CN116218514A - Fullerene derivative and nano CdS hybrid material and preparation method thereof - Google Patents

Fullerene derivative and nano CdS hybrid material and preparation method thereof Download PDF

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CN116218514A
CN116218514A CN202310268336.5A CN202310268336A CN116218514A CN 116218514 A CN116218514 A CN 116218514A CN 202310268336 A CN202310268336 A CN 202310268336A CN 116218514 A CN116218514 A CN 116218514A
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黄飞
徐东平
王澍
时雯雯
汪婧
黄珊
黄昱
崔芳磊
赵树东
徐汉卿
魏先文
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Abstract

A fullerene derivative and nano CdS hybrid material is prepared through mixing C 60 Covalent interactions between the thiol groups of the thiol derivatives and the CdS nanoparticles result. The preparation method comprises the following steps: sequentially preparing 2-phenyl-5-mercaptomethyl-3, 4-fullerene Pyrrolidine (PTMF); preparing CdS sol; and finally, hybridization of PTMF and CdS nano sol. In the fullerene derivative and nano CdS hybrid material, PTMF and CdS nano particles have no interaction in a ground state;with the addition of PTMF, the fluorescence of CdS is quenched, which occurs the charge transfer process from CdS nanoparticles to PTMF; PTMF has strong quenching ability to CdS nanometer particle fluorescence.

Description

Fullerene derivative and nano CdS hybrid material and preparation method thereof
Technical Field
The invention provides a fullerene derivative and nano CdS hybrid material and a preparation method thereof.
Background
C 60 The cage-shaped molecule has a highly symmetrical three-dimensional structure and unique optical, electric and magnetic properties, can be used as a good electron acceptor and a building module to be connected with a multifunctional molecule through covalent or non-covalent action to form C with good performance 60 The basic functional composite material can be applied to the fields of optical modulation, optical switches, photoelectric conversion and the like. C (C) 60 As natural nano-sized molecules, the nano-sized molecules have unique properties, particularly highly symmetrical three-dimensional structures, and C is introduced into functional nano-structured materials 60 The molecule may make the structural order more perfect, and simultaneously make the physical and chemical properties and performance of the molecule greatly improved. In recent years, a variety of C's have been available based on covalent attachment 60 Nanoparticle hybrids. Currently, C is utilized 60 Thiol derivatives, linking C based on covalent interactions 60 Molecular introduction of functional nanostructured materials has resulted in a variety of C' s 60 -a rice grain hybrid. In such hybridization processes based on covalently linked materials, C 60 The mercapto group in the mercapto derivative plays a vital role, and can be hybridized with Au, hg, sulfide and other inorganic nano particles. The II-VI semiconductor nanocluster has excellent optical performance due to quantum size effect, has important application value in the aspect of optoelectronic devices, and is one of the most potential luminescent and monitoring gas materials in the 21 st century, wherein the preparation and application of the CdS nanocluster are always research hot spots in the field of nano semiconductors, and composite materials formed by CdS and other substances are also becoming more important. C (C) 60 The light-emitting diode has unique properties in the aspects of light, electricity, magnetism and the like, so that the light-emitting diode is always an emerging field with active application. But up to now, C 60 Hybridization of derivatives with CdS nanoparticles has not been reported.
The invention synthesizes a C 60 Thiol derivatives realizing C by covalent interaction between thiol and CdS nanoparticles 60 Efficient hybridization with CdS nanoparticles.
Disclosure of Invention
According to the invention, 2-phenyl-5-mercaptomethyl-3, 4-fullerene Pyrrolidine (PTMF) is synthesized, and a hybrid of PTMF and CdS nano particles is formed based on covalent action by utilizing mercapto carried by molecules of the PTMF, so that respective advantages are exerted, and a novel functional material is formed.
A fullerene derivative and nano CdS hybrid material is prepared through mixing C 60 Covalent interactions between the thiol groups of the thiol derivatives and the CdS nanoparticles result.
The fullerene derivative and nano CdS hybrid material has C 60 The sulfhydryl derivative is 2-phenyl-5-sulfhydryl methyl-3, 4-fullerene Pyrrolidine (PTMF) synthesized by 1, 3-dipolar cycloaddition reaction.
The preparation method of the fullerene derivative and nano CdS hybrid material sequentially comprises the steps of preparing 2-phenyl-5-mercaptomethyl-3, 4-fullerene Pyrrolidine (PTMF); preparing CdS sol; and finally, hybridization of PTMF and CdS nano sol.
