CN104528687B - A kind of by the reunion of electrochemical redox reversible regulation and control SWCN and scattered method - Google Patents
A kind of by the reunion of electrochemical redox reversible regulation and control SWCN and scattered method Download PDFInfo
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- CN104528687B CN104528687B CN201410834876.6A CN201410834876A CN104528687B CN 104528687 B CN104528687 B CN 104528687B CN 201410834876 A CN201410834876 A CN 201410834876A CN 104528687 B CN104528687 B CN 104528687B
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Abstract
The invention belongs to the process for dispersing technical field of CNT, reunited and scattered method by electrochemical redox reversible regulation and control SWCN particularly to one. The inventive method comprises the steps: to add electrolyte mix homogeneously in supermolecule polymer-SWNTs compound water solution; Even if applying forward electromotive force nanotube in system to reunite; And then in system, apply reverse potential, make SWCN system again disperse. SWNTs is modified by the inventive method by the noncovalent interaction of pyrene Yu SWNTs, it is possible to avoid interference the intrinsic characteristic of carbon nanomaterial; The inventive method utilizes the stimulation means that this class of electrochemical redox cleans to regulate CNT dispersion in water, does not introduce impurity in system, is beneficial to and recycles.
Description
Technical field
The invention belongs to the process for dispersing technical field of CNT, reunited and scattered method by electrochemical redox reversible regulation and control SWCN particularly to one.
Background technology
As a kind one-dimensional carbon nanomaterial, CNT is of great interest over the last couple of decades due to the photo electric of its excellence, mechanical strength and chemical stability. This kind of columned nanostructured all shows good application prospect at numerous areas such as photodetector, solaode, sensor, energy conversion and storage devices. But, owing to there is attraction and the hydrophobic interaction of Van der Waals force between CNT, CNT generally exists with the form of tube bank, this results in 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 using traditional physical means such as ultrasonic and ball-milling method, it also is difficult to be dispersed and dissolved in various common solvents, especially in water. In order to solve this problem, people improve the dispersibility of carbon pipe often through covalent coupling reaction or non-covalent addition. Wherein, non-covalent modification is owing to can avoid interference the intrinsic characteristic of carbon nanomaterial, and receives the favor of more and more researcher.
For ease of better application, SWCN not only should be able to disperse in a solvent, has response characteristic simultaneously need to stimulate to external world. Utilizing water miscible stimulating responsive polymer that SWCN carries out functional modification is one of important solution. Until now, several stimulating responsive polymers have been employed successfully in non-covalent modification SWCN. Grunlan etc. utilize NIPA (PNIPAM) and poly-(N-cyclopropyl acrylamide) (PNCPA) functionalized SWCN respectively of pyrene labelling, construct temperature response type single-walled carbon nanotube dispersion liquid (J.C.Grunlanetal., Macromol.RapidCommun.2010,31,1368;J.C.Grunlanetal., J.Am.Chem.Soc.2009,131,13598). Kim etc. find to realize controlling the stripping of SWCN by the polyacrylic acid (PAA) that pH is sensitive and assemble (Y.S.Kimetal., NanoLett.2006,6,911). Based on the reversible host-guest interaction between cyclodextrin and diphenyl diimide, Feng etc. develops " intelligence " SWCN (Y.J.Fengetal., Adv.Funct.Mater.2013,23,5010) of a kind of novel photoswitch. And electrochemical redox is the stimulation means of a kind of cleaning, it is achieved not introducing impurity while electron transfer redox reaction in system, so there being reasonable repeatability, having important using value for constructing intelligent device material.
Summary of the invention
It is an object of the invention to provide a kind of by electrochemical redox reversible regulation and control SWCN (SWNTs) reunion and scattered method. The SWNTs system prepared by the method is capable of reunion and the dispersion of repeatability in aqueous.
First this project synthesizes and has constructed the end modified supermolecule polymer Polyethylene Glycol-ferrocene beta-schardinger dextrin--pyrene (PEO-Fc β-CD-Py) having pyrenyl group, interacted polymer overmold at carbon tube-surface by the π-π between pyrenyl group and carbon tube wall, owing to the hydrophilic interaction of Polyethylene Glycol (PEO) chain makes hybrid have good dispersion in aqueous. Again due to the existence of ferrocene-cyclodextrin host-guest interaction pair, under the regulation and control that electrochemical oxidation (positive potential) stimulates, ferrocene becomes positively charged lotus, from cyclodextrin cavity, de-embedding is out, so that PEO chain can depart from from carbon tube-surface, carbon pipe reassembles and becomes not disperse; Under the stimulation of electrochemical reduction (negative potential), ferrocene returns to reduction-state and can again be combined with cyclodextrin again, and system is disperseed again in aqueous phase. The dispersion of the lower carbon pipe of such electrochemical redox regulation and control can circulate repeatedly with accumulation process.
