CN110902669A - Cage-shaped AgNO3Separation and purification of chelate structures C70Method (2) - Google Patents

Cage-shaped AgNO3Separation and purification of chelate structures C70Method (2) Download PDF

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CN110902669A
CN110902669A CN201911397021.0A CN201911397021A CN110902669A CN 110902669 A CN110902669 A CN 110902669A CN 201911397021 A CN201911397021 A CN 201911397021A CN 110902669 A CN110902669 A CN 110902669A
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CN110902669B (en
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聂蓓
侯颖
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South Central Minzu University
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Abstract

The invention discloses a method for utilizing cage AgNO3Separation and purification of chelate structures C70To increase C70The purity of the product. The technical scheme of the invention comprises the following steps: AgNO synthesized in situ3Selectively extracting C from fullerene mixture by complex molecular cage and liquid-liquid interface precipitation method60Mixing C with60Impurities are extracted in the solid phase crystals; then toluene solution is used to remove AgNO from the crystal3Chelated C70Washing out to ensure C in the solution70The content of (a). The invention can combine C70The purity is improved to 99 percent, a large amount of cost is saved, a complicated synthesis process is not needed, and the separation and purification of the fullerene industrial production grade are facilitated.

Description

Cage-shaped AgNO3Separation and purification of chelate structures C70Method (2)
Technical Field
The invention relates to fullerene C70In particular by means of caged AgNO3Chelate structure pair C60/C70The industrial separation and purification method of (1).
Background
Since the discovery of fullerenes by scientists in 1985, there has been a great deal of interest due to their unique spherical structure and their widespread use in material chemistry. The compressibility of a single Bakelite fullerene molecule is 700-900 GPa, while the compressibility of diamond is only 400 GPa. In the fullerene family, C70Is fullerene with the second most abundant content, and has a plurality of performances superior to those of C60. For example: electrical conductivity, optical conductivity, and optical clipping properties. To carry out C70The research and application of its derivatives, firstly, obtaining a large amount of high-purity C70。
Currently in fullerene synthesis and industrial production. In particular C70Due to structural neutralization of C in the preparation process60Extreme similarity of (D) to (C)70The synthesis purity is low, and the purification by using a common recrystallization method is difficult. Thus, the technologies mainly used at present include: chemical reaction method, recrystallization method, column chromatography, gradient temperature sublimation method, high pressure liquid chromatography, etc. In the above process, C70Low separation efficiency, low yield, low purity and high cost.
In recent years, with the advent of supramolecular chemistry, this has marked the shift of chemists from the interest in covalent bonds to the understanding of weak intermolecular interactions, and research on fullerene receptors based on non-covalent interactions has become an active area of research. To date, many hosts have been designed in which covalent bonds and supramolecular assembly receptors are designed as fullerenes, including chelate/bowl, box/ring, and cage types, among others. The geometric matching of these all-carbon molecules to the three-dimensional cavity is enhanced, allowing the separation of specific fullerene molecules from homologues. To achieve this goal, Shinokub et al published article "Self-Assembled carbon-like Cage with a thermally amplified binding preference for Purification of High-Purity C60and C70[J]Chemistry j.org.chem.2018; 83,14667-75' design sensitive molecular tweezers to form a sandwich structure, and by adjusting the angle and distance between the included angles of the two tweezers, have the opportunity to selectively capture fullerenes (C) of appropriate size60) And (4) units. Stoddart and coworkers are in the paper "Quantitative Evaluation of Fullere Separation by LiquidC regression [ J]J.Phys.chem.C.2019, 123, 16747-56 "discloses a tetragonal prismatic porphyrin cage structure, which utilizes an electron donor-acceptor interaction mechanism to selectively extract C70. Jiang and his colleagues in the paper "Selective Extraction of C70by a Tetragonal prism Porphyrin Cage [ J]Self-assembled molecular cages that can selectively bind C by adjusting temperature are reported in j.am.chem.soc.2018, 140, 13835-4260And C70So that the purification of the specific fullerene is not required in the case of crystallization. However, these procedures involve complex molecular design and labor intensive synthesis and purification procedures, and also require high costs, which can prevent further large-scale industrial applications, even routine laboratory practice.