The preparation method of the fullerene derivative and the nano CdS hybrid material comprises the steps of 2-phenyl-5-mercaptomethyl-3, 4-fullereneThe PTMF is prepared from C 60 L-cysteine and benzaldehyde are prepared. Wherein C is 60 The purity is preferably 99%.
The preparation method of the fullerene derivative and nano CdS hybrid material comprises the following steps of: under the protection of inert gas, C is as follows 60 Fully dissolving, adding benzaldehyde and L-cysteine, heating and refluxing to obtain a reddish brown solution, cooling to room temperature, concentrating the solution, and performing column chromatography to obtain a target product; after concentration and washing, the obtained dark brown powder is 2-phenyl-5-mercaptomethyl-3, 4-fullerene Pyrrolidine (PTMF).
More specifically, the preparation method of the 2-phenyl-5-mercaptomethyl-3, 4-fullerene Pyrrolidine (PTMF) comprises the following steps: under the protection of inert gas, 0.05-0.2mol C 60 Fully dissolving in 50-100mL of freshly distilled toluene solution, stirring for 1-5h to fully dissolve to obtain a purple solution, adding 0.1-1.0mol of benzaldehyde and 0.1-0.8mol of L-cysteine, heating and refluxing for 2-6h at 80-150 ℃ to obtain a reddish brown solution, cooling to room temperature, concentrating the solution, and performing column chromatography to obtain a target product; after concentration and washing, the obtained dark brown powder is 2-phenyl-5-mercaptomethyl-3, 4-fullerene Pyrrolidine (PTMF).
The preparation method of the fullerene derivative and nano CdS hybrid material comprises the step of preparing CdS sol by adopting a microemulsion method.
Further, the specific preparation method of the CdS sol comprises the following steps: preparation of CdCl 2 Solution and Na 2 S, solution; weighing sodium bis (2-ethylhexyl) succinate (AOT), dissolving to obtain a colorless transparent solution, dripping ultrapure water into the solution, and stirring to obtain a reverse micelle; taking part of reverse micelle, and adding CdCl under the condition of intense stirring 2 Continuously stirring the solution to obtain a solution A; the rest reverse micelle is added with Na under the condition of intense stirring 2 S, continuously stirring the solution to obtain a solution B; the solution B is added into the solution A dropwise under stirring, and the yellowish green sol is obtained under stirring.
More specifically, cdS sol preparation methodThe method comprises the following steps: preparing 0.5-1.5mol/L CdCl 2 Solution and 0.5-1.5mol/L Na 2 S, solution; weighing 5-10g of sodium bis (2-ethylhexyl) succinate sulfonate (AOT), dissolving in 100-200mL of n-heptane to obtain a colorless transparent solution, dripping 1-10mL of ultrapure water into the solution, and stirring for 0.5-3h to obtain reverse micelle; taking 30-80mL reverse micelle, adding 0.1-0.5mL of 0.5-1.5mol/L CdCl under the condition of intense stirring 2 Continuously stirring the solution for 0.5-3h to obtain solution A; the rest 20-60mL reverse micelle is added with 0.1-0.5mL of 0.5-1.5mol/L Na under the condition of intense stirring 2 Continuously stirring the solution S for 0.5-3h to obtain a solution B; under stirring, the solution B is added into the solution A dropwise, and the mixture is stirred for 0.5 to 3 hours to obtain yellowish green sol.
The preparation method of the fullerene derivative and nano CdS hybrid material comprises the following steps of: dropwise adding a toluene solution of PTMF with a certain concentration into the prepared CdS sol under the magnetic stirring condition, and stirring to form a hybrid of the PTMF and the CdS sol.
More specifically, the hybridization method of PTMF and CdS nanosol comprises the following steps: dropwise adding (0.5-10.0) x 10 into the prepared CdS sol under magnetic stirring -4 5-20mL of a toluene solution of PTMF at mol/L, and stirring to form a hybrid of PTMF and CdS sol.
It can be seen that hybrids of PTMF and CdS nanoparticles were successfully prepared based on covalent interactions between PTMF and CdS nanoparticles using the active group thiol group carried by 2-phenyl-5-mercaptomethyl-3, 4-fullerene Pyrrolidine (PTMF).
