A method for preparing a two-dimensional ultrathin fullerene material

Abstract

The application discloses a method for preparing two-dimensional ultra-thin fullerene material, which uses a tetrabutylammonium hydroxide (TBAOH) aqueous solution as a liquid phase stripping solvent, adds a face-centered cubic C 60 crystal into the TBAOH aqueous solution, and realizes self-up-and-down preparation of the two-dimensional ultra-thin fullerene material through the entry of tetrabutylammonium ions (TBA + ) into the C 60 crystal, expansion of the interlayer spacing of the crystal, and stirring. The method has simple reaction process, mild and easy-to-control reaction conditions, and does not need large equipment and harsh reaction conditions, can generate the two-dimensional material of the ultra-thin face-centered cubic fullerene through the joint action of the insertion of TBA + and the stirring, and the two-dimensional material has regular morphology, uniform thickness, and a lateral size of 400nm-1um. When the two-dimensional material is used as a photoanode material of a photoelectric detector and a photocatalyst for photocatalytic degradation, the two-dimensional material has excellent photoelectric performance and catalytic performance.

Description

Technical Field

[0001] This invention belongs to the field of two-dimensional nanomaterial preparation technology, specifically relating to a method for preparing two-dimensional ultrathin fullerene materials. Background Technology

[0002] Two-dimensional (2D) photodetectors have gained significant traction in optoelectronic devices due to their unique structure and superior electronic and photoelectric properties. Despite their atomically thin thickness, 2D materials still interact strongly with light, enhancing light absorption efficiency. Among the many 2D materials used in photodetectors, 2D carbon materials are particularly noteworthy. Carbon materials composed of conjugated carbon network structures, such as C... 60 Due to its unique π-electron system, it exhibits excellent carrier transport characteristics and can interact with itself or almost all sp and sp electron systems. 2 and sp 3 Hybrid element bonding. By altering the periodic bonding motif in the hybrid carbon atom network, C... 60 The physical properties of C are highly diverse, including tunable band gaps that allow them to function as metals, semiconductors, or insulators, making them suitable for a wide range of applications in optoelectronic devices, energy storage devices, and superconductors. However, currently available C... 60 The fabrication of two-dimensional materials is currently limited to sputtering or molecular beam epitaxy (MBE) growth methods, and the high cost and technical limitations restrict their further development in optoelectronic devices. Meanwhile, C2000 materials obtained through MBE growth or sputtering... 60 Two-dimensional materials have many defects and low crystallinity. The presence of lattice defects will further slow down the carrier transport efficiency, thus affecting the performance of optoelectronic devices. Summary of the Invention

[0003] The purpose of this invention is to provide a two-dimensional ultrathin fullerene material (C2) that is simple to operate, has mild and easily controllable reaction conditions, low production cost, and exhibits regular morphology and uniform distribution. 60 Preparation method of two-dimensional materials.

[0004] To achieve the above objectives, the technical solution provided by this invention includes the following steps:

[0005] Step 1: Prepare the face-centered cubic C 60 Crystals were added to an aqueous solution of tetrabutylammonium hydroxide, resulting in a mixed solution with 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 stand for 1 to 20 days, it is stirred at room temperature for 2 to 24 hours. Then, the mixed solution is centrifuged. Concentrated nitric acid is added to the supernatant to adjust the pH of the solution to neutral. After centrifugation, the precipitate is washed with hydrogen peroxide aqueous solution and dried to obtain two-dimensional ultrathin fullerene material.

[0007] In step 1 above, it is preferred that C in the mixed solution 60 The crystal concentration is 1–20 g / L.

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

[0009] In step 2 above, it is preferable to let the mixed solution obtained in step 1 stand for 2 to 7 days to react.

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

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

[0012] In step 2 above, it is preferable to centrifuge the mixed solution at a centrifugation rate of 300 to 1000 rpm.

[0013] In step 2 above, it is preferable to add concentrated nitric acid to the obtained supernatant to adjust the pH of the solution to neutral, and then centrifuge at a centrifugation rate of 9000-14000 rpm.

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

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

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

[0017] This invention uses TBAOH aqueous solution as the intercalation and exfoliation solvent for surface-centered cubic C 60 Liquid-phase exfoliation of crystals enabled the preparation of C2 crystals with uniform morphology and size distribution, thickness of 5–10 nm, and lateral dimensions of 400 nm–1 μm at room temperature and pressure. 60 Two-dimensional materials. This invention is simple to operate, with mild and easily controllable reaction conditions, low production costs, and can generate face-centered cubic C materials with regular morphology and uniform distribution by jointly controlling the intercalation time and stirring speed with time. 60 Two-dimensional materials enable them to exhibit excellent photoelectric and catalytic properties when used as photoanode materials for photodetectors and photocatalysts for photocatalytic degradation. Attached Figure Description

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

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

[0020] Figure 3 It is C prepared in Example 1 60 An atomic force microscope image of a two-dimensional material.

[0021] Figure 4 It is C prepared in Example 2 60 TEM image of a two-dimensional material.

[0022] Figure 5 It is C prepared in Example 3 60 TEM image of a two-dimensional material.