Disclosure of Invention
The technical idea of the invention is to prepare the pair C60Has very strong selectivity to C70Cationic molecular cages without apparent selectivity, using AgNO synthesized in situ3Selective extraction of chelate structures C60This results in selective extraction of C from the fullerene mixture60And the remainder of the solution is C70. Then extracted AgNO3-C60Adding toluene into the composite crystal for cleaning, and allowing C which does not enter a molecular cage70All re-dissolved in toluene to increase C70Purity and separation rate of (2). The method solves the problems of complicated molecular cage design and synthesis preparation and high implementation process cost in the prior art, and realizes industrial C70And (5) separating, purifying and purifying.
The invention adopts the technical scheme that C is used60In situ synthesis of AgNO for a template3Separation and purification of molecular chelate structure C70The method comprises the following steps:
step 1 liquid-liquid interface precipitation method, AgNO3Equal volume diffusion of saturated solution in isopropanol or n-butanol to C60/C70Dissolving fullerene powder in nonpolar solvent, and keeping at room temperatureAging to separate out black precipitate;
step 2, transferring the mixed solution obtained after aging in the step 1 into a centrifugal tube for centrifugal separation to obtain supernatant and black sediment, wherein the black sediment is AgNO3-C60A composite crystal;
step 3, washing the black sediment by using a nonpolar solvent to obtain a nonpolar solvent suspension;
step 4, transferring the nonpolar solvent suspension obtained in the step 3 into a centrifugal tube for centrifugation, and then taking supernatant;
step 5, merging the supernatants obtained in the step 2 and the step 4, putting the merged supernatants into an oven for evaporation, and separating out C70Black crystals.
Further, step 1 is C60/C70The fullerene powder solution in the nonpolar solvent is prepared by dissolving C in water60/C70Adding non-polar solvent into fullerene powder, and ultrasonically treating with ultrasonic instrument to obtain C60/C70Dissolving fullerene powder in nonpolar solvent, filtering to remove insoluble substances, standing overnight to obtain C60/C70A solution of fullerene powder in a non-polar solvent.
Preferably, the nonpolar solvent is any one of toluene and benzene.
Further, AgNO in the step 13The saturated solution in isopropanol or n-butanol is prepared by mixing the following components in a mass/volume ratio of 1 g: 10ml of AgNO3Mixing with polar solvent, and ultrasonically treating AgNO with ultrasonic instrument3Dissolving in polar solvent, shaking on shaking table, filtering to remove insoluble substance to obtain AgNO3Saturated solution in polar solvent.
Preferably, the time for aging to separate out black sediment in the step 1 is not less than 9h/ml multiplied by v, wherein v is C60/C70Volume of the solution of fullerene powder in the non-polar solvent, said volume unit being ml.
Further, in step 2, the centrifugal speed is 7000 rpm, and the centrifugal time is 5 minutes.
Further, in the step 4, the centrifugal speed is 7000 rpm, and the centrifugal time is 5 minutes.
The invention has the advantages that: c60Fullerene and C70The fullerene has similar structure and is difficult to separate, and the invention adopts AgNO3In the presence of C60/C70Preparing molecular cage in mixed powder non-polar solvent, the molecular cage only captures C60/C70C in solution in a nonpolar solvent60And the molecular cage does not capture C70Has good selectivity and high purity to separate C60And C70(ii) a C trapped by molecular cage60Form an AgNO3-C60Composite crystals which are very stable and can be stored in nonpolar solvents without C being trapped by molecular cages70Is very easy to dissolve in non-polar solvent, so that C in the solution70Increased content of C60The content is reduced. So that the technical scheme of the invention is changed from C60/C7099% C in solution in a nonpolar solvent70Dissolving C in a nonpolar solvent after precipitation by liquid-liquid interface60Occupy only C60/C70Solution C of nonpolar solvent601% of the total content. Over the years, isopropanol and n-butanol solutions with only silver nitrate were found to diffuse into the presence of C60/C70Trapping only C in nonpolar solvents of mixed powders60The molecular cage of (1).
Compared with other separation methods, the method saves a large amount of cost, solves the problems of complicated molecular cage design and synthesis preparation and high implementation process cost, and realizes industrial C70Separating and purifying to obtain C70The purity is improved to 99%.
