CN101225546A - Solvent thermal synthesis method for CNx nano-belt and nano-tube - Google Patents
Solvent thermal synthesis method for CNx nano-belt and nano-tube Download PDFInfo
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- CN101225546A CN101225546A CNA2007101340956A CN200710134095A CN101225546A CN 101225546 A CN101225546 A CN 101225546A CN A2007101340956 A CNA2007101340956 A CN A2007101340956A CN 200710134095 A CN200710134095 A CN 200710134095A CN 101225546 A CN101225546 A CN 101225546A
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B7/00—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions
Abstract
The invention relates to a solvent-thermal synthesis method of the CNx nanobelt and the CNx nanotube, which is characterized in that: the CNx nanotube is generated through a new precursor, namely the pentachloropyridine; the dechlorination is carried out at lower temperature (180 to 300 degrees centigrade); the reaction is continued for 8 to 25 hours in the autoclave; and a certain quantity of metal K and a certain quantity of the toluene, the xylene, the benzene, the cyclohexane, the isopropanol and the n-butanol solvent are added in the autoclave; finally, the CNx nanobelt and the CNx nanotube are obtained through cooling, filtering and drying; the length of the obtained CNx nanobelt is tens of microns, and the width of that is 300 nm to one micron; and the length of the CNx nanotube is tens of microns, and the pipe diameter of that is between 50 nm and 500 nm. The solvent-thermal synthesis method of the CNx nanobelt and the CNx nanotube has the advantages that: the type of the N in the obtained CNx nanobelt and the obtained CNx nanotube is mostly pyridine N; the yield is high; the reaction temperature is relatively lower; and the nanobelt and the nanotube can be directionally synthesized.
Description
Technical field
The present invention relates to CN
xPreparation of nanomaterials, especially a kind of precursor raised growth CN that utilizes
xThe method of rice band and nanotube.
Background technology
A lot of physicochemical property height of carbon nanotube rely on the textural defect in its caliber, chirality and the pipe, and these parameters are difficult to control under present experiment condition, have therefore suppressed the research that carbon nanotube is used to a certain extent.It is found that in recent years other elements that mix in carbon nanotube can play the effect of its physical and chemical performance of cutting, the nitrogen element that wherein mixes is one of method relatively more commonly used.[(a) Stephan, O.et al.Scienc%1994,266,1683; (b) Chan, L. H.et al.Appl.Phys.Lett.2003,82,4334.] carbon atom in the carbon nanotube graphite aspect is that nitrogen-atoms replaces the variation that will cause the carbon nano electronic structure, thereby changes its physicochemical property.Because nitrogen-atoms has a pair of lone-pair electron, the electronics of its release can improve the electronic migration and the field emission performance of carbon nanotube.[(a) Golberg, D.et al.Appl.Phys.A 2003,76,499; (b) Liu, A.Y.Cohen, M.L. Science 1989,245,841.] carbon-nitrogen nano tube that obtains behind the doping nitrogen-atoms, its a lot of performances are mainly decided by its chemical constitution, thereby remedied the defective of carbon nanotube self, so the research of this respect has caused people's extensive interest.[F.Phys.Rev.B 1998,58 for (a) Dos Santos, M.C.Alvarez, and 13918; (b) Terrones, M.et al.Adv.Mater.1999,11,655; (c) Terrones, M.et al.Appl.Phys.A 2002,74,355; (d) Kudashov, A.G.et al.J.Phys.Chem.B 2004,108,9048; (e) Lee, Y.T.et al.J.Phys.Chem.B 2003,107,12958.] N atom in the CNx nanotube helps at CNx nanotube surface stagnant catalyst particle, and need not carry out functionalization to nanotube in advance.[(a) Zamudio, A.et al.Small, 2006,2,346; (b) Jiang, K.et al.Nano Lett.2003,3,275.] and there are some researches show CN
xThe type of N is to stagnant catalyst particle decisive role above the nanotube, and graphite N works by activating contiguous C atom usually, and pyridine N can the Direct Bonding transition metal atoms.[Yang, S.H.et al.Appl.Phys.Lett.2007,90,013103.] are so the CN of synthetic high pyridine N content
