Silicon-titanium dioxide-polypyrrole three-dimensional bionic composite material based on hierarchical assembly and use thereof

Abstract

The invention relates to a three-dimensional bionic composite material based on refection elimination and double-layer P/N heterojunctions. The preparation method of the composite material comprises: (1) anisotropically etching a silicon wafer with an alkaline solution, to form compactly arranged tetragonal pyramids on the surface of the silicon wafer; (2) performing hydrophilic treatment on the silicon wafer, growing TiO2 crystal seeds on the surface of the silicon wafer, and calcining the silicon wafer in a muffle furnace; (3) putting the silicon wafer obtained in the step (2) into a reaction kettle, and growing TiO2 nano-rods on the side walls of silicon cones by a hydrothermal synthesis method; and (4) depositing PPY nano-particles on the TiO2 nano-rods. The composite material has good refection elimination performance and efficient photogenerated charge separation capability, and is applicable in fields of photo-catalysis, photoelectric conversion devices, solar cells and the like.

Claims

1. A silicon-titanium dioxide-polypyrrole three-dimensional bionic composite material based on hierarchical assembly, comprising an ordered hierarchy (Si/TiO.sub.2/PPY) of monocrystalline silicon (Si), titanium dioxide (TiO.sub.2) and polypyrrole (PPY), wherein Si is 100-type monocrystalline silicon with a tapered microstructure surface and is a P-type semiconductor, and has compactly arranged silicon cone structure of tetragonal pyramids with a height of 4-10 m; TiO.sub.2 is TiO.sub.2 nano-rods of rutile phase and is an N-type semiconductor, and is quadrangular with a height of 500-4000 nm and a diameter of 40-250 nm, and orderly and vertically grown on the side walls of the silicon cones; PPY is polypyrrole nano-particles with a diameter of 10-60 nm and is a P-type semiconductor, and is uniformly grown on the surfaces of the TiO.sub.2 nano-rods; in the Si/TiO.sub.2/PPY three-dimensional bionic composite material, double P/N heterojunctions are formed on interfaces between Si and TiO.sub.2 and between TiO.sub.2 and PPY, such that the composite material can efficiently separate photo-generated charges while having a three-dimensional bionic composite structure, and can effectively reduce the reflection of incident light on the surface.

2. A preparation method of the silicon-titanium dioxide-polypyrrole three-dimensional bionic composite material based on hierarchical assembly as claimed in claim 1, comprising steps of: (1) anisotropically etching a silicon wafer with an alkaline solution under stirring, to form compactly arranged tetragonal pyramids on the surface of the silicon wafer; (2) performing hydrophilic treatment on the silicon wafer etched in the step (1), growing TiO.sub.2 crystal seeds on the surface of the silicon wafer, and calcining the silicon wafer for a period of time in a muffle furnace, followed by naturally cooling the silicon wafer; (3) putting the silicon wafer having TiO.sub.2 crystal seeds on surface thereof obtained in the step (2) into a reactor, and growing TiO.sub.2 nano-rods on the side walls of silicon cones by a hydrothermal synthesis method; and (4) depositing conductive PPY nano-particles on the TiO.sub.2 nano-rods obtained in the step (3), to obtain the three-dimensional bionic Si/TiO.sub.2/PPY.

3. The preparation method as claimed in claim 2, wherein the alkaline solution in step (1) is potassium hydroxide, tetramethylammonium hydroxide, sodium hydroxide, aqueous ammonia or EDP (a mixed solution of ethylenediamine, pyrocatechol and water), and the pH value of the alkaline solution being 12-14, the etching temperature being 50-90 C., the etching time is 5-60 min, and the stirring being mechanical stirring or magnetic stirring.

4. The preparation method as claimed in claim 2, wherein the hydrophilic treatment in the step (2) comprises putting the silicon wafer obtained in the step (1) into a mixed solution of NH.sub.3H.sub.2O, H.sub.2O.sub.2 and H.sub.2O in a volume ratio of 1:1:5 and heating at a temperature of 90 C. for 30 min.

5. The preparation method according to claim 2, wherein growing TiO.sub.2 crystal seeds in the step (2) comprises: submerging the silicon wafer after the hydrophilic treatment into a 0.05-1 mol/L solution of tetrabutyl titanate in isopropanol for pulling or spin coating, and calcining the resulting sample in the muffle furnace under 450-500 C. for 30-60 min, the pulling speed being 1-10 mm/s and the pulling being repeated 5-30 times, the spin coating speed being 500-7000 revolutions per min.

