WO2017113564A1 - 一种基于消除反射和双层p/n异质结的三维仿生复合材料及应用 - Google Patents
一种基于消除反射和双层p/n异质结的三维仿生复合材料及应用 Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 46
- 239000011664 nicotinic acid Substances 0.000 title abstract 2
- 229920000767 polyaniline Polymers 0.000 claims abstract description 67
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 53
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 53
- 239000010703 silicon Substances 0.000 claims abstract description 53
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000002105 nanoparticle Substances 0.000 claims abstract description 18
- 238000002360 preparation method Methods 0.000 claims abstract description 18
- 238000005530 etching Methods 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 11
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 10
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 8
- 238000001354 calcination Methods 0.000 claims abstract description 3
- 238000000151 deposition Methods 0.000 claims abstract description 3
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 67
- 239000002073 nanorod Substances 0.000 claims description 41
- 239000000243 solution Substances 0.000 claims description 34
- 230000003592 biomimetic effect Effects 0.000 claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 24
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 23
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 16
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 15
- 239000013078 crystal Substances 0.000 claims description 14
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 claims description 13
- 229960000907 methylthioninium chloride Drugs 0.000 claims description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 10
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 238000011065 in-situ storage Methods 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 7
- 238000013033 photocatalytic degradation reaction Methods 0.000 claims description 7
- 239000011259 mixed solution Substances 0.000 claims description 6
- 239000004065 semiconductor Substances 0.000 claims description 6
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 5
- MMCPOSDMTGQNKG-UHFFFAOYSA-N anilinium chloride Chemical compound Cl.NC1=CC=CC=C1 MMCPOSDMTGQNKG-UHFFFAOYSA-N 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 238000010907 mechanical stirring Methods 0.000 claims description 5
- 229910021421 monocrystalline silicon Inorganic materials 0.000 claims description 5
- 230000003647 oxidation Effects 0.000 claims description 5
- 238000007254 oxidation reaction Methods 0.000 claims description 5
- 229920006316 polyvinylpyrrolidine Polymers 0.000 claims description 5
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 5
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 5
- 239000003513 alkali Substances 0.000 claims description 4
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 claims description 4
- 239000002957 persistent organic pollutant Substances 0.000 claims description 4
- 230000001699 photocatalysis Effects 0.000 claims description 4
- 238000004528 spin coating Methods 0.000 claims description 4
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- HEMINMLPKZELPP-UHFFFAOYSA-N Phosdiphen Chemical compound C=1C=C(Cl)C=C(Cl)C=1OP(=O)(OCC)OC1=CC=C(Cl)C=C1Cl HEMINMLPKZELPP-UHFFFAOYSA-N 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- 229920001940 conductive polymer Polymers 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 238000003760 magnetic stirring Methods 0.000 claims description 2
- 238000007146 photocatalysis Methods 0.000 claims description 2
- 238000002310 reflectometry Methods 0.000 claims description 2
- 238000002336 sorption--desorption measurement Methods 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims 1
- 239000005977 Ethylene Substances 0.000 claims 1
- 150000001412 amines Chemical class 0.000 claims 1
- 230000008021 deposition Effects 0.000 claims 1
- 238000010438 heat treatment Methods 0.000 claims 1
- 238000002156 mixing Methods 0.000 claims 1
- 238000010899 nucleation Methods 0.000 claims 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 abstract 2
- 239000012670 alkaline solution Substances 0.000 abstract 1
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 abstract 1
- 238000012876 topography Methods 0.000 abstract 1
- 239000000463 material Substances 0.000 description 11
- 238000000926 separation method Methods 0.000 description 4
- 230000015556 catabolic process Effects 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 238000001000 micrograph Methods 0.000 description 3
- 239000002114 nanocomposite Substances 0.000 description 3
- 230000005693 optoelectronics Effects 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000011941 photocatalyst Substances 0.000 description 2