xIt is extremely important that nanotube just seems.The preparation of carbon current nitride nanotubes has several different methods, as the magnetic sputter, and [K.Suenaga, et al.Chem.Phys.Lett.1999,300,695] arc-over, [Stephan, 0.et al.Science 1994,266, and 1683] chemical gaseous phase depositing process (CVD) and solvent thermal.[(a)Terrones，M.et?al.Appl.Phys.Lett.1999，75，3932；(b)Terrones，M.et?al.Nature?1997，388，52(c)Choi，H.C.et?al.J.Phys.Chem.B?2005，109，1683；(e)Liang，E.J.et?al.Diam.Relat.Mater.2004，13，69；(f)Tang，C.Y.Bando，D.Golberg，F.Xu，Carbon?2004，42，2625.(g)Guo，Q.X.et?al.Chem.Commu.2004.26]
Make precursor with benzene, inventor group has obtained productive rate height, C nanotube that purity is good by the CVD growth method, proposed to do the carbon nanotube six-ring cluster growth mechanism of structural unit, obtained the support of original position heat analysis-mass spectrometry experimental result with the benzene six-ring.[(a) Wang, X.Z.et al.Chinese Physics, 2001,10, S76-79 (b) Yang, Y.et al.Nanotechnology 2003,14,733-737. (c) Tian, Y.et al.J.Am.Chem.Soc.2004,126,1180-1183.] further, inventor group considers the structural similarity of pyridine and benzene, and carrying out with the pyridine is precursor growth C
5The research of N nanotube.[Chen, H.et al.J.Phys.Chem.B2006,110,16422-16427.] be not although we synthesize the C of expection with the CVD method
5The N nanotube spreads symplastic growth mechanism but research has disclosed surface diffusion mutually with helping, and has further indicated synthetic C
⊥The possibility of N nanotube: as long as the suitable pyridine ring of condition just might be assembled into C
xThe N nanotube.Our minimum temperature of CVD catalytic growth CNx nanotube is 550 ℃, is lower than the B that this thermotonus can not get expecting
xThe N nanotube.
Generally speaking, solvent thermal reaction can be avoided high-temperature operation, and general temperature of reaction is below 400 ℃.According to the bond energy size, c h bond energy (414 KJ/mol) is bigger than C-Cl bond energy (347 KJ/mol), so the C-Cl key is than the easy thermal destruction of c h bond.All replacing the H atom with the Cl atom, promptly is that precursor passes through the CN that solvent thermal process might prepare high pyridine N content with the Perchloropyridine
xNanostructure, the present invention has synthesized a large amount of CNx nano belt and nanotube with solvent thermal reaction.
Summary of the invention
The objective of the invention is, utilize precursor raised growth CN
xThe method of nano belt and nanotube, improving with the pyridine is precursor growth C
5The N nanotube the purpose of this invention is to provide a kind of convenience and high yield and prepares CN in a large number
xThe method of nano belt and nanotube.
The present invention is achieved through the following technical solutions: CN
xThe solvent process for thermosynthesizing of nano belt and nanotube, with a kind of brand-new precursor---the Perchloropyridine CN that grows
xNanotube.Carrying out dechlorination under lower temperature (180～300 ℃) handles, autoclave internal reaction 8-25 hour, and the organic solvent that in autoclave, adds an a certain amount of metal K and a constant volume, generally be Perchloropyridine weight 10-300 doubly, as aromatic hydrocarbons (as toluene, dimethylbenzene, benzene, hexanaphthene etc.), Virahol, propyl carbinol equal solvent, cool off at last, filtration, drying, obtain CN
xNano belt and nanotube.
The CN of gained
xNano belt length has tens microns, and width is at 300nm to micron.CN
xNanotube length has tens microns, and caliber is between 50nm～500nm.
Carry out dechlorination and handle in enclosed autoclave, reactor can be divided into stainless die and inner liner polytetrafluoroethylene type.The scheme of optimizing is: carry out in stainless steel cauldron when temperature of reaction is higher than 220 ℃ (containing), carry out otherwise temperature of reaction is preferably in when being lower than 220 ℃ in the reactor of inner liner polytetrafluoroethylene type.
