CN109622064B - Double-layer three-dimensional bionic anti-reflection composite material and preparation method thereof - Google Patents
Double-layer three-dimensional bionic anti-reflection composite material and preparation method thereof Download PDFInfo
- Publication number
- CN109622064B CN109622064B CN201811541214.4A CN201811541214A CN109622064B CN 109622064 B CN109622064 B CN 109622064B CN 201811541214 A CN201811541214 A CN 201811541214A CN 109622064 B CN109622064 B CN 109622064B
- Authority
- CN
- China
- Prior art keywords
- tio
- composite material
- ppy
- double
- reflection
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000002131 composite material Substances 0.000 title claims abstract description 49
- 239000011664 nicotinic acid Substances 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 100
- 229920000128 polypyrrole Polymers 0.000 claims abstract description 59
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 47
- 239000011521 glass Substances 0.000 claims abstract description 30
- 239000000463 material Substances 0.000 claims abstract description 19
- 238000011065 in-situ storage Methods 0.000 claims abstract description 10
- 239000011941 photocatalyst Substances 0.000 claims abstract description 8
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 27
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 25
- 229910052710 silicon Inorganic materials 0.000 claims description 25
- 239000010703 silicon Substances 0.000 claims description 25
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 15
- 239000004408 titanium dioxide Substances 0.000 claims description 15
- 239000000243 solution Substances 0.000 claims description 14
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 12
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 10
- VYXSBFYARXAAKO-UHFFFAOYSA-N ethyl 2-[3-(ethylamino)-6-ethylimino-2,7-dimethylxanthen-9-yl]benzoate;hydron;chloride Chemical compound [Cl-].C1=2C=C(C)C(NCC)=CC=2OC2=CC(=[NH+]CC)C(C)=CC2=C1C1=CC=CC=C1C(=O)OCC VYXSBFYARXAAKO-UHFFFAOYSA-N 0.000 claims description 10
- 230000003667 anti-reflective effect Effects 0.000 claims description 9
- -1 polydimethylsiloxane Polymers 0.000 claims description 9
- 239000000975 dye Substances 0.000 claims description 8
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 7
- 238000001354 calcination Methods 0.000 claims description 6
- 238000005530 etching Methods 0.000 claims description 6
- 239000012670 alkaline solution Substances 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- 230000000295 complement effect Effects 0.000 claims description 4
- 238000013033 photocatalytic degradation reaction Methods 0.000 claims description 4
- 239000002243 precursor Substances 0.000 claims description 4
- 239000010936 titanium Substances 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- 230000005693 optoelectronics Effects 0.000 claims description 2
- 238000003825 pressing Methods 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims 1
- 230000015556 catabolic process Effects 0.000 abstract description 11
- 238000006731 degradation reaction Methods 0.000 abstract description 11
- 230000001699 photocatalysis Effects 0.000 abstract description 11
- 238000013461 design Methods 0.000 abstract description 2
- 239000010410 layer Substances 0.000 description 26
- 238000010521 absorption reaction Methods 0.000 description 10
- 230000003197 catalytic effect Effects 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000004065 semiconductor Substances 0.000 description 6
- 230000008859 change Effects 0.000 description 5
- 230000031700 light absorption Effects 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 238000002310 reflectometry Methods 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 230000003592 biomimetic effect Effects 0.000 description 3
- 239000000969 carrier Substances 0.000 description 3
- 229920001940 conductive polymer Polymers 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000004987 plasma desorption mass spectroscopy Methods 0.000 description 3
- 230000003595 spectral effect Effects 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 239000002114 nanocomposite Substances 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 239000002356 single layer Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 241000255925 Diptera Species 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 206010070834 Sensitisation Diseases 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000000861 blow drying Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 239000002096 quantum dot Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000000985 reflectance spectrum Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 230000008313 sensitization Effects 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000000935 solvent evaporation Methods 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000000411 transmission spectrum Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Images
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
- B01J31/26—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
-
- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D3/00—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances
- A62D3/10—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by subjecting to electric or wave energy or particle or ionizing radiation
- A62D3/17—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by subjecting to electric or wave energy or particle or ionizing radiation to electromagnetic radiation, e.g. emitted by a laser
- A62D3/176—Ultraviolet radiations, i.e. radiation having a wavelength of about 3nm to 400nm
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Engineering & Computer Science (AREA)
- General Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Physics & Mathematics (AREA)
- General Chemical & Material Sciences (AREA)
- Business, Economics & Management (AREA)
- Emergency Management (AREA)
- Inorganic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Optics & Photonics (AREA)
- Electromagnetism (AREA)
- Catalysts (AREA)
Abstract
The invention relates to a double-layer three-dimensional bionic anti-reflection composite material and a preparation method thereof, belonging to the field of materials science. The invention firstly constructs the front and the back surfaces of the glass respectively by the soft stamping technologyTiO for building three-dimensional pyramid structure2Then growing polypyrrole (PPy) in situ to form P-n heterojunction with artificial moth-eye structure and bionic anti-reflection structure (PPy/P-TiO)2/G/P‑TiO2the/PPy) anti-reflection composite material provides a new idea for the structural design of the photocatalyst. The anti-reflection composite material can efficiently catalyze the degradation of organic dye, has excellent anti-reflection performance and photocatalytic activity, and has simple and convenient preparation method and good industrial prospect.
