CN102874749B - Method for manufacturing nano pipes - Google Patents
Method for manufacturing nano pipes Download PDFInfo
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- CN102874749B CN102874749B CN201210336959.3A CN201210336959A CN102874749B CN 102874749 B CN102874749 B CN 102874749B CN 201210336959 A CN201210336959 A CN 201210336959A CN 102874749 B CN102874749 B CN 102874749B
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- 238000000034 method Methods 0.000 title abstract description 21
- 238000004519 manufacturing process Methods 0.000 title 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 116
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 103
- 239000002086 nanomaterial Substances 0.000 claims abstract description 67
- 239000002071 nanotube Substances 0.000 claims abstract description 54
- 238000002360 preparation method Methods 0.000 claims abstract description 34
- 238000010894 electron beam technology Methods 0.000 claims abstract description 27
- 150000001875 compounds Chemical class 0.000 claims description 39
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical group O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- 239000008367 deionised water Substances 0.000 claims description 21
- 229910021641 deionized water Inorganic materials 0.000 claims description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 17
- 239000012452 mother liquor Substances 0.000 claims description 11
- 239000002070 nanowire Substances 0.000 claims description 10
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 9
- 229910052802 copper Inorganic materials 0.000 claims description 9
- 239000010949 copper Substances 0.000 claims description 9
- 229910021389 graphene Inorganic materials 0.000 claims description 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 8
- WILFBXOGIULNAF-UHFFFAOYSA-N copper sulfanylidenetin zinc Chemical compound [Sn]=S.[Zn].[Cu] WILFBXOGIULNAF-UHFFFAOYSA-N 0.000 claims description 7
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 7
- 239000002105 nanoparticle Substances 0.000 claims description 7
- 229910052714 tellurium Inorganic materials 0.000 claims description 7
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 6
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 3
- 230000001678 irradiating effect Effects 0.000 claims description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims description 3
- 239000011733 molybdenum Substances 0.000 claims description 3
- 239000002131 composite material Substances 0.000 abstract 5
- 230000000712 assembly Effects 0.000 abstract 3
- 238000000429 assembly Methods 0.000 abstract 3
- 230000005540 biological transmission Effects 0.000 description 20
- 239000000243 solution Substances 0.000 description 17
- 238000005119 centrifugation Methods 0.000 description 16
- 239000000463 material Substances 0.000 description 11
- 238000003756 stirring Methods 0.000 description 10
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 8
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 8
- 239000011259 mixed solution Substances 0.000 description 7
- 239000000725 suspension Substances 0.000 description 7
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- 229910002804 graphite Inorganic materials 0.000 description 5
- 239000010439 graphite Substances 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- -1 polytetrafluoroethylene Polymers 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- SJUCACGNNJFHLB-UHFFFAOYSA-N O=C1N[ClH](=O)NC2=C1NC(=O)N2 Chemical compound O=C1N[ClH](=O)NC2=C1NC(=O)N2 SJUCACGNNJFHLB-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 230000006698 induction Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910021392 nanocarbon Inorganic materials 0.000 description 2
- 229910001961 silver nitrate Inorganic materials 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical class [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000003643 water by type Substances 0.000 description 2
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 1
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- 235000010323 ascorbic acid Nutrition 0.000 description 1
- 239000011668 ascorbic acid Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- QNZRVYCYEMYQMD-UHFFFAOYSA-N copper;pentane-2,4-dione Chemical compound [Cu].CC(=O)CC(C)=O QNZRVYCYEMYQMD-UHFFFAOYSA-N 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000007777 multifunctional material Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000000206 photolithography Methods 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- SITVSCPRJNYAGV-UHFFFAOYSA-N tellurous acid Chemical compound O[Te](O)=O SITVSCPRJNYAGV-UHFFFAOYSA-N 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
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Abstract
本发明提供一种纳米管的制备方法为：将纳米材料或纳米材料的组装体滴加到覆盖有碳膜的支撑物上，得到复合碳膜；使所述复合碳膜形成裂缝，得到带有裂缝的复合碳膜；用电子束照射所述带有裂缝的复合碳膜，发生卷曲，得到纳米管。本发明仅需3步即可得到纳米管，对制备条件要求较低，无需昂贵的仪器，因此本发明提供的纳米管制备方法简单。另外，由于利用碳膜的卷曲包覆纳米材料或纳米材料组装体形成纳米管，因此，本发明对纳米材料或纳米材料组装体没有限制，适用于多种纳米材料的组装。
The invention provides a method for preparing nanotubes: adding nanomaterials or nanomaterial assemblies dropwise onto a support covered with a carbon film to obtain a composite carbon film; forming cracks in the composite carbon film to obtain a composite carbon film with A composite carbon film with cracks; the composite carbon film with cracks is irradiated with an electron beam to curl up to obtain nanotubes. The invention only needs three steps to obtain nanotubes, has lower requirements on preparation conditions, and does not need expensive instruments, so the preparation method of nanotubes provided by the invention is simple. In addition, since nanotubes are formed by wrapping nanomaterials or nanomaterial assemblies with carbon films, the present invention is not limited to nanomaterials or nanomaterial assemblies, and is applicable to the assembly of various nanomaterials.
