Method for preparing two-dimensional ultrathin fullerene material

Abstract

The invention discloses a method for preparing a two-dimensional ultrathin fullerene material, which comprises the following steps: by taking a tetrabutylammonium hydroxide (TBAOH) aqueous solution as a liquid-phase stripping solvent, adding a face-centered cubic C60 crystal into the TBAOH aqueous solution, enabling tetrabutylammonium ions (TBA < + >) to enter the C60 crystal to enlarge the interlayer distance of the crystal, and combining with stirring, so that the two-dimensional ultrathin fullerene material is obtained. The top-down preparation of the two-dimensional ultrathin fullerene material is realized. The reaction process is simple, reaction conditions are mild and easy to control, large equipment and harsh reaction conditions are not needed, and the ultrathin face-centered cubic fullerene two-dimensional material with regular morphology, uniform thickness and transverse size of 400nm-1mu m can be generated under the combined action of insertion and stirring of TBA < + >. When the two-dimensional material is used as a photoanode material of a photoelectric detector and a photocatalytic degradation photocatalyst, the two-dimensional material shows excellent photoelectric performance and catalytic performance.

Description

Technical Field

[0001] The invention belongs to the technical field of two-dimensional nanomaterial preparation, and specifically relates to a method for preparing a two-dimensional ultrathin fullerene material. Background Art

[0002] Photodetectors based on two-dimensional materials have become very popular in optoelectronic devices due to their unique structure and excellent electronic and optoelectronic properties. Although the atomic thickness of two-dimensional materials is thin, they still interact strongly with light and improve the light absorption efficiency. Among the many two-dimensional materials used in photodetectors, two-dimensional carbon materials are the most eye-catching. Carbon materials composed of conjugated carbon network structures, such as C 60 Due to its unique π electron system, it exhibits excellent carrier transport properties and can react with itself or almost all sp, sp 2 and sp 3 Hybridized elements are combined. By changing the periodic bonding motifs in the hybrid carbon atom network, C 60 The physical properties of C have great diversity, including adjustable band gaps of metal, semiconductor or insulation, which makes them have many applications in optoelectronic devices, energy storage devices and superconductors. 60 The preparation of two-dimensional materials is limited to sputtering or molecular beam epitaxy. The high cost and technology limit its further development in optoelectronic devices. 60 Two-dimensional materials have many defects and low degree of crystallinity. The presence of lattice defects will further slow down the carrier transmission efficiency and thus affect the performance of optoelectronic devices. Summary of the invention

[0003] The present invention aims to provide a two-dimensional ultrathin fullerene material (C 60 Preparation method of two-dimensional materials.

[0004] To achieve the above-mentioned purpose, the technical solution provided by the present invention comprises the following steps:

[0005] Step 1: Prepare the face-centered cubic C 60 The crystals were added to a tetrabutylammonium hydroxide aqueous solution to make the resulting mixed solution C 60 The concentration of the crystals is 0.2-50 g / L; wherein the concentration of the tetrabutylammonium hydroxide aqueous solution is 2.3 wt%-50 wt%.

[0006] Step 2: After the mixed solution obtained in step 1 is allowed to react for 1 to 20 days, it is stirred at room temperature for 2 to 24 hours, and then the mixed solution is centrifuged. Concentrated nitric acid is added to the obtained supernatant to adjust the pH of the solution to neutral, and then centrifuged again. The obtained precipitate is washed with an aqueous hydrogen peroxide solution and dried to obtain a two-dimensional ultrathin fullerene material.

[0007] In the above step 1, preferably, C 60 The crystal concentration is 1 to 20 g / L.

[0008] In the above step 1, the concentration of the tetrabutylammonium hydroxide aqueous solution is preferably 10 wt % to 20 wt %.

[0009] In the above step 2, the mixed solution obtained in step 1 is preferably allowed to react for 2 to 7 days.

[0010] In the above step 2, the stirring time at room temperature is preferably 3 to 12 hours.

[0011] In the above step 2, the stirring speed is preferably 100 to 700 rpm.

[0012] In the above step 2, the mixed solution is preferably centrifuged at a centrifugal rate of 300 to 1000 rpm.

[0013] In the above step 2, concentrated nitric acid is preferably added to the obtained supernatant to adjust the pH of the solution to neutral, and then centrifuged at a centrifugal rate of 9000 to 14000 rpm.

[0014] In the above step 2, the mass concentration of the aqueous hydrogen peroxide solution is preferably 3% to 10%, and the cleaning time is 0.5 to 1.5 hours.

