CN112774719B - Limited domain inorganic perovskite Cs 3 Bi 2 Br 9 Photocatalytic film and preparation method and application thereof - Google Patents
Limited domain inorganic perovskite Cs 3 Bi 2 Br 9 Photocatalytic film and preparation method and application thereof Download PDFInfo
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- 230000001699 photocatalysis Effects 0.000 title claims abstract description 65
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 11
- 238000000967 suction filtration Methods 0.000 claims abstract description 9
- 239000002159 nanocrystal Substances 0.000 claims abstract description 8
- 238000001914 filtration Methods 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- 238000003756 stirring Methods 0.000 claims description 21
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 20
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 16
- 239000012528 membrane Substances 0.000 claims description 16
- 239000000463 material Substances 0.000 claims description 15
- 239000011259 mixed solution Substances 0.000 claims description 14
- 239000004695 Polyether sulfone Substances 0.000 claims description 12
- LYQFWZFBNBDLEO-UHFFFAOYSA-M caesium bromide Chemical compound [Br-].[Cs+] LYQFWZFBNBDLEO-UHFFFAOYSA-M 0.000 claims description 12
- 239000006185 dispersion Substances 0.000 claims description 12
- 229920006393 polyether sulfone Polymers 0.000 claims description 12
- 229920000428 triblock copolymer Polymers 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 9
- 239000000843 powder Substances 0.000 claims description 9
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 8
- 239000004698 Polyethylene Substances 0.000 claims description 8
- 239000004743 Polypropylene Substances 0.000 claims description 8
- 239000004115 Sodium Silicate Substances 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 8
- -1 polyethylene Polymers 0.000 claims description 8
- 229920000573 polyethylene Polymers 0.000 claims description 8
- 229920001155 polypropylene Polymers 0.000 claims description 8
- 239000002243 precursor Substances 0.000 claims description 8
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 8
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 8
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 6
- 239000002131 composite material Substances 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- DAJSVUQLFFJUSX-UHFFFAOYSA-M sodium;dodecane-1-sulfonate Chemical compound [Na+].CCCCCCCCCCCCS([O-])(=O)=O DAJSVUQLFFJUSX-UHFFFAOYSA-M 0.000 claims description 6
- 239000012065 filter cake Substances 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 239000003960 organic solvent Substances 0.000 claims description 4
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- 229920000642 polymer Polymers 0.000 claims description 3
- 238000005119 centrifugation Methods 0.000 claims description 2
- 238000013019 agitation Methods 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 9
- 239000011148 porous material Substances 0.000 abstract description 9
- 238000007146 photocatalysis Methods 0.000 abstract description 8
- 239000003054 catalyst Substances 0.000 abstract description 2
- 230000005669 field effect Effects 0.000 abstract description 2
- 230000002401 inhibitory effect Effects 0.000 abstract description 2
- 235000012239 silicon dioxide Nutrition 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract description 2
- 230000000694 effects Effects 0.000 description 16
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
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- 229920000463 Poly(ethylene glycol)-block-poly(propylene glycol)-block-poly(ethylene glycol) Polymers 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 229920012266 Poly(ether sulfone) PES Polymers 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
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- 230000005540 biological transmission Effects 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
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- 241001465754 Metazoa Species 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
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- 238000012986 modification Methods 0.000 description 1
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- 230000003287 optical effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 238000013032 photocatalytic reaction Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
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- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000004627 transmission electron microscopy Methods 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
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- 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
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8621—Removing nitrogen compounds
- B01D53/8625—Nitrogen oxides
- B01D53/8628—Processes characterised by a specific catalyst
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
- B01J29/0308—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41
- B01J29/0341—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/58—Fabrics or filaments
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- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
- B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
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Abstract
The invention discloses a novel domain-limited inorganic perovskite Cs 3 Bi 2 Br 9 A photocatalytic film and a preparation method and application thereof belong to the technical field of chemical catalysts and preparation thereof. The limited-domain inorganic perovskite Cs 3 Bi 2 Br 9 The preparation method of the photocatalysis film comprises mesoporous silica SBA-15 (∈), cs 3 Bi 2 Br 9 Nanocrystalline and confinement Cs 3 Bi 2 Br 9 And (3) preparing the photocatalytic film. The novel domain-limited inorganic perovskite Cs 3 Bi 2 Br 9 The photocatalytic film takes mesoporous silicon dioxide SBA-15 (∈) as a finite field framework, and Cs is filtered by a simple suction filtration method 3 Bi 2 Br 9 Filtering to obtain a finite field photocatalytic film in an SBA-15 (T) pore canal, and effectively exposing active sites and inhibiting Cs by utilizing the finite field effect of the pore canal structure 3 Bi 2 Br 9 The nano-crystal is agglomerated and denatured, so that Cs is promoted 3 Bi 2 Br 9 Catalytic activity and stability of (a).
