CN101357760A - Method for preparing single-wall carbon nanotube metal organic frame - Google Patents
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Abstract
The invention relates to a preparation method of a single-walled carbon nanotube metal-organic framework in the nanotechnology field, which comprises the following steps: a. mixing 1 weight proportion of dried single-walled carbon nanotube with 50-5000 weight proportions of strong oxidizing acid to be processed by ultrasonic treatment, stirring to react, sucking filtration and washing until the solution is neutral, and obtaining acidulated carbon nanotube after drying; b. adding zinc acetate aqueous solution drop by drop, stirring to react, sucking filtration and washing, dispersing the product in an organic solvent again, sucking filtration once again, and obtaining the product SWNT-MOF-1 after drying; c. mixing the SWNT-MOF-1 and the organic solution to be processed by the ultrasonic treatment, adding the organic solvent solution of an organic ligand, stirring to react, cooling, adding the organic solvent to leach, sucking filtration, dispersing the black products in de-ionized water again, sucking filtration once again, dialyzing the black products, and obtaining the final products after drying. The method is simple and the material with both the perfect structure of the single-walled carbon nanotube and the structure of the metal-organic framework can be obtained.
Description
Technical field
That the present invention relates to is a kind of preparation method's of field of nanometer technology, particularly a kind of single-wall carbon nanotube metal organic frame preparation method.
Background technology
Carbon nanotube (being called for short CNT) is found in recent years a kind of novel carbon structure, it is the seamless hollow carbon pipe that curls and form by the Graphene lamella that carbon atom forms, two ends respectively have the fullerene molecule end-blocking half, are a kind of One-dimensional Quantum materials with height delocalization πDian Zi conjugated system.Carbon nanotube is divided into Single Walled Carbon Nanotube (SWNT) and multi-walled carbon nano-tubes (MWNT).Single Walled Carbon Nanotube (SWNT) extensively is considered as the key player of type material and following material owing to the quantum performance and the mechanical property of its perfect structure, uniqueness.From over 1993, obtained considerable progress with regard to its characterizing method and functionalization research, wherein carbon nanotube being carried out oxidation modification, to obtain various carbon nano tube derivative technology very ripe.In recent years, the metal-organic framework structure (MOFs) that is formed by different metal and part becomes the focus in the Materials science research field.MOFs has charming topological framework, tailorability, structure diversity and is easy to carry out characteristics such as design and assembly and structure regulating, application prospect at aspects such as gas adsorption, catalysis, gas delivery is very clear and definite, cause the extensive concern of scientific circles, report synthetic to it, that modify, use emerges in an endless stream.
Carbon nano tube derivative combines with transition metal and the complex systems that forms enjoys the concern of scientific circles as a class type material.Zinc is a kind of common transition metal, has good catalytic effect, deliver again and again based on the coordination chemistry work of zinc in recent years, but about zinc Zn (II) ion functionalization is rarely had report to the work of carbon nano tube surface.If in the complex systems of carbon nano tube derivative and zine ion formation, introduce new part, be expected to obtain carbon nanotube metal organic frame (CNT-MOF).CNT-MOF is expected to the perfect structure with Single Walled Carbon Nanotube, the characteristics that charming topological framework, tailorability, the structure diversity of unique quantum performance, photoelectric properties and outstanding mechanical property and metal organic frame and being easy to carries out design and assembly and structure regulating combine, and in fields such as the separation and purification of high-selectivity catalyst and support of the catalyst, sorbent material, gas and storage, solar energy converting material, high-strength light structured material, advanced composite materials clear and definite application prospect are arranged.