6. The preparation method as claimed in claim 2, wherein the hydrothermal synthesis in the step (3) comprises: treating the silicon wafer in the reactor containing 10-20 mL of deionized water, 6-17 mL of concentrated hydrochloric acid and 0.5-5 mL of tetrabutyl titanate at a temperature of 80-200 C. for 2-19 h, then taking the sample out and blow-drying it with nitrogen.

7. The preparation method as claimed in claim 2, wherein depositing conductive PPY nano-particles on the TiO.sub.2 nano-rods in the step (4) comprises depositing PPY conductive polymer particles on the TiO.sub.2 nano-rods by an in-situ oxidation method, and the reaction condition being as follows: putting 0.01-0.06 g FeCl.sub.3, 50-150 uL pyrrole, and 5-10 mL ultrapure water into a beaker to obtain a reaction solution; putting a silicon wafer having an area of 1.5 cm1.0 cm and having the TiO.sub.2 nano-rods grown on surface thereof into the reaction solution, and stirring at room temperature for 10-60 min, to obtain the Si/TiO.sub.2/PPY three-dimensional bionic composite material.

8. A photo-catalyst for degrading an organic pollutant comprising the silicon-titanium dioxide-polypyrrole three-dimensional bionic composite material based on hierarchical assembly as claimed in claim 1, wherein the three-dimensional Si/TiO.sub.2/PPY composite material having an area of 1.5 cm1.0 cm is put into 5 mL of 1.010.sup.5 mol/L methylene blue solution, then the solution is put in dark for 1 h to achieve an adsorption-desorption balance, and then the solution is irradiated by a light source to degrade methylene blue.

9. A photocatalysis and photoelectric conversion device comprising the silicon-titanium dioxide-polypyrrole three-dimensional bionic composite material based on hierarchical assembly as claimed in claim 1.

10. A solar cell comprising the silicon-titanium dioxide-polypyrrole three-dimensional bionic composite material based on hierarchical assembly as claimed in claim 1.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIG. 1 is a scanning electron microscope image of monocrystalline silicon anisotropically etched with an alkaline solution according to embodiment 2;

(2) FIG. 2 is a scanning electron microscope image of the silicon wafer according to embodiment 2, wherein TiO.sub.2 nano-rods are assembled on the surfaces of silicon cones;

(3) FIG. 3 is a scanning electron microscope image of a three-dimensional Si/TiO.sub.2/PPY composite material obtained by hierarchically assembling on the surface of silicon cones in embodiment 2.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

Embodiment 1

(4) Step 1: Preparation of Silicon Cones

(5) 100 mL of KOH solution having a pH value of 13 was prepared, and 25 mL of isopropanol was added into the solution. A silicon wafer was put into the solution, and the silicon wafer was etched for 30 min at 70 C. under continuous stirring in a mechanical stirring manner. After etching, the silicon wafer was flushed with distilled water, and then was blow-dried with nitrogen.

(6) Step 2: Growing of TiO.sub.2 Crystal Seeds on the Side Walls of the Silicon Cones

(7) The silicon wafer with a silicon cone structure obtained in the step 1 was put into a mixed solution of NH.sub.3H.sub.2O, H.sub.2O.sub.2 and H.sub.2O in a volume ratio of 1:1:5 and heated. The heating temperature was 80 C. and the heating time was 30 min. Then, the silicon wafer was submerged into a 0.075 mol/L solution of tetrabutyl titanate in isopropanol, and the silicon wafer was pulled 20 times at a speed of 2 mm/s. Finally the sample was calcined for about 30 min in a muffle furnace under 450 C.

(8) Step 3: Preparation of TiO.sub.2 Nano-Rods Induced by TiO.sub.2 Crystal Seeds

(9) TiO.sub.2 nano-rods were grown on the silicon wafer carrying TiO.sub.2 crystal seeds on surface thereof obtained in the step 2 under a hydrothermal synthesis condition. The hydrothermal synthesis condition was as follows: the silicon wafer was treated under the temperature of 130 C. for 8 h in a reaction kettle filled with 10 mL of deionized water, 10 mL of concentrated hydrochloric acid (a mass fraction of 37%) and 0.5 mL of tetrabutyl titanate, then the sample was taken out and blow-dried with nitrogen.