Description
Technical Field
The invention belongs to the technical field of chemical catalysts and preparation thereof, and in particular relates to novel domain-limited inorganic perovskite Cs 3 Bi 2 Br 9 Photocatalytic film and its preparation method and application are provided.
Background
With the rapid development of economy and automobile industry, NO x The rapid increase of the discharge of the water-soluble polymer causes environmental phenomena such as acid rain, ozone depletion, photochemical smog and the like, and causes serious toxic effects on human bodies, animals and plants. Thus, high efficiency NO is developed x The purification technology has important scientific value and application prospect.
Photocatalytic technology has proven to be one of the effective methods for removing NO pollution. The low concentration NO in the atmosphere can be removed by oxidation under the photocatalysis of the semiconductor. Recently, all-inorganic perovskite nanocrystals have attracted extensive attention from researchers in the field of photocatalysis due to their remarkable light conversion efficiency. The all-inorganic perovskite material has the characteristics of long service life of carriers, low exciton binding energy and the like, and can effectively promote electron/hole separation and carrier migration, thereby improving the photocatalytic performance. Although the development of all-inorganic perovskite materials in the photoelectric field is rapid, the instability of the materials severely restricts the popularization and application of the materials. How to realize the efficient and stable catalytic removal of NO from all-inorganic perovskite nanocrystals is a challenging challenge to be solved.
Nano-domain catalysis is a new concept proposed in the field of catalysis in recent years, and catalytic systems designed based on the pore-domain effect have been attracting attention of researchers in recent years. The construction of the pore canal limit system can obviously improve the catalytic efficiency and the stability of the catalytic system. However, the application of finite field catalysis is concentrated in the field of organic synthesis, and research on finite field all-inorganic perovskite materials and application thereof in removing NO is not yet available. In conclusion, the research and development of the finite field all-inorganic perovskite photocatalyst with high activity and stability is of great significance in catalyzing and removing NO.
Disclosure of Invention
The primary aim of the invention is to overcome the defects and shortcomings of the prior art and provide a novel domain-limited inorganic perovskite Cs 3 Bi 2 Br 9 A preparation method of a photocatalysis film.
Another object of the present invention is to provide novel domain-limited inorganic perovskite Cs prepared by the above-mentioned preparation method 3 Bi 2 Br 9 A photocatalytic film.
It is a final object of the present invention to provide the novel domain-limited inorganic perovskite Cs described above 3 Bi 2 Br 9 Application of photocatalytic film.