Description
Technical Field
The invention relates to a double-layer three-dimensional bionic anti-reflection composite material and a preparation method thereof, belonging to the field of materials science.
Background
Anatase type TiO2The photocatalyst has the characteristics of high photocatalytic activity, good stability, low price, no toxicity and the like, and is widely and deeply researched by scientists in various countries, such as the fields of photocatalysis, dye-sensitized solar cells, lithium ion batteries, sensors, photoelectrochemical cells and the like. Nano TiO22The band gap energy is about 3.2eV, the forbidden band width is larger, and therefore, the light is absorbed only in the wavelength range of 200-400nm, and the utilization rate of the solar energy is lower. To solve this bottleneck problem, there have been studies to change TiO by various means2The surface or bulk properties of the material, such as doping metal and/or non-metal atoms, plasmon resonance (e.g., Au, Ag, etc.), quantum dot sensitization, narrow bandgap semiconductor recombination, and the like. TiO modified with narrow bandgap semiconductors2When the material is used, heterojunction is formed on the interface of the material, the separation performance of electrons and holes of the material is enhanced, and the spectrum absorption range is enlarged.
In addition to solving anatase type TiO in the aspect of solar energy utilization efficiency2Forbidden band width problem, and the need forAttention is paid to the incident light absorption efficiency. The anti-reflection film is constructed on the surface of the photoelectric material or the device, so that the interface reflection of the material can be greatly reduced, and the light absorption efficiency of the material is increased. The anti-reflection film is mainly divided into a single-layer film method, a multi-layer film method and a microstructure method. Among them, the microstructure method can overcome the defects of the single-layer film method and the multi-layer film method (such as antireflection in a wide spectral range) and is widely used. The soft imprinting technique is used to construct microstructure (such as ZnO nano array, TiO) on the surface of the device2Nano array, etc.) to enhance the absorption of the photoelectric device to light and improve the conversion efficiency of solar energy, but because only one layer of 2D grating structure is constructed on one surface of the transparent substrate, the antireflection effect of the device to light is very limited, thereby limiting the further improvement of the conversion efficiency of solar energy.
Disclosure of Invention
In order to solve the problems and improve the solar energy conversion efficiency, the invention firstly constructs TiO with three-dimensional pyramid structure on the front and back surfaces of the glass respectively by soft stamping technology2Then growing polypyrrole (PPy) in situ to form PPy/TiO with artificial moth eye structure2A double-layer three-dimensional bionic anti-reflection composite material. The proportion of two mediums refracted in the bionic moth eye structure of the double-layer three-dimensional bionic anti-reflection composite material is gradually changed, so that the refractive index of the surface is gradually changed from air to the substrate, excellent anti-reflection is realized, and a high light absorption effect is achieved.
