Preparation method of indium oxide hollow nanotube / indium zinc sulfide heterojunction photoelectric functional material

Abstract

The invention discloses a preparation method of an indium oxide hollow nanotube / indium zinc sulfide heterojunction photoelectric functional material, which mainly comprises the following steps: dissolving indium nitrate hydrate and p-xylene in N, N-dimethylformamide, preparing a precursor Laval Hill framework material MIL-68 (In) nanorod of an indium oxide hollow nanotube by a hydrothermal method, and preparing the indium oxide hollow nanotube / indium zinc sulfide heterojunction photoelectric functional material. And then mixing the In2O3 hollow nanotube with zinc chloride, indium trichloride and thioacetamide, and preparing the indium oxide hollow nanotube / indium zinc sulfide heterojunction functional material under the action of an oil bath.

Description

Technical Field

[0001] This invention specifically relates to a method for preparing indium oxide hollow nanotube / indium zinc sulfide heterojunction optoelectronic functional materials, belonging to the field of inorganic nanomaterial preparation. Background Technology

[0002] Photoelectrochemical (PEC) biosensors have attracted widespread attention due to their fast response speed, simple operation, high specificity, and high sensitivity. The most critical component of PEC biosensors is the photoelectric material that generates photoelectric signals. Nanomaterials are widely used in photoelectrochemical biosensors due to their unique advantages. The large specific surface area of ​​nanomaterials is conducive to electron transfer. For PEC biosensors, nanomaterials with high photoelectric conversion efficiency can improve analytical performance. Nanomaterials are divided into: (1) Inorganic photoelectric materials: These materials mainly refer to semiconductor photoelectric materials composed of inorganic compounds, such as Si, TiO2, CdS, CuInSe2, etc. (2) Organic photoelectric materials: Commonly used organic photoelectric materials are mainly organic small molecule photoelectric materials and polymer materials. (3) Composite materials: Composite materials are mainly formed by combining organic photoelectric materials or complex photoelectric materials with inorganic photoelectric materials, or by combining two inorganic semiconductor materials with different band gaps. Composite materials have higher photoelectric conversion efficiency than single materials. TiO2-based composite materials are the most studied type, but other wide-bandgap semiconductor oxides such as ZnO, SnO2, Nb2O5, and Al2O3 are also used to prepare composite materials.

[0003] Indium zinc sulfide (IZS), a typical ternary sulfide semiconductor, possesses a good bandgap and light absorption capability. IZS is composed of nanoflowers made up of nanosheets, providing a large specific surface area and numerous active sites, shortening the charge migration path and thus achieving better electron transfer capabilities. Compared with other traditional single-metal sulfide semiconductor materials such as zinc sulfide and cadmium sulfide, IZS has advantages such as low toxicity, simple preparation methods, and structural stability. However, the aggregation of IZS limits its surface area and some active sites. To avoid IZS aggregation and increase its surface area and active sites, a method for preparing indium oxide hollow nanotube / indium zinc sulfide heterojunction optoelectronic functional materials was developed. Summary of the Invention

[0005] Based on the advantages and existing problems of indium zinc sulfide (ZIS) materials, this invention proposes a method for preparing indium oxide hollow nanotube / indium zinc sulfide heterojunction optoelectronic functional materials. By forming a Z-heterojunction structure, the electron transport mode within the two materials is altered, promoting electron-hole separation, increasing carrier lifetime, and expanding the light absorption range. The indium oxide hollow nanotube / indium zinc sulfide heterojunction avoids the aggregation of indium zinc sulfide, increases its surface area and active sites, and significantly enhances the photoelectric signal. It has better application prospects and significant implications in carbon dioxide conversion and photoelectric biosensors.

[0006] The present invention proposes a method for preparing indium oxide hollow nanotube / indium zinc sulfide heterojunction optoelectronic functional materials as follows: (1) Dissolve indium nitrate hydrate (In(NO3)3·H2O) and p-xylene (H2BDC) in 10 mL of N,N-dimethylformamide (DMF); (2) The precursor material of indium oxide hollow nanotubes (MIL-68(In) nanorods) was prepared by hydrothermal method from step (1). (3) The MIL-68(In) nanorods obtained in step (2) are dried and calcined to obtain In2O3 hollow nanotubes; (4) Acid washing of In2O3 hollow nanotubes in a three-necked flask; (5) Add zinc chloride, indium trichloride and thioacetamide to the three-necked flask in step (4), stir for 5 min, put the mixture into an oil bath at 95°C and stir for 2 hours, then centrifuge and wash three times with ethanol, and then dry in a vacuum at 60°C to obtain indium oxide hollow nanotube / indium zinc sulfide heterojunction functional material.