Description
Technical field
The present invention relates to field of nanometer material technology, particularly the preparation method of nanotube.
Background technology
Nano material refers to have at least one dimension in nanoscale scope (1-100nm) or the material that consists of as elementary cell them in three dimensions.Nano material has many good qualities, and on the one hand, nano material has higher surface-volume ratio, thereby has very high chemism; On the other hand, it has higher draw ratio, and in a dimension direction, particle transmission does not exist constraint, is conducive to technical application.
The assembling of the preparation of nano material and nanometer primitive has become one of the most popular research field of present material scientific domain.Britain < < nature-material > > (Nature Materials, the 6th phase in 2007,841 pages) point out, the shape and size of self are not only depended in the physicochemical properties exploitation of material, also depend on the collaborative of assembly.U.S. < < nanometer wall bulletin > > (NanoLetters, the 10th phase in 2010,5103 pages) point out, thereby utilize interfacial assembly technology can effectively reduce system entropy, make mixed and disorderly overlength flexible nano line obtain orderly arrangement assembly.Therefore, the controlledly synthesis of nano material, effectively assembling, and the device based on nano material design and performance study become associated materials and move towards practical prerequisite and one of ensure.There have been at present the successful self assembly of a lot of nano materials or logical outer external action to instruct assembling.But also can carry out multicomponent assembling, obtain multifunctional material.
In the report of the assembling of nano material, the method adopting is mainly divided into from below to up and two classes from top to down.Wherein, method from top to down refers to by means of photolithography assembles nano material, as patent JP2006311905.Yet this class methods step is complicated, cost is larger, and because resolution ratio is limited, material little to particle diameter and that diameter is little is helpless.Another kind of is the method adopting from below to up, mainly by means such as interfaces, nano material is assembled, the method can avoid adopting top-down method brings due to resolution ratio limited and to particle diameter the little and little helpless problem of material of diameter.
Prior art conducts extensive research interfacial assembly nano material, as: the meeting will > > (J.Am.Chem.Soc. of < < American Chemical Society, 132 volumes in 2010,8945 pages) reported and utilized wrong your technology (LB Technique) of improved Lange to assemble one-dimensional super long nano wire at liquid-vapor interface, obtain orderly assembly, but, the method needs expensive instrument and equipment, for a long time adjustment process.The meeting will > > of < < American Chemical Society magazine (J.Am.Chem.Soc.2008,1043 pages .) reported and utilized wrong your technology (LB Technique) of Lange to assemble two-dimentional graphene nanometer sheet at liquid-vapor interface, the method needs expensive instrument and equipment, and needs long adjustment process.Germany < < advanced function material > > (958 pages of Adv.Funct.Mater.2010 20 volumes) has reported the method for utilizing solution-air-oily three phase boundary assembling one-dimensional nano line, by the ordering effect at interface, at gas-liquid interface, form orderly nano wire assembling body.But the method step is complicated, be only applicable to the assembling of nano wire, can not successfully assemble multiple nano material.
Summary of the invention
The technical problem that the present invention solves is providing a kind of preparation method of nanotube, and method is simple, is applicable to the assembling of multiple nano material.
The preparation method who the invention provides a kind of nanotube, comprises the following steps:
(A) assembly of nano material or nano material is added drop-wise on the supporter that is coated with carbon film, obtains compound carbon film;
(B) make the described compound carbon film of step (A) form crack, obtain being with crannied compound carbon film;
(C) with electron beam irradiating step (B) is described, be with crannied compound carbon film, occur curlingly, obtain nanotube.
