CN102569657B - Preparation for photo-response Pyr-AZO non-covalent decorating carbon nano tube material - Google Patents

Preparation for photo-response Pyr-AZO non-covalent decorating carbon nano tube material Download PDF

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CN102569657B
CN102569657B CN201110431536.5A CN201110431536A CN102569657B CN 102569657 B CN102569657 B CN 102569657B CN 201110431536 A CN201110431536 A CN 201110431536A CN 102569657 B CN102569657 B CN 102569657B
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pyrene
azobenzene
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CN102569657A (en
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封伟
刘红坡
冯奕钰
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Tianjin University
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Abstract

The invention discloses a preparation method for photo-response pyrene-azobenzene non-covalent decorating carbon nano tube material. The method comprises the following main processes: a few-walled carbon nano tube is added into sulfuric acid and nitric acid mixed solution so as to obtain the few-walled carbon nano tube with better dispersity; N-hydroxy sulfo-Sulfo-NHS and 1- ethyl-3-(3-Trimetlylamine propyl group) EDC HCl catalytic pyrenebutanoic acid are used for condensation reaction to nitro linear alkyl amido-azobenzene so as to obtain Pyr-AZO; then photo-response pyrene-azobenzene non-covalent decorating carbon nano tube body can be composed by using the adsorption of a pyrene structure and pi-pi electronic conjugated bonds on the surface of the carbon nano tube. In the method, through non-covalent interaction, the obtained carbon nano tube-azobenzene composite has an excellent dissolubility and has an excellent photo-response character.

Description

The preparation of optical Response pyrene-azobenzene non-covalent modification carbon nano-tube material
Technical field
The invention belongs to the preparation method of optical Response carbon nano-tube material in technical field of nano material, be specifically related to a kind of preparation of optical Response pyrene-azobenzene non-covalent modification carbon nano-tube material.
Background technology
Carbon nano-tube has good conjugated system, high electron affinity energy, and photostability is strong, and mechanical performance and photoelectric properties etc., make it aspect photoelectric device, have huge application potential preferably.Optical Response azobenzene derivatives has unique optical isomerization characteristic, functionalization by nano materials such as itself and organic conjugate body, polymer, carbon nano-tube is compound, can obtain the photoresponse functional material that desirable optics can regulate and control microstructure or photoelectric properties.
Recently, because the development of Novel Optoelectronic Device improves constantly the requirement of photoelectric material, photoresponse nano material becomes the focus of this area research.Research purpose is exactly that its reversible cis-trans isomerization in During Illumination of research changes material internal conjugated system that the change of the steric configuration that causes or dipole moment causes and the variation of microscopic appearance.The preparation of optical Response carbon nano-tube is one of them important branch.By chemical means, in carbon nano-tube, introduce azobenzene chromophore, be expected to utilize the photoisomerization characteristic of azobenzene to change the performance of the optics electricity aspect of carbon nano-tube.
Pyrene, as an organic molecule with large pi-conjugated system, can firmly be adsorbed onto carbon nano tube surface by noncovalent interaction.In azobenzene molecule, introducing pyrenyl can utilize non-covalent composite action azobenzene chromophore to be incorporated into the surface of carbon nano-tube, the photoresponse performance of the introducing Ye Nengshi azobenzene chromophore of pyrenyl changes simultaneously, is a kind of preparation method of optical Response carbon nano-tube material of simple possible.
At present not about utilizing non-covalent suction-operated between pyrenyl and carbon nano-tube to prepare report and the patent of optical Response carbon nano-tube material and photoelectric properties aspect thereof.
Summary of the invention
The preparation method who the object of the invention is to propose a kind of optical Response pyrene-azobenzene non-covalent modification carbon nano-tube material, the optical Response carbon nano-tube dissolubility that the method makes is good, has good response characteristics to light, and its preparation technology is simple.
