A nano-particle organic composite film and a preparation method thereof

Abstract

The present invention discloses a nanoparticle organic composite film and a preparation method thereof. The preparation method of the nanoparticle organic composite film comprises: uniformly mixing the target nanoparticles, octadecene and a solvent to obtain a mixed solution; heating the mixed solution to obtain a nanoparticle organic composite film. The preparation method of the nanoparticle organic composite film provided by the present invention physically disperses the target nanoparticles in a solvent, then transfers the mixed solution to deionized water for heating and heat preservation, and as the solvent evaporates, octadecene and the nanoparticles gradually form a nanoparticle organic composite film having unique structural characteristics and stably existing in the solvent.

Description

Technical Field

[0001] The invention belongs to the technical field of two-dimensional nanoparticle film preparation, and specifically relates to a nanoparticle organic composite film and a preparation method thereof. Background Art

[0002] After years of accumulation and continuous development, nanomaterials have been widely used in biomedicine, new energy, sensors, new environmental protection, military and other fields. And due to their unique surface and interface effects, small size effects, quantum size effects, macro quantum tunneling effects and other characteristics, they will also be used in a wider range of life scenarios. Among them, nanoparticles can form macroscopic two-dimensional or three-dimensional materials with different characteristics through a certain assembly method. The diversity of nanoparticle types and differences in their own assembly structures lead to variable and composite characteristics, which make them more competitive in future applications that tend to be more miniaturized, modularized and multifunctional.

[0003] At present, the method of preparing nanoparticles into two-dimensional nanoparticle films is liquid phase assembly, that is, nanoparticles are uniformly dispersed in a solvent to form a low-concentration nanoparticle solution. Through the slow volatilization of the liquid phase solvent, the nanoparticles form a layer of orderly and tightly arranged particle film on a soft template such as a polymer micelle membrane, a template-free such as a liquid-air interface, and a hard template such as a Si wafer under the action of capillary force, electrostatic force, gravity, magnetic force, etc. These methods often require further fine transfer to form components. In this process, the use of etchants when removing the template and other factors are likely to cause damage to the membrane structure.

[0004] The template-free method usually adds long-chain organic molecules to form self-supporting nanoparticle & organic composite films through the cross-linking of organic molecules between nanoparticles. The structure of this composite film still depends on the cross-linking of organic chains between particles, and the membrane structure is also easily destroyed. In addition, most nanoparticle organic composite films also have the problem of being dissolved by specific solvents and becoming unstable. Summary of the invention

[0005] The main purpose of the present invention is to provide a nanoparticle organic composite film and a preparation method thereof to overcome the deficiencies in the prior art.

[0006] To achieve the aforementioned object of the invention, the technical solution adopted by the embodiment of the present invention includes:

[0007] The embodiment of the present invention provides a method for preparing a nanoparticle organic composite film, comprising:

[0008] providing target nanoparticles;

[0009] Mixing the target nanoparticles, octadecene and a solvent uniformly to obtain a mixed solution;

[0010] The mixed solution is heated to obtain a nanoparticle organic composite film.

[0011] Furthermore, the nanoparticles include spherical Fe 3 O 4 , Fe 3 O 4 Triangular piece, heterojunction FePt / Fe 3 O 4 Or any one of spherical Au, preferably, the nanoparticles include spherical Fe 3 O 4 or heterojunction FePt / Fe 3 O 4 .

[0012] Furthermore, the solvent includes one or a mixture of two of water, ethanol, acetone, toluene and hexane.

[0013] Furthermore, the mass volume ratio of the nanoparticles to the solvent is 0.6mg-1.2mg:2ml; the mass volume ratio of the nanoparticles to octadecene is 0.6mg-1.2mg:0.25ml-0.5ml.

[0014] Furthermore, the method for preparing the nanoparticle organic composite film comprises: heating the mixed solution to 85°C-95°C and keeping it warm for 3min-10min, then continuing to heat it to 97°C-99°C and keeping it warm for 20h-30h, with a heating rate of 5-10°C / min.

[0015] The embodiment of the present invention further provides a nanoparticle organic composite film, and the nanoparticle organic composite film is prepared by the above method.

[0016] Furthermore, the nanoparticle organic composite film comprises nanoparticles and octadecene, and the nanoparticles are uniformly distributed in the nanoparticle organic composite film.

[0017] The present invention adopts a liquid phase method to physically disperse the target nanoparticles in a solvent, and then transfers the mixed liquid to deionized water for heating and insulation. As the solvent evaporates, octadecene and the nanoparticles gradually form a film structure, and the desired nanoparticle organic composite film can be obtained when the liquid is cooled to room temperature.