The present invention can high yield or directed synthetic CNx nano belt and nanotube.How much calculate productive rate according to raw material, obtain a large amount of CN 290-300 ℃ of reaction
xThe nanotube productive rate is up to 120% (have partial solvent and participate in reaction, cause more higher than theoretical value); The productive rate that obtains a large amount of CNx nanotubes (containing a small amount of nano belt) 210-230 ℃ of reaction is 90%; Obtain a large amount of CN 180-190 ℃ of reaction
xThe productive rate of nano belt (containing a small amount of nanotube) is 80%.Resulting CN
xN constituent content in nano belt and the nanotube is up to 7～16%, and the type of N is mainly pyridine N.
Device required for the present invention is an autoclave, and autoclave is divided into two kinds, and a kind of is volume 15cm
3Stainless steel autoclave, another kind is that volume is 50cm
3The autoclave of inner liner polytetrafluoroethylene.Corollary apparatus is the adjustable heated oven of a temperature.Temperature of reaction is carried out in being reflected in the stainless steel autoclave more than 220 ℃, carries out in the reactor that is reflected at inner liner polytetrafluoroethylene below 220 ℃.
The present invention prepares CN
xThe method of nano belt and nanotube is earlier certain amount of solvent to be added in the autoclave, adds little metal K (adopt granular metal K, particle diameter is no more than 0.5cm) then, adds a certain amount of Perchloropyridine (purity 98%) powder again.The sealing back is transferred to the baking oven the inside to autoclave and was reacted 15 hours under a certain temperature.
As long as the present invention is by the regulation and control temperature of reaction, just can reach when controlling ℃ to obtain a large amount of nano belt (a spot of nanotube is arranged), obtains a large amount of nanotube (containing a spot of nano belt) when 220 ℃ of left and right sides, in the time of 300 ℃, obtain whole be nanotube.Optimum temps of the present invention is 180～300 ℃.Perchloropyridine content is 98%, and the toluene equal solvent is an analytical pure, and the reaction times is about 15 hours.
Characteristics of the present invention are as follows: adopt a kind of brand-new precursor-Perchloropyridine grow CNx nano belt and nanotube.The CNx nano belt length of gained has tens microns, and width is at 300nm to micron.The CNx nanotube length has tens microns, and caliber is between 50nm～500nm.The CNx nano belt of gained and the type of the N in the nanotube mostly are pyridine N greatly.The productive rate height, temperature of reaction is relatively low, can directed synthesis of nano band and nanotube.
Description of drawings
Fig. 1: the present invention CN that grows
xTEM Fig. 1 of nanotube (a, b) and XPS Fig. 1 (c, d).The diameter of nanotube is about 100nm, and length has tens microns.XPS test shows N element mainly exists with pyridine N (398.6eV) and pyrroles N (400.1eV) form.The N constituent content is 7.5%.
Fig. 2: the present invention CN that grows
xTEM Fig. 2 of nanotube (containing a small amount of nano belt) (a, b, c) and XPS Fig. 2 (d, e).The diameter of nanotube is about 200nm, and length has tens microns.The width of nano belt has hundreds of nanometers.XPS test shows N element mainly exists with pyridine N (398.6eV) and pyrroles N (400.1eV) form.The N constituent content is 9.3%.
Fig. 3: the present invention CN that grows
xTEM Fig. 3 of nano belt (containing a small amount of nanotube) (a, b) and XPS Fig. 3 (c, d).The width of nano belt has hundreds of nanometers, and observes the nanotube of one and half volumes, and this is CN
xNanotube is to wind up the evidence the most intuitively that provides that forms by nano belt.XPS test shows N element mainly exists with pyridine N (398.6eV) and pyrroles N (400.1eV) form.The N constituent content is 12.4%.