Technical scheme of the present invention is as follows: a kind of preparation method of optical Response pyrene-azobenzene non-covalent modification carbon nano-tube material, is characterized in that comprising following process:
1) carbon nano-tube is processed: it is that 98.3% concentrated sulfuric acid and mass fraction are 65% red fuming nitric acid (RFNA) and are (1-3) by volume that carbon nano-tube is joined to mass fraction: in 1 mixed acid, make carbon nano-tube concentration for (0.5-2) mg/ml, make dispersion liquid back flow reaction 30-120 minute at temperature 50 C-90 ℃, reclaim carbon nano-tube, with deionized water, wash that to cleaning solution, to be pH be 6-7, vacuumize 12-72 hour, obtains acidification carbon nano-tube;
2) 1-amino-6-[4-(4 '-nitrobenzophenone azo) phenoxy group] hexane synthetic: under agitation, paranitroanilinum is dissolved in the 3mol/L HCl aqueous solution, being mixed with concentration is the HCl solution of 0.2-1.2mol/L paranitroanilinum, is designated as A solution, natrium nitrosum is added in deionized water, be mixed with 1.5-2.5mol/L sodium nitrite in aqueous solution, be designated as B solution, press the volume ratio (1-12.5) of A solution and B solution: 1 mixes, and under condition of ice bath, reacts 15-90 minute, is designated as C solution, phenol is dissolved in the 3.5-6mol/L NaOH aqueous solution, and being mixed with concentration is the NaOH aqueous solution of 0.2-1.2mol/L phenol, is designated as D solution, will be under ice bath reacted C solution and D solution (2-13.5) by volume: 1 mixes, ice bath reaction is after 30-180 minute, with mass fraction, be that 20% aqueous hydrochloric acid solution adjusting pH value is 5-7, separate out a large amount of precipitations, suction filtration, clarifies with deionized water washing precipitation to cleaning solution, with 50% ethanol water recrystallization, suction filtration, obtains nitro-azo phenol, to be dissolved in 0.05-0.2mol/L 1 to nitro-azo phenol, the anhydrous propanone solution of 6-dibromo-hexane, in this mixed solution, add potash, make nitro-azo phenol, 1, 6-dibromo-hexane, the ratio of potash three molal weight is successively 1: (1-4): (1-3), in mixed solution, add KI, making its concentration is 0.0083-0.415mg/ml, under nitrogen protection, heat return stirring 12-48 hour, filter out while hot the residue of reaction system, concentrated by rotary evaporation reactant liquor, add absolute methanol, produce orange precipitation, column chromatography obtains the bromo-6-[4-of 1-(4 '-nitrobenzophenone azo) phenoxy group after purifying] hexane (AZO-Br), AZO-Br is dissolved in the anhydrous DMF solution of 0.01-0.25mol/L potassium phthalimide, being mixed with concentration is the potassium phthalimide anhydrous DMF solution of 0.02-0.03mol/L AZO-Br, heating reflux reaction 6-24 hour, stop reaction, concentrated by rotary evaporation reaction solution, adding distil water makes its precipitation, and after precipitation is complete, suction filtration is also used deionized water washing precipitation, and precipitation is dried and obtained orange red solid.The hydrazine hydrate that is 85% by mass fraction adds ethanol, the mass ratio that makes ethanol and hydrazine hydrate is 1: (6.3-25.3), precipitation oven dry is obtained to orange red solid and be dissolved in this mixed solution, heating reflux reaction 8-24 hour under nitrogen protection, drip the 1mol/LHCl aqueous solution, regulating pH value is 2-6, continue backflow 30-180 minute, be cooled to room temperature, the standing white needles precipitation of separating out, suction filtration is removed white needles solid, is then spin-dried for filtrate, and column chromatography obtains 1-amino-6-[4-(4 '-nitrobenzophenone azo) phenoxy group] hexane (AZO-NH2);