The invention has the beneficial effects that:
in the fullerene derivative and nano CdS hybrid material, PTMF and CdS nano particles have no interaction in the ground state; with the addition of PTMF, the fluorescence of CdS is quenched, which occurs the charge transfer process from CdS nanoparticles to PTMF; the data show that PTMF has strong quenching capacity on fluorescence of CdS nano particles.
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In order that the invention may be more readily understood, a more particular description of the invention will be rendered by reference to specific embodiments thereof which are illustrated in the appended drawings, in which,
regarding example 1:
FIG. 1 is a synthetic route to the 2-phenyl-5-mercaptomethyl-3, 4-fullerene Pyrrolidine (PTMF);
FIG. 2 is a mass spectral characterization of the resulting PTMF;
FIG. 3 is an ultraviolet-visible absorption spectrum of the resulting PTMF in toluene solution;
FIG. 4 is an infrared spectrum of the resulting PTMF;
FIG. 5 is a graph of the ultraviolet-visible absorption spectrum of CdS nanoparticles;
FIG. 6 is a graph of fluorescence spectra of CdS nanoparticles, PTMF-CdS hybrids (λex=383 nm);
FIG. 7 is a first order exponential decay operating curve of PTMF versus nano CdS fluorescence quenching;
FIG. 8 is a Stern-Volmer operating curve of PTMF versus nano CdS fluorescence quenching;
FIG. 9 is an ultraviolet-visible absorption spectrum of CdS (a), PTMF-CdS (b) and PTMF (c);
wherein (a) CdS sol concentration is 2.67×10 -4 mol/L; (b) In the PTMF-CdS hybrid, the concentration of CdS sol is 2.67 multiplied by 10 -4 mol/L, PTMF concentration 5.65X10 -5 mol/L; (b) PTMF concentration 5.65X10 -5 mol/L;
FIG. 10 is a graph of the ultraviolet-visible absorption spectrum of PTMF-CdS hybrids;
wherein the concentration of CdS sol is 1.6X10 -3 mol/L; PTMF concentration 1#:0mol/L;2#:1.13 x 10 -4 mol/L;3#:2.26×10 -4 mol/L;4#:4.52×10 -4 mol/L。
Detailed Description
For the purposes of promoting an understanding of the invention, reference will now be made in detail to various exemplary embodiments of the invention, which should not be considered as limiting the invention in any way, but rather as describing in more detail certain aspects, features and embodiments of the invention.
Example 1
A preparation method of a fullerene derivative and nano CdS hybrid material comprises the following steps:
(1)C 60 preparation of mercapto derivative (2-phenyl-5-mercaptomethyl-3, 4-Fullerenylpyrrolidine (PTMF))
The raw materials are as follows: c (C) 60 (purity 99%), L-cysteine (biochemical reagent, BR), benzaldehyde (AR), toluene (AR, soaked with sodium silk, freshly distilled before use), petroleum ether (60-90 ℃, AR), thin layer chromatography silica gel (H, chemically pure), methanol (HPLC), n-hexane (AR, soaked with sodium silk, freshly distilled before use).
73.1mg (0.101 mmol) of C are reacted under argon (Ar) atmosphere 60 Dissolving in 70mL freshly distilled toluene, stirring for 2 hr to obtain purple solution, adding 53.87mg (0.505 mmol) benzaldehyde and 36.8mg (0.303 mmol) L-cysteine, refluxing under heating for 4 hr to obtain reddish brown solution, stopping heating, cooling to room temperature, concentrating the solution, performing column chromatography, and when the developing agent is pure petroleum ether, flushing unreacted C 60 Weighing 36.7mg; when the developing agent is V Toluene (toluene) :V Petroleum ether When the ratio is 8:1, the target product is obtained; after concentration, the mixture was washed successively with HPLC methanol (20 mL. Times.3) and n-hexane (20 mL. Times.3), and the resulting dark brown powder weighed to 27.1mg was identified as 2-phenyl-5-mercaptomethyl-3, 4-fullerene Pyrrolidine (PTMF) by mass spectrometry, UV-visible absorption spectroscopy, and infrared spectroscopy, and the yield was: 60.57% (36.7 mg C therein) 60 Unreacted). It is easily soluble in toluene and dichloromethane, soluble in o-dichlorobenzene, and slightly soluble in chloroform.