[0018] Compared with the prior art, the present invention has the following beneficial effects:

[0019] (1) In the existing nanoparticle film preparation technology, the nanoparticles usually form a particle film on the template under the action of capillary force, electrostatic force, gravity, magnetic force, etc. through the slow volatilization of the liquid phase solvent, and further fine transfer is required for the subsequent preparation of components. In this process, the use of etchants when removing the template and the weak interaction between particles are likely to cause damage to the film structure. The present invention forms a template-free organic composite film. Octadecene allows the nanoparticles to form a stable nanoparticle & organic composite film through the cross-linking of organic molecules. The film does not require the support of a substrate and can therefore be used directly without the need for separation from the substrate.

[0020] (2) The structure of the existing nanoparticle organic composite membranes prepared by the template-free method often relies on the cross-linking of organic chains between particles. The membrane structure is unstable and can be easily destroyed. In some usage environments, such as liquid environments, it will dissolve, limiting its use. The octadecene used in the present invention has unique stability and can stably exist in a variety of organic solvents, such as conventional solvents such as hexane, toluene, ethanol, and water. It shows excellent stability.

[0021] (3) The existing composite films generated by the cross-linking of organic matter between particles are usually formed by the cross-linking of organic matter linked to the surface of nanoparticles. The stability of this composite film is easily affected by van der Waals force, electrostatic force, gravity, etc., and the preparation conditions of particle films are very harsh. The nanoparticles formed in the present invention are simple to operate, and the shape, size and type of the particles will not affect the formation of the film, and the film formation is almost not restricted by various conditions.

[0022] (4) The present invention can realize a dense, large-area, highly stable, and self-supporting nanoparticle film by selecting the amount of solvent used, the temperature and time of insulation, etc. BRIEF DESCRIPTION OF THE DRAWINGS

[0023] In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the drawings required for use in the embodiments or the description of the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments recorded in the present application. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying creative work.

[0024] Figure 1 The spherical Fe 3 O 4 Transmission electron micrograph of magnetic nanoparticles.

[0025] Figure 2a , Figure 2b The spherical Fe 3 O4 Transmission electron microscope photo and magnified image of magnetic nanoparticle film.

[0026] Figure 3a , Figure 3b The spherical Fe 3 O 4 Transmission electron microscope photo and magnified image of magnetic nanoparticle film.

[0027] Figure 4a , Figure 4b The spherical Fe 3 O 4 Transmission electron microscope photo and magnified image of magnetic nanoparticle film.

[0028] Figure 5 The spherical Fe 3 O 4 Compatibility and stability tests of magnetic nanoparticle films in different solutions including hexane, toluene, deionized water and ethanol and transmission electron microscope images of samples after a series of tests.

[0029] Figure 6 The FePt / Fe prepared in Example 4 of the present invention 3 O 4 Transmission electron microscopy image of heterostructured magnetic nanoparticles.

[0030] Figure 7a , Figure 7b and Figure 7c The FePt / Fe prepared in Example 4 of the present invention 3 O 4 Transmission electron microscope photograph of the heterostructured magnetic nanoparticle film, enlarged image and corresponding schematic diagram of the morphology and size of the particles. DETAILED DESCRIPTION

[0031] The present invention will be more fully understood through the following detailed description, which should be read in conjunction with the accompanying drawings. Detailed embodiments of the present invention are disclosed herein; however, it should be understood that the disclosed embodiments are only exemplary of the present invention, which can be embodied in various forms. Therefore, the specific functional details disclosed herein should not be interpreted as limiting, but only as the basis of the claims and as a representative basis for teaching those skilled in the art to adopt the present invention in different ways in virtually any appropriate detailed embodiment.

[0032] One aspect of an embodiment of the present invention provides a method for preparing a nanoparticle organic composite film, comprising:

[0033] providing target nanoparticles;

[0034] Mixing the target nanoparticles, octadecene and a solvent uniformly to obtain a mixed solution;

[0035] The mixed solution is heated to obtain a nanoparticle organic composite film.

[0036] In some preferred embodiments, the particle size of the target nanoparticles is 1-100 nm.

[0037] In some preferred embodiments, the nanoparticles may include spherical Fe 3 O 4 , Fe 3 O 4 Triangular piece, heterojunction FePt / Fe 3 O 4 , spherical Au, etc., but not limited to these.

