CN102381698A - Controllable preparation method of fullerene sub-micron tube - Google Patents
Controllable preparation method of fullerene sub-micron tube Download PDFInfo
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- CN102381698A CN102381698A CN2011102104586A CN201110210458A CN102381698A CN 102381698 A CN102381698 A CN 102381698A CN 2011102104586 A CN2011102104586 A CN 2011102104586A CN 201110210458 A CN201110210458 A CN 201110210458A CN 102381698 A CN102381698 A CN 102381698A
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- 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 title claims abstract description 150
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 229910003472 fullerene Inorganic materials 0.000 title abstract description 28
- 239000012047 saturated solution Substances 0.000 claims abstract description 68
- 239000002904 solvent Substances 0.000 claims abstract description 49
- 238000000034 method Methods 0.000 claims abstract description 47
- 238000002425 crystallisation Methods 0.000 claims abstract description 7
- 230000008025 crystallization Effects 0.000 claims abstract description 7
- 239000000243 solution Substances 0.000 claims description 111
- 239000011521 glass Substances 0.000 claims description 27
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 22
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 21
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 21
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 18
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 15
- 238000005286 illumination Methods 0.000 claims description 15
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 14
- 238000005303 weighing Methods 0.000 claims description 14
- 239000012046 mixed solvent Substances 0.000 claims description 13
- IVSZLXZYQVIEFR-UHFFFAOYSA-N m-xylene Chemical group CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 claims description 10
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical group CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 9
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 claims description 7
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 7
- 230000010355 oscillation Effects 0.000 claims description 7
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 6
- 230000005540 biological transmission Effects 0.000 claims description 3
- 238000002156 mixing Methods 0.000 abstract description 26
- 239000000463 material Substances 0.000 abstract description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 2
- 239000011358 absorbing material Substances 0.000 abstract description 2
- 239000000446 fuel Substances 0.000 abstract description 2
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 2
- 239000001257 hydrogen Substances 0.000 abstract description 2
- 239000000969 carrier Substances 0.000 abstract 1
- 239000003054 catalyst Substances 0.000 abstract 1
- 239000011259 mixed solution Substances 0.000 abstract 1
- 239000002070 nanowire Substances 0.000 abstract 1
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- 239000000843 powder Substances 0.000 description 24
- 239000005457 ice water Substances 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- FFRBMBIXVSCUFS-UHFFFAOYSA-N 2,4-dinitro-1-naphthol Chemical group C1=CC=C2C(O)=C([N+]([O-])=O)C=C([N+]([O-])=O)C2=C1 FFRBMBIXVSCUFS-UHFFFAOYSA-N 0.000 description 12
- 239000002245 particle Substances 0.000 description 9
- 150000001875 compounds Chemical class 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
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- 238000010276 construction Methods 0.000 description 2
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- 229910002804 graphite Inorganic materials 0.000 description 2
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- 238000009776 industrial production Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000002071 nanotube Substances 0.000 description 2
- 150000004032 porphyrins Chemical class 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 238000001338 self-assembly Methods 0.000 description 2
- XVMSFILGAMDHEY-UHFFFAOYSA-N 6-(4-aminophenyl)sulfonylpyridin-3-amine Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=N1 XVMSFILGAMDHEY-UHFFFAOYSA-N 0.000 description 1
- -1 C82 Chemical compound 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
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- 230000003760 hair shine Effects 0.000 description 1
- 229960004592 isopropanol Drugs 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- SYSQUGFVNFXIIT-UHFFFAOYSA-N n-[4-(1,3-benzoxazol-2-yl)phenyl]-4-nitrobenzenesulfonamide Chemical class C1=CC([N+](=O)[O-])=CC=C1S(=O)(=O)NC1=CC=C(C=2OC3=CC=CC=C3N=2)C=C1 SYSQUGFVNFXIIT-UHFFFAOYSA-N 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
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- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
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Abstract
The invention relates to a controllable preparation method of a fullerene sub-micron tube. The controllable preparation method comprises the following steps: dissolving fullerene molecules in a good solvent at low temperature so as to obtain a saturated solution of the fullerene molecules; placing the saturated solution under a specific light source for exciting irradiation for certain time; and evenly mixing the saturated solution with a poor solvent, then placing the obtained mixed solution in a thermotank for static cultivation for certain time, and finally separating out the monocrystalline fullerene sub-micron tube with high length-diameter ratio and controllable inner and outer diameter through crystallization. The controllable preparation method has the advantages of simple process, more easily controlled technological process and good repeatability; and the fullerene sub-micron tube obtained by the preparation method has broad application prospects in the fields such as nano-micron electrodes, fuel cell electrodes, gaseous or electrochemical hydrogen storage materials, electromagnetic shielding materials, high-frequency wave-absorbing materials, catalysts and carriers thereof, nano-transistors, nano wires and the like.
Description
Technical field
The present invention relates to soccerballene submicron material field, particularly relate to the controllable method for preparing of soccerballene sub-micro mitron.