Drawings
FIG. 1 is a MALDI-MS mass spectrum of the black crystal in example 1;
FIG. 2 is a MALDI-MS mass spectrum of the supernatant of example 1;
FIG. 3 is a MALDI-MS mass spectrum of the mixed fullerene powder of example 1;
FIG. 4 shows the results obtained in example 2C dissolved in toluene60/C70MALDI-MS mass spectrum of the solution;
FIG. 5 is a MALDI-MS mass spectrum of the mixed fullerene powder in example 3;
FIG. 6 is a MALDI-MS mass spectrum of the supernatant of example 3;
FIG. 7 is a MALDI-MS mass spectrum of the black crystals of example 3;
FIG. 8 is a MALDI-MS mass spectrum of the mixed fullerene powder in example 4;
FIG. 9 is a MALDI-MS mass spectrum of the supernatant of example 4;
FIG. 10 is a MALDI-MS mass spectrum of the black crystals of example 4;
FIG. 11 is the optimum time UV absorption spectrum of the composite crystal completely precipitated in the example;
FIG. 12 cage AgNO3Separation and extraction of C from chelate structure70A schematic diagram;
FIG. 13 shows the black precipitate AgNO of example 63-C60SEM scanning electron microscopy of (a);
FIG. 14 shows sediment C in example 670SEM scanning electron microscopy of (a);
FIG. 15 shows a drawing showing a drawing in C of example 660-uv absorption profile of silver nitrate isopropanol system;
FIG. 16 shows a case C in example 670UV absorption profile of silver nitrate isopropanol system.
Detailed Description
Purification of C in a bench experiment70For example, the following examples are carried out on the premise of the technical scheme of the invention, and detailed embodiments and specific operation procedures are given, but the protection scope of the invention is not limited to the following examples.
Example 1: cage-shaped AgNO3Separation and purification of chelate structures C70The method comprises the following steps:
c to be purchased60、C70Mixing pure fullerene samples according to the mass ratio of 1:1, and taking the mixed fullerene samples30mg, adding 10ml of nonpolar solvent toluene to dissolve the sample, performing ultrasonic treatment for 2h by using an ultrasonic instrument to dissolve the sample, filtering to remove insoluble substances, and standing overnight to obtain C60/C70A saturated solution of toluene was used as a separation raw material. The detection result of the MALDI-MS mass spectrum of the mixed fullerene sample is shown in figure 3.
Weighing 0.1g AgNO3Then adding 10ml of isopropanol solution, and dissolving AgNO after ultrasonic treatment for 30min by an ultrasonic instrument3Filtering to remove insoluble substances, and oscillating on a shaking table for 2h to obtain AgNO3(isopropanol) saturated solution.
Taking 1ml of AgNO3(IPA) saturated solution was equivalently diffused to 1ml C by liquid-liquid interfacial precipitation60/C70Standing in saturated toluene solution for 12 hr to obtain obvious precipitate, brown supernatant, and detecting the supernatant as shown in FIG. 2 to obtain 8mg black precipitate3-C60The complex crystal, i.e. nitrate anion bridged fullerene complexed silver cation, forms a complex three-dimensional network structure which can convert C into C60The encapsulation is shown therein in fig. 12. The mixed solution was put into a centrifuge tube, centrifuged at 7000 rpm for 5 minutes, and the supernatant was taken out. Washing black precipitate with toluene for 3 times, and adding C which does not enter into molecular cage70And (4) dissolving. The mass of the washed black sediment was 6.7mg, and the washing solution was put into a centrifuge tube, centrifuged at 7000 rpm for 5 minutes, and the supernatant was taken out. Finally, the supernatants taken out were combined and placed in an oven, and the solution was evaporated to dryness at 60 ℃ in which case 10ml of AgNO was added3(IPA) saturated solution was equivalently diffused to 10ml C by liquid-liquid interfacial precipitation60/C70Washing in saturated toluene solution, mixing the supernatants, oven drying, and separating out 10mg black crystal at the bottom of the bottle, C70The recovery rate reaches 71 percent (C)70The saturated concentration of the solution in toluene was 1.4 mg/ml).
And (3) detecting the purity of the supernatant: detecting with matrix-assisted laser desorption time-of-flight mass spectrometer (MALDI-MS), and collecting supernatant C70Purity of 98%, detection of ionizing excitation wavelength 355nm, no matrix, room temperature, and detection result shown in FIG. 2C70And C60Determining the components in the product by the mass-to-charge ratio of C, and calibrating C by an external standard method70The purity of (2) was 98%.
And (3) detecting the purity of the black crystals: detecting by matrix-assisted laser desorption time-of-flight mass spectrometer (MALDI-MS) to obtain separated fullerene C70Purity of 98.5%, detection of ionization excitation wavelength of 355nm, no matrix, room temperature, and detection result shown in FIG. 1, from C70And C60Determining the components in the product by the mass-to-charge ratio of C, and calibrating C by an external standard method70The purity of (2) was 98.5%.
And (3) data analysis: the relative quantification of the black crystals and the constituents of the supernatant was performed using a mixed fullerene sample as external standard, and FIG. 3 shows the mass spectrum of the mixed fullerene sample, which was measured by C60-C70The mixture of (2) is precipitated in a ratio of 5: 5. M/Z721 and 841 in FIG. 3 are [ C ]60+H]+And [ C70+H]+Peak, C60The integrated peak area of (A) is 555.868, C70The integrated peak area of (a) is 1228.857, according to the formula: peak area ratio (C) of theoretical mixed sample70/C60) Is (true C)70Peak area of/actual C60Peak area of 0.9948, ionization coefficient of 0.45, referred to as "d.mems, d.hercules.quantification of biological acids direct from urine by MALDI-TOF-ms.analytical and biological chemistry.2003; 375(5):609-16 ″," p.scheier, b.d ü nser, R.
Figure BDA0002346579880000071
S.Matt,D.Muigg,G.Senn,et al.Electron impact ionization ofC60and C70:production and properties of parent and fragment ions studied witha two-sector field mass spectrometer.Int.Rev.Phys.Chem.1996；15(1):93-131.”。
C in FIG. 260Has an integrated area of 3.56, C70332.48 according to the formula: peak area ratio of fullerene in supernatant (C)60/C70) Is (true C)70Peak area of/actual C60Peak area) ionization coefficient to obtain supernatantThe ratio of the peak area of fullerene in the liquid was 42.03, and C was calculated70The purity of (2) was 98%.
C in FIG. 160Has an integrated area of 5.319, C70764.415 according to the formula: peak area ratio of actual separated sample (C)60/C70) Is (true C)70Peak area of/actual C60Peak area) of the sample to be actually separated (black crystals), the peak area ratio was found to be 64.66, and C was calculated70The purity of (A) was 98.5%, and the recovery rate was 71%.
Example 2:
c to be purchased60、C70Mixing pure sample fullerene according to the mass ratio of 1:1, taking 30mg of the mixed fullerene sample, adding 10ml of nonpolar solvent toluene to dissolve the sample, ultrasonically treating the sample for 2 hours by an ultrasonic instrument, filtering to remove insoluble substances, and standing overnight to obtain C60/C70A saturated solution of toluene was used as a separation raw material. The detection result of the MALDI-MS mass spectrum of the mixed fullerene sample is shown in figure 3.
Weighing 0.1g AgNO3Then adding 10ml of isobutanol solution, and dissolving AgNO after ultrasonic treatment for 30min by an ultrasonic instrument3Filtering to remove insoluble substances, and oscillating on a shaking table for 2h to obtain AgNO3(isobutanol) saturated solution.
Taking 1ml of AgNO3(Isobutanol) saturated solution was equivalently diffused to 1ml C by liquid-liquid interfacial precipitation60/C70Standing in saturated toluene solution for 12 hr to obtain obvious precipitate, taking out supernatant, dissolving the precipitate with 1ml toluene, changing the solution from colorless to reddish brown, and collecting supernatant60/C70Is redissolved in toluene.