(10) Step 4: In Situ Preparation of PPY Nano-Particles on the Surfaces of the TiO.sub.2 Nano-Rods

(11) PPY nano-particles were deposited on the TiO.sub.2 nano-rods obtained in the step 3 by an in-situ oxidation method. The reaction condition was as follows: putting 0.03 g FeCl.sub.3, 112.8 uL pyrrole, 6 mL ultrapure water into a beaker to obtain a reaction solution. A silicon wafer having an area of 1.5 cm1.0 cm with TiO.sub.2 nano-rods grown on surface thereof was put into the reaction solution, and stirring was performed for 25 min at room temperature. After the end of reaction, a sample was took out and flushed with a large excess of water, and then a three-dimensional Si/TiO.sub.2/PPY composite material was obtained.

(12) In the obtained three-dimensional Si/TiO.sub.2/PPY composite material, the average diameter of the PPY nano-particles was 35 nm, the average diameter of the TiO.sub.2 nano-rods was 83 nm, the average height was 818 nm, and the average height of the silicon cones was 4.1 m. By means of a ultraviolet diffuse reflection test, it is seen that the Si/TiO.sub.2/PPY hierarchical composite material showed excellent reflection elimination performance, and the light reflectivity is 9%. Upon a photocurrent test, it is obtained that the photocurrent of the Si/TiO.sub.2/PPY hierarchical composite material was about 11 times and 7 times those of pure TiO.sub.2 nano-rods and pure PPY respectively. By simulating the sunlight environment, it is found that the Si/TiO.sub.2/PPY hierarchical composite material can photo-catalytically degrade methylene blue. Furthermore, the change of concentration of the methylene blue with time was observed in combination with an ultraviolet spectrophotometer, it is known that the methylene blue dye was completely degraded within 6.5 h, and the degradation efficiency was higher than those of pure TiO.sub.2 nano-rods and pure PPY.

Embodiment 2

(13) Step 1: Preparation of Silicon Cones

(14) 100 mL of KOH solution having a pH value of 13 was prepared, and 25 mL of isopropanol was added into the solution. A silicon wafer was put into the solution, and the silicon wafer was etched for 30 min at 70 C. under continuous stirring in a mechanical stirring manner. After etching, the silicon wafer was flushed with distilled water, and then was blow-dried with nitrogen.

(15) Step 2: Growing of TiO.sub.2 Crystal Seeds on the Side Walls of the Silicon Cones

(16) The silicon wafer with a silicon cone structure obtained in the step 1 was put into a mixed solution of NH.sub.3H.sub.2O, H.sub.2O.sub.2 and H.sub.2O in a volume ratio of 1:1:5 and heated. The heating temperature was 80 C. and the heating time was 30 min. Then, the silicon wafer was submerged into a 0.075 mol/L solution of tetrabutyl titanate in isopropanol, and the silicon wafer was pulled 20 times at a speed of 2 mm/s. Finally the sample was calcined for about 30 min in a muffle furnace under 450 C.

(17) Step 3: Preparation of TiO.sub.2 Nano-Rods Induced by TiO.sub.2 Crystal Seeds

(18) TiO.sub.2 nano-rods were grown on the silicon wafer carrying TiO.sub.2 crystal seeds on surface thereof obtained in the step 2 under a hydrothermal synthesis condition. The hydrothermal synthesis condition was as follows: the silicon wafer was treated under the temperature of 130 C. for 8 h in a reaction kettle filled with 10 mL of deionized water, 10 mL of concentrated hydrochloric acid (a mass fraction of 37%) and 0.5 mL of tetrabutyl titanate, then the sample was taken out and blow-dried with nitrogen.

(19) Step 4: In Situ Preparation of PPY Nano-Particles on the Surfaces of the TiO.sub.2 Nano-Rods

(20) PPY nano-particles were deposited on the TiO.sub.2 nano-rods obtained in the step 3 by an in-situ oxidation method. The reaction condition was as follows: putting 0.03 g FeCl.sub.3, 112.8 uL pyrrole, 6 mL ultrapure water into a beaker to obtain a reaction solution. A silicon wafer having an area of 1.5 cm1.0 cm with TiO.sub.2 nano-rods grown on surface thereof was put into the reaction solution, and stirring was performed for 15 min at room temperature. After the end of reaction, a sample was took out and flushed with a large excess of water, and then a three-dimensional Si/TiO.sub.2/PPY composite material was obtained.