- 230000006798 recombination Effects 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 230000003595 spectral effect Effects 0.000 description 2
- 239000011165 3D composite Substances 0.000 description 1
- 241001387484 Chichicaste Species 0.000 description 1
- 235000005929 Cnidoscolus chayamansa Nutrition 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 230000005525 hole transport Effects 0.000 description 1
- TUJKJAMUKRIRHC-UHFFFAOYSA-N hydroxyl Chemical compound [OH] TUJKJAMUKRIRHC-UHFFFAOYSA-N 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
- B01J31/069—Hybrid organic-inorganic polymers, e.g. silica derivatized with organic groups
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/38—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of titanium, zirconium or hafnium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/33—Electric or magnetic properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/12—Oxidising
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82B—NANOSTRUCTURES FORMED BY MANIPULATION OF INDIVIDUAL ATOMS, MOLECULES, OR LIMITED COLLECTIONS OF ATOMS OR MOLECULES AS DISCRETE UNITS; MANUFACTURE OR TREATMENT THEREOF
- B82B3/00—Manufacture or treatment of nanostructures by manipulation of individual atoms or molecules, or limited collections of atoms or molecules as discrete units
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/04—Oxides; Hydroxides
- C01G23/047—Titanium dioxide
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
- C02F1/32—Treatment of water, waste water, or sewage by irradiation with ultraviolet light
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/02—Elements
- C30B29/06—Silicon
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
Definitions
- Three-dimensional biomimetic composite material based on anti-reflection and double-layer P/N heterojunction and its application
- the present invention relates to a three-dimensional biomimetic composite material based on anti-reflection and two-layer P/N heterojunction, that is, a silicon-titania-polyaniline composite material, and the same composite can be used for photoelectric conversion and photocatalytic materials. It belongs to the field of optoelectronic materials technology.
- Titanium dioxide nanomaterials have outstanding application prospects in anticorrosive coatings, sewage purification, antibacterial sterilization, etc. due to their high catalytic activity, good stability, high hydroxyl radical yield, and non-corrosion.
- Polyaniline has good environmental stability, strong absorption in the visible region, strong electron donor and excellent hole transport material. When the two are effectively combined, a heterojunction will be formed at the contact interface, which not only improves the separation efficiency of the photo-generated charge, but also increases the spectral response range of the composite material, thereby improving the utilization of sunlight.
- Patent CN102432876A and CN102866181A disclose a method for preparing a polyaniline/titanium dioxide nanocomposite;
- Patent CN104084241A discloses a 3D flower structure titanium dioxide/polyaniline photocatalyst and a preparation method thereof;
- Patent CN102389836A discloses a poly Aniline/titanium dioxide/clay nanocomposite photocatalyst and preparation method thereof; the above has solved the problems of large band gap of titanium dioxide, small spectral response range, and photoelectron-hole pair recombination.
- polyaniline/titanium dioxide composites still have problems such as poor order, easy agglomeration, photo-generated charge easy to recombine, low recovery and utilization, etc., and the absorption rate of incident light on the surface of composite materials is not considered.
- problems such as poor order, easy agglomeration, photo-generated charge easy to recombine, low recovery and utilization, etc., and the absorption rate of incident light on the surface of composite materials is not considered.
- Popularization and application of polyaniline/titanium dioxide composites technical problem
- the object of the present invention is to overcome the shortcomings of the conventional titanium dioxide/polyaniline nanocomposites such as disorder, easy agglomeration, difficult recovery and low photoelectric conversion efficiency, and provide a kind of anti-reflection and double-layer P/N heterojunction.
- the three-dimensional biomimetic composite material has good anti-reflection performance and high-efficiency separation of photo-generated charge capacity, improves the photoelectric conversion efficiency of the material, and exhibits excellent photocatalytic ability, and the composite material is supported by single crystal silicon as a carrier. Recycling of materials.
- the three-dimensional biomimetic composite material based on the anti-reflection and double-layer P/N heterojunction is silicon/titania/polyaniline (Si/Ti0 2 /PANI).
