CN109110820B - Bionic structure two-stage hole Fe2O3Film and preparation method thereof - Google Patents
Bionic structure two-stage hole Fe2O3Film and preparation method thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 239000011664 nicotinic acid Substances 0.000 title claims abstract description 24
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims abstract description 37
- 239000000758 substrate Substances 0.000 claims abstract description 27
- 239000004005 microsphere Substances 0.000 claims abstract description 21
- 108010025899 gelatin film Proteins 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 10
- 238000003837 high-temperature calcination Methods 0.000 claims abstract description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 30
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 29
- 238000010438 heat treatment Methods 0.000 claims description 19
- 239000002202 Polyethylene glycol Substances 0.000 claims description 13
- 229920001223 polyethylene glycol Polymers 0.000 claims description 13
- 239000011148 porous material Substances 0.000 claims description 13
- 238000002156 mixing Methods 0.000 claims description 12
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 9
- 239000002243 precursor Substances 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 6
- 238000004140 cleaning Methods 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- LZKLAOYSENRNKR-LNTINUHCSA-N iron;(z)-4-oxoniumylidenepent-2-en-2-olate Chemical compound [Fe].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O LZKLAOYSENRNKR-LNTINUHCSA-N 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- 239000002244 precipitate Substances 0.000 claims description 4
- 239000000243 solution Substances 0.000 claims description 4
- 239000007921 spray Substances 0.000 claims description 4
- 238000005507 spraying Methods 0.000 claims description 4
- 239000011521 glass Substances 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 229910052594 sapphire Inorganic materials 0.000 claims description 3
- 239000010980 sapphire Substances 0.000 claims description 3
- CDVAIHNNWWJFJW-UHFFFAOYSA-N 3,5-diethoxycarbonyl-1,4-dihydrocollidine Chemical compound CCOC(=O)C1=C(C)NC(C)=C(C(=O)OCC)C1C CDVAIHNNWWJFJW-UHFFFAOYSA-N 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000010453 quartz Substances 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 2
- UXGNZZKBCMGWAZ-UHFFFAOYSA-N dimethylformamide dmf Chemical compound CN(C)C=O.CN(C)C=O UXGNZZKBCMGWAZ-UHFFFAOYSA-N 0.000 claims 2
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 239000010408 film Substances 0.000 description 18
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 16
- 239000002077 nanosphere Substances 0.000 description 6
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 5
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 5
- 239000012528 membrane Substances 0.000 description 4
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 4
- 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 description 3
- 238000001027 hydrothermal synthesis Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229960000907 methylthioninium chloride Drugs 0.000 description 3
- 238000004321 preservation Methods 0.000 description 3
- 238000000862 absorption spectrum Methods 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000000231 atomic layer deposition Methods 0.000 description 1
- 230000003592 biomimetic effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000003937 drug carrier Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- YOBAEOGBNPPUQV-UHFFFAOYSA-N iron;trihydrate Chemical compound O.O.O.[Fe].[Fe] YOBAEOGBNPPUQV-UHFFFAOYSA-N 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 238000002595 magnetic resonance imaging Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 239000004038 photonic crystal Substances 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/02—Oxides; Hydroxides
- C01G49/06—Ferric oxide [Fe2O3]
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/16—Pore diameter
- C01P2006/17—Pore diameter distribution
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- Engineering & Computer Science (AREA)
- Nanotechnology (AREA)
- Crystallography & Structural Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Composite Materials (AREA)
- Materials Engineering (AREA)
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Abstract
The invention relates to a bionic structure two-stage hole Fe2O3The film comprises a large-size substrate and Fe arranged on the substrate and having two-stage holes2O3The diameter of the first-stage hole in the two-stage holes is 1-10nm, the diameter of the second-stage hole is 300-600nm, and the invention prepares the through hole Fe2O3Preparing Fe by three steps of nano microspheres, constructing gel film and high-temperature calcination2O3The film has wide application range, and can realize various two-stage hole Fe on various large-size substrates2O3The growth of the film is beneficial to reducing the production cost; in addition, the preparation equipment is mature, the process is simple, the large-scale production is convenient, and the cost is hopefully reduced by 5-20%; the invention prepares the bionic structure two-stage hole Fe2O3The film has excellent performance and the efficiency is higher than that of common Fe with single hole2O3The film can be improved by more than 2.5 times.
Description
Technical Field
The invention relates to the technical field of porous film materials, in particular to a bionic structure two-stage pore Fe2O3A film and a preparation method thereof.
Background
The ferric oxide as a transition metal oxide has the characteristics of low cost, no toxicity, no pollution, good biocompatibility and the like, and is widely applied to the fields of lithium ion batteries, targeted drug carriers, catalysts, magnetic resonance imaging and the like.