Preferably, in described step (A), described nano material is tellurium nano-wire, gold nanorods, copper-zinc-tin-sulfur nano particle, graphene nanometer sheet or nano silver wire.
Preferably, in described step (A), described nanomaterial assembly body is nano silver wire assembly.
Preferably, in described step (A), the thickness of described carbon film is 10 ~ 20nm.
Preferably, in described step (A), above support is copper mesh or molybdenum net.
Preferably, described step (A) is specially:
The assembly of nano material or nano material is scattered in solvent, obtains mother liquor; Described mother liquor is added drop-wise on the supporter that is coated with carbon film, obtains compound carbon film.
Preferably, described solvent is deionized water, n-hexane or ethanol.
Preferably, in described step (C), the intensity of described electron beam is 80 ~ 120kv.
Preferably, in described step (C), the time of described electron beam irradiation is 2 ~ 10s.
Preferably, described step (B) is specially:
On compound carbon film step (A) Suo Shu, cut and draw, make described compound carbon film form crack, obtain being with crannied compound carbon film.
Compared with prior art, first the present invention is added drop-wise to the assembly of nano material or nano material on the supporter that is coated with carbon film, obtains compound carbon film; Then make described compound carbon film form crack; Finally, with being with crannied compound carbon film described in electron beam irradiation, obtain nanotube.The top layer of compound carbon film of the present invention is nano material or nanomaterial assembly body, bottom is carbon film, when with the crannied compound carbon film of electron beam irradiation band, carbon film generation heat distributes uneven, thereby induction carbon film occurs curling at place, crack, carbon film coated, in nano material or nanomaterial assembly surface, obtains nanotube.The present invention only needs 3 steps can obtain nanotube, lower to preparation condition requirement, and without expensive instrument, therefore nanotube preparation method provided by the invention is simple.In addition, owing to utilizing curling clad nano material or the nanomaterial assembly body of carbon film to form nanotube, therefore, the present invention, to nano material or the not restriction of nanomaterial assembly body, is applicable to the assembling of multiple nano material.
Accompanying drawing explanation
Fig. 1 is the transmission electron microscope photo of the nanotube of embodiment 1 preparation;
Fig. 2 is the transmission electron microscope photo of the nanotube of embodiment 2 preparations;
Fig. 3 is the transmission electron microscope photo of the nanotube of embodiment 3 preparations;
Fig. 4 is the transmission electron microscope photo of the nanotube of embodiment 4 preparations;
Fig. 5 is the transmission electron microscope photo of the nanotube of embodiment 5 preparations;
Fig. 6 is the transmission electron microscope photo of the nanotube of embodiment 6 preparations.
The specific embodiment
In order further to understand the present invention, below in conjunction with embodiment, the preferred embodiment of the invention is described, but should be appreciated that these are described is for further illustrating the features and advantages of the present invention, rather than limiting to the claimed invention.
The preparation method who the embodiment of the invention discloses a kind of nanotube, comprises the following steps:
(A) assembly of nano material or nano material is added drop-wise on the supporter that is coated with carbon film, obtains compound carbon film;
(B) make the described compound carbon film of step (A) form crack, obtain being with crannied compound carbon film;
(C) with electron beam irradiating step (B) is described, be with crannied compound carbon film, occur curlingly, obtain nanotube.
According to the present invention, first the assembly of nano material or nano material is added drop-wise on the supporter that is coated with carbon film, obtain compound carbon film.For the ease of forming compound carbon film, first the assembly of rice material or nano material is scattered in solvent, obtain mother liquor; Again described mother liquor is added drop-wise on the supporter that is coated with carbon film, obtains compound carbon film.
Described nano material is preferably tellurium nano-wire, gold nanorods, copper-zinc-tin-sulfur nano particle, graphene nanometer sheet or nano silver wire.Described nanomaterial assembly body is preferably nano silver wire assembly.
The present invention is not particularly limited thickness and the size of described nano material or nanomaterial assembly body.The present invention is also not particularly limited the source of described nano material or nanomaterial assembly body, can adopt method preparation well known to those skilled in the art, also can be bought by market.