- Si is a 100-type single crystal silicon with a tapered microstructure on the surface, which is a P-type semiconductor.
- the shape of the silicon cone is a square pyramid with a height of 4 to 10 ⁇ , which is closely arranged.
- TiO 2 is a rutile phase of TiO 2 nanorods.
- PANI is a polyaniline nanoparticle, which is a P-type semiconductor with a particle size of 10 to 60 nm and uniformly grown on the surface of TiO 2 nanorods.
- the interface between Si and Ti0 2 in Si/Ti0 2 /PANI three-dimensional composite material and the double P/N heterojunction at the interface between TiO 2 and PANI can efficiently separate photogenerated charges, and have a three-dimensional biomimetic composite structure, which can effectively reduce incidence.
- the reflectivity of light on the surface is a polyaniline nanoparticle, which is a P-type semiconductor with a particle size of 10 to 60 nm and uniformly grown on the surface of TiO 2 nanorods.
- a method for preparing a three-dimensional biomimetic composite material based on anti-reflection and two-layer P/N heterojunction is characterized in that it comprises the following steps:
- step (1) etched silicon wafer is hydrophilically treated, TiO 2 seed crystal is grown on the surface thereof, and placed in a muffle furnace for a period of calcination and then naturally cooled;
- the silicon wafer having the surface of the TiO 2 seed crystal obtained in the step (2) is placed in the reaction vessel, and the TiO 2 nanorods are grown on the sidewall of the silicon cone by hydrothermal synthesis;
- Conductive PANI nanoparticles were deposited on the nanorods to obtain a Si/TiO 2 /PANI three-dimensional biomimetic composite.
- the hydrophilic treatment operation in the step (2) is that the silicon wafer obtained in the step (1) is placed in a mixed solution of NH 3 ⁇ 2 0, ⁇ 2 ⁇ ⁇ ⁇ 2 0, and the volume ratio is 1:1:5, temperature is 90 °C, heated for 30 min°
- the condition of the grown TiO 2 seed crystals in the step (2) is that the hydrophilic processed silicon wafer is immersed in a concentration of 0.05 ⁇ 1.
- the hydrothermal synthesis condition in the step (3) is 80 to 200.
- the reactor was treated with mL of concentrated hydrochloric acid (37% by mass) and 0.5 to 5 mL of tetrabutyl titanate for 2 to 19 h, and then the sample was taken out and dried with nitrogen.
- depositing PANI nanoparticles on the TiO 2 nanorods according to the step (4) refers to assembling PANI conductive polymer particles on the TiO 2 nanorods by in-situ oxidation, and the reaction conditions are as follows: mL 0.2 ⁇ 0.5 mol/L aniline hydrochloride solution, add 3 ⁇ 7 g ammonium persulfate and 4 g PVP (polyvinylpyrrolidone k-30), mix evenly; the area is 1.5 cm X 1.0 cm
- the silicon wafer with TiO 2 nanorods grown on the surface is placed in the reaction solution, and stirred at room temperature for 1 ⁇ 8 h to obtain a Si Ti0 2 /PANI three-dimensional biomimetic composite.
- the Si/TiO 2 /PANI three-dimensional biomimetic composite material is used for photocatalytic degradation of organic pollutants, and a three-dimensional Si/TiO 2 /PANI composite material with a size of 1.5 cm ⁇ 1.0 cm is placed in 5 mL of methylene blue.
- the solution at a concentration of 1.0 x 10 -5 mo l / L, was then placed in the dark for 1 h to reach the adsorption-desorption equilibrium, after which the solution was illuminated with a light source to degrade the methylene blue.
- this kind of biomimetic composite material is not limited to the application of photocatalytic degradation of organic pollutants, but also suitable for other fields of photocatalysis, photoelectric conversion devices, solar cells and the like.
- Ti0 2 nanorods and PANI nanoparticles are sequentially assembled at the surface of the silicon cone to form a three-dimensional biomimetic composite structure, which has excellent anti-reflection performance.