Background technology
On earth, it is believed that in early days carbon has two kinds of isomers: graphite and diamond.And H.W.Kroto in 1985 and R.E.Smalley etc. have found soccerballene families such as C60 when research laser evaporation Graphite Electrodes, and the Iijima doctor of company of NEC in 1991 has found CNT again, becomes the new isomer in the carbon family.Recently soccerballene of finding and CNT then will further extensively utilize its property to open promising prospect for human.
Found since the soccerballene C60 in 1985; The C60 molecule is because of its distinct constitutional features, perfect structural symmetry, three-dimensional conjugation, active chemical reactivity and very strong unique physicochemical property such as electron affinity; For scientific research has brought many new opportunities, one of field, international forward position and hot subject since the nineties have been become.Can whether soccerballene, particularly C60 can form new aggregated structure under certain condition, form stable shaped " pipe ", " line " by controllable growth, and the scholar is paid close attention to by the world wide material supply section.For the new aggregated structure of C60: C60 sub-micro mitron, line, rod, sheet etc., in the past few years domestic and international many research groups have carried out deep research.And the soccerballene sub-micron fibers with conjugated pi electron structure both kept fullerene molecule structure and character, have the characteristics of monodimension nanometer material as the carbon nanotube; Under cover many new properties that remain to be discovered; New function becomes the research focus of carbon material naturally.
Nakanishi etc. utilize the soccerballene long-chain alkyl derivative; With 1: 1 iso-propanol/toluene mixtures, 1-propyl alcohol, 1; 4-dioxy six alkane, THF (THF)/water mixture etc. was a solvent in 1: 1, had successfully prepared the supermolecule nano material of shapes such as spherical vesicles, fiber, wafer, cone through self-assembly.
2002, Prato etc. utilized the soccerballene derivatives of porphyrin successfully to prepare nanotube through the π-π electrostatic interaction self-assembly of porphyrin.But this kind method prepares the process more complicated, and process is restive, is unfavorable for further research and application.In the same year, the Li Yu of the Chinese Academy of Sciences very waits utilization alumina formwork method to obtain form and structure soccerballene C60 Nano/micron material preferably.But, because the preparation of soccerballene Nano/micron pipe needs template, the preparation engineering very complicated, wayward, thus be unfavorable for the mass preparation of soccerballene Nano/micron pipe.
In recent years, Miyazawa etc. utilizes the liquid-liquid interface method near room temperature, successfully to prepare soccerballene C60 with single crystal structure and the sub-micro mitron of C70 with the saturated organic solution of soccerballene and Virahol.Prepared soccerballene sub-micro mitron has the characteristics of single crystal structure, high length-diameter ratio and high purity (99.9%).There is the problem that growth cycle is long, combined coefficient is low in mitron but the Miyazawa legal system is equipped with the soccerballene sub-micro, can not stablize the enough samples that provide institute to need, and is difficult to mass preparation.
On Miyazawa method basis, Chinese patent CN 100581998C discloses simple, the preparation method of the fullerenes nano micron fibre of good reproducibility.This method comprises the fullerene material is dissolved in after being ground to metalluster and is saturated solution in the good solvent; Irradiation is colloidal solution in natural light or visible light in container; Put into the thermostat container certain hour after mixing with a certain amount of poor solvent again; Crystallization separate out the fullerenes nano micron fibre of millimeter to the monocrystalline of cm-level length; But this method is the acquisition fullerene nanotube of ability high-repetition-rate just, can't prepare the certain sub-micro mitron of inside/outside diameter size, fails to realize the controlled preparation of sub-micro mitron.
Summary of the invention
For deficiency and the defective that overcomes above-mentioned prior art; The present invention is through the shooting conditions of the saturated solution of control soccerballene good solvent; Under the prerequisite of the combined coefficient that guarantees soccerballene sub-micro mitron; A kind of controllable method for preparing of soccerballene sub-micro mitron is provided, and preparation has the soccerballene sub-micro mitron of single crystal structure, high length-diameter ratio, tubular construction inside/outside diameter size controllable growth.This procedure is simple, and process method is more easy to control, and good reproducibility is easy to mass production, and can promote industrial production.
The controllable method for preparing of a kind of soccerballene sub-micro mitron provided by the invention may further comprise the steps:
(1) preparation of soccerballene saturated solution takes by weighing fullerene powder and in clean clear-glass bottle, mixes with its good solvent, and in 0-10 ℃ of ultrasonic oscillation, ultrasonic oscillation filters above-mentioned solution rapidly after finishing, the soccerballene saturated solution;
(2) illumination of soccerballene saturated solution excites under 0-10 ℃, and above-mentioned soccerballene saturated solution is placed light transmission container, uses centre wavelength to be the green glow of 525nm or the wavelength white light 5-50min as 300-700nm as the blue light of 468nm or centre wavelength;
(3) leaving standstill of soccerballene sub-micro mitron separates out by volume 50: 1-6: 1 ratio adds poor solvent and above-mentionedly in light-struck soccerballene saturated solution, mixes, and in 0-10 ℃ incubator, leaves standstill 2-72h, and soccerballene sub-micro mitron is separated out in crystallization.
