CN102491309B - Carbon nanometer ring and preparation method thereof - Google Patents
Carbon nanometer ring and preparation method thereof Download PDFInfo
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- CN102491309B CN102491309B CN2011104033316A CN201110403331A CN102491309B CN 102491309 B CN102491309 B CN 102491309B CN 2011104033316 A CN2011104033316 A CN 2011104033316A CN 201110403331 A CN201110403331 A CN 201110403331A CN 102491309 B CN102491309 B CN 102491309B
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 122
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 114
- 238000002360 preparation method Methods 0.000 title claims abstract description 40
- 229910052751 metal Inorganic materials 0.000 claims abstract description 39
- 239000002184 metal Substances 0.000 claims abstract description 28
- 238000009830 intercalation Methods 0.000 claims abstract description 23
- 230000002687 intercalation Effects 0.000 claims abstract description 23
- 239000012298 atmosphere Substances 0.000 claims abstract description 10
- 239000000203 mixture Substances 0.000 claims abstract description 10
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 9
- 239000010439 graphite Substances 0.000 claims abstract description 9
- 230000003197 catalytic effect Effects 0.000 claims abstract description 6
- -1 alkyl anions Chemical class 0.000 claims abstract description 5
- 239000002063 nanoring Substances 0.000 claims description 79
- 229910021645 metal ion Inorganic materials 0.000 claims description 31
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 30
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 24
- 239000008367 deionised water Substances 0.000 claims description 24
- 229910021641 deionized water Inorganic materials 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- 239000002131 composite material Substances 0.000 claims description 21
- 125000002837 carbocyclic group Chemical group 0.000 claims description 20
- 238000002156 mixing Methods 0.000 claims description 18
- 239000012266 salt solution Substances 0.000 claims description 18
- 239000000243 solution Substances 0.000 claims description 17
- 150000001721 carbon Chemical class 0.000 claims description 16
- 238000005119 centrifugation Methods 0.000 claims description 14
- 229910052757 nitrogen Inorganic materials 0.000 claims description 13
- 150000003839 salts Chemical class 0.000 claims description 13
- 239000000126 substance Substances 0.000 claims description 13
- 150000002500 ions Chemical class 0.000 claims description 12
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- 125000000217 alkyl group Chemical group 0.000 claims description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 239000003513 alkali Substances 0.000 claims description 8
- 238000001354 calcination Methods 0.000 claims description 8
- 239000000706 filtrate Substances 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 8
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- 239000012065 filter cake Substances 0.000 claims description 6
- 229910052742 iron Inorganic materials 0.000 claims description 6
- 239000013049 sediment Substances 0.000 claims description 6
- DAJSVUQLFFJUSX-UHFFFAOYSA-M sodium;dodecane-1-sulfonate Chemical compound [Na+].CCCCCCCCCCCCS([O-])(=O)=O DAJSVUQLFFJUSX-UHFFFAOYSA-M 0.000 claims description 6
- 239000000725 suspension Substances 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 235000019333 sodium laurylsulphate Nutrition 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- 229910002651 NO3 Inorganic materials 0.000 claims description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 4
- 239000004141 Sodium laurylsulphate Substances 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 3
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 238000002425 crystallisation Methods 0.000 claims description 2
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- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- ONQDVAFWWYYXHM-UHFFFAOYSA-M potassium lauryl sulfate Chemical compound [K+].CCCCCCCCCCCCOS([O-])(=O)=O ONQDVAFWWYYXHM-UHFFFAOYSA-M 0.000 claims description 2
- HSJXWMZKBLUOLQ-UHFFFAOYSA-M potassium;2-dodecylbenzenesulfonate Chemical compound [K+].CCCCCCCCCCCCC1=CC=CC=C1S([O-])(=O)=O HSJXWMZKBLUOLQ-UHFFFAOYSA-M 0.000 claims description 2
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 150000002431 hydrogen Chemical group 0.000 claims 1
- 239000010410 layer Substances 0.000 abstract description 16
- 238000000034 method Methods 0.000 abstract description 15
- 239000002253 acid Substances 0.000 abstract description 4
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- 238000004146 energy storage Methods 0.000 abstract description 2
- 238000004090 dissolution Methods 0.000 abstract 1
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 239000002109 single walled nanotube Substances 0.000 description 6
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- 108010087599 lactate dehydrogenase 1 Proteins 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 238000004630 atomic force microscopy Methods 0.000 description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- MOTZDAYCYVMXPC-UHFFFAOYSA-N dodecyl hydrogen sulfate Chemical compound CCCCCCCCCCCCOS(O)(=O)=O MOTZDAYCYVMXPC-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 108010088076 lactate dehydrogenase 2 Proteins 0.000 description 2
- 108010088074 lactate dehydrogenase 3 Proteins 0.000 description 2
- 108010088351 lactate dehydrogenase 4 Proteins 0.000 description 2
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 2