Meanwhile, nanostructured thin film materials have attracted worldwide attention and extensive research in recent years due to their unique structures and properties.
Therefore, in recent years, various methods have been reported for preparing nanostructured iron sesquioxide, including direct ion co-precipitation, atomic layer deposition, hydrothermal, and sol-gel methods, among others.
Among these preparation methods, hydrothermal method for preparing ferric oxide is a more developed and mature method. However, hydrothermal method for preparing ferric oxide often requires special reaction vessels (such as hydrothermal kettles) to achieve high temperature or high pressure conditions. Needless to say, the requirement of high temperature and high pressure reaction conditions will greatly increase the complexity of the experimental scheme and the preparation cost. In addition, as is well known, single crystal materials have better electron transport characteristics, and a rough surface morphology can provide a larger active surface area; however, the existing method can not realize that the prepared ferric oxide nano material has good crystallographic characteristics and rough surface appearance.
Therefore, the single crystal ferric oxide nano material with rough surface is prepared by a simple method without high-temperature calcination, has great application and research value in a plurality of technical fields, and has wide application prospect in the fields of photocatalysis, multi-phase catalysis, solar photovoltaic cells, gas sensors, photonic crystals, biomedicine and the like.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a bionic structure two-stage hole Fe2O3A film and a preparation method thereof.
The technical scheme of the invention is as follows: bionic structure two-stage hole Fe2O3A film including a large-sized substrate, and Fe having two-stage holes provided on the substrate2O3The membrane, wherein the diameter of the first-stage pore of the two-stage pore is 1-10nm, and the diameter of the second-stage pore is 300-600 nm.
Further, the substrate may be any one of a quartz substrate, a silicon wafer substrate, a sapphire substrate, a metal substrate, and a glass substrate.
Further, the size of the substrate is 2cm × 2-2 m × 2 m.
The invention also provides a bionic structure two-stage hole Fe2O3The preparation method of the film specifically comprises the following steps:
s1), via Fe2O3Preparation of nano-microspheres
S101) mixing iron acetylacetonate (Fe (C)5H7O2)3) Oleylamine (CH)3(CH2)7CH＝CH(CH2)7CH2NH2) Mixing N, N-Dimethylformamide (DMF) according to a certain mass ratio, heating to 80-90 ℃, magnetically stirring for 30-60min, heating the mixed solution to 150-;
s102), adding excessive ethanol into the solution in the step S101), and separating by using a centrifugal machine to obtain precipitates, namely through holes Fe2O3Nano-microspheres;
s103), cleaning the through hole Fe by adopting ethanol2O3Removing residual raw materials for 3-5 times, and drying at 80-100 deg.C for 30-60min to obtain Fe with through hole2O3Nano-microspheres;
s2), preparation of gel film
S201) with a via Fe2O3Mixing the nano-microspheres, pore-forming agent and ethanol as raw materials according to the proportion of 0.1-0.2g to 0.05-0.2g to 10-50m L, heating to 40-70 ℃, and stirring for 60-120min to obtain precursor gel;
s202), uniformly spraying the precursor gel on a substrate by using a spray gun so as to obtain a uniform gel film;
s3), high-temperature calcination
S301), transferring the gel film in the step S202) into a box furnace, heating to 600 ℃ at the heating rate of 1-10 ℃ per minute, preserving the heat for 60-180 minutes, and then naturally cooling to room temperature; in the cooling process, ethanol is quickly volatilized, polyethylene glycol is slowly contracted, and then the polyethylene glycol is quickly decomposed to form 300-doped mesoporous with larger diameter of 600nm in the high-temperature heat preservation stage, and the through hole Fe2O3The nanospheres will bind together to form a continuous porous membrane.
Further, in the step S101), the mass ratio of the ferric acetylacetonate, the oleylamine and the N, N-Dimethylformamide (DMF) is 0.1-0.5:0.5-10: 0.01-0.5.
Further, in step S103), the through hole Fe2O3The aperture of the nano microsphere is 1-10 nm.
Further, in step S201), the pore-forming agent is polyethylene glycol (HO (CH)2CH2O) nH) with molecular weight of 2000-6000, analytically pure AR, 98% and above.
Further, in step S301), the Fe2O3The mesoporous aperture of the film is 300-600 nm.
The bionic structure two-stage hole Fe prepared by the invention2O3The film is used in the fields of photoelectric detectors, gas-sensitive detectors, photocatalytic degradation and the like.
The invention has the beneficial effects that:
1. the invention has wide application range and can realize various two-stage hole Fe on various large-size substrates2O3The growth of the film, the substrate includes Si, sapphire, metal, glass, etc., is favorable for reducing the production cost;
2. the preparation equipment is mature, the process is simple, the large-scale production is convenient, and the cost is hopefully reduced by 5-20%;
3. the invention prepares the bionic structure two-stage hole Fe2O3The film has excellent performance and the efficiency is higher than that of common Fe with single hole2O3The film can be improved by more than 2.5 times;
4. the invention prepares the two-stage pore Fe2O3The film has wide application range and is expected to play an active role in the fields of photoelectric detectors, gas-sensitive detectors, photocatalytic degradation and the like.