The soccerballene that the present invention adopted is C60 or C70 or C60/C70 mixture, is commercially available, does not pass through any aftertreatment, and purity is 98-99.5%, and wherein C60/C70 ≈ 85/15.Also contain a small amount of number of carbons soccerballene in the soccerballene, like C82, C84, C100, C110......C540.Described soccerballene sub-micro mitron is the submicron tubular structure that is interconnected to through covalent linkage or ionic linkage or Van der Waals force between the above-mentioned fullerene molecule.
After soccerballene placed clean clear-glass bottle, add good solvent, like pyridine or benzene or toluene or m-xylene or dithiocarbonic anhydride or its mixed solvent; The ratio of optimum solvent and soccerballene is to make soccerballene to dissolve just and gets final product; Can be mixed with arbitrary proportion between the different good solvents, for example the blending ratio of pyridine and benzene is preferably 10: 1 or 9: 1.
Because temperature has material impact for the growth of soccerballene sub-micro mitron, temperature is too high, and soccerballene is not high in the solubleness of its good solvent, makes the soccerballene source of sub-micro mitron growth not enough; Temperature is low excessively, is unfavorable for that again the dissolved fullerene molecule separates out from good solvent, makes the output of sub-micro mitron very low.See from the angle of technology, in whole formulations prepared from solutions process, be difficult to all keep low service temperature, therefore selected 0-10 ℃ temperature for use.This temperature realizes through ice-water bath control.
For soccerballene is disperseed fully; The soccerballene solution of optimum dissolution with solvents is placed in the UW container; Ultrasonic oscillation, temperature are controlled at 0-10 ℃, prevent that the rapid rising along with solution temperature sharply reduces the solubleness of soccerballene in solution in the ultra-sonic dispersion process; Even the phenomenon that reunion is separated out, solution is muddy takes place, be unfavorable for the controllable growth of follow-up sub-micro mitron.Ultrasonic concussion overlong time, power are excessive, make that temperature raises in the ultrasonic procedure, are unfavorable for temperature controlling; Ultrasonic time is too short, and power is low excessively, does not have the effect that makes the abundant dispersing and dissolving of soccerballene again.Therefore, selected ultrasonic time 5-50min for use, power 50-100W.
Above-mentioned soccerballene saturated solution through the ultrasonic oscillation preparation is placed light transmission container; Temperature still is controlled at 0-10 ℃; Different according to external diameter in needed; Adopting centre wavelength is that the white light that the blue light of 468nm or green glow that centre wavelength is 525nm or wavelength region are 300-700nm shines, and the illumination firing time is 5-50min.
Through visible light radiation, can form the transfer transport complex compound between fullerene molecule and the good solvent molecule rapidly in the soccerballene saturated solution, it has played crucial effect in the growth of crystalline nucleation and sub-micro mitron.Irradiation time is too short and long, all is unfavorable for the formation of the intermolecular transfer transport complex compound of fullerene molecule and good solvent, so the preferred 20-50min of irradiation time.In order to make the sub-micro mitron for preparing that the ratio of bigger interior external diameter arranged, guarantee combined coefficient simultaneously, advise that preferred time point is 20min, 30min, 50min.Wherein irradiation time is that 30min is the submicron bore maximum that is obtained, and tube wall is the thinnest; When irradiation time was 20min or 50min, though the submicron tube wall of gained is thick slightly when tube wall is 30min than irradiation time, combined coefficient was higher, still can satisfy use.
With adding poor solvent in the light-struck soccerballene saturated solution of above-mentioned process and mixing, the volume ratio of soccerballene saturated solution and poor solvent is 1: 6-1: 50, and poor solvent is Virahol or ethanol or methyl alcohol or hexane or the trimethyl carbinol or its mixed solvent.Because the blending ratio of soccerballene saturated solution and poor solvent has determined the combined coefficient of soccerballene sub-micro mitron; Ratio is excessive can only to obtain sheet or particulate state crystal; Ratio is too small then almost can't to prepare any crystal; Have only when ratio control just can guarantee the preparation efficiency of soccerballene sub-micro mitron, so soccerballene saturated solution and poor solvent mixed volume ratio advised that the preferred ultrasonic oscillation of its hybrid mode was uniformly dispersed preferred 1: 6 to 1: 15 at optimum range.
Place 0-10 ℃ incubator to leave standstill the 2-72h post crystallization the above-mentioned solution that mixes, separate out the soccerballene sub-micro mitron of high length-diameter ratio, single crystal structure.Crystallization time has remarkably influenced for the interior external diameter and the length of soccerballene sub-micro mitron, if incubation time is too short, the growth of sub-micro mitron is incomplete, can influence interior external diameter and its length-to-diameter ratio of sub-micro mitron, so incubation time is 2-72 hour.