Firstly, preparing a silicon template with a pyramid structure by utilizing the characteristic that monocrystalline silicon is subjected to anisotropic etching in an alkaline solution; then pouring the PDMS prepolymer on the surface of the silicon template, and curing to obtain a PDMS template with a structure complementary with that of the silicon template; pressing PDMS template with TiO drop2The solvent is slowly volatilized on the clean glass surface of the sol, the tetra-n-butyl titanate prepolymer in the sol is further condensed to form amorphous TiO2Meanwhile, the confinement effect of the PDMS template enables TiO to be formed2Forming a pyramid structure complementary with the PDMS template on the surface of the glass; then adding TiO2Calcining to convert it to anatase TiO2Increasing the TiO content2The photocatalytic ability of (c); finally in TiO2A layer of conductive polymer PPy is compounded on the surface of the pyramid, the spectral absorption range of the material and the separation efficiency of photon-generated carriers are further improved, and finally the double-layer three-dimensional bionic structure PPy/TiO with high photocatalytic capacity is obtained2A composite material (as shown in figure 1).
The first purpose of the invention is to provide an anti-reflection composite material, which has a double-layer three-dimensional bionic structure and comprises titanium dioxide with a pyramid structure and polypyrrole on the surface of a pyramid.
In one embodiment of the present invention, the method for preparing the antireflective composite material comprises:
(1) preparation of titanium dioxide having a pyramidal structure: preparing a Polydimethylsiloxane (PDMS) template in advance, and adding TiO on the PDMS template2Dissolving the sol, volatilizing the solvent and calcining to obtain the titanium dioxide with the pyramid structure;
(2) preparing an anti-reflection composite material containing surface polypyrrole: pyrrole grows in situ on titanium dioxide with a pyramid structure to obtain the anti-reflection composite material with the surface polypyrrole and the double-layer three-dimensional bionic structure.
In one embodiment of the present invention, the method for preparing the PDMS template includes: and etching the silicon wafer in an alkaline solution to obtain a silicon template with a pyramid structure, pouring the dimethyl siloxane precursor solution onto the silicon template, and curing to obtain the PDMS template with a structure complementary to that of the silicon template.
In one embodiment of the invention, the alkaline solution comprises one or both of potassium hydroxide, isopropanol.
In one embodiment of the invention, the etching temperature of the silicon wafer for preparing the silicon template is 60-100 ℃.
In one embodiment of the invention, the etching time of the silicon wafer for preparing the silicon template is 20-60 min.
In an embodiment of the present invention, the method for preparing the PDMS template further includes pouring the dimethylsiloxane precursor solution onto the silicon template, performing vacuum pumping and curing, and finally peeling the silicon template and the PDMS to obtain the PDMS template.
In one embodiment of the invention, the titanium source comprises one or more of n-butyl titanate, titanium tetrachloride and isopropyl titanate.
In one embodiment of the invention, the titanium source is present in the titanium dioxide sol in an amount of 15% to 30% by volume.
In one embodiment of the invention, the solvent comprises absolute ethanol.
In one embodiment of the present invention, the step (2) is performed in a ferric trichloride solution.
In one embodiment of the invention, the pyrrole is on TiO2The surface in-situ growth is carried out for 10-20min, and the anti-reflection composite material containing the surface polypyrrole and having a double-layer three-dimensional bionic structure can be obtained.
The second purpose of the invention is to provide a method for photocatalytic degradation of organic dyes, which uses the anti-reflection composite material with a double-layer three-dimensional bionic structure as a photocatalyst.
A third object of the present invention is to provide an optoelectronic material or device, characterized in that it comprises the above-mentioned antireflective composite.
The invention has the beneficial effects that:
(1) because the photoelectric material and the surface of the device have interface reflection, the conversion efficiency of the photoelectric material and the device to solar energy is limited, and the composite material constructs TiO on the front and back surfaces of glass2The antireflection layer is obtained by the pyramid structure, and then conductive polymer polypyrrole nano particles are loaded on the surface of the pyramid, so that the P-N heterojunction composite material with the double-layer bionic structure is successfully prepared, and the P-N heterojunction composite material has excellent antireflection performance and photocatalytic activity.
(2) The invention adopts the soft imprinting technology and the in-situ oxidation method to construct a double-layer structure, and successfully prepares a composite coating (PPy/P-TiO) with a P-n heterojunction and a bionic anti-reflection structure on the surface of the glass2/G/P-TiO2PPy) due to PPy and P-TiO2P-n heterojunction therebetweenAnd a micro-nano composite structure to ensure that the double-layer PPy/P-TiO2The glass has good anti-reflection performance and photocatalytic performance, and provides a new idea for the structural design of the photocatalyst.