Drawings
FIG. 1 is a view of a via Fe prepared in example 1 of the present invention2O3Transmission Electron Microscopy (TEM) images of the nanospheres;
FIG. 2 shows porous Fe with bionic structure prepared in example 1 of the present invention2O3Scanning Electron Microscope (SEM) images of mesopores (second-order pores) of the film;
FIG. 3 shows porous Fe with bionic structure prepared in example 1 of the present invention2O3Absorption spectrum of the film for photocatalytic degradation of methylene blue.
Detailed Description
The following further describes embodiments of the present invention with reference to the accompanying drawings:
example 1
Bionic structure two-stage hole Fe2O3The preparation method of the film specifically comprises the following steps:
s1), via Fe2O3Preparation of nano-microspheres
S101), and 0.180g of iron acetylacetonate (Fe (C) having an analytical pure AR of 99% or more5H7O2)3) 3.86g of oleylamine (CH) having a purity of 85% or more3(CH2)7CH＝CH(CH2)7CH2NH2) Mixing 0.04g of N, N-Dimethylformamide (DMF) with analytical purity AR of 95% or more, heating to 80 ℃, magnetically stirring for 60 minutes, heating the mixed solution to 180 ℃, preserving heat for 60 minutes, and then cooling to room temperature;
s102), adding excessive ethanol with analytical purity AR of 98% or above into the solution in the step S101), and separating by using a centrifuge, wherein the precipitate is through-hole Fe2O3Nano-microspheres;
s103), cleaning the through hole Fe by adopting ethanol2O3Removing residual raw materials for 3 times, drying at 90 deg.C for 30min to obtain through-hole Fe2O3Nano-microspheres, said through-holes Fe2O3The aperture of the nano-microsphere is 2 nm;
s2), preparation of gel film
S201), mixing 0.1g of through hole Fe2O3Mixing the nano-microspheres, 0.05g of pore-forming agent polyethylene glycol and 15m L of ethanol, heating to 50 ℃, and stirring for 60min to obtain precursor gel, wherein the molecular weight of the polyethylene glycol is 2000 and the chemical formula is HO (CH)2CH2O) nH, and analytically pure AR is 98% or more;
s202), uniformly spraying the precursor gel on a substrate by using a spray gun so as to obtain a uniform gel film;
s3), high-temperature calcination
S301), transferring the gel film in step S202) to a box furnace at 5 deg.C per minuteHeating to 500 ℃ at the heating rate, preserving the heat for 60min, and then naturally cooling to room temperature; in the cooling process, ethanol is quickly volatilized, polyethylene glycol is slowly contracted, and then the polyethylene glycol is quickly decomposed to form a large 450-550nm mesoporous in the high-temperature heat preservation stage, and the through hole Fe2O3The nanospheres will bind together to form a continuous porous membrane.
As shown in FIG. 1, the through-hole Fe prepared in this example2O3Transmission Electron Microscope (TEM) photograph of the nanospheres, from which Fe can be seen2O3The nanospheres are through-hole; FIG. 2 shows porous Fe with biomimetic structure prepared in this example2O3Scanning Electron Microscope (SEM) photographs of the mesopores (second-order pores) of the film, from which the mesopores formed of polyethylene glycol can be seen; FIG. 3 shows porous Fe with bionic structure prepared by the present embodiment of the invention2O3The absorption spectrum of the film for photocatalytic degradation of methylene blue; after 0.5h of degradation, the concentration of methylene blue is rapidly reduced, and the absorption intensity is reduced to 0.3 from the original nearly 3, thereby showing that the porous Fe with the bionic structure2O3The film has remarkable catalytic degradation capability.