[0015] In the above step 2, the drying temperature is preferably 100 to 150° C. and the drying time is preferably 10 to 20 hours.

[0016] The beneficial effects of the present invention are as follows:

[0017] The present invention uses TBAOH aqueous solution as intercalation stripping solvent to 60 The crystals were exfoliated in liquid phase, and the C-type crystals with uniform morphology and size distribution, thickness of 5-10nm and lateral size of 400nm-1μm were prepared at room temperature and pressure. 60 The present invention has simple operation, mild reaction conditions, easy control, low production cost, and can generate face-centered cubic C with regular morphology and uniform distribution by regulating intercalation time and stirring speed and time. 60 Two-dimensional materials exhibit excellent photoelectric and catalytic properties when used as photoanode materials for photodetectors and photocatalytic degradation photocatalysts. BRIEF DESCRIPTION OF THE DRAWINGS

[0018] Figure 1 is C prepared in Example 1 60 Two-dimensional materials and C 60 XRD pattern of the crystal.

[0019] Figure 2 is C prepared in Example 1 60 TEM image of two-dimensional materials.

[0020] Figure 3 is C prepared in Example 1 60 Atomic force microscopy image of a two-dimensional material.

[0021] Figure 4 C prepared in Example 2 60 TEM image of two-dimensional materials.

[0022] Figure 5 C prepared in Example 3 60 TEM image of two-dimensional materials.

[0023] Figure 6 C prepared in Example 4 60 TEM image of two-dimensional materials.

[0024] Figure 7 C prepared in Example 5 60 TEM image of two-dimensional materials.

[0025] Figure 8 C prepared in Example 6 60 TEM image of two-dimensional materials.

[0026] Fig. 9 C prepared in Example 7 60 TEM image of two-dimensional materials.

[0027] Fig.10 C prepared in Example 8 60 TEM image of two-dimensional materials. DETAILED DESCRIPTION

[0028] The present invention is further described in detail below in conjunction with the accompanying drawings and embodiments, but the protection scope of the present invention is not limited to these embodiments.

[0029] Example 1

[0030] Step 1: Prepare the face-centered cubic C 60 20 mg of the crystals were added to 15 mL of a 10 wt% TBAOH aqueous solution to obtain a mixed solution.

[0031] Step 2: After the mixed solution was allowed to stand for 2 days, it was stirred at room temperature for 5 hours at a stirring speed of 500 rpm; then it was centrifuged at a speed of 300 rpm to obtain a supernatant; a 98% nitric acid aqueous solution was added to the supernatant to adjust the pH of the solution to neutral, and the solution was centrifuged at a speed of 9500 rpm to obtain a precipitate, and then 20 mL of a 3% hydrogen peroxide aqueous solution was added to the precipitate for washing, and the washing time was 1 hour; finally, the precipitate was centrifuged at a speed of 9500 rpm to obtain a precipitate, and the precipitate was placed in an oven and dried at 102° C. for 12 hours to obtain C 60 Two-dimensional materials. Figure 1 It can be seen that all the diffraction peaks of the obtained product can match well with C 60 Standard card JCPDS#43-0995, C obtained after peeling 60 XRD diffraction peak results of two-dimensional materials and C 60 The crystals are consistent, indicating that the C 60 Crystal structure; from Figure 2 From the TEM images, we can see that the obtained product is composed of uniform feather-like lamellar two-dimensional materials with a lateral size of 400 to 500 nm. Figure 3 From the AFM images, it can be observed that the average thickness of the two-dimensional material is about 7nm.

[0032] Example 2

[0033] In step 1 of this embodiment, the prepared face-centered cubic C 60 10 mg of the crystals were added to 15 mL of 5 wt% TBAOH aqueous solution to obtain a mixed solution. The other steps were the same as in Example 1 to obtain C 60 Two-dimensional materials. Figure 4 It can be seen from the TEM image that the obtained product is composed of two-dimensional materials with uniform feather-like lamellae.

[0034] Example 3

[0035] In step 2 of this embodiment, the mixed solution was allowed to react for 1 day, and then stirred at room temperature for 7 hours at a stirring speed of 300 rpm. The other steps were the same as those in embodiment 1 to obtain feather-like flakes C with uniform morphology. 60 Two-dimensional materials (see Figure 5 .

[0036] Example 4

[0037] In step 2 of this embodiment, the mixed solution was allowed to react for 3 days, and then stirred at room temperature for 5 hours at a stirring speed of 700 rpm. The other steps were the same as those in embodiment 1 to obtain feather-like flakes C with uniform morphology. 60 Two-dimensional materials (see Figure 6 ).