(3) The composite material is used as a photocatalyst, has good catalytic activity, can realize high-efficiency catalytic degradation of organic dye, and almost completely degrades the dye when the illumination time reaches 4 hours.
Drawings
FIG. 1 shows a double-layer three-dimensional bionic structure PPy/TiO2Schematic diagram of composite material preparation;
FIG. 2 shows a double-layer three-dimensional biomimetic structure PPy/TiO2SEM atlas of composite Material, where (A), (C) are TiO imprinted on glass2Pyramid structure (P-TiO)2SEM spectrum of/G), (B) TiO imprinted on glass2Pyramid structure (P-TiO)2Partial enlargement of/G), (D) TiO2PPy (PPy/P-TiO) loaded on pyramid2Partial enlargement of/G), (E) and (F) are flat TiO imprinted with unpatterned PDMS2(F-TiO2/G) SEM picture, wherein P is PDMS template, G is glass;
FIG. 3 is a two-sided F-TiO2Glass (F-TiO)2/G/F-TiO2) Double-sided P-TiO2Glass P-TiO2(P-TiO2/G/P-TiO2) Double-sided PPy/P-TiO2Glass (PPy/P-TiO)2/G/P-TiO2PPy) and the like;
FIG. 4 shows a double-sided F-TiO2Glass (F-TiO)2/G/F-TiO2) Double-sided PPy/P-TiO2Glass (PPy/P-TiO)2/G/P-TiO2PPy) of the glass surface in the form of a combination of different composite materials, wherein F-TiO2Refers to the plane TiO imprinted by non-patterned PDMS2，P-TiO2The titanium dioxide is pyramid titanium dioxide without a double-layer microstructure PPy;
FIG. 5 shows a double-sided F-TiO2Glass (F-TiO)2/G/F-TiO2) Double-sided P-TiO2Glass P-TiO2(P-TiO2/G/P-TiO2) Double-sided PPy/P-TiO2Glass (PPy/P-TiO)2/G/P-TiO2PPy) and the like;
FIG. 6(A) shows PPy/P-TiO2/G/P-TiO2A degradation trend graph of Rh 6G organic dye of the/PPy structure composite material in different catalytic degradation time, (B) is a trend graph of the same catalytic degradation of materials with different structures in the same area;
FIG. 7 is a schematic diagram of a P-N heterojunction of a P-N heterojunction composite material with a double-layer biomimetic structure.
Detailed Description
Example 1 preparation of double-layer three-dimensional biomimetic Structure PPy/TiO2Composite material
Preparation of PDMS template: cleaning a silicon wafer, then placing the silicon wafer into a mixed solution of 6 wt% of potassium hydroxide and 5 vol% of isopropanol, etching the silicon wafer for 60min at 50 ℃, pouring the stirred dimethyl siloxane precursor solution onto a silicon template, and then placing the silicon template into a vacuum drier for vacuumizing to remove bubbles; and after the template is leveled and cured for 3 hours, finally stripping the silicon template and the PDMS to obtain the PDMS template.
TiO2Constructing a pyramid structure:
mechanically stirring the prepared mixed solution of 8mL of n-butyl titanate and 25mL of absolute ethyl alcohol in a water bath kettle at the temperature of 30 ℃ for 15min, dropwise adding the mixed solution of 2mL of absolute ethyl alcohol and 4mL of water into the mixed solution, and reacting in a water bath for 1h to obtain TiO2Sol; wherein the volume of the titanium source accounts for 15-30% of the total volume of the raw materials.
After glass (2cm × 2.5cm) was cleaned and hydrophilized, it was blow-dried with nitrogen for further use, and 80. mu.l TiO was dropped on one side of the glass2Collosol, namely lightly covering a PDMS template on the surface, standing for 12h, drying the PDMS template in an oven at 68 ℃ for 40min, and repeating the steps on the other surface of the same glass; finally, peeling off the PDMS template, putting the PDMS template into a vacuum tube furnace, heating to 450 ℃ at a heating rate of 3 ℃/min by taking nitrogen as protective gas, and calcining for 4h to obtain the TiO with the pyramid structure2。
In situ growthPPy: will be imprinted with TiO2The glass sheet is pasted on the wall of the beaker, and FeCl is added3Stirring the solution for 5min, adding pyrrole solution to make PPy in TiO2Growing in situ on the surface for 15min, cleaning the surface residues with clear water, and blow-drying with nitrogen to obtain the double-layer three-dimensional bionic structure PPy/TiO2A composite material.