3) pyrene-azobenzene organic molecule is synthetic: take pyrene butyric acid and be dissolved in dry DMF, being mixed with concentration is 0.005-0.022mol/L pyrene butyric acid DMF solution, add N-hydroxy thiosuccinimide (Sulfo-NHS) and DMAP (DMAP), make pyrene butyric acid, Sulfo-NHS, the DMAP successively ratio of molal weight is 1: (1-1.5): (1-1.5), mixed solution adds 1-ethyl-3-(3-front three aminopropyl) carbodiimide hydrochloride (EDCHCl) under constantly stirring in ice bath, making pyrene butyric acid and the molal weight ratio of EDCHCl is 1: (1-1.2), keep ice-water bath reaction 30-240 minute, continue room temperature reaction 8-24 hour, stop reacting in backward system and add ethyl acetate, by saturated common salt water washing organic phase, separated with separatory funnel, anhydrous sodium sulfate drying organic phase, after filtration, be spin-dried for, in products therefrom, add dry DMF and AZO-NH 2, 1-2ml triethylamine, makes AZO-NH 2concentration is 16-22mg/ml, stirring at room reaction 8-24 hour.Stop adding ethyl acetate after reaction, with deionized water, wash organic phase, separatory is extracted with ethyl acetate after merging water, after anhydrous sodium sulfate drying organic phase, is spin-dried for, and obtains pyrene-azobenzene (Pyr-AZO);
4) take step 3) pyrene-azobenzene of preparing and through step 1) carbon nano-tube processed is dissolved in respectively DMF and obtains isocyatic two kinds of solution, by these two kinds of solution according to volume ratio (1-3): (3-1) mix, room temperature sonic oscillation 2 hours, solution is with after the separated 13000r/m of supercentrifuge, get lower sediment, add in DMF, dissolve part and be optical Response pyrene-azobenzene organic molecule non-covalent modification carbon nano-tube material (Pyr-AZO/FWNT).
The invention has the advantages that: the method is introduced pyrenyl in azobenzene molecule, the pyrenyl that azobenzene molecule utilization has large pi-conjugated system is firmly adsorbed onto the carbon nano tube surface with good conjugated system by noncovalent interaction, make optical Response pyrene-azobenzene non-covalent modification carbon nano-tube material, the dissolubility of this material is good, at nitrogen dimethylformamide, acetone, dimethyl sulfoxide (DMSO), in the organic solvents such as methyl alcohol, there is good dissolubility, its preparation technology is simple, there is good response characteristics to light, light, electrical property can be by regulating azobenzene derivatives kind to regulate and control, be expected to can regulate and control for the preparation of optics the photoresponse functional material of microstructure or photoelectric properties.
accompanying drawing explanation:
Fig. 1 is the nmr spectrum of the pyrene-azobenzene (Pyr-AZO) of preparation.
In figure: the unimodal of chemical shift 6=7.2ppm place do not replace the peak of residual H completely for deuterated reagent.Be positioned at the multiplet at 6.9～8.4ppm place of low: δ=8.36 (d, 2H); 7.97 (m, 4H); 7.02 (d, 2H) comes from the coupling of the H on two phenyl ring of azobenzene, split minute, δ=8.14 (m, 9H) splits minute from the coupling of H on pyrenyl, and δ=8.03 (s, 1H) is under the jurisdiction of in amide group the coupling of H and splits minute.The coupling that the peak that 4.07 (t, 2H) and 3.41 (t, 2H) locate is under the jurisdiction of respectively the H on the carbon that hexyl long alkyl chain two ends connect oxygen atom and nitrogen-atoms is split minute.1.3 split minute from the coupling of the H on several carbon in the middle of on two alkyl chains to several groups of multiplets between 1.9, and the peak of hydrogen on the carbon being connected with pyrenyl with carbonyl lays respectively at 2.18 (t, 2H) and 2.92 (t, 2H).
Fig. 2 is the pyrene-azobenzene (Pyr-AZO) of preparation and the absorption spectrum of the compound front and back of few-wall carbon nanotube (FWCNT).