Embodiment
Embodiment 1 adds 12 milliliters of toluene in the autoclave earlier, adds 0.3 gram metal K (particle diameter of metal K is no more than 0.5 centimetre) then, adds 1 gram Perchloropyridine (purity 98%) powder again.The sealing back is transferred to autoclave in the baking oven and was reacted 15 hours down at 300 ℃.Naturally cool to room temperature after the end, with dehydrated alcohol, distilled water filtration product.Transmission electron microscope (TEM) and photoelectron spectrum (XPS) characterize as shown in Figure 1.
Embodiment 3 adds 35 milliliters of toluene in the autoclave earlier, adds 0.8 gram metal K (particle diameter of metal K is no more than 0.5 centimetre) then, adds 2 gram Perchloropyridine (purity 98%) powder again.The sealing back is transferred to autoclave in the baking oven and was reacted 15 hours down at 180 ℃.Naturally cool to room temperature after the end, with dehydrated alcohol, distilled water filtration product.Transmission electron microscope (TEM) and photoelectron spectrum (XPS) characterize as shown in Figure 3.Also obtain said products in the dimethylbenzene adding autoclave.Benzene, hexanaphthene, Virahol, propyl carbinol etc. also obtain identical result.
Embodiment 4: also can add 30 milliliters of propyl carbinols and add in the autoclave, and 0.5 gram metal K, particle diameter is no more than 0.3 centimetre, adds 2 gram Perchloropyridine (purity 98%) powder again.The sealing back is transferred to autoclave in the baking oven and was reacted 12 hours down at 220 ℃.Naturally cool to room temperature, filter in a large number nanotube with dehydrated alcohol.
Claims (4)
1.CN
xThe solvent process for thermosynthesizing of nano belt and nanotube is characterized in that with a kind of brand-new precursor---the Perchloropyridine CN that grows
xNanotube.Carrying out dechlorination under lower temperature (180～300 ℃) handles, autoclave internal reaction 8-25 hour, and the toluene, dimethylbenzene, benzene, hexanaphthene, Virahol, the propyl carbinol solvent that add an a certain amount of metal K and a constant volume in autoclave cool off, filtration, drying at last, obtain CN
xNano belt and nanotube.
2. CN according to claim 1
xThe solvent process for thermosynthesizing of nano belt and nanotube is characterized in that carrying out dechlorination and handles in enclosed autoclave, reactor can be divided into stainless die and inner liner polytetrafluoroethylene type.The scheme of optimizing is: carry out in stainless steel cauldron when temperature of reaction is higher than 220 ℃ (containing), carry out otherwise temperature of reaction is preferably in when being lower than 220 ℃ in the reactor of inner liner polytetrafluoroethylene type.
3. CN according to claim 1
xThe solvent process for thermosynthesizing of nano belt and nanotube is characterized in that obtaining a large amount of CN 290-300 ℃ of reaction
xNanotube; Obtain a large amount of CNx nanotubes (containing a small amount of nano belt) 210-230 ℃ of reaction; Obtain a large amount of CN 180-190 ℃ of reaction
xNano belt (containing a small amount of nanotube).
4. CN according to claim 1
xThe solvent process for thermosynthesizing of nano belt and nanotube, it is characterized in that adding little metal K is granular metal K, particle diameter is no more than 0.5cm.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108927202A (en) * | 2018-09-25 | 2018-12-04 | 岭南师范学院 | A kind of g-C3N4Nanobelt and the preparation method and application thereof |
| CN111517356A (en) * | 2020-04-30 | 2020-08-11 | 浙江理工大学 | Cu2O nanotube and method for producing the same |
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2007
- 2007-10-19 CN CNB2007101340956A patent/CN100572618C/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108927202A (en) * | 2018-09-25 | 2018-12-04 | 岭南师范学院 | A kind of g-C3N4Nanobelt and the preparation method and application thereof |
| CN108927202B (en) * | 2018-09-25 | 2021-05-07 | 岭南师范学院 | g-C3N4Nanobelt and preparation method and application thereof |
| CN111517356A (en) * | 2020-04-30 | 2020-08-11 | 浙江理工大学 | Cu2O nanotube and method for producing the same |
| CN111517356B (en) * | 2020-04-30 | 2022-03-29 | 浙江理工大学 | Cu2O nanotube and method for producing the same |
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