Material characterization:
the obtained double-layer three-dimensional bionic structure PPy/TiO2The composite material was analyzed by SEM and, as can be seen from FIG. 2, FIG. 2(B) shows TiO imprinted on glass2Pyramid structure (P-TiO)2G), in the following discussion, the glass is abbreviated as G, and after soft printing, the titanium dioxide pyramid array conforms to the silicon pyramid structure, indicating that the silicon pyramid structure is successfully replicated; during contact transfer and subsequent calcination, TiO is caused by volatilization of the solvent and a crystal transformation during calcination2The pyramid shrinks slightly, rigid TiO on the substrate2The film is broken; the results are shown in FIGS. 2(A) and 2(B), and TiO2There are gaps between the pyramids. FIG. 2(D) is TiO2PPy (PPy/P-TiO) loaded on pyramid2Partial enlargement of/G), it can be seen that the prepared PPy uniformly covers the pyramid in the form of nanoparticles (10-50 nm), resulting in an increase in the overall structure; FIGS. 2(E) and (F) are planar TiO imprinted with unpatterned PDMS2(F-TiO2/G) SEM photograph showing that in rigid TiO2The film is destroyed, but with respect to TiO with pyramid structure2The film has less cracking; this is due to the pyramid-structured TiO2The film has a greater shrinkage ratio during solvent evaporation, resulting in more cracking defects.
FIG. 4 shows F-TiO by spectroscopic property analysis2、P-TiO2、PPy/P-TiO2Reflectance spectra of various combinations of three materials:
preparation of double-sided P-TiO on glass2Glass (P-TiO)2/G/P-TiO2) After the structure (curve c), compared to a bilayer of F-TiO2Of the structure/G (curve a), in the visible-near infrared regionThe reflectance (R%) is reduced by about 10%;
one surface is pyramid structure and the other surface is plane structure (P-TiO)2/G/F-TiO2) The reflectivity of the sample (curve b) is reduced by about 4% due to the TiO on the glass surface2The pyramid structure increases the reflection times of incident light in the sample, thereby increasing the optical path of the incident light and reducing the surface reflectivity of the sample;
as shown by curve f, double-sided PPy/P-TiO2Glass three-dimensional bionic composite structure (PPy/P-TiO)2/G/P-TiO2PPy) the reduction in reflectance in the visible to near infrared region, especially in the visible region, is very large, since TiO2Modification of conductive polymer PPy on the surface of the structure, wherein a micron-scale structure and a nano-scale structure exist on the surface of the glass at the same time, the structure conforms to a three-stage micro-nano composite structure, is similar to a mosquito compound eye, can further reduce the change of the air-interface refractive index, and conforms to the effective medium theory;
meanwhile, the PPy is a narrow-band-gap semiconductor, so that the composite material has higher absorption in a visible-near infrared region, the reflectivity of the composite material is reduced, and the PPy/P-TiO can be seen from a transmission spectrum (figure 5) and an absorption spectrum (figure 3)2/G/P-TiO2the/PPy three-dimensional bionic composite structure has lower transmission and higher absorption, wherein the transmission rate is only 21 percent, and the absorption rate can reach about 62 percent, thereby laying a solid foundation for the high photocatalytic performance.
Example 2: double-layer three-dimensional bionic structure PPy/TiO2The composite material is applied to simulating solar photo-catalytic organic dye.
1ml of Rh 6G (10) was taken-5mol/L) in a reactor, and preparing the double-layer three-dimensional bionic structure PPy/TiO2Cutting the composite material sample into 1cm × 1.5.5 cm, placing into a reactor, catalyzing under a xenon lamp, measuring the absorbance change of the solution at 525nm by using an ultraviolet spectrophotometer, and calculating the concentration of Rh 6G in the solution;
percent Degradation (Degradation rate%) [ (C)0-C)/C0]×100％；
Wherein C is0The initial Rh 6G solution concentration, and C is the Rh 6G solution concentration after a certain time of catalytic reaction.