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) take beta-schardinger dextrin-(β-CD) to dissolve in the basic conditions, activate through paratoluensulfonyl chloride (TsCl), obtain compound shown in formula II with excessive reacting ethylenediamine;
(2) there is condensation reaction in compound shown in formula II and pyrene butanoic acid under the effect of condensing agent dicyclohexylcarbodiimide (DCC) and activator N-hydroxy-succinamide (NHS), obtains compound shown in formula I.
The preparation flow figure of polymer shown in formula I of the present invention is as in figure 2 it is shown, compound shown in formula I is abbreviated as β-CD-Py, and compound shown in formula II is abbreviated as β-CD-EDA.
Above-mentioned preparation method, in step (1), described alkali condition can be any one in sodium hydroxide, potassium hydroxide aqueous solution;
The mol ratio of described beta-schardinger dextrin-and described paratoluensulfonyl chloride can be 1:(1～3), it is preferred to 1:1.5;
The mol ratio of described formula II compound and pyrene butanoic acid, dicyclohexylcarbodiimide (DCC) and N-hydroxy-succinamide (NHS) can be (1.5～3): 1:(1.5～3): (1.5～3), it is preferred to 2:1:2:2.
Above-mentioned preparation method, solvent described in step (2) can be the one in DMF (DMF), N,N-dimethylacetamide (DMAC), dimethyl sulfoxide (DMSO), response time is 0.5～1 day, it is preferred to 0.5 day; Reaction temperature is 20 DEG C～35 DEG C, it is preferred to 25 DEG C.
Invention further provides polymer shown in formula III,
Invention also provides the preparation method of polymer 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 catalyst DMAP (DMAP), obtains polymer shown in formula III.
The preparation flow figure of polymer shown in formula III of the present invention is as it is shown on figure 3, polymer shown in formula III is abbreviated as PEO-Fc.
Above-mentioned preparation method, in step (1), the mean molecule quantity 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, it is preferred to 1:6:6:0.5.
Described solvent can be the one in dichloromethane, chloroform, and the response time is 1～3 day, it is preferred to 2 days; Reaction temperature is 20 DEG C～35 DEG C, it is preferred to 25 DEG C.
Invention further provides the application in dispersion SWCN of compound shown in formula I and polymer shown in formula III.
Invention further provides the process for dispersing of SWCN, comprise the steps:
(1) β-CD-Py and SWCN are mixed in organic solvent, filter after dispersed and vacuum drying obtains solid.
(2) solid obtained in the previous step and prepared PEO-Fc are sufficiently mixed in water, namely realize the dispersion in water of the described SWCN.
In this step water, the preparation flow figure of scattered SWCN is as it is shown in figure 1, be labeled as supermolecule polymer-SWNTs compound water solution.
Above-mentioned process for dispersing mainly utilizes the medium (as shown in Figure 1) that the pyrenyl group in compound shown in formula I connects as polymer and SWCN (SWNTs), is combined with CNT by π-π effect. Further through the host-guest interaction of ferrocene Yu beta-schardinger dextrin-, hydrophilic polymer segment PEO is modified at single tube-surface, it is thus possible to make SWCN be disperseed fully in water.
In above-mentioned process for dispersing, in step (1), the mass ratio of compound shown in described SWCN and formula I can be 1:(4～20), it is preferred to 1:4,1:10 or 1:20;
Described organic solvent is the one in DMF, DMAC, DMSO;
Compound shown in formula I and SWCN specifically can mix under ultrasonication, and ultrasonic time is 15min～30min concretely, it is preferred to 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), it is preferred to 1:2.5,1:5 or 1:10;
Described solid obtained in the previous step and SWCN 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 is on this basis, it is further provided a kind of stimulate reversible regulation and control SWCN to reunite and scattered method by electrochemical redox, comprises the steps:
Electrolyte mix homogeneously is added in supermolecule polymer-SWNTs compound water solution. In system, apply 1.0V positive potential namely realize the reunion of nanotube;And then in system, pass into-1.0V negative potential, the dispersion again of SWCN system can be realized.