The temperature of temperature in the incubator and front entire operation process should be consistent; If temperature is too high in the incubator;, solution can make fullerene molecule low excessively after putting into incubator in the solubleness of solution; Cause fullerene molecule because supersaturation and rapid nucleating growth is unfavorable for the control of soccerballene sub-micro mitron synthetic; If temperature is low excessively in the incubator, meeting can't crystallization because fullerene molecule solubleness increases after putting into incubator.
Among the present invention; Through visible light radiation, fullerene molecule and good solvent form the transfer transport complex compound, and fullerene molecule is in the be absorbed with certain rules of visible region to light; The absorption of soccerballene is lacked and more helped to incident wavelength, thereby help the formation of transfer transport complex compound.After adding poor solvent, the fullerene molecule particle surface can form because of forming the transfer transport complex compound is adsorbed on the surface by fullerenic particles good solvent resist.These fullerenic particles that coated by good solvent molecule resist are as the soccerballene source in the soccerballene sub-micro mitron process of growth, for the growth of soccerballene sub-micro mitron provides fullerene molecule.Incident wavelength is lacked and more is helped the absorption of fullerene molecule to luminous energy, when the present invention selects blue light 468nm for use, helps the formation of transfer transport complex compound most.After adding poor solvent, the fullerenic particles particle diameter is minimum, and surface coated good solvent molecule resist is the thickest, and particle is the most stable.Therefore fullerenic particles reaches trim point the most easily and stops for the continued growth of soccerballene sub-micro mitron fullerene molecule being provided, and the relative internal diameter of the soccerballene sub-micro mitron that obtain this moment is maximum, and tube wall is the thinnest.In like manner, when light application time is approximately 30min, help between fullerene molecule and good solvent forming the transfer transport complex compound most, thereby the good solvent molecule resist that forms is the thickest, the time the relative internal diameter of soccerballene sub-micro mitron that obtains maximum, tube wall is the thinnest.Based on above-mentioned principle, the present invention has realized the controlled preparation of soccerballene sub-micro mitron under different shooting conditionss.
The preparation method of soccerballene sub-micro mitron provided by the invention can regulate the excited by visible light condition as required, adjustment excitation wavelength and firing time, the controlled soccerballene sub-micro mitron of preparation tubular construction inside/outside diameter size.The inventive method process is simple, and process method is more easy to control, and good reproducibility is easy to the controlled soccerballene sub-micro mitron of mass production inside/outside diameter size, and can promotes industrial production.
Marked improvement of the present invention is with positive achievement:
1. the present invention only needs glassware and constant incubator, regulates excited by visible light wavelength and time, need not to prepare template, simple economy, environmental friendliness, easy handling, reliable and stable realization the controlled preparation of soccerballene sub-micro mitron.
2. the present invention utilizes that fullerene molecule forms the different of transfer transport complex concentration with good solvent equal solvent molecule on the fullerenic particles surface under different excitation wavelengths and the firing time.In shorter excitation wavelength, under the best firing time, the transfer transport complex concentration that the fullerenic particles surface forms is big more, and the good solvent resist of formation is thick more, thereby the soccerballene submicron pipe of preparation has bigger internal diameter and thin tube wall.Through the control shooting conditions, realize the preparation of the soccerballene sub-micro mitron that the pipe inside/outside diameter size is controlled.
3. the inventive method has realized the controlled preparation of soccerballene sub-micro mitron on the basis that guarantees high-level efficiency fullerene synthesis sub-micro mitron.Be the soccerballene sub-micro mitron that not only has fullerene molecule conjugated pi electron structure but also have carbon nanotube monodimension nanometer material characteristics; At the anisotropy nano-reactor, receive material, the electromagnetic shielding material of a micron electrode, fuel cell electrode, gaseous state or electrochemical hydrogen storage, the application in fields such as high frequency absorbing material, catalyzer and carrier thereof, nano-transistor and nm-class conducting wire lays a solid foundation.
Description of drawings
Fig. 1 presses the data point diagram of the controlled preparation of shooting conditions for soccerballene sub-micro mitron inside/outside diameter size of the present invention.
Embodiment:
Embodiment 1
The method that a kind of soccerballene sub-micro mitron may command is equipped with may further comprise the steps;
(1) take by weighing 0.01g C60 (purity＞99.5%) powder in clean clear-glass bottle, measure the 10ml pyridine in vial with C60 powder, sealed glass jars.Above-mentioned solution is put into the UW container, with frozen water control bath temperature at 8 ℃, with the ultrasonic 20min of 100W power ultrasonic, so that C60 is fully disperseed and be dissolved in the solvent.After the ultrasonic end above-mentioned solution is taken out from water-bath, filter rapidly, get the soccerballene saturated solution, solution colour is red-purple, and clear.