- 239000008204 material by function Substances 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical compound C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- FFBHFFJDDLITSX-UHFFFAOYSA-N benzyl N-[2-hydroxy-4-(3-oxomorpholin-4-yl)phenyl]carbamate Chemical compound OC1=C(NC(=O)OCC2=CC=CC=C2)C=CC(=C1)N1CCOCC1=O FFBHFFJDDLITSX-UHFFFAOYSA-N 0.000 description 1
- 239000002775 capsule Substances 0.000 description 1
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- 238000001239 high-resolution electron microscopy Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
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- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 1
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 1
- 239000002090 nanochannel Substances 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
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Abstract
The invention relates to a carbon nanometer ring and a preparation method thereof, and belongs to the technical field of carbon nanometer materials. The carbon nanometer ring consists of a single layer or a plurality of layers of carbon rings, and the carbon rings have a structure which is similar to a closed ring body coiled by a graphite flake layer; and axial sizes and radial sizes of the carbon nanometer ring are a nanometer order, and the axial sizes are smaller than the radial sizes. The invention also provides a method for preparing the carbon nanometer ring. The method comprises the following steps of: roasting long-chain alkyl anions and a lamellar double-hydroxyl composition metal oxide of a carbon source molecular intercalation in the inertia or reducing atmosphere, growing the carbon nanometer ring in interlaminar restricted domain space under the catalytic action of laminate metal elements, and removing metal and the metal oxide by acid dissolution to obtain the carbon nanometer ring. By the method, the axial sizes and radial sizes of the carbon nanometer ring and the layer number of the carbon ring can be controlled effectively. The carbon nanometer ring has a nanometer ring structure and the excellent performance of carbon materials, has more edge carbon and dangling bonds, and has a bright application prospect in fields of nanometer devices, energy storage, sensing and the like.
Description
Technical field
The invention belongs to the carbon nanomaterial technical field, particularly relate to a kind of carbon nano ring and preparation method thereof.
Background technology
Nano-rings is a kind of novel nano-material, and the novel structure of nano-rings can be used as a kind of important structure unit in the nano-device, and nano-rings is unique and good performance makes it show broad prospect of application in field of functional materials.The synthetic multiple nano-rings of people, for example metal oxide nano ring, metal nano ring, long-chain organic molecule nano-rings, still, for carbon nano ring, the carbon nano ring that particularly has the closed ring body similar structures that is rolled into graphite flake layer there is not yet report.
(the J.Liu such as J.Liu, H.Dai, J.H.Hafner, D.T.Colbert, R.E.Smalley, Fullerene ' crop circles ', Nature, 1997,385:780) when adopting laser method to prepare Single Walled Carbon Nanotube, synthesized the carbon nanotube ring, this carbon nanotube ring is the ring that the seamless link of carbon nanotube head and the tail is formed.Although also there is document that this structure is called carbon nano ring, the carbon nano ring of the closed ring body similar structures that is rolled into from having of the present invention relates to and graphite flake layer is different.
(the X.Sun such as X.Sun, S.Zaric, D.Daranciang, K.Welsher, Y.Lu, X.Li, H.Dai, Optical properties of ultrashort semiconducting single-walled carbon nanotube capsules down to sub-10nm, J.Am.Chem.Soc., 2008,130:6551) shear Single Walled Carbon Nanotube with the concentrated acid solution-treated, then adopt the density gradient ultracentrifugation method to separate according to carbon length of tube difference, obtained length below 10 nanometers even near the carbon nanotube of 1 nanometer, but its length still greater than or near the radial dimension of Single Walled Carbon Nanotube, namely therefore the ratio of axial dimension and radial dimension can only be called ultrashort carbon pipe more than or equal to 1.In addition, it is larger to carbon tubular construction destruction to process the shearing carbon nanotube with concentrated acid, therefore is difficult to obtain in order regular supershort carbon nanometer tube of marginal texture.
(the H.Chun such as H.Chun, M.G.Hahm, Y.Homma, R.Meritz, K.Kuramochi, L.Menon, L.Ci, P.M.Ajayan, Y.J.Jung, Engineering Low-Aspect Ratio Carbon Nanostructures:Nanocups, Nanorings, and Nanocontainers, ACS Nano, 2009,3:1274) take anodised aluminium with short nanochannel as template, prepare the carbon nanometer cup by chemical gaseous phase depositing process, then remove the cup end by the ion sputtering attenuate, having obtained radial dimension is 80 nanometers, axial dimension is the carbon nano ring of tens nanometers, but the maximum diameter of common many walls carbon pipe is difficult to stable existence under the larger diameter about 30 nanometers; In addition, from the high-resolution electron microscopy photo that H.Chun etc. provides, this carbon nano ring does not have the constitutional features of graphite flake layer yet, therefore, what it obtained only is the carbon film with ring texture, and the carbon nano ring of the closed ring body similar structures that is rolled into from having of the present invention relates to and graphite flake layer is different.