Above-mentioned process for dispersing mainly utilizes ferrocene to become positively charged under the regulation and control that electrochemical oxidation (positive potential) stimulates lotus, from cyclodextrin cavity, de-embedding is out, so that PEO chain can depart from from carbon tube-surface, carbon pipe reassembles and becomes not disperse; Under the stimulation of electrochemical reduction (negative potential), ferrocene returns to reduction-state and can again be combined with cyclodextrin again, and system is disperseed again in aqueous phase.
In above-mentioned process for dispersing, described electrolyte is any one in sodium dihydrogen phosphate, potassium chloride, potassium bromide, potassium nitrate, and in supermolecule polymer-SWNTs compound water solution, electrolytical concentration is 0.1mol/L～0.3mol/L, it is preferred to 0.2mol/L;
Electrochemical oxidation stimulates (applying positive potential) and electrochemical reduction stimulation (applying negative potential) can be realized by the three-electrode system of electrochemical workstation, wherein working electrode and electrode is platinized platinum, and reference electrode is Ag-AgCl electrode; Respectively 3～6 hours time of described applying positive potential and negative potential.
The invention have the benefit that
1. by the noncovalent interaction of pyrene Yu SWNTs, SWNTs is modified, it is possible to avoid interference the intrinsic characteristic of carbon nanomaterial;
2. utilize the stimulation means that this class of electrochemical redox cleans to regulate CNT dispersion in water, in system, do not introduce impurity, be beneficial to and recycle.
Accompanying drawing explanation
Fig. 1 is reunited and scattered process flow diagram by electrochemical redox reversible regulation and control SWCN;
Fig. 2 is the process chart of compound β-CD-Py shown in synthesis formula I;
Fig. 3 is the flow chart of polymer P EO-Fc shown in synthesis formula III;
Fig. 4 is the hydrogen nuclear magnetic resonance spectrogram of compound β-CD-Py shown in formula I;
Fig. 5 is the mass spectrum of compound β-CD-Py shown in formula I;
Fig. 6 is the hydrogen nuclear magnetic resonance spectrogram of polymer P EO-Fc shown in formula III;
Fig. 7 is the UV-visible-near infrared absorption figure that supermolecule polymer-SWNTs complex is before and after electrochemical redox stimulates and the SWNTs of unmodified is in water prepared by embodiment 1;
Fig. 8 is the magnified partial view of the UV-visible-near infrared absorption figure in water of the supermolecule polymer-SWNTs complex prepared by embodiment 1;
Fig. 9 is that in embodiment 1, supermolecule polymer-SWNTs complex stimulates front and back transmission electron microscope photo of dispersion liquid in water at electrochemical redox, wherein Fig. 9 (a) is the transmission electron microscope photo of scattered supermolecule polymer-SWNTs complex, and Fig. 9 (b) is the transmission electron microscope photo of the supermolecule polymer-SWNTs complex reunited;
Figure 10 is the three-electrode system apparatus structure schematic diagram of conventional chemical work station;
Number in the figure: 1-is to electrode, 2-reference electrode, 3-working electrode, 4-solution.
Detailed description of the invention
The invention provides a kind of by the reunion of electrochemical redox reversible regulation and control SWCN and scattered method, 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 conventional method.
Material used in following embodiment, reagent etc., if no special instructions, all commercially obtain. Embodiment 1
(1) synthesis β-CD-Py:
Flow chart is as shown in Figure 2.
A. taking 20g beta-schardinger dextrin-(β-CD), be scattered in 167mL water, be dissolved in 7mL water by the NaOH of 2.19g, and be slowly added dropwise in the suspension of β-CD, final suspension becomes the solution of clarification.5.04g paratoluensulfonyl chloride (TsCl) is dissolved in 10mL acetonitrile, is slowly added dropwise in the aqueous solution of β-CD under ice-water bath, produces white precipitate. After dropping completely, stirring reaction 2 hours under room temperature, turbid solution is placed in 4 DEG C of refrigerator cold-storages overnight. It is filtrated to get white precipitate recrystallization 3 times in water. Obtain target product β-CD-6-OTs2.5g, yield: 10.7%.
B. the ethylenediamine taking 5g β-CD-6-OTs and 30mL reacts 4h at 80 DEG C, after reaction terminates, is cooled to room temperature, and rotation boils off except most of responseless ethylenediamine, and product is dissolved in water-methanol (V/V=1:1), precipitates in acetone, such 3 times. Obtain target product β-CD-EDA4.68g, yield: 92.3%.