Described solvent is preferably deionized water, n-hexane or ethanol.The present invention, to the not restriction of the concentration of described mother liquor, can select according to concentration well known to those skilled in the art.
The present invention does not have specific (special) requirements to the described holder that is coated with carbon film, and the thickness of described carbon film is preferably 10 ~ 20nm, and above support is preferably copper mesh or molybdenum net.
Obtain after compound carbon film, make described compound carbon film form crack.The present invention is not particularly limited forming the mode in crack, can at compound carbon film, cut and draw by sharp objects.The shape of fracture of the present invention, size and density are not particularly limited.
Obtain being with after crannied compound carbon film, with being with crannied compound carbon film described in electron beam irradiation, occur curlingly, obtain nanotube.When selecting nanomaterial assembly system for compound carbon film, the assembling direction that is preferably nanomaterial assembly body is vertical with carbon film curl direction.The intensity of described electron beam is preferably 80 ~ 120kv, more preferably 90 ~ 110kv.The time of described electron beam irradiation is preferably 2 ~ 10s, more preferably 4 ~ 7s.
Utilize transmission electron microscope to detect the nanotube obtaining, result shows, preparation method of the present invention can obtain the nanotube of structural integrity.
Compared with prior art, first the present invention is added drop-wise to the assembly of nano material or nano material on the supporter that is coated with carbon film, obtains compound carbon film; Then make described compound carbon film form crack; Finally, with being with crannied compound carbon film described in electron beam irradiation, obtain nanotube.The top layer of compound carbon film of the present invention is nano material or nanomaterial assembly body, bottom is carbon film, when with the crannied compound carbon film of electron beam irradiation band, carbon film generation heat distributes uneven, thereby induction carbon film occurs curling at place, crack, carbon film coated, in nano material or nanomaterial assembly surface, obtains nanotube.The present invention only needs 3 steps can obtain nanotube, lower to preparation condition requirement, and without expensive instrument, therefore nanotube preparation method provided by the invention is simple.In addition, owing to utilizing curling clad nano material or the nanomaterial assembly body of carbon film to form nanotube, therefore, the present invention, to nano material or the not restriction of nanomaterial assembly body, is applicable to the assembling of multiple nano material.
In order further to understand the present invention, below in conjunction with embodiment, the preparation method of nanotube provided by the invention is described, protection scope of the present invention is not limited by the following examples.
The polyvinylpyrrolidone (PVP) that following examples are used is produced by Shanghai reagent company, and molecular weight is 40,000.
In the polytetrafluoroethylene (PTFE) hydrothermal reaction kettle of 50 milliliters, adding 1.000 gram-molecular weights is that 40,000 polyvinylpyrrolidone (PVP), 0.0922 gram of tellurous acid are received (Na
2teO
3), 33 ml waters, 1.67 milliliters of hydrazine hydrate and 3.33 milliliters of ammoniacal liquor that mass percent is 25～28% that mass percent is 85%; Adopt magnetic agitation 10 minutes, make it reach uniform solution; Polytetrafluoroethylene (PTFE) reactor is put into steel bushing, 180 ℃ reaction 3 hours, naturally cooling after, obtaining containing diameter is 7 nanometers, the tellurium nano-wire mixed liquor that length is up to a hundred microns.
Get 5 milliliters of above-mentioned tellurium nano-wire mixed liquors, add 12 milliliters of acetone, with 5000 revs/min, carry out centrifugation 5 minutes, the removal upper strata stillness of night.Add 12 ml waters, be uniformly dispersed, with 5000 revs/min, carry out centrifugation 5 minutes, the removal upper strata stillness of night.Add 12 milliliters of ethanol, be uniformly dispersed, with 5000 revs/min, carry out centrifugation 5 minutes, the removal upper strata stillness of night.Add 1 milliliter of ethanol, be uniformly dispersed, form mother liquor, then described mother liquor is dripped and covered on the copper mesh of one deck carbon film, treat ethanol volatilization.With sharp hard object, carbon film is staved, then use the electron beam irradiation carbon film 5s of 100kv, carbon film occurs curling under the irradiation of electron beam, and tellurium nano-wire is accompanied by carbon film and has together occurred curlingly, has formed the nanotube of load tellurium nano-wire.