To demonstrate PPy/P-TiO2/G/P-TiO2The photocatalysis efficiency of the PPy structure is applied to the simulation of the photocatalytic degradation of organic dyes by solar energy: fig. 6(a) shows the trend of the change of the absorption peak of the Rh 6G solution at 526nm at different catalytic degradation times, from the change of the peak intensity in the graph, the concentration of Rh 6G decreases with the increase of the irradiation time, and when the irradiation time reaches 4h, the absorption peak almost completely disappears, that is, the degradation rate of Rh 6G in the solution can reach 99.9%, and almost completely degrades; the same catalytic degradation experiment was performed with the same area of materials of different structures, and the results are shown in FIG. 6(B), and it was found that all samples can play a catalytic role in the degradation of dye molecules, PPy/P-TiO2/G/P-TiO2the/PPy structure shows the best photocatalytic degradation performance. The performance of a photocatalyst is mainly determined by three aspects: the light absorption capacity of the photocatalyst, the separation and migration capacity of photon-generated carriers and the efficiency of interface reaction. First, PPy/P-TiO can be found from the reflection spectrum2/G/P-TiO2the/PPy structure has lower reflectivity and transmissivity in the ultraviolet, visible and near infrared regions, thereby having higher absorption; next, from the SEM image, TiO was found2The pyramid structure has large specific surface area, can provide more active sites for catalytic reaction, and improves the interface reaction rate; PPy is a narrow bandgap semiconductor with TiO2The spectral absorption range of the material can be widened during compounding; also as shown in FIG. 7, PPy is a p-type semiconductor and TiO2Being an n-type semiconductor, in PPy and TiO2The p-n heterojunction can be formed at the composite interface, so that the separation efficiency of the photon-generated carriers can be improved, and the photocatalytic performance is improved. It has more excellent catalytic efficiency in the same catalytic time.
Although the present invention has been described with reference to the preferred embodiments, it should be understood that various changes and modifications can be made therein by those skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (7)
1. The anti-reflection composite material is characterized by having a double-layer three-dimensional bionic structure and comprising titanium dioxide with a pyramid structure and polypyrrole on the surface of a pyramid;
the anti-reflection composite material is TiO with a three-dimensional pyramid structure respectively constructed on the front surface and the back surface of glass2Then growing polypyrrole PPy in situ to form PPy/TiO with artificial moth eye structure2A double-layer three-dimensional bionic anti-reflection composite material;
the preparation method of the anti-reflection composite material comprises the following steps:
(1) preparation of titanium dioxide having a pyramidal structure: preparing a polydimethylsiloxane template in advance, pressing the polydimethylsiloxane template on the front surface and the back surface of the glass dripped with the titanium dioxide sol, volatilizing a solvent, and calcining to obtain titanium dioxide with a pyramid structure;
(2) preparing an anti-reflection composite material containing surface polypyrrole: in a ferric trichloride solution, pyrrole grows in situ on titanium dioxide with a pyramid structure to obtain the antireflection composite material with a double-layer three-dimensional bionic structure and containing polypyrrole on the surface.
2. The antireflective composite of claim 1, wherein the polydimethylsiloxane template is prepared by a method comprising: and etching the silicon wafer in an alkaline solution to obtain a silicon template with a pyramid structure, pouring dimethyl siloxane precursor solution onto the silicon template, and curing to obtain a dimethyl siloxane template with a structure complementary with that of the silicon template.
3. The antireflective composite of claim 2, wherein the alkaline solution is potassium hydroxide, or a mixture of potassium hydroxide and isopropyl alcohol.
4. The antireflective composite of claim 1, wherein the titanium dioxide sol has a titanium source content of 15% to 30% by volume.
5. The anti-reflective composite material according to any one of claims 1 to 4, wherein the pyrrole grows in situ on the surface of the titanium dioxide in the step (2) for 10 to 20 minutes to obtain the anti-reflective composite material with the surface polypyrrole and the double-layer three-dimensional bionic structure.
6. A method for photocatalytic degradation of Rh 6G organic dyes, characterized in that the method utilizes the antireflective composite material according to any one of claims 1 to 5 as a photocatalyst.