C. 500mg β-CD-EDA, 254mg pyrene butanoic acid and 100mgN-N-Hydroxysuccinimide (NHS) being put in the single port flask of 25mL, be codissolved in the 10mL DMF dried, ice bath is issued to stable. Separately condensing agent dicyclohexylcarbodiimide (DCC) 200mg being dissolved in the 5mL DMF dried, be added dropwise in reaction system, rear reaction is overnight. Reaction precipitates after terminating in cold acetone, is centrifuged off supernatant, so repeatedly obtains product 580mg 3 times, yield: 76.9%.
As shown in Figure 4, mass spectrum is as shown in Figure 5 for the proton nmr spectra of β-CD-Py prepared by the present embodiment.
M=1448.
(2) synthesis PEO-Fc:
Flow chart is as shown in Figure 3.
2.2gPEO, 0.5g are dissolved in the 20mL dichloromethane dewatered little over the ferrocenecarboxylic acid (FcA) of amount, 0.44g condensing agent DCC and 24mgDMAP, react 48 hours under room temperature, it is filtered to remove by-product, filtrate rotation is steamed, crude product is dissolved in chloroform, unreacted FcA is removed with NaOH solution 10mL extracting, deionized water collects chloroform phase after regulating pH value weakly acidic pH, it is deposited in diethyl ether solution, repeat dissolving-precipitation process 3 times, the white solid product vacuum drying that will obtain, obtains target product PEO-Fc1.85g, yield: 69%.
The proton nmr spectra of PEO-Fc prepared by the present embodiment is as shown in Figure 5.
Mn,NMR=5.1kDa, Mn,GPC=5.3kDa, Mw/Mn=1.05.
(3) prepare supermolecule polymer-SWNTs complex, and be dispersed in water:
A. being put into by 100mg β-CD-Py in the single port flask of 250mL, add 100mL organic solvent DMF, fully dissolve, add 20mgSWNTs, ultrasonic 30min, SWNTs are dispersed in organic solvent. With the filtering with microporous membrane of 200nm, DMF washs 2 times, vacuum drying 48h. Obtain β-CD-Py-SWNTs complex 76mg, yield: 63.3%.
B. 20mg β-CD-Py-SWNTs, 50mgPEO-Fc are put 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 is as shown in Figure 7, be can be seen that by this figure, a series of spikes at 750nm～870nm place are corresponding to the characteristic absorption of transistor, it was demonstrated that such complex obtains good dispersion in aqueous.
The transmission electron microscope photo of above-mentioned compound water solution is such as shown in Fig. 9 (a), and by this figure it can be seen that have between carbon pipe and mutually peel off preferably, what energy was obvious observes that carbon pipe outer cladding one layer of polymeric, and after compound, diameter increases.
(4) reunion in water of the electrochemical redox reversible regulation and control SWCN and dispersion:
Take and step (3) obtains homodisperse supermolecule polymer-SWNTs complex solution 6mL in water, in system, add potassium chloride 100mg mix homogeneously.In system, apply 1.0V positive potential 6h, namely realize the reunion of nanotube; And then in system, pass into-1.0V negative potential, the dispersion again of SWCN system can be realized.
After above-mentioned applying 1.0V positive potential 6h, the UV-visible-near infrared absorption of compound water solution is as shown in Figure 7, be can be seen that by this figure, originally the characteristic absorption peak of a series of transistors at 750nm～870nm place disappears, it was demonstrated that CNT is further reunited in aqueous.
After above-mentioned applying 1.0V positive potential 6h, the transmission electron microscope photo of compound water solution is such as shown in Fig. 9 (b), by this figure it can be seen that carbon pipe is reunited together again.
Embodiment 2
(1) synthesis β-CD-Py:
A-c step is with embodiment 1.
(2) synthesis PEO-Fc:
Step is with embodiment 1.
(3) prepare supermolecule polymer-SWNTs complex, and be dispersed in water:
A. being put into by 100mg β-CD-Py in the single port flask of 250mL, add 100mL organic solvent DMSO, fully dissolve, add 10mgSWNTs, ultrasonic 30min, SWNTs are dispersed in organic solvent. With the filtering with microporous membrane of 200nm, DMSO washs 2 times, vacuum drying 48h. Obtain β-CD-Py-SWNTs complex 54mg, yield: 49.1%.