(2) with the ice-water bath controlled temperature at 8 ℃, the saturated solution of C60 is used the blue-ray LED light source irradiation 30min of centre wavelength as 468nm.Irradiation back solution is purplish red, and clear.
(3) get 4 bottles of C60 saturated solutions after the above-mentioned illumination, solution is 2ml in every bottle, carefully adds the 18ml Virahol along a bottle wall, and solution colour becomes light brown red.With above-mentioned solution ultrasonic 1min in UW; After making C60 saturated solution and Virahol thorough mixing; Be statically placed in 8 ℃ of thermostat containers, separate out golden yellow group bunch shape behind the 12h in the solution, joint length reaches millimetre-sized soccerballene sub-micro mitron, this moment the sub-micro mitron average in the ratio of external diameter be 0.66.
Embodiment 2
The method that a kind of soccerballene sub-micro mitron may command is equipped with may further comprise the steps;
(1) take by weighing 0.01g C70 (purity＞99.5%) powder in clean clear-glass bottle, measure 10ml benzene in vial with C70 powder, sealed glass jars.Above-mentioned solution is put into the UW container, with frozen water control bath temperature at 5 ℃, with the ultrasonic 40min of 50W power ultrasonic, so that C70 is fully disperseed and be dissolved in the solvent.After the ultrasonic end above-mentioned solution is taken out from water-bath, filter rapidly, get the soccerballene saturated solution, solution colour is red-purple, and clear.
(2) with the ice-water bath controlled temperature at 5 ℃, the saturated solution of C70 is used the green light LED light source irradiation 30min of centre wavelength as 525nm.Irradiation back solution is purplish red, and clear.
(3) get 4 bottles of C70 saturated solutions after the above-mentioned illumination, solution is 2ml in every bottle, carefully adds 26ml ethanol along a bottle wall, and solution colour becomes light brown red.With above-mentioned solution ultrasonic 1min in UW; After making C70 saturated solution and ethanol thorough mixing; Be statically placed in 5 ℃ of thermostat containers, separate out golden yellow group bunch shape behind the 19h in the solution, joint length reaches millimetre-sized soccerballene sub-micro mitron, this moment the sub-micro mitron average in the ratio of external diameter be 0.55.
Embodiment 3
The method that a kind of soccerballene sub-micro mitron may command is equipped with may further comprise the steps;
(1) take by weighing 0.01g C60/C70 (85/15) powder in clean clear-glass bottle, measure 10ml toluene in vial with C60/C70 powder, sealed glass jars.Above-mentioned solution is put into the UW container, with frozen water control bath temperature at 3 ℃, with the ultrasonic 50min of 70W power ultrasonic, so that C60/C70 is fully disperseed and be dissolved in the solvent.After the ultrasonic end above-mentioned solution is taken out from water-bath, filter rapidly, get the soccerballene saturated solution, solution colour is red-purple, and clear.
(2) with the ice-water bath controlled temperature at 3 ℃, the saturated solution of C60/C70 is used the white LED light source irradiation 30min of centre wavelength as 300-700nm.Irradiation back solution is purplish red, and clear.
(3) get 4 bottles of C60/C70 saturated solutions after the above-mentioned illumination, solution is 2ml in every bottle, carefully adds 12ml methyl alcohol along a bottle wall, and solution colour becomes light brown red.With above-mentioned solution ultrasonic 1min in UW; After making C60/C70 saturated solution and methyl alcohol thorough mixing; Be statically placed in 3 ℃ of thermostat containers; Separate out golden yellow group bunch shape behind the 54h in the solution, joint length reaches millimetre-sized soccerballene sub-micro mitron, this moment the sub-micro mitron average in the ratio of external diameter be 0.45.
Embodiment 4
The method that a kind of soccerballene sub-micro mitron may command is equipped with may further comprise the steps;
(1) take by weighing 0.01g C70 (purity＞99.5%) powder in clean clear-glass bottle, measure the 10ml m-xylene in vial with C70 powder, sealed glass jars.Above-mentioned solution is put into the UW container, with frozen water control bath temperature at 10 ℃, with the ultrasonic 35min of 90W power ultrasonic, so that C70 is fully disperseed and be dissolved in the solvent.After the ultrasonic end above-mentioned solution is taken out from water-bath, filter rapidly, get the soccerballene saturated solution, solution colour is red-purple, and clear.
(2) with the ice-water bath controlled temperature at 10 ℃, the saturated solution of C70 is used the blue-ray LED light source irradiation 20min of centre wavelength as 468nm.Irradiation back solution is purplish red, and clear.
(3) get 4 bottles of C70 saturated solutions after the above-mentioned illumination, solution is 2ml in every bottle, carefully adds the 14ml hexane along a bottle wall, and solution colour becomes light brown red.With above-mentioned solution ultrasonic 1min in UW; After making C70 saturated solution and hexane thorough mixing; Be statically placed in 10 ℃ of thermostat containers, separate out golden yellow group bunch shape behind the 48h in the solution, joint length reaches millimetre-sized soccerballene sub-micro mitron, this moment the sub-micro mitron average in the ratio of external diameter be 0.47.