Find through literature search prior art, the Triply fused Zn-II-porphyrin oligomers:Synthesis that Cheng etc. delivered on the 12nd volume 23 phase 6062-6070 pages or leaves at " Europe chemistry " in 2006, properties, and supramolecular interactions with single-walled carbon nanotubes (SWNTs) (synthesizing of three heavy polymers of Zn (II) ion-porphyrin, performance and with the reaction of the supramolecule of single-walled nanotube), propose the technology of zinc Zn (II) ion-porphyrin functionalization in this article) to carbon nano tube surface, be specially: directly mix Zn (II) ion-porphyrin and carbon nanotube ultrasonic, utilize the supramolecule effect between Zn (II) ion-porphyrin and the carbon nanotube, make zinc Zn (II) ion-porphyrin functionalization to carbon nano tube surface, its deficiency is: owing to rely on the supramolecule effect, so zinc Zn (II) ion-porphyrin is stable inadequately with combining of carbon nanotube, the process long period has deposited phenomenon.The present invention at first carries out modification to Single Walled Carbon Nanotube, it is linked to each other with covalent linkage with carboxyl, utilize the coordination of carboxyl and metal ion to construct MOFs then, the carbon nanotube of bunchy disperses thereby make very easily, obtains stable single-wall carbon nanotube metal organic frame structure.
Summary of the invention
The objective of the invention is at the deficiencies in the prior art, a kind of preparation method of single-wall carbon nanotube metal organic frame is provided, Single Walled Carbon Nanotube and metal organic frame are combined, obtain a kind of type material that has Single Walled Carbon Nanotube perfect structure and organic metal framework structure simultaneously, can be used for fields such as the separation and purification of high-selectivity catalyst and support of the catalyst, sorbent material, gas and storage, solar energy converting material, high-strength light structured material, advanced composite material.
The present invention is achieved by the following technical solutions, the present invention carries out the presoma (SWNT-MOF-1) that coordination reaction obtains single-wall carbon nanotube metal organic frame with zinc acetate after with the Single Walled Carbon Nanotube carboxylation, and then the adding organic ligand, formed single-wall carbon nanotube metal organic frame SWNT-MOFs by coordination.
The present invention includes following steps:
Step a: 1 weight part exsiccant Single Walled Carbon Nanotube raw material and 50～5000 weight part acid with strong oxidizing property are mixed, ultrasonication, stirring reaction, suction filtration also repeatedly is neutral to solution with the deionized water repetitive scrubbing, obtains the acidifying carbon nanotube after the vacuum-drying;
Step b: with constant pressure funnel zinc acetate aqueous solution is dropwise added, stirring reaction, suction filtration and repeatedly with the deionized water repetitive scrubbing, be dispersed in the black product in the organic solvent again again after suction filtration again, obtain product S WNT-MOF-1 after the vacuum-drying;
Step c: SWNT-MOF-1 and organic solvent are mixed ultrasonication, add the organic solvent solution of organic ligand, stirring reaction.After the question response liquid cooling but, add organic solvent drip washing, behind the suction filtration, be distributed to the black product in the deionized water again after suction filtration again, repeated multiple times.Again the black product is dialysed in organic solvent, obtain product S WNT-MOFs after the vacuum-drying.
Among the above-mentioned steps a, described acid with strong oxidizing property comprises nitric acid, sulfuric acid, nitric acid and sulfuric acid mixing acid, and is added with potassium permanganate or H
2O
2Hydrochloric acid, nitric acid, sulfuric acid and mixing acid thereof in a kind of.
Among the above-mentioned steps a, described ultrasonication is meant: with 0kHz～100kHz ultrasonication 1min～100min.
Among the above-mentioned steps a, described stirring reaction, its temperature of reaction is 20 ℃～200 ℃, the reaction times is 1min～100min.
Among the above-mentioned steps a, described Single Walled Carbon Nanotube raw material is the Single Walled Carbon Nanotube of catalyse pyrolysis, arc-over, template, the preparation of chemical Vapor deposition process method.
Among the above-mentioned steps b, described organic solvent is for diethyl ether, ether, methyl-sulphoxide, chloroform, tetrahydrofuran (THF), acetone, ethanol, acetonitrile, butanone, pyridine or contain a kind of in the mixed solvent of these solvents.
