof with fluorescent characteristic - Google Patents
A kind of magnetic carbon nano-tube and preparation method thereof with fluorescent characteristic Download PDFInfo
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Abstract
A kind of magnetic carbon nano-tube and preparation method thereof with fluorescent characteristic belongs to field of nano material preparation, it is characterised in that: A, original carbon nanotubes is carried out with nitric acid acidizing pretreatment and charing pre-processes；B, using being heated to reflux and hydro-thermal method, magnetic particle is uniformly filled in the pretreatment carbon nanotube cavity that step A obtains, obtains interior filling magnetic particle modified carbon nano-tube；C, using interior filling magnetic particle modified carbon nano-tube obtained in step B as raw material, the fluorescer containing fluorophor is grafted to its surface, obtains the magnetic carbon nano-tube with fluorescent characteristic.The present invention solves carbon nanotube and disperses the problems such as poor with interface cohesion in matrices of composite material, prepared magnetic carbon nano-tube integrates mangneto orientation and tracer, will be with a wide range of applications in the fields such as the design of high-performance composite materials and preparation.
Description
Technical field:
The invention belongs to field of nano material preparation, in particular to a kind of interior filling magnetic particle simultaneously has fluorescent characteristic
The preparation method of carbon nanotube.
Background technique: carbon nanotube has excellent object because of its unique structure and high draw ratio, high mechanical strength
Reason, chemistry, electricity, mechanical property have a wide range of applications in multiple fields such as chemical industry, electronics, the energy.However, carbon nanotube
Between due to there are the effect of Van der Waals force, being easy mutually winding, gather into bundles, cause its in composite material application in group
Poly- and random distribution state, which greatly limits the performances of carbon nanotube excellent properties.Meanwhile existing means are difficult table in situ
Levying carbon nanotube, there are interface cohesions and distribution in matrices of composite material, and which also limits the high property based on carbon nanotube
It can composite Materials Design and preparation research.
Currently, realizing that the common method of carbon nanotube orientation has field of force induced orientation, electric field induced orientation and induced by magnetic field
Orientation etc..Wherein induced by magnetic field orientation is a kind of contactless method for alignment, is widely used, remarkable advantage is that magnetic field is strong
Degree size and Orientation can be arbitrarily adjusted, applied widely, while the distribution of orientations of nanoparticle is easily achieved.Induced by magnetic field
Alignment method firstly the need of preparing magnetic particle modified carbon nano-tube, existing main method be by surface loaded magnetic particle come
Magnetic carbon nano-tube is prepared, or prepares the magnetic particle of internal filling magnetic particle using capillarity principle and hydro-thermal reaction method
Modified carbon nano-tube realizes its aligning in magnetic field.Miguel A.Correa-Duarte(The Journal of
Physical Chemistry B, 2005,109 (41): 19060-19063) et al. by physical entanglement method in carbon nanotube
Surface grafting polymerization object and magnetic particle are prepared for magnetic particle in carbon nano tube surface Coated magnetic particles using coprecipitation
Modified carbon nano-tube, but such method is deposited in the product that magnetic particle and carbon nanotube binding force be not strong, magnetic particle is easy to fall off,
Modified carbon nano-tube state of orientation is difficult to the problems such as characterizing.Goh W J(Langmuir,2012,28(49):16864-16873),
Demir A (Synthetic Metals, 2014,187:75-80) et al. is aoxidized using capillarity principle and hydro-thermal method by four
Three ferromagnetic particles are filled in carbon nanotube cavity, are prepared for the modified carbon nano-tube of internal filling magnetic particle, but such
Method equally exist magnetic particle modified carbon nano-tube state of orientation and distribution can not in-situ characterization the problems such as, while gained
To magnetic particle modified carbon nano-tube in matrices of composite material there is also dispersibility with interface cohesion it is poor the deficiencies of.Therefore,
Urgent need develops excellent one kind dispersibility and interfacial bonding property in matrices of composite material, mangneto favorable orientation, magnetic particle load
Securely, it is orientated the carbon nanotube and preparation method thereof for being easy to characterize with dispersity.
Summary of the invention:
The purpose of the present invention is to provide preparation method, particular technique content is as follows:
A, nitric acid acidizing pretreatment is carried out to original carbon nanotubes and charing pre-processes；B, using being heated to reflux and hydro-thermal
Magnetic particle is uniformly filled in the pretreatment carbon nanotube cavity that step A obtains by method, and it is modified to obtain interior filling magnetic particle
Carbon nanotube；C, using interior filling magnetic particle modified carbon nano-tube obtained in step B as raw material, by the fluorescence containing fluorophor
Agent is grafted to its surface, obtains the magnetic carbon nano-tube with fluorescent characteristic.The present invention has the magnetic carbon nanometer of fluorescent characteristic
During control is standby, the carbon nanotube is that intracavity diameter range is 30-60nm.
During fluorescence modified carbon nano-tube of the present invention, fluorescer (being indicated with R) used is fluorescein isothiocynate
(FITC), RB 200 (RhoB), tetramethylisothiocyanate rhodamine (TRITC), propidium iodide (PI), phycoerythrin
One of (PE).
Present invention preparation has in the magnetic carbon nano-tube preparation process of fluorescent characteristic, it is characterised in that preparation process is such as
Under:
(1) carbon nanotube pre-processes: having carried out being acidified-carbonizing pretreatment, acidizing pretreatment first to original carbon nanotubes
Time is 0.5-1.5h, and heating rate is 3-5 DEG C/min in charing pretreatment, is warming up to 800-900 DEG C, soaking time is later
1-3h。
(2) Fe is filled in3O4The preparation of magnetic particle modified carbon nano-tube: filling magnetic particle carbon modified is received in preparation
During mitron, being heated to reflux temperature is 115-135 DEG C, and being heated to reflux the time is 1-2h.
(3) preparation of the magnetic carbon nano-tube (interior filling mode) with fluorescent characteristic: first during being grafted fluorescer
First with acidification method in surface grafting-COOH reaction active groups, acid used is the quality that 50-100ml volume ratio is 1:3
70% nitric acid of percent concentration and 70% sulfuric acid mixed acid of mass percent concentration, are stirred at reflux 30- at 90-130 DEG C
90min；ATRP method is recycled to fill magnetic particle carbon nano tube surface successively grafting-Br ,-PGMA ,-NH inside2Several reactions
Active group, every step graft reaction are after the completion filtered by vacuum product, and miillpore filter aperture is 100-200um, have filtered
After place the product in vacuum drying oven in 50-60 DEG C of dry 24-36h；Then products therefrom is dissolved in deionized water, is added
Entering quality is 0.0001-0.002g fluorescer, carries out fluorescer and is protected from light under the graft reaction step of surface, room temperature
2-12h, is washed with deionized water colourless to upper liquid repeatedly after the reaction was completed, is then filtered by vacuum, miillpore filter aperture is
100-200um.Product will be filtered and be placed in vacuum drying oven 40-60 DEG C of dry 36-48h, obtain MWCNTs-Fe3O4-R.Above-mentioned
Whole process is protected from light in all reactions and suction filtration drying process.
Further, with the interior filling Fe of acidification3O4Magnetic particle modified carbon nano-tube MWCNTs-Fe3O4- COOH is
Raw material is connect using atom transfer radical polymerization ATRP method using Silane coupling agent KH550 as reactant in carbon nano tube surface
Branch-NH2, the molal weight ratio of carbon nanotube and KH550 are 1:0.5~1:5；Using grafted amino group carbon nanotube as raw material, benefit
With ATRP method using alpha-brominated isobutyl acylbromide BIBB as reactant, in carbon nano tube surface grafting-Br, carbon nanotube and BIBB's rubs
Your mass ratio is 1:1~1:5；To be grafted bromine group carbon nanotube as raw material, using ATRP method with methyl methacrylate GMA
For reactant, in carbon nano tube surface grafting-PGMA, the molal weight ratio of carbon nanotube and GMA are 1:5~1:20；To connect
Branch polymethyl methacrylate base group carbon nanotube is raw material, using ATRP method using ethylenediamine EDA as reactant, in carbon nanotube
Surface grafting-NH2, the molal weight ratio of carbon nanotube and EDA are 1:5~1:15；To product after the completion of every step graft reaction
Be filtered by vacuum, miillpore filter aperture is 100-200um, after the completion of suction filtration place the product in vacuum drying oven in 50-60 DEG C
Dry 24-36h；
By products therefrom MWCNTs-Fe3O4-NH2It is dissolved in deionized water, fluorescer is added and carries out fluorescer in product
The molal weight ratio of the graft reaction step on surface, fluorescer and carbon nanotube is 1:1000~1:50, is protected from light under room temperature anti-
2-12h is answered, is washed repeatedly with deionized water after the reaction was completed colourless to upper liquid, is then filtered by vacuum, miillpore filter aperture is
100-200um；Product will be filtered and be placed in vacuum drying oven 40-60 DEG C of dry 36-48h, obtain MWCNTs-Fe3O4-R；Above-mentioned
Whole process is protected from light in all reactions and suction filtration drying process.
Invention effect:
(1) present invention will be filled in carbon nanotube cavity in magnetic particle, the magnetic particle and carbon nanotube loaded
It is firmly combined, it is not easily to fall off under the external conditions such as ultrasound, stirring；(2) present invention passes through organic grafting of carbon nano tube surface
Improve dispersibility and interface cohesion of the magnetic carbon nano-tube in composite resin matrix；(3) present invention is by connecing
Branch fluorescer imparts in situ tracer of the magnetic carbon nano-tube in mangneto orientation process, takes magnetic carbon nano-tube collection mangneto
Tropism and tracer make it be with a wide range of applications in the design of high-performance composite materials with fields such as preparations in one.
Detailed description of the invention:
The TEM photo of Fig. 1 magnetic carbon nano-tube prepared by the present invention.
Specific embodiment:
Embodiment of the present invention is described in detail by following embodiment.But the present invention is not limited to following implementations
Example.In each embodiment, carbon nanotube is produced by Chengdu Organical Chemical Co., Ltd., Chinese Academy of Sciences.
Embodiment 1:
Step 1: weighing the carbon nanotube of 0.5g intracavity diameter 30nm, be added in three-necked flask, and 25mL mass is added
70% nitric acid solution of percent concentration is formed by suspension and heating stirring and maintains the reflux for 0.5h under the conditions of 130 DEG C.Pre- place
After the reaction was completed, by product eccentric cleaning, centrifugal speed 4000r/min, the time is 30min/ times to reason, and washing lotion is deionization
Water, centrifugation to supernatant liquor are neutrality.It is filtered after the completion of centrifugation, filter membrane used is the miillpore filter that aperture is 200um, and washing lotion is
Deionized water filters 5 times, and after the completion of suction filtration, being placed on drying in vacuum oven, for 24 hours, drying box temperature is 50 DEG C；It is dry to complete
Acidification carbon pipe is put into charing process in horizontal retort again afterwards, heating rate is 5 DEG C/min, is warming up to 800 DEG C, later
1h is kept the temperature, pretreated carbon nanotube is obtained.
Step 2: six ferrous sulfate hydrate ammonium of 1.2g is added in the mixed solution of 40ml deionized water and hydrazine hydrate
(deionized water and the volume ratio of hydrazine hydrate be 3:1) is then added nitric acid oxidation and carbonizes pretreated carbon nanotube, lead to nitrogen
30min, re-ultrasonic dispersion are stirred 60min, adjust pH value to the 1h that flows back at 11,115 DEG C with ammonium hydroxide after ultrasound, product passes through
It filters after centrifugation purification and dries in a vacuum drying oven.Washing lotion when centrifugation filters is deionized water or ethyl alcohol.It is filled out in obtaining
Fill Fe3O4Magnetic particle modified carbon nano-tube MWCNTs-Fe3O4.Step 3: by 0.5g above prepared interior filling Fe3O4
Magnetic particle modified carbon nano-tube MWCNTs-Fe3O4It is added to 70% nitric acid of mass percent concentration that 64ml volume ratio is 1:3
In 70% sulfuric acid mixed acid of mass percent concentration, 60min is stirred at reflux at 120 DEG C, product filtration drying obtains carboxyl
Carbon nano tube；2g carboxylic carbon nano-tube, 2ml acetic acid, 98ml ethyl alcohol, 1ml silane coupling agent are added in round-bottomed flask
KH550 is mixed, and is reacted for 24 hours at 50 DEG C after sealing ultrasound 30min.Vacuum filtration, is dried in vacuo at 60 DEG C, obtains drying
Functionalized carbon nano-tube；0.8g functionalized carbon nano-tube is added in flask, 28ml tetrahydrofuran and triethylamine, device are placed in ice
After in bath, the alpha-brominated isobutyl acylbromide of 3ml is added.After dripping off, 48h is reacted at 30 DEG C.Vacuum filtration, vacuum is dry at 60 DEG C
It is dry, it obtains containing bromination carbon nanotube；The carbon nanotube that 0.2g contains bromine, 1ml methyl methacrylate are added in flask
(GMA) monomer, 0.08ml pentamethyl-diethyl triamine (PMDETA) in 15ml dimethylformamide (DMF), lead to nitrogen
30min.0.027gCuBr is added, reacts 3h at 30 DEG C.Vacuum filtration, is dried in vacuo at 60 DEG C, and it is poly- that surface grafting is made
The carbon nanotube MWCNTs-Fe of methyl methacrylate (PGMA)3O4-PGMA；0.2gMWCNTs- is added in round-bottomed flask
Fe3O4- PGMA, 40ml dehydrated alcohol, ultrasonic disperse 30min add 2ml ethylenediamine solution, ultrasonic disperse 5min, in 50 DEG C
Under the conditions of react for 24 hours.Product is washed with dehydrated alcohol, is centrifugated 6 times, 20min/ times, revolving speed 4000r/min.It is centrifuged laggard
Row vacuum filtration, miillpore filter aperture are 200um.Product will be filtered and be placed in vacuum drying oven 50 DEG C of dryings for 24 hours, obtain drying
MWCNTs-Fe3O4-NH2；200ml deionized water is added in three-necked flask, sequentially adds 1.512gNaHCO3、
0.212gNaCO3, 1.472gNaCl, 0.1g MWCNTs-Fe is added after stirring and dissolving3O4-NH2, ultrasonic disperse 30min；It is burning
1ml DMSO solution is added in cup, 0.0001g fluorescein RB 200 RhoB sufficiently dissolves under the conditions of being protected from light；By RhoB/
DMSO mixed liquor is added dropwise in three-necked flask, is protected from light 8h under room temperature.Washed repeatedly with deionized water it is colourless to upper liquid,
Then it is filtered by vacuum, miillpore filter aperture is 200um.Product will be filtered and be placed in vacuum drying oven 40 DEG C of dry 48h, obtained
MWCNTs-Fe3O4- RhoB, all processes pay attention to being protected from light.
Comparative example 1:
Retort heating rate is changed to 10 DEG C/min in step 1, remaining step is as the condition in example 1, preparation tool
There is the interior filling magnetic particle magnetic carbon nano-tube of fluorescent characteristic.As a result, it has been found that carbon nanotube structural pipe wall destroys, pass through
Transmission electron microscope finds that filling magnetic particle is less in carbon nanotube, and the magnetic particle filling rate measured by thermal weight loss is low,
Illustrate during charing process that heating rate is too fast and damaging influence caused to carbon nanotube structural pipe wall, it is final influence it is magnetic
The interior filling situation of particle.
Embodiment 2:
Step 1: weighing the nanotube of 0.5g intracavity diameter 40nm, be added in three-necked flask, and 25mL mass hundred is added
Point 70% nitric acid solution of specific concentration is formed by suspension and heating stirring and maintains the reflux for 1.5h under the conditions of 130 DEG C.Pretreatment
After the reaction was completed, by product eccentric cleaning, centrifugal speed 4000r/min, the time is 30min/ times, and washing lotion is deionized water,
Centrifugation to supernatant liquor is neutrality.It is filtered after the completion of centrifugation, filter membrane used is the miillpore filter that aperture is 200um, and washing lotion is to go
Ionized water filters 3 times, and after the completion of suction filtration, being placed on drying in vacuum oven, for 24 hours, drying box temperature is 50 DEG C；After the completion of drying
Acidification carbon pipe is put into charing process in horizontal retort again, heating rate is 3 DEG C/min, is warming up to 800 DEG C, Zhi Houbao
Warm 3h obtains pretreated carbon nanotube.
Step 2: six ferrous sulfate hydrate ammonium of 1.2g is added in the mixed solution of 40ml deionized water and hydrazine hydrate
(deionized water and the volume ratio of hydrazine hydrate be 3:1) is then added nitric acid oxidation and carbonizes pretreated carbon nanotube, lead to nitrogen
20min, re-ultrasonic dispersion are stirred 60min, adjust pH value to the 2h that flows back at 12,115 DEG C with ammonium hydroxide after ultrasound, product passes through
It filters after centrifugation purification and dries in a vacuum drying oven.Washing lotion when centrifugation filters is deionized water or ethyl alcohol.It is filled out in obtaining
Fill Fe3O4Magnetic particle modified carbon nano-tube MWCNTs-Fe3O4。
Step 3: by 0.5g above prepared interior filling Fe3O4Magnetic particle modified carbon nano-tube MWCNTs-Fe3O4
It is added to 70% nitric acid of mass percent concentration and 70% sulfuric acid mixed acid of mass percent concentration that 50ml volume ratio is 1:3
In, 30min is stirred at reflux at 120 DEG C, product filtration drying obtains carboxylic carbon nano-tube；2g carboxylic is added in round-bottomed flask
Base carbon nano tube, 2ml acetic acid, 98ml ethyl alcohol, 10ml Silane coupling agent KH550 mix, after sealing ultrasound 30min at 50 DEG C
Reaction is for 24 hours.Vacuum filtration, is dried in vacuo at 60 DEG C, obtains dry functionalized carbon nano-tube；0.8g function is added in flask
After device is placed in ice bath, the alpha-brominated isobutyl acylbromide of 0.8ml is added in energy carbon nano tube, 28ml tetrahydrofuran and triethylamine.Drop
After complete, 48h is reacted at 30 DEG C.Vacuum filtration, is dried in vacuo at 60 DEG C, obtains containing bromination carbon nanotube；In flask
The carbon nanotube that 0.2g contains bromine, 3ml methyl methacrylate (GMA) monomer, 0.05ml pentamethyl-diethyl triamine is added
(PMDETA), in 10ml dimethylformamide (DMF), lead to nitrogen 30min.1gCuBr is added, reacts 3h at 30 DEG C.Vacuum is taken out
Filter, is dried in vacuo at 60 DEG C, and the carbon nanotube MWCNTs-Fe of surface grafting polymethyl methacrylate (PGMA) is made3O4-
PGMA；0.2gMWCNTs-Fe is added in round-bottomed flask3O4- PGMA, 40ml dehydrated alcohol, ultrasonic disperse 30min, add
2ml ethylenediamine solution, ultrasonic disperse 5min react for 24 hours under the conditions of 50 DEG C.Product is washed with dehydrated alcohol, is centrifugated 6 times,
20min/ times, revolving speed 4000r/min.It is filtered by vacuum after centrifugation, miillpore filter aperture is 100um.Product will be filtered to set
60 DEG C of dryings for 24 hours, obtain dry MWCNTs-Fe in vacuum drying oven3O4-NH2；200ml deionization is added in three-necked flask
Water sequentially adds 1.512gNaHCO3、0.212gNaCO3, 1.472gNaCl, 0.1g MWCNTs- is added after stirring and dissolving
Fe3O4-NH2, ultrasonic disperse 30min；1ml DMSO solution, 0.0015g fluorescein tetramethyl isothiocyanate sieve are added in beaker
Red bright TRITC, sufficiently dissolves under the conditions of being protected from light；TRITC/DMSO mixed liquor is added dropwise in three-necked flask, is protected from light under room temperature
React 2h.It is washed with deionized water colourless to upper liquid, is then filtered by vacuum repeatedly, miillpore filter aperture is 150um.It will filter
Product is placed in vacuum drying oven 60 DEG C of dry 48h, obtains MWCNTs-Fe3O4- TRITC, all processes pay attention to being protected from light.
Comparative example 2:
The logical nitrogen time is changed to 5min in step 2, and for remaining step as the condition in example 2, preparation has fluorescence special
The interior filling magnetic particle magnetic carbon nano-tube of property.As a result, it has been found that the macroscopic magnetization of magnetic particle modified carbon nano-tube obtained is bright
Aobvious weaker, by hysteresis loop VSM test characterization, its saturation magnetization is low, illustrates that the logical nitrogen time is too short, causes in raw material
Ferrous ion be oxidized, be unfavorable for the generation of Fe 3 O 4 magnetic particle, the final product magnetic particle carbon modified that influences is received
The magnetic property of mitron.
Embodiment 3:
Step 1: weighing the carbon nanotube of 0.5g intracavity diameter 50nm, be added in three-necked flask, and 25mL mass is added
70% nitric acid solution of percent concentration is formed by suspension and heating stirring and maintains the reflux for 1h under the conditions of 130 DEG C.Pretreatment
After the reaction was completed, by product eccentric cleaning, centrifugal speed 4000r/min, the time is 30min/ times, and washing lotion is deionized water,
Centrifugation to supernatant liquor is neutrality.It is filtered after the completion of centrifugation, filter membrane used is the miillpore filter that aperture is 200um, and washing lotion is to go
Ionized water filters 4 times, and after the completion of suction filtration, being placed on drying in vacuum oven, for 24 hours, drying box temperature is 50 DEG C；After the completion of drying
Acidification carbon pipe is put into charing process in horizontal retort again, heating rate is 4 DEG C/min, is warming up to 900 DEG C, Zhi Houbao
Warm 1h obtains pretreated carbon nanotube.
Step 2: six ferrous sulfate hydrate ammonium of 1.2g is added in the mixed solution of 40ml deionized water and hydrazine hydrate
(deionized water and the volume ratio of hydrazine hydrate be 3:1) is then added nitric acid oxidation and carbonizes pretreated carbon nanotube, lead to nitrogen
30min, re-ultrasonic dispersion are stirred 60min, are adjusted in pH value to 13 ranges after ultrasound with ammonium hydroxide, flow back 1h at 135 DEG C, produces
Object is by filtering and drying in a vacuum drying oven after centrifugation purification.Washing lotion when centrifugation filters is deionized water or ethyl alcohol.?
To interior filling Fe3O4Magnetic particle modified carbon nano-tube MWCNTs-Fe3O4。
Step 3: by 0.5g above prepared interior filling Fe3O4Magnetic particle modified carbon nano-tube MWCNTs-Fe3O4
It is added to 70% nitric acid of mass percent concentration and 70% sulfuric acid mixed acid of mass percent concentration that 100ml volume ratio is 1:3
In, 90min is stirred at reflux at 120 DEG C, product filtration drying obtains carboxylic carbon nano-tube；2g carboxylic is added in round-bottomed flask
Base carbon nano tube, 2ml acetic acid, 98ml ethyl alcohol, 2ml Silane coupling agent KH550 mix, after sealing ultrasound 30min at 50 DEG C
Reaction is for 24 hours.Vacuum filtration, is dried in vacuo at 60 DEG C, obtains dry functionalized carbon nano-tube；0.8g function is added in flask
After device is placed in ice bath, the alpha-brominated isobutyl acylbromide of 4ml is added in energy carbon nano tube, 28ml tetrahydrofuran and triethylamine.It drips off
Afterwards, 48h is reacted at 30 DEG C.Vacuum filtration, is dried in vacuo at 60 DEG C, obtains containing bromination carbon nanotube；Add in flask
Enter the carbon nanotube that 0.2g contains bromine, 1ml methyl methacrylate (GMA) monomer, 1.5ml pentamethyl-diethyl triamine
(PMDETA), in 50ml dimethylformamide (DMF), lead to nitrogen 30min.0.05gCuBr is added, reacts 3h at 30 DEG C.Very
Empty pump filter, is dried in vacuo at 60 DEG C, and the carbon nanotube MWCNTs- of surface grafting polymethyl methacrylate (PGMA) is made
Fe3O4-PGMA；0.2gMWCNTs-Fe is added in round-bottomed flask3O4- PGMA, 40ml dehydrated alcohol, ultrasonic disperse 30min, then
2ml ethylenediamine solution is added, ultrasonic disperse 5min reacts for 24 hours under the conditions of 50 DEG C.Product, centrifuge separation 6 are washed with dehydrated alcohol
It is secondary, 20min/ times, revolving speed 4000r/min.It is filtered by vacuum after centrifugation, miillpore filter aperture is 150um.Product will be filtered
55 DEG C of dry 36h are placed in vacuum drying oven, dry MWCNTs-Fe is obtained3O4-NH2；In three-necked flask be added 200ml go from
Sub- water, sequentially adds 1.512gNaHCO3、0.212gNaCO3, 1.472gNaCl, 0.1g MWCNTs- is added after stirring and dissolving
Fe3O4-NH2, ultrasonic disperse 30min；1ml DMSO solution is added in beaker, 0.002g fluorescein propidium iodide PI is protected from light item
It is sufficiently dissolved under part；PI/DMSO mixed liquor is added dropwise in three-necked flask, is protected from light 12h under room temperature.It is anti-with deionized water
After backwashing is washed colourless to upper liquid, is then filtered by vacuum, and miillpore filter aperture is 100um.Product will be filtered to be placed in vacuum drying oven
50 DEG C of dry 36h, obtain MWCNTs-Fe3O4- PI, all processes pay attention to being protected from light.
Comparative example 3:
Adjusting pH value in step 2 is changed to 8, and for remaining step as the condition in example 3, preparation has fluorescent characteristic
Interior filling magnetic particle magnetic carbon nano-tube.As a result, it has been found that the macroscopic magnetization of magnetic particle modified carbon nano-tube obtained is obvious
It is weaker, it is low that its saturation magnetization is characterized by hysteresis loop VSM test, and magnetic particle generation yield is less, passes through transmission
The magnetic particle quantity that Electronic Speculum is observed is few, illustrates that reaction environment condition alkalinity dies down and is unfavorable for Fe 3 O 4 magnetic particle
It generates, the final magnetic property for influencing product magnetic particle modified carbon nano-tube.
Embodiment 4:
Step 1: weighing the carbon nanotube of 0.5g intracavity diameter 60nm, be added in three-necked flask, and 25mL mass is added
70% nitric acid solution of percent concentration is formed by suspension and heating stirring and maintains the reflux for 30min under the conditions of 130 DEG C.In advance
After the reaction was completed, by product eccentric cleaning, centrifugal speed 4000r/min, the time is 30min/ times, and washing lotion is deionization for processing
Water, centrifugation to supernatant liquor are neutrality.It is filtered after the completion of centrifugation, filter membrane used is the miillpore filter that aperture is 200um, and washing lotion is
Deionized water filters 3 times, and after the completion of suction filtration, being placed on drying in vacuum oven, for 24 hours, drying box temperature is 50 DEG C；It is dry to complete
Acidification carbon pipe is put into charing process in horizontal retort again afterwards, heating rate is 3 DEG C/min, is warming up to 850 DEG C, later
1h is kept the temperature, pretreated carbon nanotube is obtained.
Step 2: six ferrous sulfate hydrate ammonium of 1.2g is added in the mixed solution of 40ml deionized water and hydrazine hydrate
(deionized water and the volume ratio of hydrazine hydrate be 3:1) is then added nitric acid oxidation and carbonizes pretreated carbon nanotube, lead to nitrogen
30min, re-ultrasonic dispersion are stirred 60min, adjust pH value to the 1.5h that flows back at 11,135 DEG C with ammonium hydroxide after ultrasound, product is logical
It filters after crossing centrifugation purification and dries in a vacuum drying oven.Washing lotion when centrifugation filters is deionized water or ethyl alcohol.In obtaining
Fill Fe3O4Magnetic particle modified carbon nano-tube MWCNTs-Fe3O4。
Step 3: by 0.5g above prepared interior filling Fe3O4Magnetic particle modified carbon nano-tube MWCNTs-Fe3O4
It is added to 70% nitric acid of mass percent concentration and 70% sulfuric acid mixed acid of mass percent concentration that 64ml volume ratio is 1:3
In, 60min is stirred at reflux at 130 DEG C, product filtration drying obtains carboxylic carbon nano-tube；2g carboxylic is added in round-bottomed flask
Base carbon nano tube, 2ml acetic acid, 98ml ethyl alcohol, 2ml Silane coupling agent KH550 mix, after sealing ultrasound 30min at 50 DEG C
Reaction is for 24 hours.Vacuum filtration, is dried in vacuo at 60 DEG C, obtains dry functionalized carbon nano-tube；0.8g function is added in flask
After device is placed in ice bath, the alpha-brominated isobutyl acylbromide of 3ml is added in energy carbon nano tube, 28ml tetrahydrofuran and triethylamine.It drips off
Afterwards, 48h is reacted at 30 DEG C.Vacuum filtration, is dried in vacuo at 60 DEG C, obtains containing bromination carbon nanotube；Add in flask
Enter the carbon nanotube that 0.2g contains bromine, 3ml methyl methacrylate (GMA) monomer, 1ml pentamethyl-diethyl triamine
(PMDETA), in 25ml dimethylformamide (DMF), lead to nitrogen 30min.0.01gCuBr is added, reacts 3h at 30 DEG C.Very
Empty pump filter, is dried in vacuo at 60 DEG C, and the carbon nanotube MWCNTs- of surface grafting polymethyl methacrylate (PGMA) is made
Fe3O4-PGMA；0.2gMWCNTs-Fe is added in round-bottomed flask3O4- PGMA, 40ml dehydrated alcohol, ultrasonic disperse 30min, then
1ml ethylenediamine solution is added, ultrasonic disperse 5min reacts for 24 hours under the conditions of 50 DEG C.Product, centrifuge separation 6 are washed with dehydrated alcohol
It is secondary, 20min/ times, revolving speed 4000r/min.It is filtered by vacuum after centrifugation, miillpore filter aperture is 100um.Product will be filtered
50 DEG C of dry 30h are placed in vacuum drying oven, dry MWCNTs-Fe is obtained3O4-NH2；In three-necked flask be added 200ml go from
Sub- water, sequentially adds 1.512gNaHCO3、0.212gNaCO3, 1.472gNaCl, 0.1g MWCNTs- is added after stirring and dissolving
Fe3O4-NH2, ultrasonic disperse 30min；1ml DMSO solution is added in beaker, 0.0001g fluorescein phycoerythrin PE is protected from light
Under the conditions of sufficiently dissolve；PE/DMSO mixed liquor is added dropwise in three-necked flask, is protected from light 8h under room temperature.Use deionized water
It washs colourless to upper liquid, is then filtered by vacuum repeatedly, miillpore filter aperture is 200um.Product will be filtered and be placed in vacuum drying oven
In 40 DEG C of dry 36h, obtain MWCNTs-Fe3O4- PE, all processes pay attention to being protected from light.
Comparative example 4:
The additional amount of ethylenediamine is changed to 0.5ml in step 3, and as the condition in example 4, preparation has remaining step
The interior filling magnetic particle magnetic carbon nano-tube of fluorescent characteristic.As a result, it has been found that the interior filling magnetic particle magnetic of fluorescent characteristic obtained
Property carbon nanotube fluorescence response it is not strong, it is existing that apparent fluorescence response is not observed under laser scanning co-focusing microscope
As illustrating that the reduction of ethylenediamine additional amount causes the content of graft reaction group to reduce, so that fluorescein fluorescence group load capacity
It reduces, the fluorescent characteristic of the final interior filling magnetic particle magnetic carbon nano-tube for influencing to have fluorescent characteristic.
Embodiment 5:
Step 1: weighing the carbon nanotube of 0.5g intracavity diameter 30nm, be added in three-necked flask, and 25mL mass is added
70% nitric acid solution of percent concentration is formed by suspension and heating stirring and maintains the reflux for 30min under the conditions of 130 DEG C.In advance
After the reaction was completed, by product eccentric cleaning, centrifugal speed 4000r/min, the time is 30min/ times, and washing lotion is deionization for processing
Water, centrifugation to supernatant liquor are neutrality.It is filtered after the completion of centrifugation, filter membrane used is the miillpore filter that aperture is 200um, and washing lotion is
Deionized water filters 3-5 times, and after the completion of suction filtration, being placed on drying in vacuum oven, for 24 hours, drying box temperature is 50 DEG C；It has dried
Acidification carbon pipe is put into charing process in horizontal retort by Cheng Houzai, and heating rate is 3 DEG C/min, is warming up to 800 DEG C, it
After keep the temperature 1.5h, obtain pretreated carbon nanotube.
Step 2: six ferrous sulfate hydrate ammonium of 1.2g is added in the mixed solution of 40ml deionized water and hydrazine hydrate
(deionized water and the volume ratio of hydrazine hydrate be 3:1) is then added nitric acid oxidation and carbonizes pretreated carbon nanotube, lead to nitrogen
30min, re-ultrasonic dispersion are stirred 60min, adjust pH value to the 1h that flows back at 13,125 DEG C with ammonium hydroxide after ultrasound, product passes through
It filters after centrifugation purification and dries in a vacuum drying oven.Washing lotion when centrifugation filters is deionized water or ethyl alcohol.It is filled out in obtaining
Fill Fe3O4Magnetic particle modified carbon nano-tube MWCNTs-Fe3O4。
Step 3: by 0.5g above prepared interior filling Fe3O4Magnetic particle modified carbon nano-tube MWCNTs-Fe3O4
It is added to 70% nitric acid of mass percent concentration and 70% sulfuric acid mixed acid of mass percent concentration that 100ml volume ratio is 1:3
In, 30min is stirred at reflux at 130 DEG C, product filtration drying obtains carboxylic carbon nano-tube；2g carboxylic is added in round-bottomed flask
Base carbon nano tube, 2ml acetic acid, 98ml ethyl alcohol, 2ml Silane coupling agent KH550 mix, after sealing ultrasound 30min at 50 DEG C
Reaction is for 24 hours.Vacuum filtration, is dried in vacuo at 60 DEG C, obtains dry functionalized carbon nano-tube；0.8g function is added in flask
After device is placed in ice bath, the alpha-brominated isobutyl acylbromide of 3ml is added in energy carbon nano tube, 28ml tetrahydrofuran and triethylamine.It drips off
Afterwards, 48h is reacted at 30 DEG C.Vacuum filtration, is dried in vacuo at 60 DEG C, obtains containing bromination carbon nanotube；Add in flask
Enter the carbon nanotube that 0.2g contains bromine, 4ml methyl methacrylate (GMA) monomer, 1.5ml pentamethyl-diethyl triamine
(PMDETA), in 10ml dimethylformamide (DMF), lead to nitrogen 30min.0.015gCuBr is added, reacts 3h at 30 DEG C.Very
Empty pump filter, is dried in vacuo at 60 DEG C, and the carbon nanotube MWCNTs- of surface grafting polymethyl methacrylate (PGMA) is made
Fe3O4-PGMA；0.2gMWCNTs-Fe is added in round-bottomed flask3O4- PGMA, 40ml dehydrated alcohol, ultrasonic disperse 30min, then
3ml ethylenediamine solution is added, ultrasonic disperse 5min reacts for 24 hours under the conditions of 50 DEG C.Product, centrifuge separation 6 are washed with dehydrated alcohol
It is secondary, 20min/ times, revolving speed 4000r/min.It is filtered by vacuum after centrifugation, miillpore filter aperture is 200um.Product will be filtered
It is placed in vacuum drying oven 55 DEG C of dryings for 24 hours, obtains dry MWCNTs-Fe3O4-NH2；In three-necked flask be added 200ml go from
Sub- water, sequentially adds 1.512gNaHCO3、0.212gNaCO3, 1.472gNaCl, 0.1g MWCNTs- is added after stirring and dissolving
Fe3O4-NH2, ultrasonic disperse 30min；1ml DMSO solution, 0.0005g fluorescein isothiocyanate fluorescein are added in beaker
FITC sufficiently dissolves under the conditions of being protected from light；FITC/DMSO mixed liquor is added dropwise in three-necked flask, is protected from light under room temperature
10h.It is washed with deionized water colourless to upper liquid, is then filtered by vacuum repeatedly, miillpore filter aperture is 200um.It is produced filtering
Object is placed in vacuum drying oven 40 DEG C of dry 40h, obtains MWCNTs-Fe3O4- FITC, all processes pay attention to being protected from light.
Comparative example 5:
The additional amount of FITC is changed to 0.0001g in step 3, and as the condition in example 5, preparation has remaining step
The interior filling magnetic particle magnetic carbon nano-tube of fluorescent characteristic.As a result, it has been found that the interior filling magnetic particle magnetic of fluorescent characteristic obtained
Property carbon nanotube fluorescence response it is not strong, it is existing that apparent fluorescence response is not observed under laser scanning co-focusing microscope
As, illustrate that the reduction of FITC additional amount leads to the reduction of fluorescein fluorescence group load capacity, it is final to influence that there is the interior of fluorescent characteristic
Fill the fluorescent characteristic of magnetic particle magnetic carbon nano-tube.
Embodiment 6:
Step 1: weighing the carbon nanotube of 0.5g intracavity diameter 60nm, be added in three-necked flask, and 25mL mass is added
70% nitric acid solution of percent concentration is formed by suspension and heating stirring and maintains the reflux for 30min under the conditions of 130 DEG C.In advance
After the reaction was completed, by product eccentric cleaning, centrifugal speed 4000r/min, the time is 30min/ times, and washing lotion is deionization for processing
Water, centrifugation to supernatant liquor are neutrality.It is filtered after the completion of centrifugation, filter membrane used is the miillpore filter that aperture is 200um, and washing lotion is
Deionized water filters 3-5 times, and after the completion of suction filtration, being placed on drying in vacuum oven, for 24 hours, drying box temperature is 50 DEG C；It has dried
Acidification carbon pipe is put into charing process in horizontal retort by Cheng Houzai, and heating rate is 5 DEG C/min, is warming up to 800 DEG C, it
After keep the temperature 2h, obtain pretreated carbon nanotube.
Step 2: six ferrous sulfate hydrate ammonium of 1.2g is added in the mixed solution of 40ml deionized water and hydrazine hydrate
(deionized water and the volume ratio of hydrazine hydrate be 3:1) is then added nitric acid oxidation and carbonizes pretreated carbon nanotube, lead to nitrogen
30min, re-ultrasonic dispersion are stirred 60min, adjust pH value to the 2h that flows back at 12,115 DEG C with ammonium hydroxide after ultrasound, product passes through
It filters after centrifugation purification and dries in a vacuum drying oven.Washing lotion when centrifugation filters is deionized water or ethyl alcohol.It is filled out in obtaining
Fill Fe3O4Magnetic particle modified carbon nano-tube MWCNTs-Fe3O4。
Step 3: by 0.5g above prepared interior filling Fe3O4Magnetic particle modified carbon nano-tube MWCNTs-Fe3O4
It is added to 70% nitric acid of mass percent concentration and 70% sulfuric acid mixed acid of mass percent concentration that 64ml volume ratio is 1:3
In, 90min is stirred at reflux at 120 DEG C, product filtration drying obtains carboxylic carbon nano-tube；2g carboxylic is added in round-bottomed flask
Base carbon nano tube, 2ml acetic acid, 98ml ethyl alcohol, 2ml Silane coupling agent KH550 mix, after sealing ultrasound 30min at 50 DEG C
Reaction is for 24 hours.Vacuum filtration, is dried in vacuo at 60 DEG C, obtains dry functionalized carbon nano-tube；0.8g function is added in flask
After device is placed in ice bath, the alpha-brominated isobutyl acylbromide of 3ml is added in energy carbon nano tube, 28ml tetrahydrofuran and triethylamine.It drips off
Afterwards, 48h is reacted at 30 DEG C.Vacuum filtration, is dried in vacuo at 60 DEG C, obtains containing bromination carbon nanotube；Add in flask
Enter the carbon nanotube that 0.2g contains bromine, 2ml methyl methacrylate (GMA) monomer, 0.05ml pentamethyl-diethyl triamine
(PMDETA), in 45ml dimethylformamide (DMF), lead to nitrogen 30min.0.09gCuBr is added, reacts 3h at 30 DEG C.Very
Empty pump filter, is dried in vacuo at 60 DEG C, and the carbon nanotube MWCNTs- of surface grafting polymethyl methacrylate (PGMA) is made
Fe3O4-PGMA；0.2gMWCNTs-Fe is added in round-bottomed flask3O4- PGMA, 40ml dehydrated alcohol, ultrasonic disperse 30min, then
1ml ethylenediamine solution is added, ultrasonic disperse 5min reacts for 24 hours under the conditions of 50 DEG C.Product, centrifuge separation 6 are washed with dehydrated alcohol
It is secondary, 20min/ times, revolving speed 4000r/min.It is filtered by vacuum after centrifugation, miillpore filter aperture is 200um.Product will be filtered
60 DEG C of dry 36h are placed in vacuum drying oven, dry MWCNTs-Fe is obtained3O4-NH2；In three-necked flask be added 200ml go from
Sub- water, sequentially adds 1.512gNaHCO3、0.212gNaCO3, 1.472gNaCl, 0.1g MWCNTs- is added after stirring and dissolving
Fe3O4-NH2, ultrasonic disperse 30min；1ml DMSO solution, 0.002g fluorescein isothiocyanate fluorescein are added in beaker
FITC sufficiently dissolves under the conditions of being protected from light；FITC/DMSO mixed liquor is added dropwise in three-necked flask, is protected from light 4h under room temperature.