Embodiment 5
The method that a kind of soccerballene sub-micro mitron may command is equipped with may further comprise the steps;
(1) take by weighing 0.01g C60/C70 (85/15) powder in clean clear-glass bottle, measure 10ml dithiocarbonic anhydride in vial with C60/C70 powder, sealed glass jars.Above-mentioned solution is put into the UW container, with frozen water control bath temperature at 7 ℃, with the ultrasonic 20min of 60W power ultrasonic, so that C60/C70 is fully disperseed and be dissolved in the solvent.After the ultrasonic end above-mentioned solution is taken out from water-bath, filter rapidly, get the soccerballene saturated solution, solution colour is red-purple, and clear.
(2) with the ice-water bath controlled temperature at 7 ℃, the saturated solution of C60/C70 is used the blue-ray LED light source irradiation 50min of centre wavelength as 468nm.Irradiation back solution is purplish red, and clear.
(3) get 4 bottles of C60/C70-dithiocarbonic anhydride saturated solutions after the above-mentioned illumination, solution is 2ml in every bottle, carefully adds the 16ml trimethyl carbinol along a bottle wall, and solution colour becomes light brown red.With above-mentioned solution ultrasonic 1min in UW; After making C60/C70 saturated solution and trimethyl carbinol thorough mixing; Be statically placed in 7 ℃ of thermostat containers; Separate out golden yellow group bunch shape behind the 30h in the solution, joint length reaches millimetre-sized soccerballene sub-micro mitron, this moment the sub-micro mitron average in the ratio of external diameter be 0.48.
Embodiment 6
The method that a kind of soccerballene sub-micro mitron may command is equipped with may further comprise the steps;
(1) take by weighing 0.01g C60 (purity＞99.5%) powder in clean clear-glass bottle, the mixed solvent (blending ratio is 9: 1) of measuring 10ml pyridine and toluene in vial with C60 powder, sealed glass jars.Above-mentioned solution is put into the UW container, with frozen water control bath temperature at 6 ℃, with the ultrasonic 45min of 80W power ultrasonic, so that C60 is fully disperseed and be dissolved in the solvent.After the ultrasonic end above-mentioned solution is taken out from water-bath, filter rapidly, get the soccerballene saturated solution, solution colour is red-purple, and clear.
(2) with the ice-water bath controlled temperature at 6 ℃, the saturated solution of C60 is used the green light LED light source irradiation 20min of centre wavelength as 525nm.Irradiation back solution is purplish red, and clear.
(3) get 4 bottles of C60 saturated solutions after the above-mentioned illumination, solution is 2ml in every bottle, carefully adds the 20ml trimethyl carbinol along a bottle wall, and solution colour becomes light brown red.With above-mentioned solution ultrasonic 1min in UW; After making C60 saturated solution and trimethyl carbinol thorough mixing; Be statically placed in 6 ℃ of thermostat containers, separate out golden yellow group bunch shape behind the 36h in the solution, joint length reaches millimetre-sized soccerballene sub-micro mitron, this moment the sub-micro mitron average in the ratio of external diameter be 0.42.
Embodiment 7
The method that a kind of soccerballene sub-micro mitron may command is equipped with may further comprise the steps;
(1) take by weighing 0.01g C60/C70 (85/15) powder in clean clear-glass bottle, the mixed solvent (blending ratio is 9: 1) of measuring 10ml pyridine and benzene in vial with C60/C70 powder, sealed glass jars.Above-mentioned solution is put into the UW container, with frozen water control bath temperature at 2 ℃, with the ultrasonic 5min of 100W power ultrasonic, so that C60/C70 is fully disperseed and be dissolved in the solvent.After the ultrasonic end above-mentioned solution is taken out from water-bath, filter rapidly, get the soccerballene saturated solution, solution colour is red-purple, and clear.
(2) with the ice-water bath controlled temperature at 2 ℃, the saturated solution of C60/C70 is used the green light LED light source irradiation 50min of centre wavelength as 525nm.Irradiation back solution is purplish red, and clear.
(3) get 4 bottles of C60/C70 saturated solutions after the above-mentioned illumination, solution is 2ml in every bottle, carefully adds the 100ml Virahol along a bottle wall, and solution colour becomes light brown red.With above-mentioned solution ultrasonic 1min in UW; After making C60/C70 solution and Virahol thorough mixing; Be statically placed in 2 ℃ of thermostat containers, separate out golden yellow group bunch shape behind the 2h in the solution, joint length reaches millimetre-sized soccerballene sub-micro mitron, this moment the sub-micro mitron average in the ratio of external diameter be 0.48.
Embodiment 8
The method that a kind of soccerballene sub-micro mitron may command is equipped with may further comprise the steps;
(1) take by weighing 0.01g C60 (purity＞99.5%) powder in clean clear-glass bottle, mixed solvent (blending ratio is 9: the 1) solution of measuring 10ml m-xylene and dithiocarbonic anhydride in vial with C60 powder, sealed glass jars.Above-mentioned solution is put into the UW container, with frozen water control bath temperature at 4 ℃, with the ultrasonic 15min of 85W power ultrasonic, so that C60 is fully disperseed and be dissolved in the solvent.After the ultrasonic end above-mentioned solution is taken out from water-bath, filter rapidly, get the soccerballene saturated solution, solution colour is red-purple, and clear.
(2) with the ice-water bath controlled temperature at 4 ℃, the saturated solution of C60 is used the white LED light source irradiation 20min of centre wavelength as 300-700nm.Irradiation back solution is purplish red, and clear.
(3) get 4 bottles of C60 saturated solutions after the above-mentioned illumination, solution is 2ml in every bottle, carefully adds 24ml methyl alcohol along a bottle wall, and solution colour becomes light brown red.With above-mentioned solution ultrasonic 2min in UW; After making C60 solution and methyl alcohol thorough mixing; Be statically placed in 4 ℃ of thermostat containers, separate out golden yellow group bunch shape behind the 72h in the solution, joint length reaches millimetre-sized soccerballene sub-micro mitron, this moment the sub-micro mitron average in the ratio of external diameter be 0.369.
Embodiment 9
The method that a kind of soccerballene sub-micro mitron may command is equipped with may further comprise the steps;
(1) take by weighing 0.01g C70 (purity＞99.5%) powder in clean clear-glass bottle, the mixed solvent (blending ratio is 9: 1) of measuring 10ml pyridine and dithiocarbonic anhydride in vial with C70 powder, sealed glass jars.Above-mentioned solution is put into the UW container, with frozen water control bath temperature at 0 ℃, with the ultrasonic 20min of 75W power ultrasonic, so that C70 is fully disperseed and be dissolved in the solvent.After the ultrasonic end above-mentioned solution is taken out from water-bath, filter rapidly, get the soccerballene saturated solution, solution colour is red-purple, and clear.
(2) with the ice-water bath controlled temperature at 0 ℃, the saturated solution of C70 is used the white LED light source irradiation 50min of centre wavelength as 300-700nm.Irradiation back solution is purplish red, and clear.
(3) get 4 bottles of C70 saturated solutions after the above-mentioned illumination, solution is 2ml in every bottle, carefully adds 30ml ethanol along a bottle wall, and solution colour becomes light brown red.With above-mentioned solution ultrasonic 1min in UW; After making C70 saturated solution and ethanol thorough mixing; Be statically placed in 0 ℃ of thermostat container, separate out golden yellow group bunch shape behind the 24h in the solution, joint length reaches millimetre-sized soccerballene sub-micro mitron, this moment the sub-micro mitron average in the ratio of external diameter be 0.369.
Embodiment 10
The method that a kind of soccerballene sub-micro mitron may command is equipped with may further comprise the steps;
(1) take by weighing 0.01g C70 (purity＞99.5%) powder in clean clear-glass bottle, measure 10ml dithiocarbonic anhydride in vial with C70 powder, sealed glass jars.Above-mentioned solution is put into the UW container, with frozen water control bath temperature at 1 ℃, with the ultrasonic 20min of 75W power ultrasonic, so that C70 is fully disperseed and be dissolved in the solvent.After the ultrasonic end above-mentioned solution is taken out from water-bath, filter rapidly, get the soccerballene saturated solution, solution colour is red-purple, and clear.
(2) with the ice-water bath controlled temperature at 1 ℃, the saturated solution of C70 is used the blue-ray LED light source irradiation 5min of centre wavelength as 468nm.Irradiation back solution is purplish red, and clear.
(3) get 4 bottles of C70 saturated solutions after the above-mentioned illumination, solution is 2ml in every bottle, carefully adds the mixed solvent (blending ratio is 1: 1) of 34ml ethanol and hexane along the bottle wall, and solution colour becomes light brown red.With above-mentioned solution ultrasonic 1min in UW; After making C70 saturated solution and ethanol thorough mixing; Be statically placed in 1 ℃ of thermostat container, separate out golden yellow group bunch shape behind the 24h in the solution, joint length reaches millimetre-sized soccerballene sub-micro mitron, this moment the sub-micro mitron average in the ratio of external diameter be 0.45.
Embodiment 11
The method that a kind of soccerballene sub-micro mitron may command is equipped with may further comprise the steps;
(1) take by weighing 0.01g C60 (purity＞99.5%) powder in clean clear-glass bottle, the mixed solvent (blending ratio is 9: 1) of measuring 10ml pyridine and m-xylene in vial with C60 powder, sealed glass jars.Above-mentioned solution is put into the UW container, with frozen water control bath temperature at 5 ℃, with the ultrasonic 20min of 75W power ultrasonic, so that C60 is fully disperseed and be dissolved in the solvent.After the ultrasonic end above-mentioned solution is taken out from water-bath, filter rapidly, get the soccerballene saturated solution, solution colour is red-purple, and clear.