Wherein, all reflux reaction operations are carried out in a Schlenk system (anhydrous and anaerobic system) under the protection of argon; concentrating the liquid by a rotary evaporator (RE-5220D) connected with a circulating water type multipurpose vacuum pump (SHB-IIIA); drying the sample with a vacuum drying oven (ZK-82A type, shanghai); nuclear magnetic resonance spectrum @ 1 HNMR) was measured using Bruker AV300 NMR apparatus (TMS as internal standard, CDCl) 3 Is a solvent); the model of the ultraviolet visible light absorption spectrum (UV-Vis) is Shimadzu UV-4100; the infrared spectrum is measured by a Shimadzu FTIR-8400S type infrared spectrometer; mass spectra were determined using a matrix assisted laser desorption ionization time of flight mass spectrometer MALDI-TOF-MS (Bruker, germany).
MALDI-TOF-MS image of PTMF (matrix 1-P-methylphenyl, 2-p-nitrophenylaethylene) as shown in FIG. 2, molecular ion peaks m/z 885.329 are identified, which substantially correspond to the theoretical values m/z 885.0. Wherein 720.139 is C 60 Molecular ion peaks of (2).
The UV-visible absorption spectrum of PTMF is shown in FIG. 3, in which 328nm is C 60 Characteristic absorption peak of sphere, 432nm is C 60 The characteristic absorption peak of the monoaddition derivative is consistent with the report of the literature, and the experimental data show that the PTMF is synthesized.
The infrared spectrum of PTMF is shown in FIG. 4, 3313cm -1 、1600cm -1 、779cm -1 Attributable to the-NH characteristic absorption, 2584cm -1 Characteristic absorption attributed to-SH, 1454cm -1 、1153cm -1 、524cm -1 Ascribed to C 60 This further confirms the structure of PTMF.
The above test shows that: in C 60 The cysteine and the benzaldehyde are used as raw materials, and the 1, 3-dipolar cycloaddition reaction is utilized to synthesize the 2-phenyl-5-mercaptomethyl-3, 4-fullerene pyrrolidine, the structure of which is confirmed by characterization, thus laying a foundation for realizing hybridization with CdS semiconductor nano particles.
(2) Preparation of PTMF and CdS nanoparticle hybrids
The raw materials are as follows: cdCl 2 ·2.5H 2 O(AR),Na 2 S·9H 2 O (AR), sodium bis (2-ethylhexyl) sulfosuccinate (AOT) (96%, alfa Aesar Co.), n-heptane (AR), toluene (AR), and all of the experimental water was double distilled water.
(a) Preparation of CdS sols
CdS nano particles are prepared by adopting a micro-emulsion method. The method comprises the following specific steps: preparation of 1.0mol/LCdCl 2 Solution and 1.0mol/L Na 2 S, solution; 7.0008g of sodium bis (2-ethylhexyl) succinate sulfonate (AOT) is weighed and dissolved in 100mL of n-heptane to obtain a colorless transparent solution, 2.0mL of ultrapure water is dripped into the solution, and the solution is stirred for 1h to obtain reverse micelles; 60mL of reverse micelle was taken and added with vigorous stirring with 0.24mL of 1.0mol/L CdCl 2 Stirring the solution for 1h to obtain solution A; the remaining 40mL of reverse micelle was added under vigorous stirring0.16mL of 1.0mol/L Na 2 S, continuously stirring the solution for 1h to obtain a solution B; under stirring, the solution B is added into the solution A dropwise, and the mixture is stirred for 1h to obtain yellowish green sol.
Characterization of CdS nanoparticles: the ultraviolet-visible absorption spectra of the prepared CdS sol are shown in figures 1-5, and the CdS sol is absorbed at 400nm, and experimental data are consistent with literature reports, so that the CdS sol is prepared.
(b) Hybridization of PTMF and CdS nanosols
Under the magnetic stirring condition, different concentrations (0 mol/L,1.13×10) are respectively added dropwise into 20mL of the CdS sol prepared above -4 mol/L,2.26×10 -4 mol/L,4.52×10 -4 mol/L and 9.05X10 -4 mol/L) of PTMF in toluene 10mL (as shown in Table 1). Stirring for 12 hours to form hybrids of PTMF and CdS sols. The prepared hybrid is characterized by fluorescence spectrum and ultraviolet-visible absorption spectrum.
Wherein the ultraviolet-visible spectrophotometer is Hitachi U-4100, and the fluorescence spectrophotometer is Hitachi F-4500fluorescence spectrometer.