- the three-dimensional Si/Ti0 2 /PANI composite material has a high specific surface area, increases the effective catalytic activity point of the surface, and has certain use value in photocatalytic degradation of pollutants.
- Example 1 is a scanning electron microscope image of single crystal silicon subjected to anisotropic etching of lye in Example 1;
- Example 2 is a scanning electron microscope image of TiO 2 nanorods assembled on the surface of a silicon cone in Example 1.
- Example 3 is a scanning electron microscope image of a Si/TiO 2 /PANI three-dimensional biomimetic composite material assembled on the surface of a silicon cone in Example 1.
- Step 1 Preparation of a silicon cone
- Step 2 Growth of TiO 2 seed crystals on the sidewall of the silicon cone
- the silicon wafer having the silicon cone structure obtained in the first step is placed in a mixed solution of NH 3 H 2 0, H 2 0 2 and H 2 0, and the volume ratio is 1:1:5, and the temperature is 80 °. C, heated for 30 minutes. Then, it is immersed in a solution of tetrabutyl titanate in a concentration of 0.075 mol/L in an isopropanol solution, and the pulling speed is 2
- Step 3 Preparation of Ti0 2 nanorods by Ti0 2 seed crystals
- the silicon wafer with the TiO 2 seed crystals obtained on the surface obtained in the second step is subjected to hydrothermal conditions to grow the TiO 2 nanorods.
- the hydrothermal synthesis conditions were carried out at a temperature of 130 ° C in a reaction vessel containing 10 mL of deionized water, 10 mL of concentrated hydrochloric acid (37% by mass) and 0.5 mL of tetrabutyl titanate for 8 h, and then the sample was taken out. Dry with nitrogen.
- Step 4 In situ preparation of PANI nanoparticles on the surface of TiO 2 nanorods
- PANI nanoparticles were deposited on the TiO 2 nanorods obtained in step two by in situ oxidation.
- the reaction conditions were as follows: 100 mL of 0.3 mol/L aniline hydrochloride solution was prepared, and 5 g of ammonium persulfate and 4 g of PVP (polyvinylpyrrolidone k-30) were added and mixed uniformly; the area was 1.5 cm X A 1.0 cm surface wafer with TiO 2 nanorods was placed in the reaction solution, and stirred at room temperature for 3 h to obtain a Si/TiO 2 /PANI three-dimensional biomimetic composite.
- the average particle diameter of the PANI nanoparticles is 44 nm
- the average diameter of the TiO 2 nanorods is 83 nm
- the average height is 818 nm
- the average height of the silicon cones is 4.1 ⁇ .
- the UV diffuse reflectance test shows that the Si/TiO 2 / ⁇ layer composite exhibits excellent antireflection and the light reflectance is 4%.
- the photocurrent test shows the photocurrent of the Si Ti0 2 /PANI layer composite.
- Step 1 Preparation of a silicon cone
- Step 2 Growth of TiO 2 seed crystals on the sidewall of the silicon cone
- the silicon wafer having the silicon cone structure obtained in the first step is placed in a mixed solution of NH 3 H 2 0, H 2 0 2 fPH 2 0, the volume ratio is 1:1:5, and the temperature is 80 ° C. , heated for 30 minutes. Then, it is immersed in a solution of tetrabutyl titanate in a concentration of 0.075 mol/L in an isopropanol solution, and the pulling speed is 2 Mm/s, repeated pulling 20 times, and finally the above sample was calcined in a muffle furnace at 450 ° C for about 30 min.
- Step 3 Preparation of Ti0 2 nanorods by Ti0 2 seed crystals
- the silicon wafer with the TiO 2 seed crystal on the surface obtained in the second step was placed under hydrothermal conditions to grow the TiO 2 nanorods.
- the hydrothermal synthesis conditions were carried out at a temperature of 130 ° C in a reaction vessel containing 10 mL of deionized water, 10 mL of concentrated hydrochloric acid (37% by mass) and 0.5 mL of tetrabutyl titanate for 8 h, and then the sample was taken out. Dry with nitrogen.