(2) with the ice-water bath controlled temperature at 5 ℃, the saturated solution of C60 is used the green light LED light source irradiation 5min of centre wavelength as 525nm.Irradiation back solution is purplish red, and clear.
(3) get 4 bottles of C60 saturated solutions after the above-mentioned illumination, solution is 2ml in every bottle, carefully adds the mixed solvent (blending ratio is 1: 3) of 56ml methyl alcohol and hexane along the bottle wall, and solution colour becomes light brown red.With above-mentioned solution ultrasonic 1min in UW; After making C60 saturated solution and ethanol thorough mixing; Be statically placed in 5 ℃ of thermostat containers, separate out golden yellow group bunch shape behind the 48h in the solution, joint length reaches millimetre-sized soccerballene sub-micro mitron, this moment the sub-micro mitron average in the ratio of external diameter be 0.38.
Embodiment 12
The method that a kind of soccerballene sub-micro mitron may command is equipped with may further comprise the steps;
(1) take by weighing 0.01g C60/C70 (85/15) powder in clean clear-glass bottle, the mixed solvent (blending ratio is 9: 1) of measuring 10ml benzene and dithiocarbonic anhydride in vial with C60/C70 powder, sealed glass jars.Above-mentioned solution is put into the UW container, with frozen water control bath temperature at 9 ℃, with the ultrasonic 20min of 75W power ultrasonic, so that C60/C70 is fully disperseed and be dissolved in the solvent.After the ultrasonic end above-mentioned solution is taken out from water-bath, filter rapidly, get the soccerballene saturated solution, solution colour is red-purple, and clear.
(2) with the ice-water bath controlled temperature at 9 ℃, the saturated solution of C60/C70 is used the white LED light source irradiation 5min of centre wavelength as 300-700nm.Irradiation back solution is purplish red, and clear.
(3) get 4 bottles of C60/C70 saturated solutions after the above-mentioned illumination, solution is 2ml in every bottle, carefully adds the mixed solvent (blending ratio is 1: 4) of the 100ml trimethyl carbinol and hexane along the bottle wall, and solution colour becomes light brown red.With above-mentioned solution ultrasonic 1min in UW; After making C60/C70 saturated solution and ethanol thorough mixing; Be statically placed in 9 ℃ of thermostat containers; Separate out golden yellow group bunch shape behind the 72h in the solution, joint length reaches millimetre-sized soccerballene sub-micro mitron, this moment the sub-micro mitron average in the ratio of external diameter be 0.36.
Claims (7)
1. the controllable method for preparing of a soccerballene sub-micro mitron is characterized in that: may further comprise the steps:
(1) preparation of soccerballene saturated solution takes by weighing fullerene powder and in clean clear-glass bottle, mixes with its good solvent, and in 0-10 ℃ of ultrasonic oscillation, ultrasonic oscillation filters above-mentioned solution rapidly after finishing, the soccerballene saturated solution;
(2) illumination of soccerballene saturated solution excites under 0-10 ℃, and above-mentioned soccerballene saturated solution is placed light transmission container, uses centre wavelength to be the green glow of 525nm or the wavelength white light 5-50min as 300-700nm as the blue light of 468nm or centre wavelength;
(3) leaving standstill of soccerballene sub-micro mitron separates out by volume 50: 1-6: 1 ratio joins poor solvent above-mentioned in light-struck soccerballene saturated solution; Mix; In 0-10 ℃ incubator, leave standstill 2-72h, soccerballene sub-micro mitron is separated out in crystallization.
2. the controllable method for preparing of soccerballene sub-micro mitron according to claim 1 is characterized in that: described soccerballene is C60 or C70 or C60/C70 mixture.
3. the controllable method for preparing of soccerballene sub-micro mitron according to claim 1 is characterized in that: described good solvent is pyridine or benzene or toluene or m-xylene or dithiocarbonic anhydride or its mixed solvent.
4. the controllable method for preparing of soccerballene sub-micro mitron according to claim 1 is characterized in that: described ultrasonic power is 50-100W, and ultrasonic time is 5-50min.
5. the controllable method for preparing of soccerballene sub-micro mitron according to claim 1 is characterized in that: the preferred 20-50min of the said irradiation time of step (2).
6. the controllable method for preparing of soccerballene sub-micro mitron according to claim 1 is characterized in that: described poor solvent is Virahol or ethanol or methyl alcohol or hexane or the trimethyl carbinol or its mixed solvent.
7. the controllable method for preparing of soccerballene sub-micro mitron according to claim 1 is characterized in that: the volume ratio preferred 6 of poor solvent and soccerballene saturated solution: 1-15: 1.
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