TABLE 1 PTMF and CdS nanosols of different concentrations in toluene (1.6X10) -3 mol/L) hybridization
Figure BDA0004133859800000081
In order to compare whether the solution environment of CdS sol has influence on fluorescence, the method for preparing CdS sol is the same except that CdCl is not added in the preparation process 2 And Na (Na) 2 S, preparing a blank comparative sol without CdS; taking 20mL of blank sol, dripping 10mL of toluene, stirring for 12h, and obtaining a sample which is recorded as 6 # . FIG. 6 is 1 # ~6 # And a fluorescence spectrum of CdS sol, wherein the excitation wavelength is 383nm.
To study the interaction of PTMF with CdS nanoparticles, different concentrations of PTMF were added to CdS sol and the change in the luminescent behavior of the hybrids and the interaction mechanism between them was observed. FIG. 6 is a diagram ofTheir fluorescence spectrum, excitation wavelength is 383nm. The CdS nano-particle has two typical characteristic emission peaks, namely an exciton emission peak of 350-500 nm crystal body formed by recombination of excited states and a surface state emission peak of 500-700 nm formed by recombination of electron holes of a surface well. As can be seen from fig. 6, the fluorescence emission peak of CdS nanoparticles prepared by the microemulsion method is at 555nm, which is a surface state emission peak formed by electron hole recombination of surface traps; when toluene solvent is added for dilution, the fluorescence emission peak is at 485nm, and is the exciton emission peak of the crystal body recombined from an excited state, and the possible reason for the change of the emission peak position is that the fluorescence is expressed as eigenstate fluorescence after the CdS sol is diluted; when the toluene solution of PTMF with different concentration is added, its emission peak belongs to the surface state emission peak, the fluorescence intensity is reduced, the fluorescence is quenched, and with the increasing concentration of PTMF, the emission peak intensity is reduced until it is close to zero, and the peak position is red shifted. As can be seen from FIG. 6, the blank is comparative sample 6 # The fluorescent light is not generated basically, and the environment of the visible solution has no influence on the fluorescence of the hybrid. Therefore, the reason for the change of the emission peak position may be that PTMF is added, the state of the surface of the CdS nanoparticle is changed, and the reason for the continuous decrease of the intensity of the emission peak of the CdS surface state may be that charge transfer occurs between the CdS nanoparticle in the excited state and the electron acceptor PTMF, which is yet to be confirmed by transient absorption spectrum.
Fluorescence quenching of nano CdS by PTMF with different concentrations accords with an exponential decay equation and a Stern-Volmer equation. Indicating that the quenching corresponds to the collision quenching type. Wherein, the first-order exponential decay equation of PTMF to nano CdS with different concentrations is as follows:
IFL=1810.04363e -C/0.97318 +131.42821 (C is 10 in units -4 mol/L), r= 0.99773, as shown in fig. 7.
FIG. 8 is a Stern-Volmer operating curve of fluorescence quenching of nano-CdS by PTMF at different concentrations. The slope k value of the calculated linear fit result is 19376.0.
FIG. 9 is an ultraviolet-visible absorption spectrum of CdS (a), PTMF-CdS (b) and PTMF (c), and it can be seen from FIGS. 1-9 (c) that the characteristic absorption peaks of PTMF are at 332nm and 432nm; FIGS. 1-9 (a) show that the characteristic absorption of CdS nanoparticles is at 407nm; the PTMF-CdS nanohybrids have characteristic absorption of both in the ultraviolet-visible spectrum, but no new peaks appear, indicating that they have no interaction in the ground state. In FIGS. 3-10, the concentration of fixed CdS sol (1.6X10 -3 mol/L) was unchanged, and the concentration of PTMF was changed (0 mol/L, 1.13X10) -4 mol/L,2.26×10 -4 mol/L and 4.52X10 -4 mol/L). It is apparent that as PTMF increases, so does the intensity of the absorption peaks of PTMF and CdS nanoparticles.
FIG. 10 is a graph of the ultraviolet-visible absorption spectrum of PTMF-CdS hybrids.