B. 20mg β-CD-Py-SWNTs, 100mgPEO-Fc are put 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 compound water solution prepared by the present embodiment and the UV-visible-near infrared absorption (Fig. 7) of the compound water solution of preparation in embodiment 1 are without substantive difference, it is possible to learn: such complex obtains good dispersion in aqueous.
The transmission electron microscope photo of compound water solution prepared by the present embodiment and the transmission electron microscope photo (Fig. 9) of the compound water solution of preparation in embodiment 1 are without significant difference, it is possible to learn: such complex obtains good dispersion in aqueous.
(4) reunion in water of the electrochemical redox reversible regulation and control SWCN and dispersion:
Take and step (3) obtains homodisperse supermolecule polymer-SWNTs complex solution 6mL in water, in system, add potassium bromide 160mg mix homogeneously. In system, apply 1.0V positive potential 5h, namely realize the reunion of nanotube; And then in system, pass into-1.0V negative potential, the dispersion again of SWCN system can be realized.
Prepared by the present embodiment apply after the 1.0V positive potential 5h UV-visible-near infrared absorption of compound water solution with in embodiment 1 preparation apply after 1.0V positive potential 5h that the UV-visible-near infrared absorption (Fig. 7) of compound water solution is without essential distinction, as seen from the figure: CNT is further reunited in aqueous.
After above-mentioned applying 1.0V positive potential 5h prepared by the present embodiment in the transmission electron microscope photo of compound water solution and embodiment 1 preparation apply after 1.0V positive potential 5h the transmission electron microscope photo (Fig. 9) of compound water solution without significant difference, by this figure it can be seen that carbon pipe is reunited together again.
Embodiment 3
(1) synthesis β-CD-Py:
Flow chart is as shown in Figure 2.
A. taking 20g beta-schardinger dextrin-(β-CD), be scattered in 167mL water, be dissolved in 7mL water by the NaOH of 2.19g, and be slowly added dropwise in the suspension of β-CD, final suspension becomes the solution of clarification.10g paratoluensulfonyl chloride (TsCl) is dissolved in 20mL acetonitrile, is slowly added dropwise in the aqueous solution of β-CD under ice-water bath, produces white precipitate. After dropping completely, stirring reaction 2 hours under room temperature, turbid solution is placed in 4 DEG C of refrigerator cold-storages overnight. It is filtrated to get white precipitate recrystallization 3 times in water. Obtain target product β-CD-6-OTs2.8g, yield: 11.2%.
B. the ethylenediamine taking 5g β-CD-6-OTs and 30mL reacts 4h at 80 DEG C, after reaction terminates, is cooled to room temperature, and rotation boils off except most of responseless ethylenediamine, and product is dissolved in water-methanol (V/V=1:1), precipitates in acetone, such 3 times. Obtain target product β-CD-EDA4.82g, yield: 93.7%.
C. 800mg β-CD-EDA, 5mg pyrene butanoic acid and 200mgN-N-Hydroxysuccinimide (NHS) being put in the single port flask of 25mL, be codissolved in the 20mL DMSO dried, ice bath is issued to stable. Separately condensing agent dicyclohexylcarbodiimide (DCC) 400mg being dissolved in the 10mL DMSO dried, be added dropwise in reaction system, rear reaction is overnight. Reaction precipitates after terminating in cold acetone, is centrifuged off supernatant, so repeatedly obtains product 608mg 3 times, yield: 79.5%.
(2) synthesis PEO-Fc:
Step is with embodiment 1.
(3) prepare supermolecule polymer-SWNTs complex, and be dispersed in water:
A. being put into by 200mg β-CD-Py in the single port flask of 250mL, add 100mL organic solvent DMF, fully dissolve, add 10mgSWNTs, ultrasonic 30min, SWNTs are dispersed in organic solvent. With the filtering with microporous membrane of 200nm, DMF washs 2 times, vacuum drying 48h. Obtain β-CD-Py/SWNTs complex 57mg, yield: 50.9%.
B. 20mg β-CD-Py-SWNTs, 200mgPEO-Fc are put 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 of compound water solution prepared by the present embodiment and the UV-visible-near infrared absorption (Fig. 7) of the compound water solution of preparation in embodiment 1 are without substantive difference, it is possible to learn: such complex obtains good dispersion in aqueous.
The transmission electron microscope photo of compound water solution prepared by the present embodiment and the transmission electron microscope photo (Fig. 9) of the compound water solution of preparation in embodiment 1 are without significant difference, it is possible to learn: such complex obtains good dispersion in aqueous.