Example 2
Bionic structure two-stage hole Fe2O3The preparation method of the film specifically comprises the following steps:
s1), via Fe2O3Preparation of nano-microspheres
S101), and 0.1g of iron acetylacetonate (Fe (C) having an analytical pure AR of 99% or more5H7O2)3) 2g oleylamine (CH) having a purity of 85% or more3(CH2)7CH＝CH(CH2)7CH2NH2) Mixing 0.03g of N, N-Dimethylformamide (DMF) with an analytical purity AR of 95% or more, heating to 85 ℃, magnetically stirring for 60min, heating the mixed solution to 200 ℃, keeping the temperature for 60min, and cooling to room temperature;
s102), adding excessive ethanol with analytical purity AR of 98% or above into the solution in the step S101), and separating by using a centrifuge, wherein the precipitate is through-hole Fe2O3Nano-microspheres;
s103), cleaning the through hole Fe by adopting ethanol2O3Removing residual raw materials for 4 times, and drying at 80 deg.C for 30min to obtain through-hole Fe2O3Nano-microspheres, said through-holes Fe2O3The aperture of the nano-microsphere is 1.6 nm;
s2), preparation of gel film
S201), mixing 0.1g of through hole Fe2O3Mixing the nano-microspheres, 0.1g of pore-forming agent polyethylene glycol and 20m L of ethanol, heating to 60 ℃, and stirring for 60min to obtain precursor gel, wherein the molecular weight of the polyethylene glycol is 6000 and the chemical formula is HO (CH)2CH2O) nH, and analytically pure AR is 98% or more;
s202), uniformly spraying the precursor gel on a substrate by using a spray gun so as to obtain a uniform gel film;
s3), high-temperature calcination
S301), transferring the gel film in the step S202) into a box furnace, heating to 600 ℃ at a heating rate of 10 ℃ per minute, preserving heat for 60min, and then naturally cooling to room temperature; in the cooling process, ethanol is quickly volatilized, polyethylene glycol is slowly contracted, and then the polyethylene glycol is quickly decomposed to form 480-520 nm-large mesopores in the high-temperature heat preservation stage, and the through holes Fe2O3The nanospheres will bind together to form a continuous porous membrane.
The foregoing embodiments and description have been presented only to illustrate the principles and preferred embodiments of the invention, and various changes and modifications may be made therein without departing from the spirit and scope of the invention as hereinafter claimed.
Claims (7)
1. Bionic structure two-stage hole Fe2O3The preparation method of the film comprises a large-size substrate and Fe with two-stage holes arranged on the substrate2O3A film;
the method is characterized by comprising the following steps:
s1), via Fe2O3Preparation of nano-microspheres
S101) mixing iron acetylacetonate (Fe (C)5H7O2)3) Oleylamine (CH)3(CH2)7CH＝CH(CH2)7CH2NH2) Mixing N, N-dimethylformamide DMF according to a certain mass ratio, heating to 80-90 ℃, magnetically stirring for 30-60min, heating the mixed solution to 150-;
s102), adding excessive ethanol into the solution in the step S101), and separating by using a centrifugal machine to obtain precipitates, namely through holes Fe2O3Nano-microspheres;
s103), cleaning the through hole Fe by adopting ethanol2O3Removing residual raw materials for 3-5 times, and drying at 80-100 deg.C for 30-60min to obtain Fe with through hole2O3Nano-microspheres;
s2), preparation of gel film
S201) with a via Fe2O3Mixing the nano-microspheres, pore-forming agent and ethanol as raw materials according to the proportion of 0.1-0.2g to 0.05-0.2g to 10-50m L, heating to 40-70 ℃, and stirring for 60-120min to obtain precursor gel;
s202), uniformly spraying the precursor gel on a substrate by using a spray gun so as to obtain a uniform gel film;
s3), high-temperature calcination
S301), transferring the gel film in the step S202) into a box furnace, heating to 450-600 ℃ at a heating rate of 1-10 ℃ per minute, preserving heat for 60-180min, and naturally cooling to room temperature to obtain the bionic structure two-stage hole Fe2O3A film.
2. The bionic structural two-stage pore Fe as claimed in claim 12O3The preparation method of the film is characterized by comprising the following steps: the substrate is any one of a quartz substrate, a silicon wafer substrate, a sapphire substrate, a metal substrate and a glass substrate.
3. The bionic structure two-stage pore Fe as claimed in claim 22O3The preparation method of the film is characterized in that the size of the substrate is 2cm × 2-2 m × 2 m.
4. The bionic structural two-stage pore Fe as claimed in claim 12O3The preparation method of the film is characterized by comprising the following steps: in the step S101), the mass ratio of the ferric acetylacetonate to the oleylamine to the N, N-dimethylformamide DMF is 0.1-0.5:0.5-10: 0.01-0.5.
5. The bionic structural two-stage pore Fe as claimed in claim 12O3The preparation method of the film is characterized by comprising the following steps: in step S103), the through hole Fe2O3The aperture of the nano-microsphere is 1-10 nm.
6. The bionic structure two-stage pore Fe as claimed in claim 42O3The preparation method of the film is characterized by comprising the following steps: in step S201), the pore-forming agent is polyethylene glycol (HO (CH)2CH2O) nH) having a molecular weight of 2000-6000 and an analytically pure AR of 98% or more.
7. The bionic structural two-stage pore Fe as claimed in claim 12O3The preparation method of the film is characterized by comprising the following steps: in step S301), Fe2O3The mesoporous aperture of the film is 300-600 nm.
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