- Step 4 In situ preparation of PANI nanoparticles on the surface of TiO 2 nanorods
- PANI nanoparticles were deposited on the TiO 2 nanorods obtained in step two by in situ oxidation.
- the reaction conditions were as follows: 100 mL of 0.3 mol/L aniline hydrochloride solution was prepared, and 7 g of ammonium persulfate and 4 g of PVP (polyvinylpyrrolidone k-30) were added and mixed uniformly; the area was 1.5 cm X A 1.0 cm surface wafer with TiO 2 nanorods was placed in the reaction solution, and stirred at room temperature for 4 h to obtain a Si/TiO 2 /PANI three-dimensional biomimetic composite.
- the average particle diameter of the PANI nanoparticles is 44 nm
- the average diameter of the TiO 2 nanorods is 83 nm
- the average height is 818 nm
- the average height of the silicon cones 4.1 ⁇ . .
- the UV diffuse reflectance test shows that the Si/TiO 2 / ⁇ layer composite exhibits excellent anti-reflection performance with a light reflectance of 6%.
- the photocurrent test shows that the photocurrent of the Si Ti0 2 /PANI layer composite is approximately 18 times and 11 times of pure TiO 2 nanorods and pure PANI; photocatalytic degradation of methylene blue by Si/TiO 2 /PANI layer composites by simulated solar environment, combined with UV spectrophotometer to investigate the variation of methylene blue concentration with daytime The dye methylene blue was completely degraded within 5.5 h, and the degradation efficiency was higher than that of pure TiO 2 nanorods and pure PANI.
- Step 1 Preparation of a silicon cone
- Step 2 Growth of TiO 2 seed crystals on the sidewall of the silicon cone
- the silicon wafer having the silicon cone structure obtained in the first step is placed in a mixed solution of NH 3 H 2 0, H 2 0 2 and H 2 0 in a volume ratio of 1:1:5 and a temperature of 90 °. C, heated for 30 minutes. Then, immersed in a concentration of 0.1 The mol/L tetrabutyl titanate is extracted in an isopropanol solution, and the pulling speed is 2
- Step 3 Preparation of Ti0 2 nanorods by Ti0 2 seed crystals
- the silicon wafer with the TiO 2 seed crystal on the surface obtained in the second step was placed under hydrothermal conditions to grow the TiO 2 nanorods.
- the hydrothermal synthesis conditions were 120 ° C, and treated in a reaction vessel containing 10 mL of deionized water, 10 mL of concentrated hydrochloric acid (37% by mass) and 0.5 mL of tetrabutyl titanate for 8 h, and then the sample was taken out. Dry with nitrogen.
- Step 4 In situ preparation of PANI nanoparticles on the surface of TiO 2 nanorods
- PANI nanoparticles were deposited on the TiO 2 nanorods obtained in step two by in situ oxidation.
- the reaction conditions were as follows: 100 mL of 0.3 mol/L aniline hydrochloride solution was prepared, and 7 g of ammonium persulfate and 4 g of PVP (polyvinylpyrrolidone k-30) were added and mixed uniformly; the area was 1.5 cm X A 1.0 cm surface wafer with TiO 2 nanorods was placed in the reaction solution, and stirred at room temperature for 5 h to obtain a Si/TiO 2 /PANI three-dimensional biomimetic composite.
- the average particle diameter of the PANI nanoparticles is 52 nm
- the average diameter of the TiO 2 nanorods is 83 nm
- the average height is 818 nm
- the photocurrent test shows the photocurrent of the Si Ti0 2 /PANI layer composite.
- Si/TiO 2 /PANI layer composites photocatalyticly degrade methylene blue by simulated solar environment, and the concentration of methylene blue with diurnal changes was investigated by UV spectrophotometer.
- the dye methylene blue was completely degraded within 7 h, and the degradation efficiency was higher than that of pure TiO 2 nanorods and pure PANI.
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