(4) reunion in water of the electrochemical redox reversible regulation and control SWCN and dispersion:
Take and step (3) obtains homodisperse supermolecule polymer-SWNTs complex solution 6mL in water, in system, add potassium nitrate 136mg mix homogeneously. In system, apply 1.0V positive potential 4h, namely realize the reunion of nanotube; And then in system, pass into-1.0V negative potential, the dispersion again of SWCN system can be realized.
Prepared by the present embodiment apply after the 1.0V positive potential 4h UV-visible-near infrared absorption of compound water solution with in embodiment 1 preparation apply after 1.0V positive potential 4h that the UV-visible-near infrared absorption (Fig. 7) of compound water solution is without essential distinction, as seen from the figure: CNT is further reunited in aqueous.
After above-mentioned applying 1.0V positive potential 4h prepared by the present embodiment in the transmission electron microscope photo of compound water solution and embodiment 1 preparation apply after 1.0V positive potential 4h the transmission electron microscope photo (Fig. 9) of compound water solution without significant difference, by this figure it can be seen that carbon pipe is reunited together again.
Embodiment 4
(1) synthesis β-CD-Py:
A-c step is with embodiment 3.
(2) synthesis PEO-Fc:
Flow chart is as shown in Figure 3.
The ferrocenecarboxylic acid (FcA) of 2.2gPEO, 0.8g, 0.66g condensing agent DCC and 24mgDMAP are dissolved in the 20mL dichloromethane dewatered, react 72 hours under room temperature, it is filtered to remove by-product, filtrate rotation is steamed, crude product is dissolved in chloroform, unreacted FcA is removed with NaOH solution 15mL extracting, deionized water collects chloroform phase after regulating pH value weakly acidic pH, it is deposited in diethyl ether solution, repeat dissolving-precipitation process 3 times, the white solid product vacuum drying that will obtain, obtains target product PEO-Fc1.92g, yield: 74.2%.
(3) prepare supermolecule polymer-SWNTs complex, and be dispersed in water:
A. being put into by 200mg β-CD-Py in the single port flask of 250mL, add 100mL organic solvent DMF, fully dissolve, add 10mgSWNTs, ultrasonic 30min, SWNTs are dispersed in organic solvent. With the filtering with microporous membrane of 200nm, DMF washs 2 times, vacuum drying 48h. Obtain β-CD-Py-SWNTs complex 57mg, yield: 50.9%.
B. 20mg β-CD-Py-SWNTs, 200mgPEO-Fc are put 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 of compound water solution prepared by the present embodiment and the UV-visible-near infrared absorption (Fig. 7) of the compound water solution of preparation in embodiment 1 are without substantive difference, it is possible to learn: such complex obtains good dispersion in aqueous.
The transmission electron microscope photo of compound water solution prepared by the present embodiment and the transmission electron microscope photo (Fig. 9) of the compound water solution of preparation in embodiment 1 are without significant difference, it is possible to learn: such complex obtains good dispersion in aqueous.
(4) reunion in water of the electrochemical redox reversible regulation and control SWCN and dispersion: take and obtain homodisperse supermolecule polymer-SWNTs complex solution 6mL in water in step (3), adds potassium nitrate 136mg mix homogeneously in system. In system, apply 1.0V positive potential 4h, namely realize the reunion of nanotube; And then in system, pass into-1.0V negative potential, the dispersion again of SWCN system can be realized.
Prepared by the present embodiment apply after the 1.0V positive potential 4h UV-visible-near infrared absorption of compound water solution with in embodiment 1 preparation apply after 1.0V positive potential 4h that the UV-visible-near infrared absorption (Fig. 7) of compound water solution is without essential distinction, as seen from the figure: CNT is further reunited in aqueous.
After above-mentioned applying 1.0V positive potential 4h prepared by the present embodiment in the transmission electron microscope photo of compound water solution and embodiment 1 preparation apply after 1.0V positive potential 4h the transmission electron microscope photo (Fig. 9) of compound water solution without significant difference, by this figure it can be seen that carbon pipe is reunited together again.
Embodiment 5
(1) synthesis β-CD-Py:
A-c step is with embodiment 4.
(2) synthesis PEO-Fc:
Step is with embodiment 4.
(3) prepare supermolecule polymer-SWNTs complex, and be dispersed in water:
A. being put into by 100mg β-CD-Py in the single port flask of 250mL, add 50mL organic solvent DMF, fully dissolve, add 10mgSWNTs, ultrasonic 30min, SWNTs are dispersed in organic solvent.With the filtering with microporous membrane of 200nm, DMF washs 2 times, vacuum drying 48h. Obtain β-CD-Py-SWNTs complex 53mg, yield: 48.9%.