Pyr-AZO 266,277,328 and 344nm place there is the chromophoric absworption peak of condensed-nuclei aromatics, shown the existence of the pi-electron conjugated system of pyrenyl in Pyr-AZO.In addition, there is a wider absworption peak in Pyr-AZO at 376nm place, this is the π → π by trans azobenzene chromophore *transition causes.After compound, the absworption peak that occurs Pyr-AZO on the spectrogram of Pyr-AZO/FWNT, and absorb baseline and compare obvious raising with Pyr-AZO, show that both combine closely, simultaneously the absworption peak of the upper pyrenyl of Pyr-AZO with compound before compare, there is slight red shift (1～2nm), show that the electron conjugated structure of compound rear system changes, delocalization degree improves, π → π *transition institute energy requirement decreases.
Embodiment
Provide 5 embodiment of the present invention below, be to further illustrate of the present invention, rather than limit the scope of the invention.
Embodiment 1:
1) carbon nano-tube is processed: it is that 98.3% concentrated sulfuric acid and mass fraction are in the 65% red fuming nitric acid (RFNA) volume ratio mixed solution of 3: 1 that 20mg few-wall carbon nanotube is joined to 20ml mass fraction, makes mixed liquor back flow reaction 40 minutes under temperature 70 C.With filtered and recycled filter cake after deionized water dilution mixed acid solution, with deionized water washing leaching cake, to filtrate pH, be 6-7, vacuumize 48 hours;
2) 1-amino-6-[4-(4 '-nitrobenzophenone azo) phenoxy group] hexane synthetic: under agitation, 1.38g paranitroanilinum is dissolved in the 20ml 3mol/LHCl aqueous solution, is designated as A solution; 0.83g natrium nitrosum is added in 5ml deionized water, be designated as B solution; Press A solution and mix with B solution, be designated as C solution; Under water bath condition, react 40 minutes.0.94g phenol, 4gNaOH are dissolved in to 20ml deionized water, are designated as D solution; To under ice bath, mix with D solution by reacted C solution; Ice-water bath reaction, after 1 hour, is that 20% aqueous hydrochloric acid solution adjusting pH value is 5-7 with mass fraction, separates out precipitation.Suction filtration, clarifies with deionized water washing precipitation to cleaning solution.Get 50% ethanol water recrystallization, suction filtration, obtains nitro-azo phenol 1.63g.Will be to nitro-azo phenol 486mg; 1; 6-dibromo-hexane 1.464g, potash 496mg, is dissolved in 40ml anhydrous propanone; the KI that adds 3.3mg; under nitrogen protection, heat return stirring 24 hours, filter out while hot the residue of reaction system, concentrated by rotary evaporation reactant liquor; add absolute methanol, produce orange precipitation.Column chromatography obtains the bromo-6-[4-of 0.53g 1-(4 '-nitrobenzophenone azo) phenoxy group after purifying] hexane (AZO-Br).The sylvite 185mg that gets AZO-Br406mg and phthalimide is dissolved in 50ml dry DMF, heating reflux reaction 12 hours, stop reaction, concentrated by rotary evaporation reaction solution, adding distil water makes its precipitation, after precipitation is complete, suction filtration is also used deionized water water washing solid three times, dries and obtains orange red solid.This orange red solid is dissolved in to 40ml absolute ethyl alcohol, adding 500mg mass fraction is 85% hydrazine hydrate, under nitrogen protection, heating reflux reaction is 16 hours, drips rare HCl, and regulating pH value is 3, continue to reflux 1 hour, be cooled to room temperature, standing a few hours are separated out a large amount of white needles precipitations, and suction filtration is removed white needles solid, then be spin-dried for filtrate, column chromatography obtains 0.29g 1-amino-6-[4-(4 '-nitrobenzophenone azo) phenoxy group] hexane (AZO-NH2);