[0038] The sources of the nanoparticles in the embodiments of the present invention are not limited, and the nanoparticles can be obtained commercially, or prepared by nanoparticle assembly methods in the prior art.

[0039] In some more preferred embodiments, the nanoparticles include spherical Fe 3 O 4 or heterojunction FePt / Fe 3 O 4 .

[0040] In some more preferred embodiments, the spherical Fe 3 O 4 The preparation method comprises:

[0041] The mixed system of ferric chloride hexahydrate and sodium oleate is heated and kept warm in an organic solvent and deionized water to form a synthetic product;

[0042] separating, washing and drying the synthesized product to obtain iron oleate;

[0043] The oleic acid iron is placed in oleic acid and 1-octadecene, heated and kept warm under the protection of inert gas, separated and purified to obtain spherical Fe 3 O 4 Particles.

[0044] In some more preferred embodiments, the heterojunction FePt / Fe 3 O 4 The preparation method comprises:

[0045] Platinum acetylacetonate is dissolved in benzyl ether, and protective gas is introduced, and the mixture is heated and kept warm;

[0046] During the heat preservation period, oleylamine, carbonyl iron and oleic acid are added respectively, and then the mixed reaction product is heated and kept warm;

[0047] After the reaction is completed, the temperature is lowered, the protective gas is turned off, and the cleaning and separation are performed to obtain the heterojunction FePt / Fe 3 O 4 Nanocomposite particles.

[0048] In some preferred embodiments, the solvent may include one or a mixture of two of water, ethanol, acetone, toluene, hexane, etc., but is not limited thereto.

[0049] In some more preferred embodiments, the mass volume ratio of the nanoparticles to the solvent is 0.6 mg-1.2 mg: 2 ml.

[0050] In some more preferred embodiments, the mass volume ratio of the nanoparticles to octadecene is 0.6 mg-1.2 mg: 0.25 ml-0.5 ml.

[0051] In some preferred embodiments, the mixed solution is heated to 85° C.-95° C. and kept warm for 3 min-10 min, and then continued to be heated to 97° C.-99° C. and kept warm for 20 h-30 h.

[0052] In some preferred embodiments, the heating rate is 5-10°C / min.

[0053] The preparation method of the invention is simple and easy to implement, and by means of the preparation method, a nano-particle organic composite film having unique structural characteristics and being stably present in a solvent can be obtained.

[0054] Another aspect of the embodiments of the present invention further provides a nanoparticle organic composite film, wherein the nanoparticle organic composite film is prepared by the aforementioned method.

[0055] In some preferred embodiments, the nanoparticle organic composite film comprises nanoparticles and octadecene, and the nanoparticles are uniformly distributed in the nanoparticle organic composite film.

[0056] Embodiment 1:

[0057] Take ferric chloride hexahydrate (FeCl 3 6H 2 O, 1.081 g, 4 mmol) and sodium oleate (C 17 H 33 CO 2 Na, 3.653g, 12mmol), put it into a flask filled with ethanol (8ml), n-hexane (14ml), and deionized water (6ml), and slowly heat it to 70℃ at a heating rate of 5℃ / min, and keep it warm for 4h. The synthesized product was separated from the flask, washed, and placed in a forced air drying oven at 70℃ for 4h. The synthesized product iron oleate (0.200g) was placed in a flask filled with oleic acid (C18 H 34 O 2 , 0.040 g, 0.14 mmol), 1-octadecene (C 18 H 36 , 20ml) flask, inert gas argon (Ar 2 ) for about 15 minutes, the temperature was raised to 317℃ at a heating rate of 3.3℃ / min by the intelligent electric control heating system, and the reaction was kept warm for 5 hours. The reaction product was finally separated and purified by alcohol and n-hexane (ratio 1:1) in an ultrasonic cleaner and a high-speed centrifuge to obtain Fe 3 O 4 The nanoparticles can be effectively and evenly dispersed in hexane to obtain uniform and stable spherical iron oxide magnetic nanoparticles with a particle size of 17 nm. The transmission electron microscope photo is shown in Figure 1 shown.

[0058] In this embodiment, 1-octadecene (C 18 H 36 (ODE, 0.5 ml) and spherical Fe uniformly dispersed in n-hexane (2 ml) 3 O 4 Nanoparticles (0.6 mg / ml, 2 ml) were mixed evenly, and then the mixture was slowly transferred to a flask containing 40 ml of deionized water and allowed to stand for 1 min. The heating rate was set at 8 °C / min, heated to 95 °C for 5 min, and then continued to heat to 99 °C for 24 h. After the liquid cooled to room temperature, it was washed three times with hexane and alcohol respectively, and finally the film was stored in water.