7. An optoelectronic material or device comprising the antireflective composite of any one of claims 1 to 5.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811541214.4A CN109622064B (en) | 2018-12-17 | 2018-12-17 | Double-layer three-dimensional bionic anti-reflection composite material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811541214.4A CN109622064B (en) | 2018-12-17 | 2018-12-17 | Double-layer three-dimensional bionic anti-reflection composite material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109622064A CN109622064A (en) | 2019-04-16 |
| CN109622064B true CN109622064B (en) | 2020-07-03 |
Family
ID=66074350
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811541214.4A Active CN109622064B (en) | 2018-12-17 | 2018-12-17 | Double-layer three-dimensional bionic anti-reflection composite material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109622064B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112374562B (en) * | 2020-10-30 | 2022-05-20 | 哈尔滨工业大学 | Preparation method and application of polypyrrole photothermal film for intercepting volatile organic matters in water pollution |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105642367B (en) * | 2015-12-28 | 2018-06-22 | 江南大学 | A kind of level composite material and application using monocrystalline silicon as the reflection bilayer P/N hetero-junctions that disappears of carrier |
| ES2806677T3 (en) * | 2016-03-31 | 2021-02-18 | Fund Imdea Nanociencia | Polymeric composites with functional surfaces |
| CN105964233B (en) * | 2016-05-12 | 2019-03-01 | 江南大学 | One kind, which disappears, reflects hetero-junctions composite coating and preparation method thereof |
-
2018
- 2018-12-17 CN CN201811541214.4A patent/CN109622064B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN109622064A (en) | 2019-04-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Liu et al. | Advance in photonic crystal solar cells | |
| Yu et al. | TiO2 inverse opal photonic crystals: Synthesis, modification, and applications-A review | |
| Shanmugam et al. | Anti-reflective coating materials: A holistic review from PV perspective | |
| Gaucher et al. | Ultrathin epitaxial silicon solar cells with inverted nanopyramid arrays for efficient light trapping | |
| Hou et al. | Inverted pyramidally-textured PDMS antireflective foils for perovskite/silicon tandem solar cells with flat top cell | |
| Lee et al. | ZnO nanostructures as efficient antireflection layers in solar cells | |
| WO2017107783A1 (en) | Self-cleaning reflection reduction film and method of preparing same | |
| Zhu et al. | Nanodome solar cells with efficient light management and self-cleaning | |
| Mihi et al. | Spectral response of opal-based dye-sensitized solar cells | |
| Yu et al. | Strong light absorption of self-organized 3-D nanospike arrays for photovoltaic applications | |
| Lin et al. | Dual-layer nanostructured flexible thin-film amorphous silicon solar cells with enhanced light harvesting and photoelectric conversion efficiency | |
| Wang et al. | Development of nanopatterned fluorine-doped tin oxide electrodes for dye-sensitized solar cells with improved light trapping | |
| Yoo et al. | Newly developed broadband antireflective nanostructures by coating a low-index MgF2 film onto a SiO2 moth-eye nanopattern | |
| Kim et al. | Boosting light harvesting in perovskite solar cells by biomimetic inverted hemispherical architectured polymer layer with high haze factor as an antireflective layer | |
| Li et al. | Broadband antireflection TiO2–SiO2 stack coatings with refractive-index-grade structure and their applications to Cu (In, Ga) Se2 solar cells | |
| Hiralal et al. | Nanowire-based multifunctional antireflection coatings for solar cells | |
| CN103474576A (en) | Organic solar cell and manufacturing method thereof | |
| US20090114278A1 (en) | Dye-sensitized solar cell and fabrication method thereof | |
| CN105964233B (en) | One kind, which disappears, reflects hetero-junctions composite coating and preparation method thereof | |
| TW200919743A (en) | Dye-sensitized solar cell | |
| Wang et al. | Large-scale bio-inspired flexible antireflective film with scale-insensitivity arrays | |
| Xie et al. | Simulation study on improving efficiencies of perovskite solar cell: Introducing nano textures on it | |
| KR20120029235A (en) | Solar cell and method of forming the same | |
| Leem et al. | Multifunctional microstructured polymer films for boosting solar power generation of silicon-based photovoltaic modules | |
| Li et al. | Efficient gatherer of sunlight based on two-sided bio-inspired antireflective micro-pyramids with PPy/TiO2 |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |