CN104528687A - Method for reversibly regulating and controlling agglomeration and dispersion of single-walled carbon nanotubes (SWNTs) by virtue of electrochemical oxidation-reduction - Google Patents
Method for reversibly regulating and controlling agglomeration and dispersion of single-walled carbon nanotubes (SWNTs) by virtue of electrochemical oxidation-reduction Download PDFInfo
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Abstract
The invention belongs to the technical field of methods for dispersing carbon nanotubes and particularly relates to a method for reversibly regulating and controlling agglomeration and dispersion of single-walled carbon nanotubes (SWNTs) by virtue of electrochemical redox. The method comprises the following steps: adding an electrolyte into an aqueous solution of a supramolecular polymer-SWNTs composite and uniformly mixing; applying a positive potential to the system so that nanotubes are agglomerated; and applying a reverse potential to the system so that the SWNTs are re-dispersed. According to the method, by the non-covalent interaction of pyrene and the SWNTs, the SWNTs are modified so as to avoid the interference of inherent characteristics of carbon nano-materials; and the dispersion of carbon nanotubes in water is regulated by virtue of the electrochemical redox clean stimulating means and no impurity is introduced into the system to facilitate the recycling.
Description
Technical field
The invention belongs to the dispersing method technical field of carbon nanotube, particularly a kind of method of reuniting by the reversible regulation and control Single Walled Carbon Nanotube of electrochemical redox and disperseing.
Background technology
As a kind one-dimensional carbon nanomaterial, carbon nanotube is paid close attention to widely because the photo electric of its excellence, physical strength and chemical stability receive over the last couple of decades.This kind of columned nanostructure all shows good application prospect at numerous areas such as photodetector, solar cell, sensor, energy transformation and storing devices.But, owing to there is attraction and the hydrophobic interaction of Van der Waals force between carbon nanotube, carbon nanotube exists with the form of tube bank usually, this just causes the generation of interaction energy (about 1000eV) between carbon pipe, not only bring great puzzlement to product manufacturing, also seriously limit their application.Therefore the Study on dispersity of this kind of carbon nanomaterial is had great importance.But even if use traditional physical means as ultrasonic and ball milled, it is also difficult to disperse and be dissolved in various common solvents, especially in water.In order to address this problem, people improve the dispersiveness of carbon pipe often through covalent coupling reaction or non-covalent addition.Wherein, non-covalent modification owing to can avoid interference the intrinsiccharacteristic of carbon nanomaterial, and receives the favor of more and more investigator.
For ease of better application, Single Walled Carbon Nanotube not only should be able to be disperseed in a solvent, needs to stimulate to external world have response characteristic simultaneously.Utilizing water miscible stimulating responsive polymer to carry out functional modification to Single Walled Carbon Nanotube is one of important solution.Until now, several stimulating responsive polymer has been employed successfully in non-covalent modification Single Walled Carbon Nanotube.The NIPA (PNIPAM) that Grunlan etc. utilize pyrene to mark and poly-(N-cyclopropyl acrylamide) (PNCPA) functionalized Single Walled Carbon Nanotube respectively, construct temperature response type single-walled carbon nanotube dispersion liquid (J.C.Grunlan et al., Macromol.Rapid Commun.2010,31,1368; J.C.Grunlan et al., J.Am.Chem.Soc.2009,131,13598).Kim etc. find stripping and the gathering (Y.S.Kim et al., Nano Lett.2006,6,911) that can realize controlling Single Walled Carbon Nanotube by the polyacrylic acid (PAA) of pH sensitivity.Based on the reversible host-guest interaction between cyclodextrin and nitrogen benzide, Feng etc. develop " intelligence " Single Walled Carbon Nanotube (Y.J.Feng et al., Adv.Funct.Mater.2013,23,5010) of a kind of novel photoswitch.And electrochemical redox is a kind of clean stimulation means, while realizing transfer transport redox reaction, in system, not introducing impurity, so there is reasonable repeatability, having important using value for constructing intelligent device material.
Summary of the invention
The object of the present invention is to provide a kind of method of reuniting by the reversible regulation and control Single Walled Carbon Nanotube (SWNTs) of electrochemical redox and disperseing.The SWNTs system prepared by the method can realize repeatable reunion and dispersion in aqueous.
First synthesize in this project and constructed the end modified supermolecule polymer polyoxyethylene glycol-ferrocene@beta-cyclodextrin-pyrene (PEO-Fc@β-CD-Py) having pyrenyl group, interacted by polymer overmold at carbon tube-surface by the π-π between pyrenyl group and carbon tube wall, the hydrophilic interaction due to polyoxyethylene glycol (PEO) chain makes hybrid have good dispersion in aqueous.Again due to existence that ferrocene-cyclodextrin host-guest interaction is right, under the regulation and control that electrochemical oxidation (positive potential) stimulates, ferrocene becomes positively charged lotus, from cyclodextrin cavity, de-embedding out, thus PEO chain can be departed from from carbon tube-surface, and carbon pipe reassembles and becomes and do not disperse; Under the stimulation of electrochemical reduction (negative potential), ferrocene is got back to reduction-state and can be again combined with cyclodextrin again, and system is disperseed again in aqueous phase.Dispersion and the accumulation process of the lower carbon pipe of such electrochemical redox regulation and control can circulate repeatedly.
Compound shown in formula I provided by the invention,
Invention also provides the preparation method of compound shown in above-mentioned formula I, comprise the steps:
(1) get beta-cyclodextrin (β-CD) to dissolve in the basic conditions, through Tosyl chloride (TsCl) activation, obtain compound shown in formula II with excessive reacting ethylenediamine;
(2) there is condensation reaction in compound shown in formula II and pyrene butyric acid under the effect of condensing agent dicyclohexylcarbodiimide (DCC) and activator N-hydroxy-succinamide (NHS), obtains compound shown in formula I.
As shown in Figure 2, shown in formula I, compound is abbreviated as β-CD-Py to the preparation flow figure of polymkeric substance shown in formula I, and shown in formula II, compound is abbreviated as β-CD-EDA.
Above-mentioned preparation method, in step (1), described alkaline condition can be any one in sodium hydroxide, potassium hydroxide aqueous solution;
The mol ratio of described beta-cyclodextrin and described Tosyl chloride can be 1:(1 ~ 3), be preferably 1:1.5;
The mol ratio of described formula II compound and pyrene butyric acid, dicyclohexylcarbodiimide (DCC) and N-hydroxy-succinamide (NHS) can be (1.5 ~ 3): 1:(1.5 ~ 3): (1.5 ~ 3), are preferably 2:1:2:2.
Above-mentioned preparation method, solvent described in step (2) can be the one in DMF (DMF), N,N-dimethylacetamide (DMAC), methyl-sulphoxide (DMSO), reaction times is 0.5 ~ 1 day, is preferably 0.5 day; Temperature of reaction is 20 DEG C ~ 35 DEG C, is preferably 25 DEG C.
Invention further provides polymkeric substance shown in formula III,
Invention also provides the preparation method of polymkeric substance shown in above-mentioned formula III, comprise the steps:
(1) there is condensation reaction in poly glycol monomethyl ether and ferrocenecarboxylic acid under the effect of condensing agent dicyclohexylcarbodiimide (DCC) and catalyzer DMAP (DMAP), obtains polymkeric substance shown in formula III.
As shown in Figure 3, shown in formula III, polymkeric substance is abbreviated as PEO-Fc to the preparation flow figure of polymkeric substance shown in formula III of the present invention.
Above-mentioned preparation method, in step (1), the molecular-weight average of described poly glycol monomethyl ether is 5000, is purchased from Sigma-Aldrich.
The mol ratio of described poly glycol monomethyl ether and ferrocenecarboxylic acid, dicyclohexylcarbodiimide (DCC) and DMAP (DMAP) can be 1:(5 ~ 10): (5 ~ 10): 0.5, are preferably 1:6:6:0.5.
Described solvent can be the one in methylene dichloride, trichloromethane, and the reaction times is 1 ~ 3 day, is preferably 2 days; Temperature of reaction is 20 DEG C ~ 35 DEG C, is preferably 25 DEG C.
Invention further provides the application of polymkeric substance shown in compound shown in formula I and formula III in dispersion Single Walled Carbon Nanotube.
Invention further provides the dispersing method of Single Walled Carbon Nanotube, comprise the steps:
(1) β-CD-Py and Single Walled Carbon Nanotube are mixed in organic solvent, dispersed rear filtration vacuum-drying obtains solid.
(2) solid obtained in the previous step and prepared PEO-Fc are fully mixed in water, namely realize the dispersion of described Single Walled Carbon Nanotube in water.
The preparation flow figure of the Single Walled Carbon Nanotube of disperseing in this step water as shown in Figure 1, is labeled as supermolecule polymer-SWNTs compound water solution.
The medium (as shown in Figure 1) that above-mentioned dispersing method mainly utilizes the pyrenyl group in compound shown in formula I to be connected with Single Walled Carbon Nanotube (SWNTs) as polymkeric substance, is acted on by π-π and combining with carbon nanotube.Again by the host-guest interaction of ferrocene and beta-cyclodextrin, hydrophilic polymer segment PEO is modified at single tube-surface, Single Walled Carbon Nanotube thus can be made to be disperseed fully in water.
In above-mentioned dispersing method, in step (1), shown in described Single Walled Carbon Nanotube and formula I, the mass ratio of compound can be 1:(4 ~ 20), be preferably 1:4,1:10 or 1:20;
Described organic solvent is the one in DMF, DMAC, DMSO;
Compound and Single Walled Carbon Nanotube shown in formula I specifically can mix under ultrasonication, and ultrasonic time specifically can be 15min ~ 30min, are preferably 20min; Described filter operation can use the filtering with microporous membrane 2 times of 200nm, and the vacuum-drying time can be 2 days.
In step (2), the mass ratio of described solid obtained in the previous step and polymer P EO-Fc can be 1:(2 ~ 10), be preferably 1:2.5,1:5 or 1:10;
Described solid obtained in the previous step and Single Walled Carbon Nanotube specifically can mix under ultrasonication, and ultrasonic time is preferably 30min; And then with centrifugal under centrifuge speed 4000rpm ~ 8000rpm, centrifugation time is preferably 10min.
The present invention on this basis, further provides a kind of method stimulating reversible regulation and control Single Walled Carbon Nanotube to reunite and disperse by electrochemical redox, comprises the steps:
In supermolecule polymer-SWNTs compound water solution, add ionogen and mix.The reunion that namely 1.0V positive potential realizes nanotube is applied in system; And then-1.0V negative potential is passed in system, the dispersion again of Single Walled Carbon Nanotube system can be realized.
Become positively charged under the regulation and control that above-mentioned dispersing method mainly utilizes ferrocene to stimulate at electrochemical oxidation (positive potential) lotus, from cyclodextrin cavity, de-embedding out, thus PEO chain can be departed from from carbon tube-surface, carbon pipe reassembles and becomes and do not disperse; Under the stimulation of electrochemical reduction (negative potential), ferrocene is got back to reduction-state and can be again combined with cyclodextrin again, and system is disperseed again in aqueous phase.
In above-mentioned dispersing method, described ionogen is any one in SODIUM PHOSPHATE, MONOBASIC, Repone K, Potassium Bromide, saltpetre, and in supermolecule polymer-SWNTs compound water solution, electrolytical concentration is 0.1mol/L ~ 0.3mol/L, is preferably 0.2mol/L;
Electrochemical oxidation stimulates (applying positive potential) and electrochemical reduction stimulation (applying negative potential) to realize by the three-electrode system of electrochemical workstation, wherein working electrode and be platinized platinum to electrode, and reference electrode is Ag-AgCl electrode; The time of described applying positive potential and negative potential is respectively 3 ~ 6 hours.
Beneficial effect of the present invention is:
1. by the noncovalent interaction of pyrene and SWNTs, SWNTs is modified, the intrinsiccharacteristic of carbon nanomaterial can be avoided interference;
2. the stimulation means utilizing this class of electrochemical redox to clean regulate the dispersion of carbon nanotube in water, do not introduce impurity, be beneficial to recycle in system.
Accompanying drawing explanation
Fig. 1 is reunited and the process flow diagram disperseed by the reversible regulation and control Single Walled Carbon Nanotube of electrochemical redox;
Fig. 2 is the process flow sheet of-CD-Py of compound β shown in synthesis type I;
Fig. 3 is the schema of polymer P EO-Fc shown in synthesis formula III;
Fig. 4 is the hydrogen nuclear magnetic resonance spectrogram of-CD-Py of compound β shown in formula I;
Fig. 5 is the mass spectrum of-CD-Py of compound β shown in formula I;
Fig. 6 is the hydrogen nuclear magnetic resonance spectrogram of the EO-Fc of polymer P shown in formula III;
Supermolecule polymer-SWNTs the mixture of Fig. 7 prepared by embodiment 1 stimulates the UV-visible-near infrared absorption figure of SWNTs in water of front and back and unmodified at electrochemical redox;
The magnified partial view of the supermolecule polymer-SWNTs mixture UV-visible-near infrared absorption figure in water of Fig. 8 prepared by embodiment 1;
Fig. 9 is the transmission electron microscope photo that in embodiment 1, supermolecule polymer-SWNTs mixture stimulates front and back dispersion liquid in water at electrochemical redox, wherein Fig. 9 (a) is the transmission electron microscope photo of the supermolecule polymer-SWNTs mixture of dispersion, and Fig. 9 (b) is the transmission electron microscope photo of the supermolecule polymer-SWNTs mixture of reuniting;
Figure 10 is the three-electrode system apparatus structure schematic diagram of conventional chemical workstation;
Number in the figure: 1-is to electrode, 2-reference electrode, 3-working electrode, 4-solution.
Embodiment
The invention provides a kind of method of being reunited by the reversible regulation and control Single Walled Carbon Nanotube of electrochemical redox and being disperseed, below in conjunction with the drawings and specific embodiments, the present invention will be further described.
The experimental technique used in following embodiment if no special instructions, is ordinary method.
Material used in following embodiment, reagent etc., if no special instructions, all can obtain from commercial channels.Embodiment 1
(1) β-CD-Py is synthesized:
Schema as shown in Figure 2.
A. get 20g beta-cyclodextrin (β-CD), be scattered in 167mL water, be dissolved in 7mL water by the NaOH of 2.19g, and be slowly added drop-wise in the suspension liquid of β-CD, final suspension liquid becomes clear soln.5.04g Tosyl chloride (TsCl) is dissolved in 10mL acetonitrile, is slowly added drop-wise in the aqueous solution of β-CD under ice-water bath, produces white precipitate.Drip completely, stirred at ambient temperature reacts 2 hours, and turbid solution is placed in 4 DEG C of refrigerator cold-storages and spends the night.Filtration obtains white precipitate, and in water recrystallization 3 times.Obtain target product β-CD-6-OTs 2.5g, yield: 10.7%.
B. get 5g β-CD-6-OTs and at 80 DEG C, react 4h with the quadrol of 30mL, after reaction terminates, cool to room temperature, revolve and boil off except most of responseless quadrol, product is dissolved in water-methanol (V/V=1:1), precipitates in acetone, 3 times like this.Obtain target product β-CD-EDA 4.68g, yield: 92.3%.
C. drop in the single port flask of 25mL by 500mg β-CD-EDA, 254mg pyrene butyric acid and 100mg N-hydroxy-succinamide (NHS), be dissolved in the DMF of 10mL drying altogether, ice bath is issued to stable.Another DMF condensing agent dicyclohexylcarbodiimide (DCC) 200mg being dissolved in 5mL drying, dropwise join in reaction system, rear reaction is spent the night.Precipitate in cold acetone after reaction terminates, centrifugal removing supernatant liquor, obtains product 580mg, yield 3 times: 76.9% so repeatedly.
As shown in Figure 4, mass spectrum as shown in Figure 5 for the proton nmr spectra of β-CD-Py prepared by the present embodiment.
M＝1448。
(2) PEO-Fc is synthesized:
Schema as shown in Figure 3.
2.2g PEO, 0.5g are dissolved in the methylene dichloride that 20mL dewatered little over ferrocenecarboxylic acid (FcA), 0.44g condensing agent DCC and the 24mgDMAP of amount, react 48 hours under room temperature, cross and filter by product, filtrate revolves steaming, crude product is dissolved in trichloromethane, unreacted FcA is removed with NaOH solution 10mL extracting, trichloromethane phase is collected after deionized water adjust ph weakly acidic pH, be deposited in diethyl ether solution, redissolve-precipitation process 3 times, by the white solid product vacuum-drying obtained, obtain target product PEO-Fc1.85g, yield: 69%.
The proton nmr spectra of PEO-Fc prepared by the present embodiment as shown in Figure 5.
M
n,NMR＝5.1kDa,M
n,GPC＝5.3kDa,M
w/M
n＝1.05.
(3) prepare supermolecule polymer-SWNTs mixture, and be dispersed in water:
A. dropped into by 100mg β-CD-Py in the single port flask of 250mL, add 100mL organic solvent DMF, fully dissolve, add 20mg SWNTs, ultrasonic 30min, SWNTs are in organic solvent dispersed.With the filtering with microporous membrane of 200nm, DMF washs 2 times, vacuum-drying 48h.Obtain β-CD-Py-SWNTs mixture 76mg, yield: 63.3%.
B. 20mg β-CD-Py-SWNTs, 50mg PEO-Fc are dropped in the single port flask of 50mL, add 20mL water, ultrasonic 30min under room temperature.And then with 10min centrifugal under centrifuge speed 4000rpm, obtain homodisperse supermolecule polymer-SWNTs complex solution in water.
The UV-visible-near infrared absorption of above-mentioned compound water solution as shown in Figure 7, as can be seen from this figure, a series of spikes at 750nm ~ 870nm place correspond to the characteristic absorbance of transistor, prove that such mixture obtains good dispersion in aqueous.
The transmission electron microscope photo of above-mentioned compound water solution, as shown in Fig. 9 (a), as can be seen from this figure, has between carbon pipe and mutually peels off preferably, obvious carbon pipe outer cladding of observing can one layer of polymeric, and after compound, diameter increases.
(4) reunion of the reversible regulation and control Single Walled Carbon Nanotube of electrochemical redox in water and dispersion:
Get in step (3) and obtain homodisperse supermolecule polymer-SWNTs complex solution 6mL in water, in system, add Repone K 100mg and mix.In system, apply 1.0V positive potential 6h, namely realize the reunion of nanotube; And then-1.0V negative potential is passed in system, the dispersion again of Single Walled Carbon Nanotube system can be realized.
After above-mentioned applying 1.0V positive potential 6h, the UV-visible-near infrared absorption of compound water solution as shown in Figure 7, as can be seen from this figure, the charateristic avsorption band of a series of transistors originally at 750nm ~ 870nm place disappears, and proves that carbon nanotube is reunited again in aqueous further.
After above-mentioned applying 1.0V positive potential 6h, the transmission electron microscope photo of compound water solution is as shown in Fig. 9 (b), and as can be seen from this figure, carbon pipe is reunited together again.
Embodiment 2
(1) β-CD-Py is synthesized:
A-c step is with embodiment 1.
(2) PEO-Fc is synthesized:
Step is with embodiment 1.
(3) prepare supermolecule polymer-SWNTs mixture, and be dispersed in water:
A. dropped into by 100mg β-CD-Py in the single port flask of 250mL, add 100mL organic solvent DMSO, fully dissolve, add 10mg SWNTs, ultrasonic 30min, SWNTs are in organic solvent dispersed.With the filtering with microporous membrane of 200nm, DMSO washs 2 times, vacuum-drying 48h.Obtain β-CD-Py-SWNTs mixture 54mg, yield: 49.1%.
B. 20mg β-CD-Py-SWNTs, 100mg PEO-Fc are dropped in the single port flask of 50mL, add 20mL water, ultrasonic 30min under room temperature.And then with 10min centrifugal under centrifuge speed 4000rpm, obtain homodisperse supermolecule polymer-SWNTs complex solution in water.
The UV-visible-near infrared absorption (Fig. 7) of the compound water solution prepared in the UV-visible-near infrared absorption of compound water solution prepared by the present embodiment and embodiment 1, without substantive difference, can be learnt: such mixture obtains good dispersion in aqueous.
The transmission electron microscope photo (Fig. 9) of the compound water solution prepared in the transmission electron microscope photo of compound water solution prepared by the present embodiment and embodiment 1, without significant difference, can be learnt: such mixture obtains good dispersion in aqueous.
(4) reunion of the reversible regulation and control Single Walled Carbon Nanotube of electrochemical redox in water and dispersion:
Get in step (3) and obtain homodisperse supermolecule polymer-SWNTs complex solution 6mL in water, in system, add Potassium Bromide 160mg and mix.In system, apply 1.0V positive potential 5h, namely realize the reunion of nanotube; And then-1.0V negative potential is passed in system, the dispersion again of Single Walled Carbon Nanotube system can be realized.
After the applying 1.0V positive potential 5h prepared in the UV-visible-near infrared absorption of compound water solution and embodiment 1 after applying 1.0V positive potential 5h prepared by the present embodiment, the UV-visible-near infrared absorption (Fig. 7) of compound water solution is without essential distinction, as seen from the figure: carbon nanotube is reunited again in aqueous further.
After the applying 1.0V positive potential 5h prepared in the transmission electron microscope photo of compound water solution and embodiment 1 after above-mentioned applying 1.0V positive potential 5h prepared by the present embodiment, the transmission electron microscope photo (Fig. 9) of compound water solution is without significant difference, as can be seen from this figure, carbon pipe is reunited together again.
Embodiment 3
(1) β-CD-Py is synthesized:
Schema as shown in Figure 2.
A. get 20g beta-cyclodextrin (β-CD), be scattered in 167mL water, be dissolved in 7mL water by the NaOH of 2.19g, and be slowly added drop-wise in the suspension liquid of β-CD, final suspension liquid becomes clear soln.10g Tosyl chloride (TsCl) is dissolved in 20mL acetonitrile, is slowly added drop-wise in the aqueous solution of β-CD under ice-water bath, produces white precipitate.Drip completely, stirred at ambient temperature reacts 2 hours, and turbid solution is placed in 4 DEG C of refrigerator cold-storages and spends the night.Filtration obtains white precipitate, and in water recrystallization 3 times.Obtain target product β-CD-6-OTs 2.8g, yield: 11.2%.
B. get 5g β-CD-6-OTs and at 80 DEG C, react 4h with the quadrol of 30mL, after reaction terminates, cool to room temperature, revolve and boil off except most of responseless quadrol, product is dissolved in water-methanol (V/V=1:1), precipitates in acetone, 3 times like this.Obtain target product β-CD-EDA 4.82g, yield: 93.7%.
C. drop in the single port flask of 25mL by 800mg β-CD-EDA, 5mg pyrene butyric acid and 200mg N-hydroxy-succinamide (NHS), be dissolved in altogether in the DMSO of 20mL drying, ice bath is issued to stable.Another DMSO condensing agent dicyclohexylcarbodiimide (DCC) 400mg being dissolved in 10mL drying, dropwise join in reaction system, rear reaction is spent the night.Precipitate in cold acetone after reaction terminates, centrifugal removing supernatant liquor, obtains product 608mg, yield 3 times: 79.5% so repeatedly.
(2) PEO-Fc is synthesized:
Step is with embodiment 1.
(3) prepare supermolecule polymer-SWNTs mixture, and be dispersed in water:
A. dropped into by 200mg β-CD-Py in the single port flask of 250mL, add 100mL organic solvent DMF, fully dissolve, add 10mg SWNTs, ultrasonic 30min, SWNTs are in organic solvent dispersed.With the filtering with microporous membrane of 200nm, DMF washs 2 times, vacuum-drying 48h.Obtain β-CD-Py/SWNTs mixture 57mg, yield: 50.9%.
B. 20mg β-CD-Py-SWNTs, 200mg PEO-Fc are dropped in the single port flask of 50mL, add 30mL water, ultrasonic 30min under room temperature.And then with 10min centrifugal under centrifuge speed 4000rpm, obtain homodisperse supermolecule polymer/SWNTs complex solution in water.
The UV-visible-near infrared absorption (Fig. 7) of the compound water solution prepared in the UV-visible-near infrared absorption of compound water solution prepared by the present embodiment and embodiment 1, without substantive difference, can be learnt: such mixture obtains good dispersion in aqueous.
The transmission electron microscope photo (Fig. 9) of the compound water solution prepared in the transmission electron microscope photo of compound water solution prepared by the present embodiment and embodiment 1, without significant difference, can be learnt: such mixture obtains good dispersion in aqueous.
(4) reunion of the reversible regulation and control Single Walled Carbon Nanotube of electrochemical redox in water and dispersion:
Get in step (3) and obtain homodisperse supermolecule polymer-SWNTs complex solution 6mL in water, in system, add saltpetre 136mg and mix.In system, apply 1.0V positive potential 4h, namely realize the reunion of nanotube; And then-1.0V negative potential is passed in system, the dispersion again of Single Walled Carbon Nanotube system can be realized.
After the applying 1.0V positive potential 4h prepared in the UV-visible-near infrared absorption of compound water solution and embodiment 1 after applying 1.0V positive potential 4h prepared by the present embodiment, the UV-visible-near infrared absorption (Fig. 7) of compound water solution is without essential distinction, as seen from the figure: carbon nanotube is reunited again in aqueous further.
After the applying 1.0V positive potential 4h prepared in the transmission electron microscope photo of compound water solution and embodiment 1 after above-mentioned applying 1.0V positive potential 4h prepared by the present embodiment, the transmission electron microscope photo (Fig. 9) of compound water solution is without significant difference, as can be seen from this figure, carbon pipe is reunited together again.
Embodiment 4
(1) β-CD-Py is synthesized:
A-c step is with embodiment 3.
(2) PEO-Fc is synthesized:
Schema as shown in Figure 3.
The ferrocenecarboxylic acid (FcA) of 2.2g PEO, 0.8g, 0.66g condensing agent DCC and 24mg DMAP are dissolved in the methylene dichloride that 20mL dewatered, react 72 hours under room temperature, cross and filter by product, filtrate revolves steaming, crude product is dissolved in trichloromethane, unreacted FcA is removed with NaOH solution 15mL extracting, trichloromethane phase is collected after deionized water adjust ph weakly acidic pH, be deposited in diethyl ether solution, redissolve-precipitation process 3 times, by the white solid product vacuum-drying obtained, obtain target product PEO-Fc 1.92g, yield: 74.2%.
(3) prepare supermolecule polymer-SWNTs mixture, and be dispersed in water:
A. dropped into by 200mg β-CD-Py in the single port flask of 250mL, add 100mL organic solvent DMF, fully dissolve, add 10mg SWNTs, ultrasonic 30min, SWNTs are in organic solvent dispersed.With the filtering with microporous membrane of 200nm, DMF washs 2 times, vacuum-drying 48h.Obtain β-CD-Py-SWNTs mixture 57mg, yield: 50.9%.
B. 20mg β-CD-Py-SWNTs, 200mg PEO-Fc are dropped in the single port flask of 50mL, add 30mL water, ultrasonic 30min under room temperature.And then with 10min centrifugal under centrifuge speed 4000rpm, obtain homodisperse supermolecule polymer-SWNTs complex solution in water.
The UV-visible-near infrared absorption (Fig. 7) of the compound water solution prepared in the UV-visible-near infrared absorption of compound water solution prepared by the present embodiment and embodiment 1, without substantive difference, can be learnt: such mixture obtains good dispersion in aqueous.
The transmission electron microscope photo (Fig. 9) of the compound water solution prepared in the transmission electron microscope photo of compound water solution prepared by the present embodiment and embodiment 1, without significant difference, can be learnt: such mixture obtains good dispersion in aqueous.
(4) reunion of electrochemical redox reversible regulation and control Single Walled Carbon Nanotube in water and dispersion: get in step (3) and obtain homodisperse supermolecule polymer-SWNTs complex solution 6mL in water, add saltpetre 136mg and mix in system.In system, apply 1.0V positive potential 4h, namely realize the reunion of nanotube; And then-1.0V negative potential is passed in system, the dispersion again of Single Walled Carbon Nanotube system can be realized.
After the applying 1.0V positive potential 4h prepared in the UV-visible-near infrared absorption of compound water solution and embodiment 1 after applying 1.0V positive potential 4h prepared by the present embodiment, the UV-visible-near infrared absorption (Fig. 7) of compound water solution is without essential distinction, as seen from the figure: carbon nanotube is reunited again in aqueous further.
After the applying 1.0V positive potential 4h prepared in the transmission electron microscope photo of compound water solution and embodiment 1 after above-mentioned applying 1.0V positive potential 4h prepared by the present embodiment, the transmission electron microscope photo (Fig. 9) of compound water solution is without significant difference, as can be seen from this figure, carbon pipe is reunited together again.
Embodiment 5
(1) β-CD-Py is synthesized:
A-c step is with embodiment 4.
(2) PEO-Fc is synthesized:
Step is with embodiment 4.
(3) prepare supermolecule polymer-SWNTs mixture, and be dispersed in water:
A. dropped into by 100mg β-CD-Py in the single port flask of 250mL, add 50mL organic solvent DMF, fully dissolve, add 10mg SWNTs, ultrasonic 30min, SWNTs are in organic solvent dispersed.With the filtering with microporous membrane of 200nm, DMF washs 2 times, vacuum-drying 48h.Obtain β-CD-Py-SWNTs mixture 53mg, yield: 48.9%.
B. 20mg β-CD-Py-SWNTs, 200mg PEO-Fc are dropped in the single port flask of 50mL, add 30mL water, ultrasonic 30min under room temperature.And then with 10min centrifugal under centrifuge speed 4000rpm, obtain homodisperse supermolecule polymer-SWNTs complex solution in water.
The UV-visible-near infrared absorption (Fig. 7) of the compound water solution prepared in the UV-visible-near infrared absorption of compound water solution prepared by the present embodiment and embodiment 1, without substantive difference, can be learnt: such mixture obtains good dispersion in aqueous.
The transmission electron microscope photo (Fig. 9) of the compound water solution prepared in the transmission electron microscope photo of compound water solution prepared by the present embodiment and embodiment 1, without significant difference, can be learnt: such mixture obtains good dispersion in aqueous.
(4) reunion of the reversible regulation and control Single Walled Carbon Nanotube of electrochemical redox in water and dispersion:
Get in step (3) and obtain homodisperse supermolecule polymer-SWNTs complex solution 6mL in water, in system, add Repone K 100mg and mix.In system, apply 1.0V positive potential 6h, namely realize the reunion of nanotube; And then-1.0V negative potential is passed in system, the dispersion again of Single Walled Carbon Nanotube system can be realized.
After the applying 1.0V positive potential 6h prepared in the UV-visible-near infrared absorption of compound water solution and embodiment 1 after applying 1.0V positive potential 6h prepared by the present embodiment, the UV-visible-near infrared absorption (Fig. 7) of compound water solution is without essential distinction, as seen from the figure: carbon nanotube is reunited again in aqueous further.
After the applying 1.0V positive potential 6h prepared in the transmission electron microscope photo of compound water solution and embodiment 1 after above-mentioned applying 1.0V positive potential 6h prepared by the present embodiment, the transmission electron microscope photo (Fig. 9) of compound water solution is without significant difference, as can be seen from this figure, carbon pipe is reunited together again.
Claims (31)
1. reunited and a method of disperseing by the reversible regulation and control Single Walled Carbon Nanotube of electrochemical redox, it is characterized in that, comprise the steps:
In supermolecule polymer-SWNTs compound water solution, add ionogen and mix; Even if apply positive potential nanotube to reunite in system; And then negative potential is applied in system, Single Walled Carbon Nanotube system is disperseed again.
2. a kind of method of reuniting by the reversible regulation and control Single Walled Carbon Nanotube of electrochemical redox and disperseing according to claim 1, it is characterized in that, described ionogen is any one in SODIUM PHOSPHATE, MONOBASIC, Repone K, Potassium Bromide, saltpetre, and in supermolecule polymer-SWNTs compound water solution, electrolytical concentration is 0.1mol/L ~ 0.3mol/L.
3. a kind of method of being reunited by the reversible regulation and control Single Walled Carbon Nanotube of electrochemical redox and being disperseed according to claim 1, it is characterized in that, in described supermolecule polymer-SWNTs compound water solution, electrolytical concentration is 0.2mol/L.
4. a kind of method of reuniting by the reversible regulation and control Single Walled Carbon Nanotube of electrochemical redox and disperseing according to claim 1, it is characterized in that, the three-electrode system of electrochemical workstation is used to apply electromotive force, wherein working electrode and platinized platinum is to electrode, reference electrode is Ag-AgCl electrode; The time of described applying positive potential and negative potential is respectively 3 ~ 6 hours.
5. a kind of method of being reunited by the reversible regulation and control Single Walled Carbon Nanotube of electrochemical redox and being disperseed according to claim 1, it is characterized in that, the preparation method of described supermolecule polymer-SWNTs compound water solution comprises the steps:
β-CD-Py and Single Walled Carbon Nanotube are mixed in organic solvent, dispersed rear filtration vacuum-drying obtains solid; Gained solid and PEO-Fc are fully mixed and disperse in water, obtains supermolecule polymer-SWNTs compound water solution.
6. a kind of method of reuniting by the reversible regulation and control Single Walled Carbon Nanotube of electrochemical redox and disperseing according to claim 5, it is characterized in that, the structural formula of described β-CD-Py is as follows:
7. a kind of method of being reunited by the reversible regulation and control Single Walled Carbon Nanotube of electrochemical redox and being disperseed according to claim 6, it is characterized in that, the preparation method of described β-CD-Py comprises the steps:
Get beta-cyclodextrin to dissolve in the basic conditions, through tolysulfonyl chlorine activation, obtain β-CD-EDA with excessive reacting ethylenediamine; There is condensation reaction in β-CD-EDA and pyrene butyric acid, obtain β-CD-Py under the effect of condensing agent dicyclohexylcarbodiimide and activator N-hydroxy-succinamide.
8. a kind of method of reuniting by the reversible regulation and control Single Walled Carbon Nanotube of electrochemical redox and disperseing according to claim 7, it is characterized in that, the structural formula of described β-CD-EDA is as follows:
9. a kind of method of being reunited by the reversible regulation and control Single Walled Carbon Nanotube of electrochemical redox and being disperseed according to claim 7, it is characterized in that, described alkaline condition is sodium hydroxide or potassium hydroxide aqueous solution.
10. a kind of method of reuniting by the reversible regulation and control Single Walled Carbon Nanotube of electrochemical redox and disperseing according to claim 7, it is characterized in that, the mol ratio of described beta-cyclodextrin and Tosyl chloride is 1:(1 ~ 3).
11. a kind of methods of being reunited by the reversible regulation and control Single Walled Carbon Nanotube of electrochemical redox and being disperseed according to claim 10, it is characterized in that, the mol ratio of described beta-cyclodextrin and Tosyl chloride is 1:1.5.
12. a kind of methods of reuniting by the reversible regulation and control Single Walled Carbon Nanotube of electrochemical redox and disperseing according to claim 7, it is characterized in that, described β-CD-EDA is (1.5 ~ 3) with the mol ratio of pyrene butyric acid, dicyclohexylcarbodiimide and N-hydroxy-succinamide: 1:(1.5 ~ 3): (1.5 ~ 3).
13. a kind of methods of reuniting by the reversible regulation and control Single Walled Carbon Nanotube of electrochemical redox and disperseing according to claim 12, it is characterized in that, described β-CD-EDA is 2:1:2:2 with the mol ratio of pyrene butyric acid, dicyclohexylcarbodiimide and N-hydroxy-succinamide.
14. a kind of methods of reuniting by the reversible regulation and control Single Walled Carbon Nanotube of electrochemical redox and disperseing according to claim 7, it is characterized in that, the solvent that condensation reaction uses occurs under the effect of condensing agent dicyclohexylcarbodiimide and activator N-hydroxy-succinamide for described β-CD-EDA and pyrene butyric acid is N, dinethylformamide, N, one in N-N,N-DIMETHYLACETAMIDE and methyl-sulphoxide, the reaction times is 0.5 ~ 1 day; Temperature of reaction is 20 DEG C ~ 35 DEG C.
15. a kind of methods of reuniting by the reversible regulation and control Single Walled Carbon Nanotube of electrochemical redox and disperseing according to claim 14, it is characterized in that, the reaction times that condensation reaction occurs under the effect of condensing agent dicyclohexylcarbodiimide and activator N-hydroxy-succinamide for described β-CD-EDA and pyrene butyric acid is 0.5 day, and temperature of reaction is 25 DEG C.
16. a kind of methods of reuniting by the reversible regulation and control Single Walled Carbon Nanotube of electrochemical redox and disperseing according to claim 5, it is characterized in that, the mass ratio of described Single Walled Carbon Nanotube and β-CD-Py is 1:(4 ~ 20).
17. a kind of methods of being reunited by the reversible regulation and control Single Walled Carbon Nanotube of electrochemical redox and being disperseed according to claim 16, it is characterized in that, the mass ratio of described Single Walled Carbon Nanotube and β-CD-Py is 1:4,1:10 or 1:20.
18. a kind of methods of reuniting by the reversible regulation and control Single Walled Carbon Nanotube of electrochemical redox and disperseing according to claim 5, it is characterized in that, described organic solvent is the one in DMF, N,N-dimethylacetamide and methyl-sulphoxide.
19. a kind of methods of reuniting by the reversible regulation and control Single Walled Carbon Nanotube of electrochemical redox and disperseing according to claim 5, it is characterized in that, described β-CD-Py and Single Walled Carbon Nanotube mix under ultrasonication, and ultrasonic time is 15min ~ 30min.
20. a kind of methods of being reunited by the reversible regulation and control Single Walled Carbon Nanotube of electrochemical redox and being disperseed according to claim 19, it is characterized in that, described ultrasonic time is 20min.
21. a kind of methods of being reunited by the reversible regulation and control Single Walled Carbon Nanotube of electrochemical redox and being disperseed according to claim 5, is characterized in that, the filtering with microporous membrane of described filter operation use 200nm 2 times, the vacuum-drying time is 2 days.
22. a kind of methods of reuniting by the reversible regulation and control Single Walled Carbon Nanotube of electrochemical redox and disperseing according to claim 5, it is characterized in that, the structural formula of described PEO-Fc is as follows:
23. a kind of methods of being reunited by the reversible regulation and control Single Walled Carbon Nanotube of electrochemical redox and being disperseed according to claim 22, it is characterized in that, the preparation method of described PEO-Fc comprises the steps:
There is condensation reaction in poly glycol monomethyl ether and ferrocenecarboxylic acid, obtain PEO-Fc under the effect of condensing agent dicyclohexylcarbodiimide and catalyzer DMAP.
24. a kind of methods of being reunited by the reversible regulation and control Single Walled Carbon Nanotube of electrochemical redox and being disperseed according to claim 23, it is characterized in that, the molecular-weight average of described poly glycol monomethyl ether is 5000.
25. a kind of methods of reuniting by the reversible regulation and control Single Walled Carbon Nanotube of electrochemical redox and disperseing according to claim 23, it is characterized in that, the mol ratio of described poly glycol monomethyl ether and ferrocenecarboxylic acid, dicyclohexylcarbodiimide and DMAP is 1:(5 ~ 10): (5 ~ 10): 0.5.
26. a kind of methods of reuniting by the reversible regulation and control Single Walled Carbon Nanotube of electrochemical redox and disperseing according to claim 23, it is characterized in that, the mol ratio of described poly glycol monomethyl ether and ferrocenecarboxylic acid, dicyclohexylcarbodiimide and DMAP is 1:6:6:0.5.
27. a kind of methods of reuniting by the reversible regulation and control Single Walled Carbon Nanotube of electrochemical redox and disperseing according to claim 23, it is characterized in that, the solvent that condensation reaction uses occurs under the effect of condensing agent dicyclohexylcarbodiimide and catalyzer DMAP for described poly glycol monomethyl ether and ferrocenecarboxylic acid is methylene dichloride or trichloromethane, and the reaction times is 1 ~ 3 day; Temperature of reaction is 20 DEG C ~ 35 DEG C.
28. a kind of methods of reuniting by the reversible regulation and control Single Walled Carbon Nanotube of electrochemical redox and disperseing according to claim 23, it is characterized in that, the reaction times that condensation reaction occurs under the effect of condensing agent dicyclohexylcarbodiimide and catalyzer DMAP for described poly glycol monomethyl ether and ferrocenecarboxylic acid is 2 days, and temperature of reaction is 25 DEG C.
29. a kind of methods of reuniting by the reversible regulation and control Single Walled Carbon Nanotube of electrochemical redox and disperseing according to claim 5, it is characterized in that, the mass ratio of described solid and PEO-Fc is 1:(2 ~ 10).
30. a kind of methods of being reunited by the reversible regulation and control Single Walled Carbon Nanotube of electrochemical redox and being disperseed according to claim 29, it is characterized in that, the mass ratio of described solid and PEO-Fc is 1:2.5,1:5 or 1:10.
31. a kind of methods of being reunited by the reversible regulation and control Single Walled Carbon Nanotube of electrochemical redox and being disperseed according to claim 5, it is characterized in that, described solid and PEO-Fc carry out blending dispersion under ultrasonication, and ultrasonic time is 15min ~ 30min.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106082173A (en) * | 2016-06-20 | 2016-11-09 | 青岛科技大学 | A kind of carbon nano tube dispersion method |
| CN109232906A (en) * | 2018-09-20 | 2019-01-18 | 福建师范大学 | Polyfluoroalkyl axial substituted silicon (IV) phthalocyanine-carbon nanotube supramolecular system and the preparation method and application thereof |
| CN110316722A (en) * | 2019-08-13 | 2019-10-11 | 中国人民解放军军事科学院防化研究院 | A kind of preparation method of oxide/carbon nanometer tube |
| CN110670352A (en) * | 2019-10-24 | 2020-01-10 | 中国科学院山西煤炭化学研究所 | Method for reversibly modifying carbon fiber |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SE1100140A1 (en) * | 2011-03-01 | 2012-09-02 | Joachim Karthaeuser | Methods for producing metallized carbon nanoparticles |
| CN104140483A (en) * | 2014-07-10 | 2014-11-12 | 清华大学 | Dispersion method of single-walled carbon nanotube |
-
2014
- 2014-12-26 CN CN201410834876.6A patent/CN104528687B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SE1100140A1 (en) * | 2011-03-01 | 2012-09-02 | Joachim Karthaeuser | Methods for producing metallized carbon nanoparticles |
| CN104140483A (en) * | 2014-07-10 | 2014-11-12 | 清华大学 | Dispersion method of single-walled carbon nanotube |
Non-Patent Citations (3)
| Title |
|---|
| BYUMSEOK KOH ET AL.: "Mechanisms of Carbon Nanotube Aggregation and the Reversion of Carbon Nanotube Aggregates in Aqueous Medium", 《LANGMUIR》, vol. 30, 21 August 2014 (2014-08-21), pages 10899 - 10909 * |
| QIANG YAN ET AL.: "Redox-switchable supramolecular polymers for responsive self-healing nanofibers in water", 《POLYMER CHEMISTRY》 * |
| QIANG YAN ET AL.: "Redox-switchable supramolecular polymers for responsive self-healing nanofibers in water", 《POLYMER CHEMISTRY》, vol. 4, 6 November 2012 (2012-11-06) * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106082173A (en) * | 2016-06-20 | 2016-11-09 | 青岛科技大学 | A kind of carbon nano tube dispersion method |
| CN106082173B (en) * | 2016-06-20 | 2019-06-28 | 青岛科技大学 | A kind of carbon nano tube dispersion method |
| CN109232906A (en) * | 2018-09-20 | 2019-01-18 | 福建师范大学 | Polyfluoroalkyl axial substituted silicon (IV) phthalocyanine-carbon nanotube supramolecular system and the preparation method and application thereof |
| CN110316722A (en) * | 2019-08-13 | 2019-10-11 | 中国人民解放军军事科学院防化研究院 | A kind of preparation method of oxide/carbon nanometer tube |
| CN110316722B (en) * | 2019-08-13 | 2022-07-01 | 中国人民解放军军事科学院防化研究院 | Preparation method of carbon oxide nanotube |
| CN110670352A (en) * | 2019-10-24 | 2020-01-10 | 中国科学院山西煤炭化学研究所 | Method for reversibly modifying carbon fiber |
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