It is washed with deionized water colourless to upper liquid, is then filtered by vacuum repeatedly, miillpore filter aperture is 100um.Product will be filtered to set
50 DEG C of dry 40h, obtain MWCNTs-Fe in vacuum drying oven3O4- FITC, all processes pay attention to being protected from light.
Comparative example 6:
Being protected from light the time in step 3 is changed to 2h, and for remaining step as the condition in example 6, preparation has fluorescence special
The interior filling magnetic particle magnetic carbon nano-tube of property.As a result, it has been found that the interior filling magnetic particle magnetic carbon of fluorescent characteristic obtained is received
The fluorescence response of mitron is not strong, and apparent fluorescence response phenomenon, explanation are not observed under laser scanning co-focusing microscope
In fluorescein fluorescence group graft reaction step, the reduction in reaction time leads to the reduction of fluorescein fluorescence group grafting amount, most
The fluorescent characteristic with the interior filling magnetic particle magnetic carbon nano-tube of fluorescent characteristic is influenced eventually.
Claims (6)
1. a kind of preparation method of the magnetic carbon nano-tube with fluorescent characteristic, it is characterised in that: A, to original carbon nanotubes into
Row nitric acid acidizing pretreatment and charing pretreatment；B, using being heated to reflux and hydro-thermal method, magnetic particle is uniformly filled in step A
In obtained pretreatment carbon nanotube cavity, interior filling magnetic particle modified carbon nano-tube is obtained；C, with interior obtained in step B
Filling magnetic particle modified carbon nano-tube is raw material, and the fluorescer containing fluorophor is grafted to its surface, is obtained with fluorescence
The magnetic carbon nano-tube of characteristic.
2. preparation method according to claim 1, it is characterised in that the original carbon nanotubes are that intracavity diameter range is
30-60nm。
3. preparation method according to claim 1, it is characterised in that carried out being acidified-carbonizing first to original carbon nanotubes
Pretreatment, acidizing pretreatment time are 0.5-1.5h, and heating rate is 3-5 DEG C/min in charing pretreatment, is warming up to 800-900
DEG C, soaking time is 1-3h later.
4. preparation method according to claim 1, it is characterised in that fill magnetic particle modified carbon nano-tube in preparation
In the process, being heated to reflux temperature is 115-135 DEG C, and being heated to reflux the time is 1-2h.
5. preparation method according to claim 1, it is characterised in that the fluorescer is fluorescein isothiocynate, tetraethyl
One of rhodamine, tetramethylisothiocyanate rhodamine, propidium iodide, phycoerythrin.
6. preparation method according to claim 1, it is characterised in that during being grafted fluorescer:
(1) first with acidification method in surface grafting-COOH reaction active groups, acid used is that 50-100ml volume ratio is
70% nitric acid of mass percent concentration and 70% sulfuric acid mixed acid of mass percent concentration of 1:3, is stirred back at 90-130 DEG C
Flow 30-90min；
(2) with the interior filling Fe of acidification3O4Magnetic particle modified carbon nano-tube MWCNTs-Fe3O4- COOH is raw material, is utilized
Atom transfer radical polymerization ATRP method is using Silane coupling agent KH550 as reactant, in carbon nano tube surface grafting-NH2, carbon receives
The molal weight ratio of mitron and KH550 are 1:0.5~1:5；Using grafted amino group carbon nanotube as raw material, using ATRP method with α-
Bromo isobutyl acylbromide BIBB is reactant, and in carbon nano tube surface grafting-Br, the molal weight ratio of carbon nanotube and BIBB are
1:1~1:5；To be grafted bromine group carbon nanotube as raw material, using ATRP method using methyl methacrylate GMA as reactant,
The molal weight ratio of carbon nano tube surface grafting-PGMA, carbon nanotube and GMA are 1:5~1:20；To be grafted polymethyl
Sour methyl esters group carbon nanotube is raw material, using ATRP method using ethylenediamine EDA as reactant, in carbon nano tube surface grafting-
NH2, the molal weight ratio of carbon nanotube and EDA are 1:5~1:15；Vacuum pumping is carried out to product after the completion of every step graft reaction
Filter, miillpore filter aperture are 100-200um, after the completion of suction filtration place the product in vacuum drying oven in 50-60 DEG C of dry 24-36h；
(3) by products therefrom MWCNTs-Fe3O4-NH2It is dissolved in deionized water, fluorescer is added and carries out fluorescer in product table
The molal weight ratio of the graft reaction step in face, fluorescer and carbon nanotube is 1:1000~1:50, is protected from light under room temperature
2-12h, is washed with deionized water colourless to upper liquid repeatedly after the reaction was completed, is then filtered by vacuum, miillpore filter aperture is
100-200um；Product will be filtered and be placed in vacuum drying oven 40-60 DEG C of dry 36-48h, obtain MWCNTs-Fe3O4-R；The R
For fluorescer, whole process is protected from light in above-mentioned all reactions and suction filtration drying process.
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| CN101723311A (en) * | 2009-11-06 | 2010-06-09 | 武汉理工大学 | Magnetic flourescent nano material for magnetic-photo sensor and preparation method thereof |
| CN102513086A (en) * | 2011-11-09 | 2012-06-27 | 中国科学院福建物质结构研究所 | Compound material of carbon nano tube (CNT) and preparation method thereof |
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| CN101058418A (en) * | 2007-04-12 | 2007-10-24 | 上海交通大学 | Poly(glycidyl methacrylate), carbon nano-tube modified by derivative of the same and preparation method thereof |
| CN101723311A (en) * | 2009-11-06 | 2010-06-09 | 武汉理工大学 | Magnetic flourescent nano material for magnetic-photo sensor and preparation method thereof |
| CN102513086A (en) * | 2011-11-09 | 2012-06-27 | 中国科学院福建物质结构研究所 | Compound material of carbon nano tube (CNT) and preparation method thereof |
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