Summary of the invention
For solving the problems of the technologies described above, the object of the present invention is to provide a kind of carbon nano ring, it is the carbon nano ring that a kind of carbocyclic ring with similar closed ring body that is rolled into by graphite flake layer forms.
The present invention also aims to provide the preparation method of above-mentioned carbon nano ring.
For achieving the above object, the present invention at first provides a kind of carbon nano ring, it is comprised of the coaxial carbocyclic ring of single or multiple lift, and described carbocyclic ring has the similar structure of closed ring body that is rolled into graphite flake layer, axial dimension and the radial dimension of this carbon nano ring are nanometer scale, and axial dimension is less than radial dimension.
Carbocyclic ring in the carbon nano ring provided by the present invention also can be considered as a kind of extremely short carbon nanotube, its carbon atom arrange with carbon nanotube in the carbon atom arrangement mode basic identical.Carbon nano ring provided by the invention can be comprised of one or more layers coaxial carbocyclic ring, and the similar of the carbocyclic ring is here rolled and the closed ring body that forms in graphite flake.
In the present invention, " axial dimension " refer to from a lateral section of carbocyclic ring to the distance in opposite side cross section, i.e. the height of carbocyclic ring, and " radial dimension " refers to the diameter of outermost layer carbocyclic ring, as shown in Figure 1.
According to concrete technical scheme of the present invention, the axial dimension of carbon nano ring provided by the present invention is the 0.5-1.0 nanometer, and radial dimension is the 2-30 nanometer.
According to concrete technical scheme of the present invention, the axial dimension of carbon nano ring provided by the present invention and the ratio of radial dimension are 0.01-0.5.Carbon nano ring provided by the present invention has less length-to-diameter ratio, is a kind of typical ring texture.
According to concrete technical scheme of the present invention, carbon nano ring provided by the present invention can be the single or multiple lift structure, and the number of plies of carbocyclic ring can be the 1-25 layer.
According to concrete technical scheme of the present invention, when carbon nano ring was comprised of the coaxial carbocyclic ring of multilayer, the distance of between layers (adjacent layer between) of carbocyclic ring can be identical, and this distance is the 0.31-0.37 nanometer.
The present invention also provides the preparation method of above-mentioned carbon nano ring, it is the interlayer with chain alkyl negatively charged ion and carbon source molecule insertion layered di-hydroxyl composite metal oxidate, then with the roasting under inertia or reducing atmosphere of this intercalation compound, utilize the katalysis of the metallic element on the laminate and the confinement space growth carbon nano ring of lamellar compound interlayer, remove metal simple-substance and metal oxide by sour dissolving method at last, obtain the target product carbon nano ring.Above-mentioned preparation method's provided by the invention technical process can comprise following concrete steps as shown in Figure 2:
(1), with divalent-metal ion M
2+Soluble salt, trivalent metal ion M '
3+Soluble salt, chain alkyl negatively charged ion A
-Soluble salt and carbon source molecule C mix, be dissolved in that preparation obtains mixing salt solution in the deionized water of decarbonation;
Under nitrogen protection, described mixing salt solution is mixed with alkali lye; under nitrogen protection, reacted crystallization 6-10 hour at 60-80 ℃; obtain suspension liquid; filter; be 7-7.5 with deionized water wash to filtrate pH value; then with filter cake at 50-60 ℃ of dry 6-12 hour, obtain having the layered di-hydroxyl composite metal oxidate of intercalation configuration, its chemical constitution general formula is:
[M
2+ 1-xM′
3+ x(OH)
2]
x+A
- x·αC·βH
20
Wherein, x is 0.2-0.33, and α is 0.5-4, and β is 0.5-2;
(2), in inert atmosphere or reducing atmosphere, with the layered di-hydroxyl composite metal oxidate of intercalation configuration calcining 0.5-3 hour, obtain calcinate, wherein, inert atmosphere is nitrogen or argon gas etc., and reducing atmosphere is hydrogen etc., and calcining temperature is 600-800 ℃;
(3), the solid-to-liquid ratio according to 2-5g/L places salpeter solution with calcinate, supersound process 0.5-2 hour, solution is removed in centrifugation, be 6.5-7 with deionized water with lower sediment filtration washing to the filtrate pH value that centrifugation obtains, then at 50-60 ℃ of dry 6-12 hour, obtain carbon nano ring.
In the layered di-hydroxyl composite metal oxidate with intercalation configuration of step (1) preparation, divalent-metal ion M
2+With trivalent metal ion M '
3+Be positioned on the main body laminate chain alkyl negatively charged ion A
-, carbon source molecule C and H
2The O molecule is positioned at the layered di-hydroxyl composite metal oxidate interlayer.
In above-mentioned preparation method provided by the invention, the divalent-metal ion M that adopts
2+Soluble salt be in nitrate, vitriol, oxalate and the muriate etc. of Mg, Fe, Co, Ni, Cu and Zn etc. one or more; The trivalent metal ion M ' that adopts
3+Soluble salt be in nitrate, vitriol, oxalate and the muriate etc. of Al, Fe and Co etc. one or more.Divalent-metal ion M
2+With trivalent metal ion M '
3+In at least a be the ion with metallic element of catalytic activity, this metallic element with catalytic activity can play good katalysis in the process of growth of carbon nano ring.Preferably, above-mentioned metallic element with catalytic activity is Fe, Co and Ni etc.