[0007] In step (1) of this invention, 0.8-0.85 g of indium nitrate hydrate (In(NO3)3·H2O) and 0.4-0.5 g of p-xylene (H2BDC) are dissolved in 10 mL of N,N-dimethylformamide (DMF) under stirring and sonication.

[0008] In step (2) of this invention, the hydrothermal method is used to prepare Lavasil framework materials (MIL-68(In) nanorods): the solution from step (1) is transferred to a high-pressure reactor lined with polytetrafluoroethylene, reacted at 100 °C for 24 hours, cooled to room temperature, and the white precipitate is collected by centrifugation. The precipitate is washed three times with ethanol by centrifugation and finally dried at 60 °C for 12 hours. The resulting Lavasil framework series materials (MIL-68(In) hollow nanorods) are precursors of indium oxide.

[0009] In step (3) of this invention, the MIL-68(In) nanorods are dried in a vacuum environment at 150°C for 2 hours.

[0010] In step (3) of the present invention, In2O3 hollow nanotubes are obtained by calcination: In a muffle furnace, the temperature is raised to 400°C in half an hour, then to 500°C in two hours, and then cooled to room temperature to obtain In2O3 hollow nanotubes.

[0011] In step (4) of this invention, the In2O3 hollow nanotubes are acid-washed: 10 mL of hydrochloric acid solution (pH=2.5) and 70-75 mg of indium oxide prepared in step (3) are added to a three-necked flask and stirred for 30 min.

[0012] In step (5) of this invention, 27-28 mg of zinc chloride, 44-45 mg of indium trichloride and 30-35 mg of thioacetamide are added to the three-necked flask.

[0013] The indium oxide hollow nanotube / indium zinc sulfide heterojunction optoelectronic functional material provided by this invention has the following beneficial effects: (1) Indium zinc sulfide is uniformly distributed on the surface of indium oxide hollow nanotubes, providing a larger specific surface area and more active sites, shortening the charge migration path, and obtaining better electron transfer ability. (2) By altering the electron transport mode within the two materials through the heterojunction structure, electron-hole separation is promoted, carrier lifetime is increased, and the light absorption range is expanded. (3) The photoelectric signal of the indium oxide hollow nanotube / indium zinc sulfide heterojunction material is significantly enhanced compared with the signal before the two are formed into a heterojunction. It has broad application prospects and great significance in carbon dioxide conversion and photoelectric biosensors. Attached Figure Description

[0014] Appendix Figure 1 X-ray diffraction (XRD) patterns of indium zinc sulfide (a), indium oxide (b), and indium oxide / zinc zinc sulfide (c). Appendix Figure 2 Scanning electron microscopy (SEM) images of indium zinc sulfide (a), indium oxide (b), and indium oxide / indium zinc sulfide (c). Appendix Figure 3 a) Indium zinc sulfide, b) Indium oxide, and c) Photocurrent signals of indium oxide / indium zinc sulfide Detailed Implementation Plan

[0015] Example 1 Photoelectric performance testing of indium oxide hollow nanotubes / indium zinc sulfide heterojunction optoelectronic functional materials: (1) Dissolve 0.81g In(NO3)3·H2O and 0.4g H2BDC in 10 mL DMF and dissolve under stirring and sonication.

[0016] (2) The solution from step (1) was transferred to a high-pressure reactor lined with polytetrafluoroethylene and reacted at 100 °C for 24 hours. After cooling to room temperature, the white precipitate was collected by centrifugation, washed three times with ethanol by centrifugation, and finally dried at 60 °C for 12 hours. The resulting Lavasil framework series materials (MIL-68(In) hollow nanorods) are precursors of indium oxide.

[0017] (3) MIL-68(In) nanorods were dried in a vacuum environment at 150°C for 2 hours, then removed and placed in a crucible in a muffle furnace. The temperature was raised to 400°C within half an hour, and then to 500°C within two hours. After cooling to room temperature, indium oxide hollow nanotubes (In2O3) were obtained and characterized by XRD and SEM tests (see Figure 1 , Figure 2 ).

[0018] (4) Add 10 mL of hydrochloric acid (pH=2.5) and 75 mg of indium oxide prepared in step (3) to a three-necked flask and stir for 30 min.