With transmission electron microscope, to obtaining nanotube, detect, as shown in Figure 1, Fig. 1 is the transmission electron microscope photo of the nanotube of embodiment 1 preparation to result, and result shows, the present invention has prepared nanotube.
Embodiment 2
Get 0.130 gram of acetylacetone copper, 0.073 gram of zinc acetate, 0.045 gram of stannic chloride and 0.033 gram of sulphur and join in 10 milliliters of oleyl amines, stir, then join in 25 milliliters of there-necked flasks; Then under the atmosphere of nitrogen, be heated to 110 ℃, heat 30 minutes at 110 ℃, solution has become brown.Be heated to again 280 ℃, at 280 ℃, heat 1 hour, obtain the mixed liquor that contains copper-zinc-tin-sulfur nano particle.
Get 5 milliliters of above-mentioned mixed liquors that contain copper-zinc-tin-sulfur nano particle, add 12 ml n-hexanes, with 5000 revs/min, carry out centrifugation 5 minutes, the removal upper strata stillness of night.Add 12 ml n-hexanes, be uniformly dispersed, with 5000 revs/min, carry out centrifugation 5 minutes, the removal upper strata stillness of night.Add 12 milliliters of ethanol, be uniformly dispersed, with 5000 revs/min, carry out centrifugation 5 minutes, the removal upper strata stillness of night.Add 1 milliliter of ethanol, be uniformly dispersed, form mother liquor, then described mother liquor is dripped and covered on the copper mesh of one deck carbon film, treat ethanol volatilization.With sharp hard object, carbon film is staved, then use the electron beam irradiation carbon film 5s of 100kv, carbon film occurs curling under the irradiation of electron beam, and copper-zinc-tin-sulfur nano particle is accompanied by carbon film and has together occurred curlingly, has formed the nanotube of load copper-zinc-tin-sulfur nano particle.
With transmission electron microscope, to obtaining nanotube, detect, as shown in Figure 2, Fig. 2 is the transmission electron microscope photo of the nanotube of embodiment 2 preparation to result, and result shows, the present invention has prepared nanotube.
Embodiment 3
Get the softex kw solution that chlorauric acid solution that 0.25 ml concn is 0.01mol/L and 9.75 concentration are 0.1mol/L and mix, stir.The sodium borohydride solution of getting 0.6 ml concn and be 0.01mol/L joins in above-mentioned mixed solution, then stirs rapidly 2 minutes, more at room temperature standing 2 hours, this mixed solution is as seed solution.Then by 30 ml concns, be that the softex kw solution that the chlorauric acid solution of 0.01 mole every liter, liquor argenti nitratis ophthalmicus that 6 ml concns are 0.1 and 600 ml concns are 0.1 mixes, stir, then the concentration that adds 4.8 milliliters of new configurations is the ascorbic acid solution of 0.1 mole every liter, adding 12 ml concns is the hydrochloric acid solution of 0.1 mole every liter again, the color of mixed solution is become colorless by yellow at once, and this solution is as growth solution.Then get 1.4 milliliters of seed solutions and join in growth solution, stir, standing 6 hours.The gold nanorods obtaining.
Get 5 milliliters of above-mentioned gold nanorods mother liquors, add 12 ml deionized water, with 5000 revs/min, carry out centrifugation 5 minutes, the removal upper strata stillness of night.Add 12 ml deionized water, be uniformly dispersed, with 5000 revs/min, carry out centrifugation 5 minutes, the removal upper strata stillness of night.Add 12 ml deionized water, be uniformly dispersed, with 5000 revs/min, carry out centrifugation 5 minutes, the removal upper strata stillness of night.Add 1 ml deionized water, be uniformly dispersed, then dripped and covering on the copper mesh of one deck carbon film, treat deionized water volatilization.With sharp hard object, carbon film is staved, then use the electron beam irradiation carbon film breakage 5s of 100kv, carbon film occurs curling under the irradiation of electron beam, and gold nanorods is accompanied by carbon film and has together occurred curlingly, has formed the nano-carbon film pipe of load gold nano rod.
With transmission electron microscope, to obtaining nanotube, detect, as shown in Figure 3, Fig. 3 is the transmission electron microscope photo of the nanotube of embodiment 3 preparation to result, and result shows, the present invention has prepared nanotube.
Embodiment 4
In the situation that constantly stirring, by 1 gram of graphite and 0.5 gram of NaNO
3join 23 ml concns and be in 98% the concentrated sulfuric acid, reactant is cooling in ice bath after mixing; Under vigorous stirring, by 3 grams of KMnO
4add in reaction suspension, in this process, careful control adds speed to surpass 20 ℃ to prevent suspension temperature; Then remove ice bath, the temperature of suspension will be gone up to about 35 ℃, react and become taupe pastel after 30 minutes; Then, 46 ml distilled waters are added drop-wise in pastel, simultaneously vigorous stirring, causes producing strong foamed phenomenon, and temperature rises to rapidly 98 ℃, and the suspension after dilution keeps 15 minutes at 98 ℃, with warm water, is diluted to 140 milliliters, uses afterwards H
2o
2process and generate glassy yellow suspension; Finally with a large amount of distilled water, clean suspension until pH value of solution is stabilized in 4.0 rapidly, then be dispersed in water, just obtained the graphite oxide aqueous solution.
The described graphite oxide aqueous solution is rocked to 6h with the speed of 160rpm, centrifugal to remove a small amount of non-sheet-like particle, obtain graphite oxide; Graphite oxide is dispersed in 100 ml distilled waters, and its concentration is 2 mg/ml, and then adding polyethylene glycol oxide bay ether (Brj-35) aqueous solution and the 4 grams of concentration that 6 grams of concentration are 10wt% is 5wt% hydrazine solution, mixes; Mixture stirred after 5 minutes, moved in the baking oven of 80 ℃ and placed 8 hours, finally obtained the stable suspension of black, was graphene nanometer sheet mixed liquor, and the content of graphene nanometer sheet is 0.1 mg/ml.
Get the graphene nanometer sheet mixed liquor described in 5 milliliters, add 12 ml deionized water, with 5000 revs/min, carry out centrifugation 5 minutes, the removal upper strata stillness of night.Add 12 ml deionized water, be uniformly dispersed, with 5000 revs/min, carry out centrifugation 5 minutes, the removal upper strata stillness of night.Add 12 ml deionized water, be uniformly dispersed, with 5000 revs/min, carry out centrifugation 5 minutes, the removal upper strata stillness of night.Add 1 ml deionized water, be uniformly dispersed, then dripped and covering on the copper mesh of one deck carbon film, treat deionized water volatilization.With sharp hard object, carbon film is staved, then use the electron beam irradiation carbon film breakage 5s of 100kv, carbon film occurs curling under the irradiation of electron beam, and graphene nanometer sheet is accompanied by carbon film and has together occurred curlingly, has formed the carbon film pipe of load graphene nanometer sheet.
With transmission electron microscope, to obtaining nanotube, detect, as shown in Figure 4, Fig. 4 is the transmission electron microscope photo of the nanotube of embodiment 4 preparation to result, and result shows, the present invention has prepared nanotube.
5.86 grams of PVPs (PVP) and 190 milliliters of glycerine are joined in 500 milliliters of round-bottomed flasks, stir, add 1.58 grams of silver nitrates, obtain mixed solution.Then 59 grams of sodium chloride and 0.5 ml water are joined in 10 milliliters of described mixed solutions, then within 20 minutes, from room temperature, be heated to 210 ℃, naturally cooling, add 10 ml deionized water, obtain nano silver wire mixed liquor.
Get the nano silver wire mixed liquor described in 5 milliliters, add 12 ml deionized water, with 5000 revs/min, carry out centrifugation 5 minutes, the removal upper strata stillness of night.Add 12 ml deionized water, be uniformly dispersed, with 5000 revs/min, carry out centrifugation 5 minutes, the removal upper strata stillness of night.Add 12 ml deionized water, be uniformly dispersed, with 5000 revs/min, carry out centrifugation 5 minutes, the removal upper strata stillness of night.Add 1 ml deionized water, be uniformly dispersed, then dripped and covering on the copper mesh of one deck carbon film, treat deionized water volatilization.With sharp hard object, carbon film is staved, then use the electron beam irradiation carbon film breakage 5s of 100kv, carbon film occurs curling under the irradiation of electron beam, and nano silver wire is accompanied by carbon film and has together occurred curlingly, has formed the carbon film pipe of load nano silver wire.
With transmission electron microscope, to obtaining nanotube, detect, as shown in Figure 5, Fig. 5 is the transmission electron microscope photo of the nanotube of embodiment 5 preparation to result, and result shows, the present invention has prepared nanotube.
Embodiment 6
5.86 grams of PVPs (PVP) and 190 milliliters of glycerine are joined in 500 milliliters of round-bottomed flasks, stir, add 1.58 grams of silver nitrates, obtain mixed solution.Then 59 grams of sodium chloride and 0.5 ml water are joined in 10 milliliters of described mixed solutions, then within 20 minutes, from room temperature, be heated to 210 ℃, naturally cooling, add 10 ml deionized water, obtain nano silver wire mixed liquor.
Get the nano silver wire mixed liquor described in 5 milliliters, add 12 milliliters of acetone, with 5000 revs/min, carry out centrifugation 5 minutes, the removal upper strata stillness of night.Lower sediment thing is dissolved in to 10 milliliters by DMF and chloroform (CHCl
3) be in the mixed liquor of 1:1 by volume.With microsyringe, above-mentioned nano silver wire solution is added drop-wise to the two-phase interface of the water-air that LB film groove provides.Wait for 15 minutes, start press mold; By constantly reducing to assemble area along Interfacial Edge along inside mechanical force, along with reducing of assembling area, surface pressure constantly increases, until while there is fold in the nano silver wire film of assembling, pressure is now made as to goal pressure, and keep this pressure constant lasting 10 hours, obtain nano silver wire assembly.
By dripping, covering on the copper mesh of one deck carbon film, treating deionized water volatilization.With sharp hard object, carbon film is staved, then use the electron beam irradiation carbon film breakage 5s of 100kv, carbon film occurs curling under the irradiation of electron beam, and nano silver wire assembly is accompanied by carbon film and has together occurred curlingly, has formed the nano-carbon film pipe of load nano silver wire assembly.
With transmission electron microscope, to obtaining nanotube, detect, as shown in Figure 6, Fig. 6 is the transmission electron microscope photo of the nanotube of embodiment 6 preparation to result, and result shows, the present invention has prepared nanotube.
The explanation of above embodiment is just for helping to understand method of the present invention and core concept thereof.It should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention, can also carry out some improvement and modification to the present invention, these improvement and modification also fall in the protection domain of the claims in the present invention.
Above-mentioned explanation to the disclosed embodiments, makes professional and technical personnel in the field can realize or use the present invention.To the multiple modification of these embodiment, will be apparent for those skilled in the art, General Principle as defined herein can, in the situation that not departing from the spirit or scope of the present invention, realize in other embodiments.Therefore, the present invention will can not be restricted to these embodiment shown in this article, but will meet the widest scope consistent with principle disclosed herein and features of novelty.
Claims (7)
1. a preparation method for nanotube, comprises the following steps:
(A) assembly of nano material or nano material is added drop-wise on the supporter that is coated with carbon film, obtains compound carbon film;
Described nano material is tellurium nano-wire, gold nanorods, copper-zinc-tin-sulfur nano particle, graphene nanometer sheet or nano silver wire; Described nanomaterial assembly body is nano silver wire assembly;
(B) make the described compound carbon film of step (A) form crack, obtain being with crannied compound carbon film;
(C) with electron beam irradiating step (B) is described, be with crannied compound carbon film, occur curlingly, obtain nanotube.
2. preparation method according to claim 1, is characterized in that, in described step (A), the thickness of described carbon film is 10～20nm.
3. preparation method according to claim 1, is characterized in that, in described step (A), above support is copper mesh or molybdenum net.
4. preparation method according to claim 1, is characterized in that, described step (A) is specially:
The assembly of nano material or nano material is scattered in solvent, obtains mother liquor; Described mother liquor is added drop-wise on the supporter that is coated with carbon film, obtains compound carbon film;
Described solvent is deionized water, n-hexane or ethanol.
5. preparation method according to claim 1, is characterized in that, in described step (C), the intensity of described electron beam is 100kv.
6. preparation method according to claim 1, is characterized in that, in described step (C), the time of described electron beam irradiation is 5s.
7. preparation method according to claim 1, is characterized in that, described step (B) is specially:
On compound carbon film step (A) Suo Shu, cut and draw, make described compound carbon film form crack, obtain being with crannied compound carbon film.
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