In above-mentioned preparation method provided by the invention, preferably, in step (1), divalent-metal ion M
2+With trivalent metal ion M '
3+Mol ratio be 2-4: 1.
In above-mentioned preparation method provided by the invention, preferably, in the mixing salt solution of step (1), divalent-metal ion M
2+With trivalent metal ion M '
3+Total concn be 0.2-0.5mol/L.
In above-mentioned preparation method provided by the invention, preferably, the chain alkyl negatively charged ion A that adopts
-Soluble salt be in sodium lauryl sulphate, sodium laurylsulfonate, Sodium dodecylbenzene sulfonate, dodecyl sulphate potassium, dodecyl sodium sulfonate potassium and the Potassium dodecylbenzenesulfonate etc. one or more.
In above-mentioned preparation method provided by the invention, preferably, in the mixing salt solution of step (1), chain alkyl negatively charged ion A
-Mole number and trivalent metal ion M '
3+Mole number equate i.e. chain alkyl negatively charged ion A
-The add-on of soluble salt should make chain alkyl negatively charged ion A
-Mole number and trivalent metal ion M '
3+Mole number equate.
In above-mentioned preparation method provided by the invention, preferably, the carbon source molecule C that adopts is one or more in methyl methacrylate, Skellysolve A, benzene,toluene,xylene and the vinylbenzene etc.In the mixing salt solution of step (1), the mole number of carbon source molecule C is trivalent metal ion M '
3+The 1.2-12 of mole number doubly.
In above-mentioned preparation method provided by the invention, preferably, in step (1), the alkali lye that adopts is for to be dissolved in the solution that is made in the deionized water of decarbonation with sodium hydroxide or potassium hydroxide, and its concentration is 2-5mol/L.The mole number of alkali is divalent-metal ion M in the alkali lye
2+With trivalent metal ion M '
3+2 times of total mole number.
In above-mentioned preparation method provided by the invention, preferably, in step (3), the concentration of the salpeter solution that adopts is 10-30 quality %.
In above-mentioned preparation method provided by the invention, preferably, in step (3), the rotating speed of centrifugation is 3000-9000 rev/min, and the time is 1-10 minute.
Adopt laser Raman spectrometer to characterize the Raman active of carbon nano ring provided by the invention, typical Raman spectrogram as shown in figure 10, the G peak among the figure belongs to sp in the six-ring
2The hydridization carbon atom, the D peak belongs to the edge defect carbon atom, compares with carbon nanotube, and the D peak of carbon nano ring obviously strengthens, and shows that carbon nano ring provided by the invention has more edge carbon and outstanding key; In addition, carbon nano ring all shows Raman active at the 2G band that multiplex RBM in characterizing Single Walled Carbon Nanotube was with and characterized Graphene, and this illustrates that carbon nano ring provided by the invention has some characteristic of carbon nanotube and Graphene simultaneously.
Carbon nano ring provided by the invention is a kind of allotropic substance of carbon, has the novel structure of nanometer ring-type and the excellent properties of carbon material, can be used as a kind of important structure unit in the nano-device, has wide development prospect.And carbon nano ring provided by the present invention has some performances of carbon nanotube and Graphene concurrently, and has more edge carbon and outstanding key, and reactive behavior is high, also has significant application value in field of functional materials such as energy storage, sensings.In addition, it is simple that the preparation method of carbon nano ring provided by the present invention has an operating procedure, can be to advantages such as carbon nano ring axial dimension, radial dimension and the carbocyclic ring number of plies control effectively.