[0019] (5) Then, add 27.2 mg zinc chloride, 44.2 mg indium trichloride and 30 mg thioacetamide to the solution from step (4) and stir for 5 min. Place the mixture in an oil bath at 95 °C and stir for 2 h. Centrifuge, wash three times with ethanol, and then dry in a vacuum at 60 °C to obtain the ZIS / In2O3 sample. Perform XRD and SEM characterization (see [link to sample]). Figure 1 , Figure 2 In comparison, bare ZIS nanosheets can be prepared without adding In2O3 as a substrate under the same reaction conditions.

[0020] (6) Take 8 mg of In2O3 obtained in step (3), ZIS obtained in step (5) and ZIS / In2O3 respectively and disperse them in 4 mL of water to obtain three solutions of 2 mg / mL. Drop them onto indium tin oxide (ITO) conductive glass and place them at room temperature for 12 h to obtain the working electrode.

[0021] (7) Prepare 0.1M Tris-HCl, and use the working electrode from step (6), the platinum electrode as the counter electrode, and Ag / AgCl as the reference electrode to form a three-electrode system. Use a xenon lamp as the light source and test the photocurrent in a CHI 760D workstation to obtain the attached... Figure 3 The photocurrent signal in the middle.

Claims

1. A method for preparing indium oxide hollow nanotube / indium zinc sulfide heterojunction optoelectronic functional materials, characterized in that: Includes the following steps: (1) Dissolve indium nitrate hydrate and p-xylene (H2BDC) in 10 mL of N,N-dimethylformamide (DMF); (2) The precursor material of indium oxide hollow nanotubes (MIL-68(In) nanorods) is prepared from step (1). (3) The MIL-68(In) nanorods in step (2) are dried and then calcined to obtain In2O3 hollow nanotubes; (4) Acid washing of In2O3 hollow nanotubes in a three-necked flask; (5) Add zinc chloride, indium trichloride and thioacetamide to the three-necked flask in step (4), stir for 5 min, put the mixture into an oil bath at 95°C and stir for 2 hours, centrifuge and wash three times with ethanol, and then dry in a vacuum at 60°C to obtain indium oxide hollow nanotube / indium zinc sulfide heterojunction functional material.

2. The method for preparing an indium oxide hollow nanotube / indium zinc sulfide heterojunction optoelectronic functional material according to claim 1, characterized in that: The indium nitrate hydrate 0.8-0.85 g (In(NO3)3·H2O) and p-xylene 0.4-0.5 g (H2BDC) mentioned in step (1) were dissolved in 10 mL of N,N-dimethylformamide (DMF) under stirring and sonication.

3. The method for preparing an indium oxide hollow nanotube / indium zinc sulfide heterojunction optoelectronic functional material according to claim 1, characterized in that: In step (2), the Lavasil framework material (MIL-68(In) nanorods) was prepared by transferring the solution from step (1) into a high-pressure reactor lined with polytetrafluoroethylene and reacting it at 100 °C for 24 hours. After cooling to room temperature, the white precipitate was collected by centrifugation, washed three times with ethanol by centrifugation, and finally dried at 60 °C for 12 hours to obtain MIL-68(In) hollow nanorods as the precursor of indium oxide.

4. The method for preparing an indium oxide hollow nanotube / indium zinc sulfide heterojunction optoelectronic functional material according to claim 1, characterized in that: Step (3) Drying of MIL-68(In) nanorods: Drying at 150°C in a vacuum environment for 2 hours.

5. The method for preparing an indium oxide hollow nanotube / indium zinc sulfide heterojunction optoelectronic functional material according to claim 1, characterized in that: Step (3) Calcination of In2O3 hollow nanotubes: Placed in a muffle furnace, the temperature is raised to 400°C within half an hour and then to 500°C within two hours. After cooling to room temperature, In2O3 hollow nanotubes are obtained.

6. The method for preparing an indium oxide hollow nanotube / indium zinc sulfide heterojunction optoelectronic functional material according to claim 1, characterized in that: Step (4) Acid washing of In2O3 hollow nanotubes: Add 10 mL of hydrochloric acid solution (pH=2.5) and 70-75 mg of indium oxide from step (3) to a three-necked flask and stir for 30 minutes.

7. The method for preparing an indium oxide hollow nanotube / indium zinc sulfide heterojunction optoelectronic functional material according to claim 1, characterized in that: In step (5), add 27-28 mg of zinc chloride, 44-45 mg of indium trichloride and 30-35 mg of thioacetamide to the three-necked flask.

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