C dissolved in p-toluene60/C70And (3) detection: detecting with matrix-assisted laser desorption time-of-flight mass spectrometer (MALDI-MS), and collecting supernatant C70Purity of 48%, detection of ionizing excitation wavelength of 355nm, no matrix, room temperature, and detection result shown in FIG. 4, represented by C70And C60Determining the components in the product by the mass-to-charge ratio of C, and calibrating C by an external standard method70The purity of (2) was 48%.
And (3) data analysis: the relative quantification of the black crystals and the constituents of the supernatant was performed using a mixed fullerene sample as external standard, and FIG. 3 shows the mass spectrum of the mixed fullerene sample, which was measured by C60-C70The mixture of (2) is precipitated in a ratio of 5: 5. M/Z721 and 841 in FIG. 3 are [ C ]60+H]+And [ C70+H]+Peak, C60The integrated peak area of (A) is 555.868, C70The integrated peak area of (a) is 1228.857, according to the formula: peak area ratio (C) of theoretical mixed sample70/C60) Is (true C)70Peak area of/actual C60Peak area) the ionization coefficient was 0.9948, the ionization coefficient was 0.45.
C in FIG. 460Has an integrated area of 1371.926, C702856.281 according to the formula: peak area ratio of fullerene in supernatant (C)60/C70) Is (true C)70Peak area of/actual C60Peak area) of the fullerene, the peak area ratio of the fullerene in the supernatant was found to be 0.937, and C was calculated70The purity of (A) is 48%, it can be known that AgNO3(Isobutanol) system does not completely capture C60So as to subject it to C70And (4) purifying.
Example 3:
c to be purchased60、C70Mixing pure sample fullerene according to the mass ratio of 3:7, taking 30mg of the mixed fullerene sample, adding 10ml of nonpolar solvent toluene to dissolve the sample, ultrasonically treating the sample for 2 hours by an ultrasonic instrument, filtering to remove insoluble substances, and standing overnight to obtain C60/C70A saturated solution of toluene was used as a separation raw material. The detection result of MALDI-MS mass spectrum of the mixed fullerene sample is shown in FIG. 5.
Weighing 0.1g AgNO3Then adding 10ml of isopropanol solution, carrying out ultrasonic treatment for 30min by an ultrasonic instrument, filtering to remove insoluble substances, and oscillating on a shaking table for 2h to obtain AgNO3(isopropanol) saturated solution.
Taking 1ml of AgNO3The (IPA) saturated solution is equivalently diffused into 1ml of sample separation raw material solution by a liquid-liquid interface precipitation method, and obvious phenomenon appears after standing for 12hThe precipitate, the supernatant was brown to give 5mg of a black precipitate which was AgNO3-C60And (4) compounding crystals. The mixed solution was put into a centrifuge tube, centrifuged at 7000 rpm for 5 minutes, and the supernatant was taken out. Washing black precipitate with toluene for 3 times, and adding C which does not enter into molecular cage70And (4) dissolving. The mass of the washed black sediment was 4.1mg, and the washing solution was put into a centrifuge tube, centrifuged at 7000 rpm for 5 minutes, and the supernatant was taken out. And finally, merging the taken supernatants, putting the merged supernatants into an oven, and evaporating the solution at 60 ℃ until black crystals are separated out at the bottom of the bottle.
And (3) detecting the purity of the supernatant: detecting with matrix-assisted laser desorption time-of-flight mass spectrometer (MALDI-MS), and collecting supernatant C70Purity of 98%, detection of ionizing excitation wavelength of 355nm, no matrix, room temperature, and detection result shown in FIG. 6, represented by formula C70And C60Determining the components in the product by the mass-to-charge ratio of C, and calibrating C by an external standard method70The purity of (2) was 98%.
Detection of black crystal purity x: detecting by matrix-assisted laser desorption time-of-flight mass spectrometer (MALDI-MS), and separating to obtain fullerene C70Purity of 99.2%, detection of ionizing excitation wavelength of 355nm, no matrix, room temperature, and detection results shown in FIG. 7, from C70And C60Determining the components in the product by the mass-to-charge ratio of C, and calibrating C by an external standard method70The purity of (2) was 99.2%.