[0059] Figure 2a and Figure 2b The spherical Fe 3 O 4 Transmission electron micrograph and magnified image of magnetic nanoparticle film.

[0060] from Figure 1 , Figure 2a , Figure 2b It can be seen that the Fe 3 O 4 The size of the magnetic nanoparticles is about 17 nm. 3 O 4 Magnetic nanoparticle films, and Fe 3 O 4 The morphology of magnetic nanoparticles did not change significantly and they were evenly distributed in the film.

[0061] Figure 5 a- Figure 5 f is the spherical Fe 3 O4 Compatibility and stability tests of magnetic nanoparticle films in different solutions of hexane, toluene, deionized water, and ethanol, and TEM morphology of samples after a series of tests. 3 O 4 The octadecene / octadecene composite films are very stable in conventional solvents such as hexane, toluene, ethanol and water.

[0062] Embodiment 2:

[0063] In this embodiment, the same method as in Example 1 was used to prepare a uniform and stable spherical Fe 3 O 4 Nanoparticles, obtained Fe 3 O 4 The nanoparticles can be effectively and uniformly dispersed in hexane.

[0064] 1-octadecene (C 18 H 36 (ODE, 0.5 ml) and spherical Fe uniformly dispersed in n-hexane (2 ml) 3 O 4 Nanoparticles (1.2 mg / ml, 2 ml) were mixed evenly, and then the mixture was slowly transferred to a flask containing 40 ml of deionized water and allowed to stand for 1 min. The temperature was set at a rate of 5 °C / min, heated to 85 °C for 3 min, and then continued to be heated to 97 °C for 20 h. After the liquid cooled to room temperature, it was washed three times with hexane and alcohol respectively, and finally the film was stored in water.

[0065] Figure 3a and Figure 3b The spherical Fe 3 O 4 Transmission electron micrograph and magnified image of magnetic nanoparticle film.

[0066] from Figure 1 , Figure 3a , Figure 3b It can be seen that the Fe 3 O 4 The size of the magnetic nanoparticles is about 17 nm. 3 O 4 Magnetic nanoparticle films, and Fe 3 O 4 The morphology of magnetic nanoparticles did not change significantly and they were evenly distributed in the film.

[0067] Embodiment 3:

[0068] In this embodiment, the same method as in Example 1 was used to prepare a uniform and stable spherical Fe3 O 4 Nanoparticles, obtained Fe 3 O 4 The nanoparticles can be effectively and uniformly dispersed in hexane.

[0069] 1-octadecene (C 18 H 36 (ODE, 0.25 ml) and spherical Fe uniformly dispersed in n-hexane (2 ml) 3 O 4 Nanoparticles (1.2 mg / ml, 2 ml) were mixed evenly, and then the mixture was slowly transferred to a flask containing 40 ml of deionized water and allowed to stand for 1 min. The heating rate was set at 10 °C / min, heated to 90 °C for 10 min, and then continued to heat to 98 °C for 30 h. After the liquid cooled to room temperature, it was washed three times with hexane and alcohol respectively, and finally the film was stored in water.

[0070] Figure 4a and Figure 4b The spherical Fe 3 O 4 Transmission electron micrograph and magnified image of magnetic nanoparticle film.

[0071] from Figure 1 , Figure 4a , Figure 4b It can be seen that the Fe 3 O 4 The size of the magnetic nanoparticles is about 17 nm. 3 O 4 Magnetic nanoparticle films, and Fe 3 O 4 The morphology of magnetic nanoparticles did not change significantly and they were evenly distributed in the film.

[0072] Embodiment 4:

[0073] Take acetylacetonate platinum (C 10 H 14 O 4 Pt, 0.196 g, 0.5 mmol) was dissolved in benzyl ether (C 14 H 14 O, 20 ml) flask, set up a high-temperature liquid phase reaction device, and introduce a protective atmosphere of argon / hydrogen mixed gas (Ar 2 &8% H2) for 15 min. Then the solution was heated to 120°C at a rate of 5°C / min and kept warm for 5 min. During this time, oleylamine (C 18 H 37 N, 1 ml, 3.04 mmol), carbonyl iron (Fe(CO)5 , 260 μl, 1.95 mmol) and oleic acid (C 18 H 34 O 2 , 1ml, 3.16mmol), and then the mixed reaction product was heated to 220℃ at a rate of 5℃ / min and kept warm for 90min. After the reaction was completed and the temperature was lowered, the protective gas was turned off, and the product was washed and separated with ethanol and n-hexane in a ratio of 1:1 to obtain FePt / Fe 3 O 4 Nanocomposite particles can be effectively and evenly dispersed in hexane, with FePt / Fe particles with a particle size of 9 nm. 3 O 4 Nanocomposite particles, the transmission electron microscope photo is as follows Figure 6 shown.