It can be seen that the above hybrid of PTMF and CdS nanoparticles was successfully prepared based on covalent interactions between PTMF and CdS nanoparticles using the active group thiol group carried by 2-phenyl-5-mercaptomethyl-3, 4-fullerene Pyrrolidine (PTMF). The ultraviolet-visible absorption spectrum shows that: the PTMF and CdS nano particles have no interaction in the ground state; fluorescence data indicate that: with the addition of PTMF, fluorescence of CdS is quenched, and charge transfer from CdS nanoparticles to PTMF may occur; fluorescence quenching of nano CdS by PTMF with different concentrations simultaneously accords with an exponential decay equation and a Stern-Volmer equation, which shows that the quenching accords with the collision quenching type, and the Stern-Volmer linear analysis shows that: PTMF has strong quenching ability to CdS nanometer particle fluorescence.
It is apparent that the above examples are given by way of illustration only and are not limiting of the embodiments. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. And obvious variations or modifications thereof are contemplated as falling within the scope of the present invention.

Claims (8)

1. A fullerene derivative and nano CdS hybrid material is characterized in that the fullerene derivative and nano CdS hybrid material is prepared by C 60 Covalent interaction between mercapto group of mercapto derivative and CdS nanometer particle to obtain C 60 Hybrid materials with nano CdS particles.
2. The hybrid fullerene derivative and nano CdS material according to claim 1, wherein C 60 The sulfhydryl derivative is 2-phenyl-5-sulfhydryl methyl-3, 4-fullerene Pyrrolidine (PTMF) synthesized by 1, 3-dipolar cycloaddition reaction.
3. The method for preparing a fullerene derivative and nano CdS hybrid material according to claim 1 or 2, which comprises the steps of preparing 2-phenyl-5-mercaptomethyl-3, 4-fullerene Pyrrolidine (PTMF); preparing CdS sol; and finally, hybridization of PTMF and CdS nano sol.
4. The method for preparing a hybrid material of fullerene derivative and nano CdS according to claim 3, wherein the 2-phenyl-5-mercaptomethyl-3, 4-fullerene Pyrrolidine (PTMF) is prepared from C 60 L-cysteine and benzaldehyde are prepared.
5. The method for preparing the hybridized material of fullerene derivative and nano CdS according to claim 3 or 4, wherein the preparation method of 2-phenyl-5-mercaptomethyl-3, 4-fullerene Pyrrolidine (PTMF) comprises the following steps: under the protection of inert gas, 0.05-0.2mol of C 60 Fully dissolving in 50-100mL of toluene solution, stirring for 1-5h to fully dissolve to obtain a purple solution, adding 0.1-1.0mol of benzaldehyde and 0.1-0.8mol of L-cysteine, heating and refluxing at 80-150 ℃ for 2-6h to obtain a reddish brown solution, cooling to room temperature, concentrating the solution, and performing column chromatography to obtain a target product; after concentration and washing, the obtained dark brown powder is 2-phenyl-5-mercaptomethyl-3, 4-fullerene Pyrrolidine (PTMF).
6. The method for preparing the fullerene derivative and nano CdS hybrid material according to claim 3, wherein the CdS sol is prepared by a micro-emulsion method.
7. The method for preparing a fullerene derivative and nano CdS hybrid material according to claim 3 or 6, characterized in thatThe preparation method of the CdS sol comprises the following steps: preparing 0.5-1.5mol/L CdCl 2 Solution and 0.5-1.5mol/L Na 2 S, solution; weighing 5-10g of sodium bis (2-ethylhexyl) succinate (AOT), dissolving in 100-200mL of n-heptane, and dissolving to obtain colorless transparent solution; dripping 1-10mL of ultrapure water into the solution, and stirring for 0.5-3h to obtain reverse micelle; taking 30-80mL reverse micelle, adding 0.1-0.5mL of 0.5-1.5mol/L CdCl under the condition of intense stirring 2 Continuously stirring the solution for 0.5-3h to obtain solution A; the rest 20-60mL reverse micelle is added with 0.1-0.5mL of 0.5-1.5mol/L Na under the condition of intense stirring 2 Continuously stirring the solution S for 0.5-3h to obtain a solution B; under stirring, the solution B is added into the solution A dropwise, and the mixture is stirred for 0.5 to 3 hours to obtain yellowish green sol.
8. The method for preparing the fullerene derivative and nano CdS hybrid material according to claim 3, wherein the method for hybridizing PTMF and CdS nanosol is as follows: dropwise adding (0.5-10.0) x 10 into the prepared CdS sol under magnetic stirring -4 5-20mL of a toluene solution of PTMF at mol/L, and stirring to form a hybrid of PTMF and CdS sol.
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