And (3) data analysis: the relative quantification of the components in the black crystals was performed using the mixed fullerene sample as an external standard, and FIG. 5 shows the mass spectrum of the mixed fullerene sample consisting of C60-C70The mixture of (2) is precipitated in a ratio of 3: 7. M/Z721 and 841 in FIG. 5 are [ C ]60+H]+And [ C70+H]+Peak, C60The integrated peak area of (A) is 392.821, C70The integrated peak area of (a) is 1349.278, according to the formula: peak area ratio (C) of theoretical mixed sample70/C60) Is (true C)70Peak area of/actual C60Peak area) ionization coefficient was 2.3, ionization coefficient was 0.68.
C in FIG. 660Has an integrated area of 11.012, C70684.514 according to the formula: peak area ratio of fullerene in supernatant (C)60/C70) Is (true C)70Peak area of/actual C60Peak area) of the fullerene, the peak area ratio of the fullerene in the supernatant was found to be 42.21, and C was calculated70The purity of (2) was 98%.
C in FIG. 760Has an integrated area of 4.967, C70980.668 according to the formula: peak area ratio (C) of actually separated sample (black crystal)60/C70) Is (true C)70Peak area of/actual C60Peak area) of the sample to be actually separated, the peak area ratio of the sample to be actually separated was obtained as 134.06, and C was calculated70The purity of (2) was 99.2%.
Example 4:
c to be purchased60、C70Mixing pure sample fullerene according to the mass ratio of 1:9, taking 30mg of the mixed fullerene sample, adding 10ml of nonpolar solvent toluene to dissolve the sample, ultrasonically treating the sample for 2 hours by an ultrasonic instrument, filtering to remove insoluble substances, and standing overnight to obtain C60/C70A saturated solution of toluene was used as a separation raw material. The detection result of MALDI-MS mass spectrum of the mixed fullerene sample is shown in FIG. 8.
Weighing 0.1g AgNO3Then adding 10ml of isopropanol solution, carrying out ultrasonic treatment for 30min by an ultrasonic instrument, filtering to remove insoluble substances, and oscillating on a shaking table for 2h to obtain AgNO3(isopropanol) saturated solution.
Taking 1ml of AgNO3Equivalently diffusing the (IPA) saturated solution into 1ml of sample separation raw material solution by a liquid-liquid interface precipitation method, standing for 12h to obtain obvious precipitate, and brown supernatant to obtain 3mg of black precipitate3-C60And (4) compounding crystals. The mixed solution was put into a centrifuge tube, centrifuged at 7000 rpm for 5 minutes, and the supernatant was taken out. Washing black precipitate with toluene for 3 times, and adding C which does not enter into molecular cage70And (4) dissolving. The mass of the washed sediment is 2mg, and the washing liquid is put into a centrifugal tubeThe mixture was centrifuged at 7000 rpm for 5 minutes, and the supernatant was taken out. And finally, merging the taken supernatants, putting the merged supernatants into an oven, and evaporating the solution at 60 ℃ until black crystals are separated out at the bottom of the bottle.
And (3) detecting the purity of the supernatant: detecting with matrix-assisted laser desorption time-of-flight mass spectrometer (MALDI-MS), and collecting supernatant C70Purity of 98%, detection of ionizing excitation wavelength of 355nm, no matrix, room temperature, and detection result shown in FIG. 9, represented by formula C70And C60Determining the components in the product by the mass-to-charge ratio of C, and calibrating C by an external standard method70The purity of (2) was 98%.
And (3) detecting the purity of the black crystals: detecting by matrix-assisted laser desorption time-of-flight mass spectrometer (MALDI-MS), and separating to obtain fullerene C70Purity of 99.4%, detection of ionization excitation wavelength of 355nm, no matrix, room temperature, and detection result shown in FIG. 10, from C70And C60Determining the components in the product by the mass-to-charge ratio of C, and calibrating C by an external standard method70The purity of (2) was 99.4%.
And (3) data analysis: the relative quantification of the components in the black crystals was performed using the mixed fullerene sample as an external standard, and FIG. 8 shows the mass spectrum of the mixed fullerene sample, which is represented by C60-C70The mixture of (2) is precipitated in a ratio of 1: 9. M/Z721 and 841 in FIG. 8 are [ C ]60+H]+And [ C70+H]+Peak, C60The integrated peak area of (A) is 1059.914, C70The integrated peak area of (a) is 15982.235, according to the formula: peak area ratio (C) of theoretical mixed sample70/C60) Is (true C)70Peak area of/actual C60Peak area) the ionization coefficient was 9, the ionization coefficient was 0.60.