[0074] In this embodiment, 1-octadecene (C 18 H 36 (ODE, 0.5 ml) and FePt / Fe uniformly dispersed in n-hexane (2 ml) 3 O 4 Nanocomposite particles (0.6 mg / ml, 2 ml) were mixed evenly, and then the mixture was slowly transferred to a flask containing 40 ml of deionized water and allowed to stand for 1 min. The heating rate was set at 8 °C / min, heated to 95 °C for 5 min, and then continued to heat to 99 °C for 24 h. After the liquid cooled to room temperature, it was washed three times with hexane and alcohol respectively, and finally the film was stored in water.

[0075] Figure 7a , Figure 7b and Figure 7c The FePt / Fe 3 O 4 Transmission electron microscope photograph of the nanocomposite particle film, enlarged image and schematic diagram of the corresponding morphology and size of the particles.

[0076] from Figure 6 , Figure 7a , Figure 7b and Figure 7c It can be seen that the FePt / Fe 3 O 4 The size of the nanocomposite particles is about 9 nm. The single-layer, dense FePt / Fe 3 O 4 Nanocomposite particle films, and FePt / Fe 3 O 4 The morphology of the nanocomposite particles did not change significantly and was evenly distributed in the film.

[0077] In addition, the inventors of this case also referred to the aforementioned embodiments and conducted experiments with other raw materials, process operations, and process conditions described in this specification, and obtained relatively ideal results.

[0078] Although the present invention has been described with reference to illustrative embodiments, it will be understood by those skilled in the art that various other changes, omissions and / or additions may be made without departing from the spirit and scope of the present invention and that the elements of the embodiments may be replaced by substantial equivalents. In addition, many modifications may be made without departing from the scope of the present invention to adapt specific circumstances or materials to the teachings of the present invention. Therefore, it is not intended herein to limit the present invention to the disclosed specific embodiments for performing the present invention, but it is intended that the present invention will include all embodiments within the scope of the appended claims. In addition, unless specifically stated, any use of the terms first, second, etc. does not indicate any order or importance, but rather uses the terms first, second, etc. to distinguish one element from another.

Claims

1. A preparation method of a nanoparticle organic composite film, characterized in that, comprising: providing target nanoparticles; uniformly mixing the target nanoparticles, 1-octadecene and a solvent to obtain a mixed solution; heating the mixed solution at a heating rate of 5-10 °C / min to 85°C - 95 °C and holding for 3 min - 10 min, then continuing to heat to 97°C - 99 °C and holding for 20 h - 30 h, wherein the 1-octadecene enables the nanoparticles to form a stable nanoparticle organic composite film through the cross-linking action of organic molecules; Among them, the target nanoparticles are spherical Fe 3 O 4 、Fe 3 O 4 triangle flakes, heterojunction FePt / Fe 3 O 4 、spherical Au, or any one of them; the mass-volume ratio of the target nanoparticles to 1-octadecene is 0.6 mg - 1.2 mg: 0.25 ml - 0.5 ml.

2. The preparation method of the nanoparticle organic composite film according to claim 1, characterized in that: the particle size of the target nanoparticles is 1-100 nm.

3. The preparation method of the nanoparticle organic composite film according to claim 1, characterized in that: The target nanoparticles are spherical Fe 3 O 4 or the heterojunction FePt / Fe 3 O 4 .

4. The preparation method of the nanoparticle organic composite film according to claim 1, characterized in that: the solvent is any one or a combination of two or more of water, ethanol, acetone, toluene, and hexane.

5. The preparation method of the nanoparticle organic composite film according to any one of claims 1-4, characterized in that: the mass-volume ratio of the target nanoparticles to the solvent is 0.6 mg - 1.2 mg: 2 ml.

6. A nanoparticle organic composite film, characterized in that, the nanoparticle organic composite film is prepared by the method according to any one of claims 1-5.

7. The nanoparticle organic composite film according to claim 6, characterized in that, comprising nanoparticles, and the nanoparticles are uniformly distributed in the nanoparticle organic composite film.

Images