(21) In the obtained three-dimensional Si/TiO.sub.2/PPY composite material, the average diameter of the PPY nano-particles was 19 nm, the average diameter of the TiO.sub.2 nano-rods was 83 nm, the average height was 818 nm, and the average height of the silicon cones was 4.1 m. By means of an ultraviolet diffuse reflection test, it is seen that the Si/TiO.sub.2/PPY hierarchical composite material showed excellent reflection elimination performance, and the light reflectivity is 6%. Upon a photocurrent test, it is obtained that the photocurrent of the Si/TiO.sub.2/PPY hierarchical composite material was about 15 times and 10 times those of pure TiO.sub.2 nano-rods and pure PPY, respectively. By simulating the sunlight environment, it is found that the Si/TiO.sub.2/PPY hierarchical composite material can photo-catalytically degrade methylene blue. Furthermore, the change of concentration of the methylene blue with time was observed in combination with an ultraviolet spectrophotometer, it is known that the methylene blue dye was completely degraded within 5.5 h, and the degradation efficiency was higher than those of pure TiO.sub.2 nano-rods and pure PPY.

Embodiment 3

(22) Step 1: Preparation of Silicon Cones

(23) 100 mL of KOH solution having a pH value of 14 was prepared, and 25 mL of isopropanol was added into the solution. A silicon wafer was put into the solution, and the silicon wafer was etched for 15 min at 50 C. under continuous stirring in a mechanical stirring manner. After etching, the silicon wafer was flushed with distilled water, and then was blow-dried with nitrogen.

(24) Step 2: Growing of TiO.sub.2 Crystal Seeds on the Side Walls of the Silicon Cones

(25) The silicon wafer with a silicon cone structure obtained in the step 1 was put into a mixed solution of NH.sub.3H.sub.2O, H.sub.2O.sub.2 and H.sub.2O in a volume ratio of 1:1:5 and heated. The heating temperature was 90 C. and the heating time was 30 min. Then, the silicon wafer was submerged into a 0.1 mol/L solution of tetrabutyl titanate in isopropanol, and the silicon wafer was pulled 10 times at a speed of 2 mm/s. Finally the sample was calcined for about 30 min in a muffle furnace under 500 C.

(26) Step 3: Preparation of TiO.sub.2 Nano-Rods Induced by TiO.sub.2 Crystal Seeds

(27) TiO.sub.2 nano-rods were grown on the silicon wafer carrying TiO.sub.2 crystal seeds on surface thereof obtained in the step 2 under a hydrothermal synthesis condition. The hydrothermal synthesis condition was as follows: the silicon wafer was treated under the temperature of 120 C. for 8 h in a reaction kettle filled with 10 mL of deionized water, 10 mL of concentrated hydrochloric acid (a mass fraction of 37%) and 0.5 mL of tetrabutyl titanate, then the sample was taken out and blow-dried with nitrogen.

(28) Step 4: In Situ Preparation of PPY Nano-Particles on the Surfaces of the TiO.sub.2 Nano-Rods

(29) PPY nano-particles were deposited on the TiO.sub.2 nano-rods obtained in the step 3 by an in-situ oxidation method. The reaction condition was as follows: putting 0.03 g FeCl.sub.3, 112.8 uL pyrrole, 6 mL ultrapure water into a beaker to obtain a reaction solution. A silicon wafer having an area of 1.5 cm1.0 cm with TiO.sub.2 nano-rods grown on surface thereof was put into the reaction solution, and stirring was performed for 10 min at room temperature. After the end of reaction, a sample was took out and flushed with a large excess of water, and then a three-dimensional Si/TiO.sub.2/PPY composite material was obtained.

(30) In the obtained three-dimensional Si/TiO.sub.2/PPY composite material, the average diameter of the PPY nano-particles was 12 nm, the average diameter of the TiO.sub.2 nano-rods was 83 nm, the average height was 818 nm, and the average height of the silicon cones was 3.3 m. By means of ultraviolet diffuse reflection test, it is seen that the Si/TiO.sub.2/PPY hierarchical composite material showed excellent reflection elimination performance, and the light reflectivity is 4%. Upon a photocurrent test, it is obtained that the photocurrent of the Si/TiO.sub.2/PPY hierarchical composite material was about 21 times and 14 times those of pure TiO.sub.2 nano-rods and pure PPY, respectively. By simulating the sunlight environment, it is found that the Si/TiO.sub.2/PPY hierarchical composite material can photo-catalytically degrade methylene blue. Furthermore, the change of concentration of the methylene blue with time was observed in combination with an ultraviolet spectrophotometer, it is known that the methylene blue dye was completely degraded within 5 h, and the degradation efficiency was higher than those of pure TiO.sub.2 nano-rods and pure PPY.

(31) The above description is only preferred embodiments of the present invention and not intended to limit the present invention, it should be noted that those of ordinary skill in the art can further make various modifications and variations without departing from the technical principles of the present invention, and these modifications and variations also should be considered to be within the scope of protection of the present invention.