C in FIG. 960Has an integrated area of 43.17, C702849.995 according to the formula: peak area ratio of fullerene in supernatant (C)60/C70) Is (true C)70Peak area of/actual C60Peak area) of fullerene in the supernatant was found to be 39.41, and C was calculated70The purity of (2) was 98%.
C in FIG. 1060Has an integrated area of 17.086, C705124.016 according to the formula: peak area ratio (C) of actually separated sample (black crystal)60/C70) Is (true C)70Peak area of/actual C60Peak area) of the sample to be actually separated, the peak area ratio of the sample to be actually separated was obtained as 179.04, and C was calculated70The purity of (2) was 99.4%.
Example 5
At room temperature, taking C60Preparation of 5 carbon atoms from Fullerene powder and toluene60Toluene saturation of the solution sample, AgNO3(IPA) saturated solution (500ul) was equally diffused C by liquid-liquid interfacial precipitation60In a toluene saturated solution (500ul), the supernatant (toluene) was taken out every 2 hours to measure the ultraviolet absorption, C60The ultraviolet absorption peak of (2) is at 400-650nm, and it can be seen from FIG. 11 that the intensity gradually decreases with the increase of time, and C is at 12h60Has an ultraviolet absorption of approximately 0, at 500ulC60In saturated toluene solution, C60The optimal time for the composite crystal to settle is 12 h. By reaction of C in a nonpolar solvent60All trapped in molecular cages in polar solvents.
Example 6
Get purchased C separately60、C70Respectively dissolving pure sample fullerene 15mg in nonpolar solvent toluene 10ml to obtain two samples, dissolving the samples with ultrasonic for 2h, filtering to remove insoluble substances, standing overnight to obtain C60Toluene solution and C70Toluene solution.
Taking 10ml of AgNO3(IPA) saturated solution was equivalently diffused to 10ml C by liquid-liquid interfacial precipitation60Standing in toluene solution for 12 hr to obtain obvious precipitate, and colorless supernatant to obtain 14mg black precipitate3-C60Composite crystal, fig. 13. The mixed solution was put into a centrifuge tube, centrifuged at 7000 rpm for 5 minutes, and the supernatant was taken out. Cleaning the black precipitate with toluene for 3 times, the mass of the black precipitate after cleaning is 14mg, placing the cleaning solution into a centrifuge tube, and centrifuging at 7000 r/min for 5 timesAfter a while, the supernatant was removed and the supernatant was colorless.
Taking 10ml of AgNO3(IPA) saturated solution was equivalently diffused to 10ml C by liquid-liquid interfacial precipitation70Standing in toluene solution for 12 hr to obtain precipitate, and light brown supernatant to obtain 5mg precipitate containing mainly C70Nanorods, as in FIG. 14. The mixed solution was put into a centrifuge tube, centrifuged at 7000 rpm for 5 minutes, and the supernatant was taken out. The sediment was washed with toluene 3 times, and after washing, there was no sediment and the solution was tan.
To C60-silver nitrate isopropanol system: diluting the following solutions with toluene 2 times, detecting with ultraviolet-visible spectrophotometer, and determining from ultraviolet absorption spectrum 15, C60The toluene solution has a main absorption peak at 538nm and C at 538nm60The absorption value of the original solution was 0.972, C after toluene dissolution60Solution (toluene washed sediment C)60Solution) and C60The supernatant after sedimentation had almost no absorption, and was found in C60The molar absorption coefficient (538nm) in toluene was 918L cm-1·mol-1Luoqiping, etc., using ultraviolet-visible absorption spectroscopy to simultaneously quantitatively analyze C60And C70[J]Journal of Beijing university (Nature science edition), 1995,31(4), 432-: obtaining C by changing A to epsilon bc60The concentration of the original solution was 1.06X 10-3mol·L-1Can yield C60Almost all is captured in the molecular cage.