Description of drawings
Fig. 1 is the structural representation of carbon nano ring provided by the present invention;
Fig. 2 is the process flow diagram that the present invention prepares carbon nano ring;
Fig. 3 is the X-ray diffractogram of the layered di-hydroxyl composite metal oxidate of the intercalation configuration of preparation among the embodiment 1, and X-coordinate is angle 2 θ, and unit is: degree (°), ordinate zou is diffracted intensity, unit is: absolute units (a.u.);
Fig. 4 is the high-resolution-ration transmission electric-lens photo of the layered di-hydroxyl composite metal oxidate of the intercalation configuration of preparation among the embodiment 1;
Fig. 5 is the infrared spectrum of the layered di-hydroxyl composite metal oxidate of methyl methacrylate (being abbreviated as MMA), sodium lauryl sulphate (being abbreviated as SDS) and intercalation configuration among the embodiment 1, and X-coordinate is wave number, and unit is: centimetre
-1(cm
-1), ordinate zou is transmitance, unit is: percentage ratio (%);
Fig. 6 is the methyl methacrylate 1800-1680cm before and after intercalation among the embodiment 1
-1The infrared spectrum of scope changes comparison diagram, and X-coordinate is wave number, and unit is: centimetre
-1(cm
-1), ordinate zou is transmitance, unit is: percentage ratio (%);
Fig. 7 is the high-resolution-ration transmission electric-lens photo of the carbon nano ring of preparation among the embodiment 1;
Fig. 8 is the atomic force microscopy of the carbon nano ring of preparation among the embodiment 1;
Fig. 9 is the height map at the white line position that identifies among Fig. 8, and X-coordinate is horizontal throw, and unit is: nanometer (nm), ordinate zou are vertical range, and unit is: nanometer (nm);
Figure 10 is the Raman spectrogram of the carbon nano ring of preparation among the embodiment 1, and wherein, X-coordinate is wave number, and unit is: centimetre
-1(cm
-1), ordinate zou is peak intensity, unit is: absolute units (a.u.);
Figure 11 is the X-ray diffractogram of the layered di-hydroxyl composite metal oxidate of embodiment 2,3 and 4 intercalation configurations that prepare, and X-coordinate is angle 2 θ, and unit is: degree (°), ordinate zou is diffracted intensity, unit is: absolute units (a.u.);
Figure 12 is the high-resolution-ration transmission electric-lens photo of the carbon nano ring of preparation among the embodiment 2;
Figure 13 is the high-resolution-ration transmission electric-lens photo of the carbon nano ring of preparation among the embodiment 3;
Figure 14 is the high-resolution-ration transmission electric-lens photo of the carbon nano ring of preparation among the embodiment 4.
Embodiment
With 0.075mol Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES (Co (NO
3)
26H
2O), 0.025mol aluminum nitrate (Al (NO
3)
39H
2O), (the dodecyl sulphate root is abbreviated as DS to the 0.025mol sodium lauryl sulphate
-) and 0.25mol methyl methacrylate (MMA) be dissolved in the deionized water of 300mL decarbonation, under nitrogen protection, mix 20 minutes, obtain the mixing salt solution of pink colour clear;
In nitrogen protection and under constantly stirring, dripping the concentration that is made into the decarbonation deionized water in the above-mentioned mixing salt solution is the NaOH solution 80mL of 2.5mol/L, obtains mixed solution;
Under nitrogen atmosphere, make above-mentioned mixed solution 80 ℃ of reactions 8 hours, the suspension liquid that obtains is filtered, be 7.2 with deionized water washing reaction product to filtrate pH value, then filter cake was descended dry 12 hours at 50 ℃, obtain the layered di-hydroxyl composite metal oxidate of intercalation configuration, be designated as LDH-1.Fig. 3 and Fig. 4 are respectively X-ray diffractogram and the high-resolution-ration transmission electric-lens photo of LDH-1.The data that provide according to Fig. 3 can draw, and LDH-1 is laminate structure, and it is 2.34 nanometers that 003 peak has characterized interlamellar spacing.According to Fig. 4, can draw 003 spacing is 2.3 nanometers.Fig. 5 is the infrared spectrum of methyl methacrylate, sodium lauryl sulphate and LDH-1.Fig. 6 is methyl methacrylate before and after intercalation at 1800-1680cm
-1The infrared spectrum of scope changes comparison diagram.Can be found out by Fig. 5 and Fig. 6, obvious variation has occured in the characteristic peak of MMA before and after intercalation: behind the MMA intercalation, cause the C-O key to move to lower wave number because the O atom in its C-O key and the hydroxyl on the layered di-hydroxyl composite metal oxidate laminate interact, this proof MMA has inserted the interlayer of layered di-hydroxyl composite metal oxidate really.Record the metallic element ratio by inductively coupled plasma atomic emission spectrum, as shown in table 1; Record the quality percentage composition that C, H, four kinds of elements of O, S account for total mass by organic element analysis, as shown in table 2; By calculating the molar content of each element, as shown in table 3, obtain its chemical constitution and be: [Co
2+ 0.75Al
3+ 0.25(OH)
2]
0.25+(DS
-)
0.252.3MMA0.8H
2O.
Table 1 inductively coupled plasma atomic emission spectrum data
Table 2 organic element analysis data
The molar content of the various elements of table 3
Under nitrogen atmosphere, make the layered di-hydroxyl composite metal oxidate of above-mentioned intercalation configuration 800 ℃ of calcinings 1 hour, obtain calcinate;
It is the salpeter solution of 30 quality % that the 1g calcinate is placed 200mL concentration, supersound process 1 hour, then with 9000 rev/mins rotating speed centrifugation 1 minute, the lower sediment that centrifugation is obtained with deionized water wash to the pH value be 6.5, remove metal simple-substance and oxide compound, obtain target product carbon nano ring C1.