B. 20mg β-CD-Py-SWNTs, 200mgPEO-Fc are put 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 of compound water solution prepared by the present embodiment and the UV-visible-near infrared absorption (Fig. 7) of the compound water solution of preparation in embodiment 1 are without substantive difference, it is possible to learn: such complex obtains good dispersion in aqueous.
The transmission electron microscope photo of compound water solution prepared by the present embodiment and the transmission electron microscope photo (Fig. 9) of the compound water solution of preparation in embodiment 1 are without significant difference, it is possible to learn: such complex obtains good dispersion in aqueous.
(4) reunion in water of the electrochemical redox reversible regulation and control SWCN and dispersion:
Take and step (3) obtains homodisperse supermolecule polymer-SWNTs complex solution 6mL in water, in system, add potassium chloride 100mg mix homogeneously. In system, apply 1.0V positive potential 6h, namely realize the reunion of nanotube; And then in system, pass into-1.0V negative potential, the dispersion again of SWCN system can be realized.
Prepared by the present embodiment apply after the 1.0V positive potential 6h UV-visible-near infrared absorption of compound water solution with in embodiment 1 preparation apply after 1.0V positive potential 6h that the UV-visible-near infrared absorption (Fig. 7) of compound water solution is without essential distinction, as seen from the figure: CNT is further reunited in aqueous.
After above-mentioned applying 1.0V positive potential 6h prepared by the present embodiment in the transmission electron microscope photo of compound water solution and embodiment 1 preparation apply after 1.0V positive potential 6h the transmission electron microscope photo (Fig. 9) of compound water solution without significant difference, by this figure it can be seen that carbon pipe is reunited together again.
Claims (22)
1. reunited and scattered method by electrochemical redox reversible regulation and control SWCN for one kind, it is characterised in that comprise the steps:
Electrolyte mix homogeneously is added in supermolecule polymer-SWNTs compound water solution; Even if applying positive potential nanotube in system to reunite; And then in system, apply negative potential, make SWCN system again disperse;
The preparation method of described supermolecule polymer-SWNTs compound water solution comprises the steps:
β-CD-Py and SWCN are mixed in organic solvent, filters after dispersed and vacuum drying obtains solid; Gained solid and PEO-Fc are sufficiently mixed in water and disperse, obtains supermolecule polymer-SWNTs compound water solution;
The structural formula of described β-CD-Py is as follows:
The structural formula of described PEO-Fc is as follows:
2. one according to claim 1 is reunited and scattered method by electrochemical redox reversible regulation and control SWCN, it is characterized in that, described electrolyte is any one in sodium dihydrogen phosphate, potassium chloride, potassium bromide, potassium nitrate, and in supermolecule polymer-SWNTs compound water solution, electrolytical concentration is 0.1mol/L～0.3mol/L.
3. one according to claim 1 is reunited and scattered method by electrochemical redox reversible regulation and control SWCN, it is characterised in that in described supermolecule polymer-SWNTs compound water solution, electrolytical concentration is 0.2mol/L.
4. one according to claim 1 is reunited and scattered method by electrochemical redox reversible regulation and control SWCN, it is characterized in that, the three-electrode system using electrochemical workstation applies electromotive force, wherein working electrode and electrode is platinized platinum, reference electrode is Ag-AgCl electrode; Respectively 3～6 hours time of described applying positive potential and negative potential.
5. one according to claim 1 is reunited and scattered method by electrochemical redox reversible regulation and control SWCN, it is characterised in that the preparation method of described β-CD-Py comprises the steps:
Take beta-schardinger dextrin-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 butanoic acid, obtain β-CD-Py under the effect of condensing agent dicyclohexylcarbodiimide and activator N-hydroxy-succinamide;
The mol ratio of described beta-schardinger dextrin-and paratoluensulfonyl chloride is 1:(1～3);
The mol ratio of described β-CD-EDA and pyrene butanoic acid, dicyclohexylcarbodiimide and N-hydroxy-succinamide is (1.5～3): 1:(1.5～3): (1.5～3);
Described β-CD-EDA and pyrene butanoic acid occur the solvent that condensation reaction uses to be N under the effect of condensing agent dicyclohexylcarbodiimide and activator N-hydroxy-succinamide, dinethylformamide, N, one in N-dimethyl acetylamide and dimethyl sulfoxide, the response time is 0.5～1 day; Reaction temperature is 20 DEG C～35 DEG C.