[0023] Figure 6 It is C prepared in Example 4 60 TEM image of a two-dimensional material.

[0024] Figure 7 It is C prepared in Example 5 60 TEM image of a two-dimensional material.

[0025] Figure 8 It is C prepared in Example 6 60 TEM image of a two-dimensional material.

[0026] Figure 9 It is C prepared in Example 7 60 TEM image of a two-dimensional material.

[0027] Figure 10 It is C prepared in Example 8 60 TEM image of a two-dimensional material. Detailed Implementation

[0028] The present invention will be further described in detail below with reference to the accompanying drawings and embodiments, but the scope of protection 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 crystals were added to 15 mL of 10 wt% TBAOH aqueous solution to obtain a mixed solution.

[0031] Step 2: After allowing the mixed solution to stand for 2 days, stir at room temperature for 5 hours at a stirring speed of 500 rpm; then centrifuge at 300 rpm to obtain the supernatant; add 98% nitric acid aqueous solution to the supernatant to adjust the pH of the solution to neutral, centrifuge at 9500 rpm to obtain the precipitate, then add 20 mL of 3% hydrogen peroxide aqueous solution to the precipitate for washing for 1 hour; finally centrifuge at 9500 rpm to obtain the precipitate, place the precipitate in an oven and dry at 102℃ for 12 hours to obtain C. 60 Two-dimensional materials. (From) Figure 1 It can be seen that all the diffraction peaks of the obtained product match C very well. 60 Standard card JCPDS#43-0995, C obtained after peeling 60 XRD diffraction peak results of two-dimensional materials and C 60 The uniformity of the crystals indicates that the C crystals were not damaged during the peeling process. 60 Crystal structure; from Figure 2 The TEM images show that the obtained product consists of uniform, feather-like two-dimensional material with a lateral dimension of 400–500 nm; from Figure 3 The AFM images show that the average thickness of the two-dimensional material is about 7 nm.

[0032] Example 2

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

[0034] Example 3

[0035] In step 2 of this embodiment, after the mixed solution is allowed to stand for 1 day, it is stirred at room temperature for 7 hours at a stirring speed of 300 rpm. The other steps are the same as in Example 1, resulting in a uniformly shaped feather-like layer C. 60 Two-dimensional materials (see) Figure 5 .

[0036] Example 4

[0037] In step 2 of this embodiment, after the mixed solution is allowed to stand for 3 days, it is stirred at room temperature for 5 hours at a stirring speed of 700 rpm. The other steps are the same as in Example 1, resulting in uniformly shaped feather-like layers C. 60 Two-dimensional materials (see) Figure 6 ).

[0038] Example 5

[0039] In step 2 of this embodiment, centrifugation at 800 rpm is performed to obtain a supernatant. A 98% nitric acid aqueous solution is added to the supernatant to adjust the pH to neutral. The solution is then centrifuged at 10000 rpm to separate the precipitate. 20 mL of a 3% hydrogen peroxide aqueous solution is added to the precipitate for washing for 2 hours. Other steps are the same as in Example 1, resulting in uniformly morphological feather-like plates C. 60 Two-dimensional materials (see) Figure 7 ).

[0040] Example 6

[0041] In step 2 of this embodiment, centrifugation at 300 rpm is performed to obtain a supernatant. A 98% nitric acid aqueous solution is added to the supernatant to adjust the pH to neutral. The solution is then centrifuged at 9000 rpm to separate the precipitate. 50 mL of a 3% hydrogen peroxide aqueous solution is added to the precipitate for washing for 1 hour. Other steps are the same as in Example 1, resulting in uniformly morphological feather-like plates C. 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. Other steps were the same as in Example 1, yielding uniformly morphological feather-like lamellar plates C. 60 Two-dimensional materials (see) Figure 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. Other steps were the same as in Example 1, yielding uniformly morphological feather-like lamellar plates C. 60 Two-dimensional materials (see) Figure 10 ).

Claims

1. A method for preparing two-dimensional ultrathin fullerene materials, characterized in that: The method consists of the following steps: Step 1: Prepare the face-centered cubic C 60 Crystals were added to an aqueous solution of tetrabutylammonium hydroxide, resulting in a mixed solution with 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%. Step 2: After the mixed solution obtained in Step 1 is allowed to stand for 1 to 20 days, it is stirred at room temperature for 2 to 24 hours. Then, the mixed solution is centrifuged. Concentrated nitric acid is added to the supernatant to adjust the pH of the solution to neutral. After centrifugation, the precipitate is washed with hydrogen peroxide aqueous solution and dried to obtain two-dimensional ultrathin fullerene material.

2. The method for preparing two-dimensional ultrathin fullerene materials according to claim 1, characterized in that: In step 1, C in the mixed solution 60 The crystal concentration is 1–20 g / L.

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

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

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

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

7. The method for preparing two-dimensional ultrathin fullerene materials according to claim 1, characterized in that: In step 2, the mixed solution is centrifuged at a speed of 300–1000 rpm.

8. The method for preparing two-dimensional ultrathin fullerene materials according to claim 1, characterized in that: 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 centrifugation rate of 9000-14000 rpm.

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

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

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