Adopt high-resolution-ration transmission electric-lens that carbon nano ring C1 is characterized, obtain transmission electron microscope photo as shown in Figure 7, the carbocyclic ring number of plies of this carbon nano ring C1 is 10 layers as can be seen from Figure, and radial dimension is about 16 nanometers.Adopt atomic force microscope that carbon nano ring C1 is characterized, obtain atomic force microscopy as shown in Figure 8, Fig. 9 is the height map at the white line position that identifies among Fig. 8, and the axial dimension of this carbon nano ring is about 0.8 nanometer as seen from Figure 9, and the ratio of axial dimension and radial dimension is 0.05.
The Raman spectrogram of carbon nano ring C1 as shown in figure 10, the G peak among the figure belongs to sp in the six-ring
2The hydridization carbon atom, the D peak belongs to the edge defect carbon atom.Compare with carbon nanotube, the D peak of carbon nano ring obviously strengthens, and shows that carbon nano ring has more edge carbon and outstanding key; In addition, carbon nano ring all shows Raman active at the 2G band that multiplex RBM in characterizing Single Walled Carbon Nanotube was with and characterized Graphene, and this explanation carbon nano ring has some characteristic of carbon nanotube and Graphene simultaneously.
With 0.025mol Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES (Co (NO
3)
26H
2O), 0.025mol magnesium nitrate (Mg (NO
3)
26H
2O), 0.025mol aluminum nitrate (Al (NO
3)
39H
2O), (the dodecyl sodium sulfonate root is abbreviated as DSO to the 0.025mol sodium laurylsulfonate
-) and 0.75mol Skellysolve A (P) be dissolved in the deionized water of 150mL decarbonation, under nitrogen protection, mix 20 minutes, obtain the mixing salt solution of pink colour clear;
In nitrogen protection and under constantly stirring, dripping the concentration that is made into the decarbonation deionized water in the above-mentioned mixing salt solution is the NaOH solution 30mL of 5mol/L, obtains mixed solution;
Under nitrogen atmosphere, make above-mentioned mixed solution 70 ℃ of reactions 10 hours, the suspension liquid that obtains is filtered, be 7.5 with deionized water washing reaction product to filtrate pH value, then filter cake was descended dry 8 hours at 60 ℃, obtain the layered di-hydroxyl composite metal oxidate of intercalation configuration, be designated as LDH-2.The X-ray diffractogram of LDH-2 as shown in figure 11.Record the metallic element ratio by inductively coupled plasma atomic emission spectrum, as shown in table 4; Record the quality percentage composition that C, H, four kinds of elements of O, S account for total mass by organic element analysis, as shown in table 5; By calculating the molar content of each element, as shown in table 6, obtain its chemical constitution and be: [Co
2+ 0.33Mg
2+ 0.33Al
3+ 0.33(OH)
2]
0.33+(DSO
-)
0.333.7P0.6H
2O.
Table 4 inductively coupled plasma atomic emission spectrum data
Table 5 organic element analysis data
The molar content of the various elements of table 6
Under nitrogen atmosphere, make the layered di-hydroxyl composite metal oxidate of above-mentioned intercalation configuration 600 ℃ of calcinings 3 hours, obtain calcinate;
It is the salpeter solution of 20 quality % that the 1g calcinate is placed 500mL concentration, supersound process 0.5 hour, with 7000 rev/mins rotating speed centrifugations 5 minutes, the lower sediment that centrifugation is obtained with deionized water wash to the pH value be 7.0, remove metal simple-substance and oxide compound, obtain target product carbon nano ring C2.
Adopt high-resolution-ration transmission electric-lens that carbon nano ring C2 is characterized, as shown in figure 12, the carbocyclic ring number of plies that can find this carbon nano ring is 4 layers, and radial dimension is about 5.6 nanometers, and axial dimension is 0.76 nanometer, and the ratio of axial dimension and radial dimension is 0.14.
With 0.1mol zinc nitrate (Zn (NO
3)
26H
2O), 0.01mol iron nitrate (Fe (NO
3)
39H
2O), 0.015mol aluminum nitrate (Al (NO
3)
3.9H
2O), (the Witco 1298 Soft Acid root is abbreviated as DBS to the 0.025mol Sodium dodecylbenzene sulfonate
-) and 0.5mol toluene (MB) be dissolved in the deionized water of 625mL decarbonation, under nitrogen protection, mix 20 minutes, obtain the mixing salt solution of yellow clear;
In nitrogen protection and under constantly stirring, dripping the concentration that is made into the decarbonation deionized water in the above-mentioned mixing salt solution is the NaOH solution 100mL of 2.5mol/L, obtains mixed solution;
Under nitrogen atmosphere, make above-mentioned mixed solution 60 ℃ of reactions 6 hours, the suspension liquid that obtains is filtered, be 7.0 with deionized water washing reaction product to filtrate pH value, filter cake was descended dry 6 hours at 55 ℃, obtain the layered di-hydroxyl composite metal oxidate of intercalation configuration, be designated as LDH-3.The X-ray diffractogram of LDH-3 as shown in figure 11.Record the metallic element ratio by inductively coupled plasma atomic emission spectrum, as shown in table 7; Record the quality percentage composition that C, H, four kinds of elements of O, S account for total mass by organic element analysis, as shown in table 8; By calculating the molar content of each element, as shown in table 9, obtain its chemical constitution and be: [Zn
2+ 0.8Fe
3+ 0.08Al
3+ 0.12(OH)
2]
0.2+(DBS
-)
0.21.6MB1.3H
2O.