3) pyrene-azobenzene organic molecule is synthetic: take pyrene butyric acid 128mg and be dissolved in 40ml dry DMF, add N-hydroxy thiosuccinimide (Sulfo-NHS) 120mg, DMAP (DMAP) 65mg, under constantly stirring, add 85mg 1-ethyl-3-(3-front three aminopropyl) carbodiimide hydrochloride (EDCHCl) in ice-water bath, keep ice-water bath reaction 1 hour, continue room temperature reaction 12 hours, stop reacting in backward system and add ethyl acetate, by saturated common salt water washing organic phase 2 times, separated with separatory funnel, anhydrous sodium sulfate drying organic phase, after filtration, be spin-dried for.In products therefrom, add 10ml dry DMF, 160mgAZO-NH 2, and several triethylamines, stirring at room reaction is spent the night.Stop adding ethyl acetate after reaction, with deionized water, wash organic phase twice, separatory is extracted with ethyl acetate once after merging water, after anhydrous sodium sulfate drying organic phase, is spin-dried for, and obtains 0.16g pyrene-azobenzene organic molecule (Pyr-AZO);
4) take step 3) the Pyr-AZO solid 10mg for preparing and through step 1) the carbon nano-tube 10mg that processes is dissolved in respectively DMF and obtains concentration and be two kinds of solution of 0.5mg/ml, above-mentioned two kinds of solution that make are mixed according to volume ratio at 1: 1, under room temperature, sonic oscillation is 2 hours, solution is with after the separated 13000r/m of supercentrifuge, get lower sediment, add in DMF, dissolve part and be optical Response pyrene-azobenzene organic molecule non-covalent modification carbon nano-tube material (Pyr-AZO/FWNT).This material photoisomerization kinetic constant is 0.059s -1.
Embodiment 2:
1) carbon nano-tube is processed: it is that 98.3% concentrated sulfuric acid and mass fraction are in the 65% red fuming nitric acid (RFNA) volume ratio mixed solution of 3: 1 that 20mg few-wall carbon nanotube is joined to 20ml mass fraction, makes mixed liquor back flow reaction 40 minutes under temperature 70 C.With filtered and recycled filter cake after deionized water dilution mixed acid solution, with deionized water washing leaching cake, to filtrate pH, be 6-7, vacuumize 48 hours;
2) 1-amino-6-[4-(4 '-nitrobenzophenone azo) phenoxy group] hexane synthetic: with in embodiment 1 2) identical;
3) pyrene-azobenzene organic molecule is synthetic: take pyrene butyric acid 128mg and be dissolved in 80ml dry DMF, add N-hydroxy thiosuccinimide (Sulfo-NHS) 96mg, DMAP (DMAP) 54mg, under constantly stirring, add 68mg 1-ethyl-3-(3-front three aminopropyl) carbodiimide hydrochloride (EDCHCl) in ice-water bath, keep ice-water bath reaction 30 minutes, continue room temperature reaction 8 hours, stop reacting in backward system and add ethyl acetate, by saturated common salt water washing organic phase 2 times, separated with separatory funnel, anhydrous sodium sulfate drying organic phase, after filtration, be spin-dried for.In products therefrom, add 10ml dry DMF, 150mgAZO-NH 2, and several triethylamines, stirring at room reaction is spent the night.Stop adding ethyl acetate after reaction, with deionized water, wash organic phase twice, separatory is extracted with ethyl acetate once after merging water, after anhydrous sodium sulfate drying organic phase, is spin-dried for, and obtains 0.11g pyrene-azobenzene organic molecule (Pyr-AZO);
4) take step 3) the Pyr-AZO solid 10mg for preparing and through step 1) the carbon nano-tube 10mg that processes is dissolved in respectively DMF and obtains concentration and be two kinds of solution of 0.5mg/ml, above-mentioned two kinds of solution that make are mixed according to volume ratio at 1: 3,
Under room temperature, sonic oscillation is 2 hours, and solution, with after the separated 13000r/m of supercentrifuge, is got lower sediment, adds in DMF, dissolves part and is optical Response pyrene-azobenzene organic molecule non-covalent modification carbon nano-tube material (Pyr-AZO/FWNT).This material photoisomerization kinetic constant is 0.047s -1.
Embodiment 3:
1) carbon nano-tube is processed: it is that 98.3% concentrated sulfuric acid and mass fraction are in the 65% red fuming nitric acid (RFNA) volume ratio mixed solution of 3: 1 that 20mg few-wall carbon nanotube is joined to 20ml mass fraction, makes mixed liquor back flow reaction 40 minutes under temperature 70 C.With filtered and recycled filter cake after deionized water dilution mixed acid solution, with deionized water washing leaching cake, to filtrate pH, be 6-7, vacuumize 48 hours;
2) 1-amino-6-[4-(4 '-nitrobenzophenone azo) phenoxy group] hexane synthetic: with in embodiment 1 2) identical;
3) pyrene-azobenzene organic molecule is synthetic: take pyrene butyric acid 128mg and be dissolved in 20ml dry DMF, add N-hydroxy thiosuccinimide (Sulfo-NHS) 180mg, DMAP (DMAP) 98mg, under constantly stirring, add 102mg 1-ethyl-3-(3-front three aminopropyl) carbodiimide hydrochloride (EDCHCl) in ice-water bath, keep ice-water bath reaction 30 minutes, continue room temperature reaction 24 hours, stop reacting in backward system and add ethyl acetate, by saturated common salt water washing organic phase 2 times, separated with separatory funnel, anhydrous sodium sulfate drying organic phase, after filtration, be spin-dried for.In products therefrom, add 10ml dry DMF, 220mg AZO-NH 2, and several triethylamines, stirring at room reaction is spent the night.Stop adding ethyl acetate after reaction, with deionized water, wash organic phase twice, separatory is extracted with ethyl acetate once after merging water, after anhydrous sodium sulfate drying organic phase, is spin-dried for, and obtains 0.14g pyrene-azobenzene organic molecule (Pyr-AZO);
4) take step 3) the Pyr-AZO solid 10mg for preparing and through step 1) the carbon nano-tube 10mg that processes is dissolved in respectively DMF and obtains concentration and be two kinds of solution of 0.5mg/ml, above-mentioned two kinds of solution that make are mixed according to volume ratio at 3: 1, under room temperature, sonic oscillation is 2 hours, solution is with after supercentrifuge separated (13000r/m), get lower sediment, add in DMF, dissolve part and be optical Response pyrene-azobenzene organic molecule non-covalent modification carbon nano-tube material (Pyr-AZO/FWNT).This material photoisomerization kinetic constant is 0.056s -1.
Embodiment 4:
1) carbon nano-tube is processed: it is that 98.3% concentrated sulfuric acid and mass fraction are in the 65% red fuming nitric acid (RFNA) volume ratio mixed solution of 3: 1 that 20mg few-wall carbon nanotube is joined to 10ml mass fraction, makes mixed liquor back flow reaction 30 minutes under temperature 50 C.With filtered and recycled filter cake after deionized water dilution mixed acid solution, with deionized water washing leaching cake, to filtrate pH, be 6-7, vacuumize 12 hours.
2) 1-amino-6-[4-(4 '-nitrobenzophenone azo) phenoxy group] hexane synthetic: with in embodiment 1 2) identical;
3) pyrene-azobenzene organic molecule is synthetic: with in embodiment 1 3) identical;
4) take step 3) the Pyr-AZO solid 10mg for preparing and through step 1) the carbon nano-tube 10mg that processes is dissolved in respectively DMF and obtains concentration and be two kinds of solution of 0.5mg/ml, above-mentioned two kinds of solution that make are mixed according to volume ratio at 1: 1, under room temperature, sonic oscillation is 2 hours, solution is with after the separated 13000r/m of supercentrifuge, get lower sediment, add in DMF, dissolve part and be optical Response pyrene-azobenzene organic molecule non-covalent modification carbon nano-tube material (Pyr-AZO/FWNT).This material photoisomerization kinetic constant is 0.054s -1.
Embodiment 5:
1) carbon nano-tube is processed: it is that 98.3% concentrated sulfuric acid and mass fraction are in the 65% red fuming nitric acid (RFNA) volume ratio mixed solution of 3: 1 that 20mg few-wall carbon nanotube is joined to 40ml mass fraction, make mixed liquor back flow reaction 120 minutes at 90 ℃ of temperature, with filtered and recycled filter cake after deionized water dilution mixed acid solution, with deionized water washing leaching cake, to filtrate pH, be 6-7, vacuumize 72 hours;
2) 1-amino-6-[4-(4 '-nitrobenzophenone azo) phenoxy group] hexane synthetic: with in embodiment 1 2) identical;
3) pyrene-azobenzene organic molecule is synthetic: with in embodiment 1 3) identical;
4) take step 3) the Pyr-AZO solid 10mg for preparing and through step 1) the carbon nano-tube 10mg that processes is dissolved in respectively DMF and obtains concentration and be two kinds of solution of 0.5mg/ml, above-mentioned two kinds of solution that make are mixed according to volume ratio at 1: 1, under room temperature, sonic oscillation is 2 hours, solution is with after the separated 13000r/m of supercentrifuge, get lower sediment, add in DMF, dissolve part and be optical Response pyrene-azobenzene organic molecule non-covalent modification carbon nano-tube material (Pyr-AZO/FWNT).This material photoisomerization kinetic constant is 0.051s -1.

Claims (1)

1. a preparation method for optical Response pyrene-azobenzene non-covalent modification carbon nano-tube material, is characterized in that comprising following process:
1) carbon nano-tube is processed: it is that 98.3% concentrated sulfuric acid and mass fraction are 65% red fuming nitric acid (RFNA) and are (1-3) by volume that carbon nano-tube is joined to mass fraction: in 1 mixed acid, make carbon nano-tube concentration for (0.5-2) mg/ml, make dispersion liquid back flow reaction 30-120 minute at temperature 50 C-90 ℃, reclaim carbon nano-tube, with deionized water, wash that to cleaning solution, to be pH be 6-7, vacuumize 12-72 hour, obtains acidification carbon nano-tube;
2) 1-amino-6-[4-(4 '-nitrobenzophenone azo) phenoxy group] hexane synthetic: under agitation, paranitroanilinum is dissolved in 3mol/L hydrochloride aqueous solution, be mixed with the aqueous hydrochloric acid solution that concentration is 0.2-1.2mol/L paranitroanilinum, be designated as A solution, natrium nitrosum is added in deionized water, be mixed with 1.5-2.5mol/L sodium nitrite in aqueous solution, be designated as B solution, press the volume ratio (1-12.5) of A solution and B solution: 1 mixes, and under condition of ice bath, reacts 15-90 minute, is designated as C solution, phenol is dissolved in 3.5-6mol/L sodium hydrate aqueous solution, and being mixed with concentration is the NaOH aqueous solution of 0.2-1.2mol/L phenol, is designated as D solution, will be under ice bath reacted C solution and D solution (2-13.5) by volume: 1 mixes, ice bath reaction is after 30-180 minute, with mass fraction, be that 20% aqueous hydrochloric acid solution adjusting pH value is 5-7, separate out a large amount of precipitations, suction filtration, clarifies with deionized water washing precipitation to cleaning solution, with 50% ethanol water recrystallization, suction filtration, obtains nitro-azo phenol, to be dissolved in 0.05-0.2mol/L1 to nitro-azo phenol, the anhydrous propanone solution of 6-dibromo-hexane, in this mixed solution, add potash, make nitro-azo phenol, 1, 6-dibromo-hexane, the ratio of potash three molal weight is successively 1: (1-4): (1-3), in mixed solution, add KI, making its concentration is 0.0083-0.415mg/ml, under nitrogen protection, heat return stirring 12-48 hour, filter out while hot the residue of reaction system, concentrated by rotary evaporation reactant liquor, add absolute methanol, produce orange precipitation, column chromatography obtains the bromo-6-[4-of 1-(4 ' nitrobenzophenone azo) phenoxy group after purifying] hexane, by the bromo-6-[4-of 1-(4 '-nitrobenzophenone azo) phenoxy group] hexane is dissolved in the anhydrous nitrogen dimethylformamide solution of 0.01-0.25mol/L potassium phthalimide, being mixed with concentration is the bromo-6-[4-of 0.02-0.03mol/L1-(4 '-nitrobenzophenone azo) phenoxy group] the anhydrous nitrogen dimethylformamide solution of potassium phthalimide of hexane, heating reflux reaction 6-24 hour, stop reaction, concentrated by rotary evaporation reaction solution, adding distil water makes its precipitation, after precipitation is complete, suction filtration is also used deionized water washing precipitation, precipitation is dried and obtained orange red solid, the hydrazine hydrate that is 85% by mass fraction adds ethanol, the mass ratio that makes ethanol and hydrazine hydrate is 1: (6.3-25.3), precipitation oven dry is obtained to orange red solid and be dissolved in this mixed solution, heating reflux reaction 8-24 hour under nitrogen protection, drip the 1mol/LHCl aqueous solution, regulating pH value is 2-6, continue backflow 30-180 minute, be cooled to room temperature, the standing white needles precipitation of separating out, suction filtration is removed white needles solid, then be spin-dried for filtrate, column chromatography obtains 1-amino-6-[4-(4 '-nitrobenzophenone azo) phenoxy group] hexane,
3) pyrene-azobenzene organic molecule is synthetic: take pyrene butyric acid and be dissolved in anhydrous nitrogen dimethylformamide, being mixed with concentration is 0.005-0.022mol/L pyrene butyric acid nitrogen dimethylformamide solution, add N-hydroxy thiosuccinimide and DMAP, make pyrene butyric acid, N-hydroxy thiosuccinimide, the DMAP successively ratio of molal weight is 1: (1-1.5): (1-1.5), mixed solution adds 1-ethyl-3-(3-front three aminopropyl) carbodiimide hydrochloride under constantly stirring in ice bath, making the molal weight ratio of pyrene butyric acid and 1-ethyl-3-(3-front three aminopropyl) carbodiimide hydrochloride is 1: (1-1.2), keep ice-water bath reaction 30-240 minute, continue room temperature reaction 8-24 hour, stop reacting in backward system and add ethyl acetate, by saturated common salt water washing organic phase, separated with separatory funnel, anhydrous sodium sulfate drying organic phase, after filtration, be spin-dried for, in products therefrom, add anhydrous nitrogen dimethylformamide and 1-amino-6-[4-(4 '-nitrobenzophenone azo) phenoxy group] hexane, 1-2ml triethylamine, making 1-amino-6-[4-(4 '-nitrobenzophenone azo) phenoxy group] hexane concentration is 16-22mg/ml, stirring at room reaction 8-24 hour, stop adding ethyl acetate after reaction, with deionized water, wash organic phase, separatory is extracted with ethyl acetate after merging water, after anhydrous sodium sulfate drying organic phase, be spin-dried for, obtain pyrene-azobenzene organic molecule,
4) take step 3) pyrene-azobenzene of preparing and through step 1) carbon nano-tube processed is dissolved in respectively nitrogen dimethylformamide and obtains isocyatic two kinds of solution, by these two kinds of solution according to volume ratio (1-3): mix (3-1), room temperature sonic oscillation 2 hours, solution is with after the separated 13000r/m of supercentrifuge, get lower sediment, add in nitrogen dimethylformamide, dissolve part and be optical Response pyrene-azobenzene organic molecule non-covalent modification carbon nano-tube material.
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