To C70-silver nitrate isopropanol system: diluting the following solutions with toluene 15 times, detecting with ultraviolet-visible spectrophotometer, and determining from ultraviolet absorption spectrum 16, C70The main absorption peak of the toluene solution is 472nm, and C is 472nm70Absorption value of the original solution was 2.13, C after toluene dissolution70Solution (toluene washed sediment C)70Solution) absorption value of 2.0, C70The supernatant after sedimentation had an absorbance of 0.126, found in C70The molar absorption coefficient (472nm) in toluene was 17400L cm-1·mol-1From lambert-beer law: obtaining C by changing A to epsilon bc70The concentration of the original solution was 1.22X 10- 4mol·L-1C after toluene dissolution70Solution (toluene washed sediment C)70Solution) concentration of 1.15X 10-4mol·L-1，C70The supernatant concentration after sedimentation was 0.72X 10-5mol·L-1Can yield C70Cannot be trapped in the molecular cage.
Compared with other separation methods, the method saves a large amount of cost, does not need complicated synthesis process, is favorable for industrialized separation and purification, and can separate C70The purity is improved to 99%.
The invention mainly uses silver nitrate (isopropanol) saturated solution to equivalently diffuse to C under a liquid-liquid interface60/C70Forming molecular cage in toluene solution to capture C therein60C trapped by molecular cages60Form an AgNO3-C60Composite crystals which are very stable and can be stored in toluene without C being trapped by the molecular cages70Is very easy to dissolve in toluene, so that C in the solution is obtained70Increased content of C60The content is reduced.
The separation effect achieved by the invention is that C in the final separation product70And C60Is 99%, 1%, respectively, and wherein the reduced sample is C60。

Claims (7)

1. Cage-shaped AgNO3Separation and purification of chelate structures C70The method is characterized by comprising the following steps:
step 1 liquid-liquid interface precipitation method, AgNO3Equal volume diffusion of saturated solution in isopropanol or n-butanol to C60/C70Aging the fullerene powder in a solution of a nonpolar solvent at room temperature to separate out a black precipitate;
step 2, transferring the mixed solution aged in the step 1 into a centrifugal tube for centrifugal separation to obtain supernatant and black sediment, wherein the black sediment is AgNO3-C60A composite crystal;
step 3, washing the black sediment by using a nonpolar solvent to obtain a nonpolar solvent suspension;
step 4, transferring the nonpolar solvent suspension obtained in the step 3 into a centrifugal tube for centrifugation, and then taking supernatant;
step 5, merging the supernatants obtained in the step 2 and the step 4, putting the merged supernatants into an oven for evaporation, and separating out C70Black crystals.
2. Isolation and purification C according to claim 170Is characterized in that step 1 is C60/C70The solution of the nonpolar solvent is prepared by mixing C60/C70Adding fullerene powder into nonpolar solvent, and ultrasonically treating with ultrasonic instrument to obtain C60/C70Dissolving fullerene powder in nonpolar solvent, filtering to remove insoluble substances, standing overnight to obtain C60/C70Saturated solutions of non-polar solvents.
3. The separation and purification method according to any one of claims 1 to 270The method of (1), wherein the nonpolar solvent is any one of toluene and benzene.
4. Isolation and purification C according to claim 170The method of (1), wherein AgNO is used in the step of (1)3The saturated solution in isopropanol or n-butanol is prepared by mixing the following components in a mass/volume ratio of 1 g: 10ml of AgNO3Mixing with isopropanol or n-butanol, and ultrasonically treating AgNO with ultrasonic instrument3Self-assembly reaction in isopropanol or n-butanol, shaking on a shaking table, filtering to remove insoluble substances to obtain AgNO3Saturated solutions in isopropanol or n-butanol.
5. Isolation and purification C according to claim 170Is characterized in that the time for aging to separate out black sediment in the step 1 is not less than 9h/ml x v, v is C60/C70Volume of solution of non-polar solvent, saidThe volume unit is ml.
6. Isolation and purification C according to claim 170The method of (3), wherein in step 2, the centrifugation speed is 7000 rpm and the centrifugation time is 5 minutes.
7. Isolation and purification C according to claim 170The method of (4), wherein in the step (4), the centrifugal rotation speed is 7000 rpm, and the centrifugal time is 5 minutes.
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