Table 7 inductively coupled plasma atomic emission spectrum data
Table 8 organic element analysis data
The molar content of the various elements of table 9
Under nitrogen atmosphere, make the layered di-hydroxyl composite metal oxidate of above-mentioned intercalation configuration 700 ℃ of calcinings 0.5 hour, obtain calcinate;
It is the salpeter solution of 10 quality % that the 1.5g calcinate is placed 500mL concentration, supersound process 1.5 hours, with 5000 rev/mins rotating speed centrifugations 7 minutes, the lower sediment that centrifugation is obtained with deionized water wash to the pH value be 6.8, remove metal simple-substance and oxide compound, obtain target product carbon nano ring C3.
Adopt high-resolution-ration transmission electric-lens that carbon nano ring C3 is characterized, as shown in figure 13, the radial dimension that can find this carbon nano ring is 4.4 nanometers, and axial dimension is 0.68 nanometer, and the ratio of axial dimension and radial dimension is 0.15.
With 0.0375mol nickelous chloride (NiCl
26H
2O), 0.025mol iron protochloride (FeCl
24H
2O), 0.025mol aluminum chloride (AlCl
36H
2O), (the dodecyl sulphate root is abbreviated as DS to the 0.025mol sodium lauryl sulphate
-) and 0.125mol vinylbenzene (S) be dissolved in the deionized water of 220mL decarbonation, under agitation fully mixed 20 minutes, obtain the mixing salt solution of green clear;
In nitrogen protection and under constantly stirring, dripping the concentration that is made into the decarbonation deionized water in the above-mentioned mixing salt solution is the NaOH solution 50mL of 3.5mol/L, obtains mixed solution;
Under nitrogen atmosphere, above-mentioned mixed solution after 7 hours, is filtered the suspension liquid that obtains 75 ℃ of reactions, be 7.3 with deionized water washing reaction product to filtrate pH value, filter cake was descended dry 10 hours at 55 ℃, obtain the layered di-hydroxyl composite metal oxidate of intercalation configuration, be designated as LDH-4.The X-ray diffractogram of LDH-4 as shown in figure 11.Record the metallic element ratio by inductively coupled plasma atomic emission spectrum, as shown in table 10; Record the quality percentage composition that C, H, four kinds of elements of O, S account for total mass by organic element analysis, as shown in table 11; By calculating the molar content of each element, as shown in table 12, obtain its chemical constitution and be: [Ni
2+ 0.44Fe
2+ 0.28Al
3+ 0.28(OH)
2]
0.28+(DS
-)
0.280.7S1.9H
2O.
Table 10 inductively coupled plasma atomic emission spectrum data
Table 11 organic element analysis data
The molar content of the various elements of table 12
Under nitrogen atmosphere, make the layered di-hydroxyl composite metal oxidate of above-mentioned intercalation configuration 750 ℃ of calcinings 2 hours, obtain calcinate;
It is the salpeter solution of 20wt% that the 1g calcinate is placed 250mL concentration, supersound process 2 hours, with 3000 rev/mins rotating speed centrifugations 10 minutes, the lower sediment that centrifugation is obtained with deionized water wash to the pH value be 6.7, remove metal simple-substance and oxide compound, obtain target product carbon nano ring C4.
Adopt high-resolution-ration transmission electric-lens that carbon nano ring C4 is characterized, as shown in figure 14, the radial dimension that can find this carbon nano ring is 24.4 nanometers, and axial dimension is 0.74 nanometer, and the ratio of axial dimension and radial dimension is 0.03.
Claims (15)
1. carbon nano ring, it is characterized in that the carbocyclic ring coaxial by single or multiple lift forms, and described carbocyclic ring has the similar structure of closed ring body that is rolled into graphite flake layer, axial dimension and the radial dimension of this carbon nano ring are nanometer scale, and axial dimension is less than radial dimension;
Wherein, the axial dimension of this carbon nano ring is the 0.5-1.0 nanometer, and radial dimension is the 2-30 nanometer;
The axial dimension of this carbon nano ring and the ratio of radial dimension are 0.01-0.5.
2. carbon nano ring according to claim 1 is characterized in that, wherein, the number of plies of described carbocyclic ring is the 1-25 layer.
3. carbon nano ring according to claim 1 and 2 is characterized in that, wherein, in the carbon nano ring that is comprised of the coaxial carbocyclic ring of multilayer, the distance between layers of carbocyclic ring is identical, and this distance is the 0.31-0.37 nanometer.