[0038] Example 5

[0039] In step 2 of this embodiment, centrifugation is performed at 800 rpm to obtain a supernatant, a 98% nitric acid aqueous solution is added to the supernatant to adjust the pH of the solution to neutral, and centrifugation is performed at 10000 rpm to obtain a precipitate, and then 20 mL of a 3% hydrogen peroxide aqueous solution is added to the precipitate for washing, and the washing time is 2 hours. The other steps are the same as those in Example 1, and feather-like flakes C with uniform morphology are obtained. 60 Two-dimensional materials (see Figure 7 ).

[0040] Example 6

[0041] In step 2 of this embodiment, centrifugation is performed at 300 rpm to obtain a supernatant, a nitric acid aqueous solution with a mass concentration of 98% is added to the supernatant to adjust the pH of the solution to neutral, and centrifugation is performed at a speed of 9000 rpm to obtain a precipitate, and then 50 mL of a hydrogen peroxide aqueous solution with a mass concentration of 3% is added to the precipitate for washing, and the washing time is 1 hour. The other steps are the same as in Example 1, and a feather-like layer C with uniform morphology is obtained. 60 Two-dimensional materials (see Figure 8 ).

[0042] Example 7

[0043] In step 1 of this embodiment, the prepared face-centered cubic C 60 250 mg of crystals were added to 15 mL of 10 wt% TBAOH aqueous solution to obtain a mixed solution. The other steps were the same as in Example 1 to obtain feather-like flakes C with uniform morphology. 60 Two-dimensional materials (see Fig. 9 ).

[0044] Example 8

[0045] In step 1 of this embodiment, the prepared face-centered cubic C 60 1000 mg of crystals were added to 20 mL of 50 wt% TBAOH aqueous solution to obtain a mixed solution. The other steps were the same as in Example 1 to obtain feather-like flakes C with uniform morphology. 60 Two-dimensional materials (see Fig.10 ).

Claims

1. A method for preparing two-dimensional ultrathin fullerene materials, Features: The method consists of the following steps: Step 1: Prepare the face-centered cubic C 60 The crystals were added to a tetrabutylammonium hydroxide aqueous solution to make the resulting mixed solution C 60 The concentration of the crystals is 0.2 to 50 g / L; wherein the concentration of the tetrabutylammonium hydroxide aqueous solution is 2.3 wt% to 50 wt%; Step 2: After the mixed solution obtained in step 1 is allowed to react for 1 to 20 days, it is stirred at room temperature for 2 to 24 hours, and then the mixed solution is centrifuged. Concentrated nitric acid is added to the obtained supernatant to adjust the pH of the solution to neutral, and then centrifuged again. The obtained precipitate is washed with an aqueous hydrogen peroxide solution and dried to obtain a two-dimensional ultrathin fullerene material.

2. The method for preparing a two-dimensional ultrathin fullerene material according to claim 1, Features: In step 1, the mixed solution contains C 60 The crystal concentration is 1 to 20 g / L.

3. The method for preparing a two-dimensional ultrathin fullerene material according to claim 1, Features: In step 1, the concentration of the tetrabutylammonium hydroxide aqueous solution is 10wt% to 20wt%.

4. The method for preparing a two-dimensional ultrathin fullerene material according to claim 1, Features: In step 2, the mixed solution obtained in step 1 is allowed to react for 2 to 7 days.

5. The method for preparing a two-dimensional ultrathin fullerene material according to claim 1, Features: In step 2, the stirring time at room temperature is 3 to 12 hours.

6. The method for preparing a two-dimensional ultrathin fullerene material according to claim 1 or 5, Features: In step 2, the stirring speed is 100 to 700 rpm.

7. The method for preparing a two-dimensional ultrathin fullerene material according to claim 1, Features: In step 2, the mixed solution is centrifuged at a centrifugal rate of 300 to 1000 rpm.

8. The method for preparing a two-dimensional ultrathin fullerene material according to claim 1, Features: In step 2, concentrated nitric acid is added to the obtained supernatant to adjust the pH of the solution to neutral, and then centrifuged at a centrifugal rate of 9000 to 14000 rpm.

9. The method for preparing a two-dimensional ultrathin fullerene material according to claim 1, Features: In step 2, the mass concentration of the aqueous hydrogen peroxide solution is 3% to 10%, and the cleaning time is 0.5 to 1.5 hours.

10. The method for preparing a two-dimensional ultrathin fullerene material according to claim 1, Features: In step 2, the drying temperature is 100-150° C. and the drying time is 10-20 hours.

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