Among the above-mentioned steps c, described organic solvent is for diethyl ether, ether, methyl-sulphoxide, chloroform, tetrahydrofuran (THF), acetone, ethanol, acetonitrile, butanone, pyridine or contain a kind of in the mixed solvent of these solvents.
Among the above-mentioned steps c, described organic ligand, be 2,2 '-dipyridyl, 4,4 '-dipyridyl, 2,2:6,2-terpyridyl, 2,2 ': 6 ', 2 ": 6 ", 2-tetrad pyridine, 2,2 ': 4 ', 4 ": 2 ", 2-tetrad pyridine, 2,2 ': 6 ', 2 ": 6 ", 2:6,2-5-linked pyridine, 2,2 ': 6 ', 2 ": 6 ", 2:6,2:6, a kind of in the organic ligands such as 2-six dipyridyls.
Among the above-mentioned steps c, described ultrasonication is meant: with 0kHz～100kHz ultrasonication 1min～100min.
Among the above-mentioned steps c, described stirring reaction, its temperature is 10 ℃～100 ℃, the reaction times is 20h～100h.
Preparation method provided by the invention is simple, controllability is strong, and the topological framework by Infrared spectroscopy, nuclear magnetic spectrum analysis, ultraviolet absorption spectroscopy and X-ray photoelectron spectroscopic analysis sign products therefrom has shown that zinc Zn (II) ion and organic ligand functionalization have arrived the surface of carbon nanotube.
Description of drawings
The transmission electron microscope figure of Fig. 1: SWNT-MOF-2 (a and b) and SWNT-MOF-3 (c and d).
Fig. 2: SWNT-MOF-2 and SWNT-MOF-3's
1The H nmr spectrum.
Embodiment
Below in conjunction with accompanying drawing embodiments of the invention are elaborated: present embodiment is being to implement under the prerequisite with the technical solution of the present invention, provided detailed embodiment and concrete operating process, but protection scope of the present invention is not limited to following embodiment.
Embodiment 1
Single Walled Carbon Nanotube with the chemical Vapor deposition process preparation is an initial raw material, acidified, by and zinc acetate between coordination reaction obtained the presoma (SWNT-MOF-1) of single-wall carbon nanotube metal organic frame, add organic ligand 2 then, 2 '-dipyridyl has formed Single Walled Carbon Nanotube/zinc/second bipyridine framework (SWNT-MOF-2) by coordination.
Step a: in single neck round-bottomed flask of magnetic agitation rotor is housed, add 0.30g carbon nanometer tube material and 225mL nitric acid and sulfuric acid mixed solution, with 40kHz ultrasonication 25min post-heating to 80 ℃, stir reaction 55min down, with ф 0.22 μ m tetrafluoroethylene millipore filtration suction filtration, repeatedly to neutral, obtain acidifying carbon nanotube behind 50 ℃ of vacuum-drying 24h with a large amount of deionized water repetitive scrubbings;
Step b: 200mg SWNT-COOH and 200mL deionized water are joined in the single neck round-bottomed flask of exsiccant 500mL, and ultrasonic 30min dropwise adds 20mL zinc acetate aqueous solution (50mmol/L) with constant pressure funnel, is warming up to 50 ℃, stirs reaction 48h down.After the question response liquid cooling but, add the deionized water dilution, with the mixed fine filter membrane suction filtration of 0.22 μ m, be distributed to the black product in the deionized water again after suction filtration again, 3 times repeatedly.Again suction filtration again after being distributed to the black product in the ethanol again, 50 ℃ of following vacuum-drying 12h obtain product S WNT-MOF-1;
Step c: 120mg SWNT-MOF-1,10mL deionized water and 90mL ethanol are joined in the single neck round-bottomed flask of exsiccant 250mL, and pre-ultrasonic 1h adds 80mL 2,2 '-dipyridyl ethanolic soln (63mmol/L), is warming up to 25 ℃, stirs reaction 48h down.After the question response liquid cooling but, add ethanol drip washing (4x5ml), with the mixed fine filter membrane suction filtration of 0.22 μ m, be distributed to the black product in the deionized water again after suction filtration again, 3 times repeatedly.Be to dialyse 3 days in the solution again with ethanol with the black product, 50 ℃ of following vacuum-drying 12h obtain product S WNT-MOF-2.
Single Walled Carbon Nanotube with the catalytic pyrolysis method preparation is an initial raw material, acidified, by and zinc acetate between coordination reaction obtained the presoma (SWNT-MOF-1) of single-wall carbon nanotube metal organic frame, add organic ligand 4 then, 4 '-dipyridyl has formed Single Walled Carbon Nanotube/zinc/second bipyridine framework (SWNT-MOF-3) by coordination.
Step a: in single neck round-bottomed flask of magnetic agitation rotor is housed, add 0.30g carbon nanometer tube material and 225mL nitric acid and sulfuric acid mixed solution, with 40kHz ultrasonication 25min post-heating to 80 ℃, stir reaction 55min down, with ф 0.22 μ m tetrafluoroethylene millipore filtration suction filtration, repeatedly to neutral, obtain acidifying carbon nanotube behind 50 ℃ of vacuum-drying 24h with a large amount of deionized water repetitive scrubbings;
Step b: 200mg SWNT-COOH and 200mL deionized water are joined in the single neck round-bottomed flask of exsiccant 500mL, and ultrasonic 30min dropwise adds 20mL zinc acetate aqueous solution (50mmol/L) with constant pressure funnel, is warming up to 50 ℃, stirs reaction 48h down.After the question response liquid cooling but, add the deionized water dilution, with the mixed fine filter membrane suction filtration of 0.22 μ m, be distributed to the black product in the deionized water again after suction filtration again, 3 times repeatedly.Again suction filtration again after being distributed to the black product in the tetrahydrofuran (THF) again, 50 ℃ of following vacuum-drying 12h obtain product S WNT-MOF-1;
Step c: 120mg SWNT-MOF-1,10mL deionized water and 90mL tetrahydrofuran (THF) are joined in the single neck round-bottomed flask of exsiccant 250mL, pre-ultrasonic 1h adds 80mL 4,4 '-dipyridyl tetrahydrofuran solution (63mmol/L), be warming up to 25 ℃, stir reaction 48h down.After the question response liquid cooling but, add tetrahydrofuran (THF) drip washing (4x5ml), with the mixed fine filter membrane suction filtration of 0.22 μ m, be distributed to the black product in the deionized water again after suction filtration again, 3 times repeatedly.Be to dialyse 3 days in the solution again with the tetrahydrofuran (THF) with the black product, 50 ℃ of following vacuum-drying 12h obtain product S WNT-MOF-3.
Single Walled Carbon Nanotube with the chemical Vapor deposition process preparation is an initial raw material, acidified, by and zinc acetate between coordination reaction obtained the presoma (SWNT-MOF-1) of single-wall carbon nanotube metal organic frame, add organic ligand 2 then, 2 ': 6 ', 2 ": 6 ", 2-tetrad pyridine has formed Single Walled Carbon Nanotube/zinc/second bipyridine framework (SWNT-MOF-4) by coordination.
Step a: in single neck round-bottomed flask of magnetic agitation rotor is housed, add 0.35g carbon nanometer tube material and 120mL nitric acid and sulfuric acid mixed solution, with 40kHz ultrasonication 45min post-heating to 55 ℃, stir reaction 45min down, with ф 0.22 μ m tetrafluoroethylene millipore filtration suction filtration, repeatedly to neutral, obtain acidifying carbon nanotube behind 50 ℃ of vacuum-drying 24h with a large amount of deionized water repetitive scrubbings;
Step b: 150mg SWNT-COOH and 150mL deionized water are joined in the single neck round-bottomed flask of exsiccant 500mL, and ultrasonic 30min dropwise adds 20mL zinc acetate aqueous solution (50mmol/L) with constant pressure funnel, is warming up to 50 ℃, stirs reaction 48h down.After the question response liquid cooling but, add the deionized water dilution, with the mixed fine filter membrane suction filtration of 0.22 μ m, be distributed to the black product in the deionized water again after suction filtration again, 3 times repeatedly.Again suction filtration again after being distributed to the black product in the acetone again, 50 ℃ of following vacuum-drying 12h obtain product S WNT-MOF-1;
Step c: 100mg SWNT-MOF-1,10mL deionized water and 90mL acetone are joined in the single neck round-bottomed flask of exsiccant 250mL, and pre-ultrasonic 1h adds 80mL2,2 ': 6 ', 2 ": 6 ", 2-tetrad pyridine solution (63mmol/L), be warming up to 25 ℃, stir reaction 48h down.After the question response liquid cooling but, add acetone drip washing (4x5ml), with the mixed fine filter membrane suction filtration of 0.22 μ m, be distributed to the black product in the deionized water again after suction filtration again, 3 times repeatedly.Be to dialyse 3 days in the solution again with acetone with the black product, 50 ℃ of following vacuum-drying 12h obtain product S WNT-MOF-4.
Embodiment 4
Single Walled Carbon Nanotube with the catalytic pyrolysis method preparation is an initial raw material, acidified, by and zinc acetate between coordination reaction obtained the presoma (SWNT-MOF-1) of single-wall carbon nanotube metal organic frame, add organic ligand 2 then, 2 '-dipyridyl and 4,4 '-dipyridyl has formed Single Walled Carbon Nanotube/zinc/second bipyridine framework (SWNT-MOF-5) by coordination.
Step a: in single neck round-bottomed flask of magnetic agitation rotor is housed, add 0.30g carbon nanometer tube material and 225mL nitric acid and sulfuric acid mixed solution, with 40kHz ultrasonication 25min post-heating to 80 ℃, stir reaction 55min down, with ф 0.22 μ m tetrafluoroethylene millipore filtration suction filtration, repeatedly to neutral, obtain acidifying carbon nanotube behind 50 ℃ of vacuum-drying 24h with a large amount of deionized water repetitive scrubbings;
Step b: 200mg SWNT-COOH and 200mL deionized water are joined in the single neck round-bottomed flask of exsiccant 500mL, and ultrasonic 30min dropwise adds 20mL zinc acetate aqueous solution (50mmol/L) with constant pressure funnel, is warming up to 50 ℃, stirs reaction 48h down.After the question response liquid cooling but, add the deionized water dilution, with the mixed fine filter membrane suction filtration of 0.22 μ m, be distributed to the black product in the deionized water again after suction filtration again, 3 times repeatedly.Again suction filtration again after being distributed to the black product in the acetonitrile again, 50 ℃ of following vacuum-drying 12h obtain product S WNT-MOF-1;
Step c: 120mg SWNT-MOF-1,10mL deionized water and 90mL acetonitrile are joined in the single neck round-bottomed flask of exsiccant 250mL, and pre-ultrasonic 45min adds 80mL 2,2 ': 6 ', 2 ": 6 ", 2:6,2-5-linked pyridine acetonitrile liquid (63mmol/L) is warming up to 25 ℃, stirs reaction 48h down.After the question response liquid cooling but, add acetonitrile drip washing (4x5ml), with the mixed fine filter membrane suction filtration of 0.22 μ m, be distributed to the black product in the deionized water again after suction filtration again, 3 times repeatedly.Be to dialyse 3 days in the solution again with the acetonitrile with the black product, 50 ℃ of following vacuum-drying 15h obtain product S WNT-MOF-5.
Embodiment 5
Single Walled Carbon Nanotube with the catalytic pyrolysis method preparation is an initial raw material, acidified, by and zinc acetate between coordination reaction obtained the presoma (SWNT-MOF-1) of single-wall carbon nanotube metal organic frame, add organic ligand 2 then, 2 '-dipyridyl and 4,4 '-dipyridyl has formed Single Walled Carbon Nanotube/zinc/second bipyridine framework (SWNT-MOF-6) by coordination.
Step a: in single neck round-bottomed flask of magnetic agitation rotor is housed, add 0.30g carbon nanometer tube material and 225mL nitric acid and sulfuric acid mixed solution, with 40kHz ultrasonication 25min post-heating to 80 ℃, stir reaction 55min down, with ф 0.22 μ m tetrafluoroethylene millipore filtration suction filtration, repeatedly to neutral, obtain acidifying carbon nanotube behind 50 ℃ of vacuum-drying 24h with a large amount of deionized water repetitive scrubbings;
Step b: 200mg SWNT-COOH and 200mL deionized water are joined in the single neck round-bottomed flask of exsiccant 500mL, and ultrasonic 30min dropwise adds 20mL zinc acetate aqueous solution (50mmol/L) with constant pressure funnel, is warming up to 50 ℃, stirs reaction 48h down.After the question response liquid cooling but, add the deionized water dilution, with the mixed fine filter membrane suction filtration of 0.22 μ m, be distributed to the black product in the deionized water again after suction filtration again, 3 times repeatedly.Again suction filtration again after being distributed to the black product in the ethanol again, 50 ℃ of following vacuum-drying 12h obtain product S WNT-MOF-1;
Step c: 120mg SWNT-MOF-1,10mL deionized water and 90mL ethanol are joined in the single neck round-bottomed flask of exsiccant 250mL, pre-ultrasonic 45min, add 80mL 2,2 ': 6 ' 2,2 ': 6 ', 2 ": 6 ", 2:6,2:6,2-six dipyridyl ethanol liquid (63mmol/L), be warming up to 25 ℃, stir reaction 48h down.After the question response liquid cooling but, add ethanol drip washing (4x5ml), with the mixed fine filter membrane suction filtration of 0.22 μ m, be distributed to the black product in the deionized water again after suction filtration again, 3 times repeatedly.Be to dialyse 3 days in the solution again with ethanol with the black product, 50 ℃ of following vacuum-drying 15h obtain product S WNT-MOF-6.
The foregoing description has prepared Single Walled Carbon Nanotube-zinc-dipyridyl frame material (SWNT-MOFs) by coordination.By FTIR,
1Characterization methods such as H NMR, UV spectrum have confirmed the formation of single-wall carbon nanotube metal organic frame structure (SWNT-MOFs), XPS result has illustrated the coordination mechanism of SWNT-MOFs, the result of FE-SEM, HR-TEM shows that further SWNT-MOF-2 and SWNT-MOF-3 have different topological frameworks, and wherein the latter's boundling degree is higher.Use this simple method, a series of transition metal and carbon nanotube system can be integrated, and then construct out novel supramolecular structure, and can pass through to add the regulation and control of different part realizations to the SWNT-MOFs performance, and then be applied to research fields such as Chu Qing, catalysis.
As shown in Figure 1, the transmission electron microscope figure of SWNT-MOF-2 (a and b) and SWNT-MOF-3 (c and d).Can see that by low magnification Fig. 1 a and 1c the MOF layer of band " spot " is wrapped in carbon nano tube surface equably, further can more clearly observe " spot " pattern by high-amplification-factor Fig. 1 b and 1d.Because the internal structure that the MOF layer has blocked carbon nanotube causes the tube wall of carbon nanotube to become and can not differentiate.
As shown in Figure 2, SWNT-MOF-2 and SWNT-MOF-3
1The H nmr spectrum, occur 2,2 '-dipyridyl and 4,4 '-the characterization displacement study of dipyridyl, for the formation of SWNT-MOF-2 and SWNT-MOF-3 skeleton construction provides strong evidence.
Claims (10)
1. the preparation method of a single-wall carbon nanotube metal organic frame is characterized in that, may further comprise the steps:
Step a: 1 weight part exsiccant Single Walled Carbon Nanotube raw material and 50～5000 weight part acid with strong oxidizing property are mixed, ultrasonication, stirring reaction, suction filtration also repeatedly is neutral to solution with the deionized water repetitive scrubbing, obtains the acidifying carbon nanotube after the vacuum-drying;
Step b: with constant pressure funnel zinc acetate aqueous solution is dropwise added, stirring reaction, suction filtration and repeatedly with the deionized water repetitive scrubbing, be dispersed in the black product in the organic solvent again again after suction filtration again, obtain product S WNT-MOF-1 after the vacuum-drying;
Step c: SWNT-MOF-1 and organic solvent are mixed ultrasonication, the organic solvent solution that adds organic ligand, stirring reaction, after the question response liquid cooling but, add organic solvent drip washing, behind the suction filtration, again suction filtration again after being distributed to the black product in the deionized water, repeated multiple times is dialysed the black product again in organic solvent, obtain product S WNT-MOFs after the vacuum-drying.
2. the preparation method of single-wall carbon nanotube metal organic frame according to claim 1 is characterized in that, among the step a, described acid with strong oxidizing property comprises nitric acid, sulfuric acid, nitric acid and sulfuric acid mixing acid, and is added with potassium permanganate or H
2O
2Hydrochloric acid, nitric acid, sulfuric acid and mixing acid thereof in a kind of.
3. the preparation method of single-wall carbon nanotube metal organic frame according to claim 1 is characterized in that, among the step a, described ultrasonication is meant: with 0kHz～100kHz ultrasonication 1min～100min.
4. the preparation method of single-wall carbon nanotube metal organic frame according to claim 1 is characterized in that, among the step a, and described stirring reaction, its temperature of reaction is 20 ℃～200 ℃, the reaction times is 1min～100min.
5. the preparation method of single-wall carbon nanotube metal organic frame according to claim 1, it is characterized in that, among the step a, described Single Walled Carbon Nanotube raw material is the Single Walled Carbon Nanotube of catalyse pyrolysis, arc-over, template, the preparation of chemical Vapor deposition process method.
6. the preparation method of single-wall carbon nanotube metal organic frame according to claim 1, it is characterized in that, among the step b, described organic solvent is for diethyl ether, ether, methyl-sulphoxide, chloroform, tetrahydrofuran (THF), acetone, ethanol, acetonitrile, butanone, pyridine or contain a kind of in the mixed solvent of these solvents.
7. the preparation method of single-wall carbon nanotube metal organic frame according to claim 1, it is characterized in that, among the step c, described organic solvent is for diethyl ether, ether, methyl-sulphoxide, chloroform, tetrahydrofuran (THF), acetone, ethanol, acetonitrile, butanone, pyridine or contain a kind of in the mixed solvent of these solvents.
8. the preparation method of single-wall carbon nanotube metal organic frame according to claim 1 is characterized in that, among the step c, described organic ligand is 2,2 '-dipyridyl, 4,4 '-dipyridyl, 2,2:6, the 2-terpyridyl, 2,2 ': 6 ', 2 ": 6 ", 2-tetrad pyridine, 2,2 ': 4 ', 4 ": 2 ", 2-tetrad pyridine, 2,2 ': 6 ', 2 ": 6 ", 2:6,2-5-linked pyridine, 2,2 ': 6 ', 2 ": 6 ", 2:6,2:6, a kind of in 2-six dipyridyls.
9. the preparation method of single-wall carbon nanotube metal organic frame according to claim 1 is characterized in that, among the step c, described ultrasonication is meant: with 0kHz～100kHz ultrasonication 1min～100min.
10. the preparation method of single-wall carbon nanotube metal organic frame according to claim 1 is characterized in that, among the step c, and described stirring reaction, its temperature is 10 ℃～100 ℃, the reaction times is 20h～100h.
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