4. the preparation method of a carbon nano ring claimed in claim 1 is characterized in that,, may further comprise the steps:
(1), with divalent-metal ion M
2+Soluble salt, trivalent metal ion M'
3+Soluble salt, chain alkyl negatively charged ion A
-Soluble salt and carbon source molecule C mix, be dissolved in that preparation obtains mixing salt solution in the deionized water of decarbonation;
Under nitrogen protection, described mixing salt solution is mixed with alkali lye, under nitrogen protection at 60-80
oC reaction crystallization 6-10 hour obtains suspension liquid, filter, be 7-7.5 with deionized water wash to filtrate pH value, then with filter cake at 50-60
oDry 6-12 hour of C obtains having the layered di-hydroxyl composite metal oxidate of intercalation configuration, and its chemical constitution general formula is:
[M
2+ 1-x?M'
3+ x(OH)
2]
x+A
- x·αC·βH
2O
Wherein, x is 0.2-0.33, and α is 0.5-4, and β is 0.5-2;
(2), in inert atmosphere or reducing atmosphere, with the layered di-hydroxyl composite metal oxidate of described intercalation configuration calcining 0.5-3 hour, obtain calcinate, wherein, described inert atmosphere is nitrogen or argon gas, and described reducing atmosphere is hydrogen, and described calcining temperature is 600-800
oC;
(3), according to the solid-to-liquid ratio of 2-5g/L described calcinate is placed salpeter solution, ultrasonic 0.5-2 hour, solution was removed in centrifugation, is 6.5-7 with deionized water with lower sediment filtration washing to the filtrate pH value that centrifugation obtains, then at 50-60
oDry 6-12 hour of C obtains described carbon nano ring;
Described divalent-metal ion M
2+Soluble salt be in nitrate, vitriol, oxalate and the muriate of Mg, Fe, Co, Ni, Cu and Zn one or more; Described trivalent metal ion M'
3+Soluble salt be in nitrate, vitriol, oxalate and the muriate of Al, Fe and Co one or more;
Described divalent-metal ion M
2+With trivalent metal ion M'
3+In at least a be the metallic element with catalytic activity.
5. preparation method according to claim 4 is characterized in that, wherein, described metallic element with catalytic activity is Fe, Co and Ni.
6. preparation method according to claim 4 is characterized in that, wherein, and described divalent-metal ion M
2+With trivalent metal ion M'
3+Mol ratio be 2-4:1.
7. preparation method according to claim 4 is characterized in that, wherein, in described mixing salt solution, divalent-metal ion M
2+With trivalent metal ion M'
3+Total concn be 0.2-0.5 mol/L.
8. preparation method according to claim 4 is characterized in that, wherein, and described chain alkyl negatively charged ion A
-Soluble salt be in sodium lauryl sulphate, sodium laurylsulfonate, Sodium dodecylbenzene sulfonate, dodecyl sulphate potassium, dodecyl sodium sulfonate potassium and the Potassium dodecylbenzenesulfonate one or more.
9. preparation method according to claim 4 is characterized in that, wherein, in described mixing salt solution, described chain alkyl negatively charged ion A
-Mole number and described trivalent metal ion M'
3+Mole number equate.
10. preparation method according to claim 4 is characterized in that, wherein, described carbon source molecule C is one or more in methyl methacrylate, Skellysolve A, benzene,toluene,xylene and the vinylbenzene.
11. preparation method according to claim 4 is characterized in that, wherein, in described mixing salt solution, the mole number of described carbon source molecule C is described trivalent metal ion M'
3+The 1.2-12 of mole number doubly.
12. preparation method according to claim 4 is characterized in that, wherein, in step (1), described alkali lye is for to be dissolved in the solution that is made in the deionized water of decarbonation with sodium hydroxide or potassium hydroxide, and its concentration is 2-5 mol/L.
13. according to claim 4 or 12 described preparation methods, it is characterized in that wherein, the mole number of alkali is described divalent-metal ion M in the described alkali lye
2+With trivalent metal ion M'
3+2 times of total mole number.
14. preparation method according to claim 4 is characterized in that, wherein, in step (3), the concentration of described salpeter solution is 10-30 quality %.
15. preparation method according to claim 4 is characterized in that, wherein, in step (3), the rotating speed of described centrifugation is 3000-9000 rev/min, and the time is 1-10 minute
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| CN101214947A (en) * | 2008-01-18 | 2008-07-09 | 中国科学技术大学 | Method for preparing carbon nano-tube by catalyzing and carbonizing polymer and /or asphalt |
| WO2011111719A1 (en) * | 2010-03-08 | 2011-09-15 | 国立大学法人名古屋大学 | Carbon nanoring and method for producing a ring-shaped compound suitable as a starting material for production of the same |
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| CN101214947A (en) * | 2008-01-18 | 2008-07-09 | 中国科学技术大学 | Method for preparing carbon nano-tube by catalyzing and carbonizing polymer and /or asphalt |
| WO2011111719A1 (en) * | 2010-03-08 | 2011-09-15 | 国立大学法人名古屋大学 | Carbon nanoring and method for producing a ring-shaped compound suitable as a starting material for production of the same |
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