6. one according to claim 5 is reunited and scattered method by electrochemical redox reversible regulation and control SWCN, it is characterised in that the structural formula of described β-CD-EDA is as follows:
7. one according to claim 5 is reunited and scattered method by electrochemical redox reversible regulation and control SWCN, it is characterised in that described alkali condition is sodium hydroxide or potassium hydroxide aqueous solution.
8. one according to claim 5 is reunited and scattered method by electrochemical redox reversible regulation and control SWCN, it is characterised in that the mol ratio of described beta-schardinger dextrin-and paratoluensulfonyl chloride is 1:1.5.
9. one according to claim 5 is reunited and scattered method by electrochemical redox reversible regulation and control SWCN, it is characterized in that, the mol ratio of described β-CD-EDA and pyrene butanoic acid, dicyclohexylcarbodiimide and N-hydroxy-succinamide is 2:1:2:2.
10. one according to claim 5 is reunited and scattered method by electrochemical redox reversible regulation and control SWCN, it is characterized in that, described β-CD-EDA and pyrene butanoic acid occur the response time of condensation reaction to be 0.5 day under the effect of condensing agent dicyclohexylcarbodiimide and activator N-hydroxy-succinamide, and reaction temperature is 25 DEG C.
11. one according to claim 1 is reunited and scattered method by electrochemical redox reversible regulation and control SWCN, it is characterised in that the mass ratio of described SWCN and β-CD-Py is 1:(4～20).
12. one according to claim 11 is reunited and scattered method by electrochemical redox reversible regulation and control SWCN, it is characterised in that the mass ratio of described SWCN and β-CD-Py is 1:4,1:10 or 1:20.
13. one according to claim 1 is reunited and scattered method by electrochemical redox reversible regulation and control SWCN, it is characterized in that, described organic solvent is the one in DMF, N,N-dimethylacetamide and dimethyl sulfoxide.
14. one according to claim 1 is reunited and scattered method by electrochemical redox reversible regulation and control SWCN, it is characterized in that, described β-CD-Py and SWCN mix under ultrasonication, and ultrasonic time is 15min～30min.
15. one according to claim 14 is reunited and scattered method by electrochemical redox reversible regulation and control SWCN, it is characterised in that described ultrasonic time is 20min.
16. one according to claim 1 is reunited and scattered method by electrochemical redox reversible regulation and control SWCN, it is characterised in that the filtering with microporous membrane of described filter operation use 200nm 2 times, the vacuum drying time is 2 days.
17. one according to claim 1 is reunited and scattered method by electrochemical redox reversible regulation and control SWCN, it is characterised 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 catalyst DMAP;
The mean molecule quantity of described poly glycol monomethyl ether is 5000;
The mol ratio of described poly glycol monomethyl ether and ferrocenecarboxylic acid, dicyclohexylcarbodiimide and DMAP is 1:(5～10): (5～10): 0.5;
Described poly glycol monomethyl ether and ferrocenecarboxylic acid occur the solvent that condensation reaction uses to be dichloromethane or chloroform under the effect of condensing agent dicyclohexylcarbodiimide and catalyst DMAP, and the response time is 1～3 day; Reaction temperature is 20 DEG C～35 DEG C.
18. one according to claim 17 is reunited and scattered method by electrochemical redox reversible regulation and control SWCN, 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.
19. one according to claim 17 is reunited and scattered method by electrochemical redox reversible regulation and control SWCN, it is characterized in that, described poly glycol monomethyl ether and ferrocenecarboxylic acid occur the response time of condensation reaction to be 2 days under the effect of condensing agent dicyclohexylcarbodiimide and catalyst DMAP, and reaction temperature is 25 DEG C.
20. one according to claim 1 is reunited and scattered method by electrochemical redox reversible regulation and control SWCN, it is characterised in that the mass ratio of described solid and PEO-Fc is 1:(2～10).
21. one according to claim 20 is reunited and scattered method by electrochemical redox reversible regulation and control SWCN, it is characterised in that the mass ratio of described solid and PEO-Fc is 1:2.5,1:5 or 1:10.
22. one according to claim 1 is reunited and scattered method by electrochemical redox reversible regulation and control SWCN, it is characterised in that described solid and PEO-Fc carry out mixing dispersion under ultrasonication, and ultrasonic time is 15min～30min.
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