The aim of the invention is achieved by the following technical scheme:
novel domain-limited inorganic perovskite Cs 3 Bi 2 Br 9 The preparation method of the photocatalytic film comprises the following steps:
(1) Preparation of mesoporous silica SBA-15 (∈): dissolving polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer (PEO-PPO-PEO, triblock copolymer P123) in water, stirring in water bath, adding cetyl trimethyl ammonium bromide and sodium dodecyl sulfonate, and continuing stirring in water bath to obtain mixed solution; then pouring the mixed solution into a sodium silicate aqueous solution, standing, filtering to obtain a filter cake, washing, drying and roasting to obtain mesoporous silica SBA-15 (∈) powder material;
(2)Cs 3 Bi 2 Br 9 preparation of nanocrystals: csBr and BiBr are taken 3 Dissolving in dimethyl sulfoxide to form Cs 3 Bi 2 Br 9 A precursor solution; then the prepared precursor solution is rapidly injected into isopropanol under stirring, and mixed solution is obtained after stirring; centrifuging the mixture, removing precipitate to obtain yellow supernatant as uniformly dispersed Cs 3 Bi 2 Br 9 A nanocrystalline;
(3) Limited domain Cs 3 Bi 2 Br 9 Preparation of the photocatalytic film: dissolving the mesoporous silica SBA-15 (∈T) powder material obtained in the step (1) in an organic solvent to form an SBA-15 (∈T) solution; then taking the polymer porous membrane as a carrier, and combining SBA-15 (∈) solution and Cs 3 Bi 2 Br 9 Sequentially carrying out suction filtration on the dispersion liquid into a PES film, and drying to obtain SBA-15 (∈) limit domain Cs immobilized on the PES film 3 Bi 2 Br 9 The composite membrane is the finite field inorganic perovskite Cs 3 Bi 2 Br 9 A photocatalytic film.
The polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer described in step (1) and water are preferably calculated according to a mass (g) to volume (mL) ratio of 1:20-100; more preferably in terms of a mass (g) to volume (mL) ratio of 1:25-72.
The water bath stirring conditions in the step (1) are preferably as follows: stirring in water bath at 30-70 deg.c for 0.5-12 hr; more preferably in a 45℃water bath for 1h.
The polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer, cetyltrimethylammonium bromide and sodium dodecyl sulfonate described in step (1) are preferably calculated in a mass ratio of 0.7 to 2:0.75:1.
The concentration of the sodium silicate aqueous solution in the step (1) is preferably 10.0-100.0 mmol/L; more preferably 80.0mmol/L.
The mixed solution and the sodium silicate aqueous solution in the step (1) are preferably calculated according to the volume ratio of 1:1-5.
The standing condition in the step (1) is preferably 20-60 ℃ for 12-24 hours; more preferably, the mixture is left standing at 45 ℃ for 12 to 24 hours.
The washed reagent in step (1) is preferably water; more preferably distilled water.
The drying condition in the step (1) is preferably 40-70 ℃ drying; more preferably 60 ℃.
The roasting condition in the step (1) is preferably 500-700 ℃ for 5-7 hours; more preferably at 600 c for 6 hours.
CsBr and BiBr as described in step (2) 3 Preferably in a molar ratio of 3:2.
The CsBr and dimethyl sulfoxide in the step (2) are preferably calculated according to a mass ratio of 5-15:1.
The dimethyl sulfoxide and the isopropanol in the step (2) are preferably calculated according to the volume ratio of 1:20-40.
The centrifugation conditions described in step (2) are preferably: the rotating speed is 3000-5000 rpm, and the time is 4-6 minutes.
The organic solvent in step (3) is preferably isopropanol.
The polymeric porous membrane in step (3) is preferably a polyethersulfone membrane; the pore diameter of the polyethersulfone membrane is preferably 0.2-0.5 μm.
The suction filtration step in the step (3) is preferably SBA-15 (∈) solution and Cs 3 Bi 2 Br 9 Dispersion, SBA-15 (∈) solution, cs 3 Bi 2 Br 9 A dispersion; more preferably 1-2 mL SBA-15 (∈) solution and 1-2 mL Cs 3 Bi 2 Br 9 Dispersing liquid, 1-2 mL SBA-15 (∈) solution and 1-2 mL Cs 3 Bi 2 Br 9 And (3) a dispersion.
The drying in step (3) is preferably vacuum drying; the conditions of vacuum drying are preferably as follows: vacuum drying for 3-5 min at 20-30 ℃; more preferably at 25℃for 3 to 5 minutes.
Novel domain-limited inorganic perovskite Cs 3 Bi 2 Br 9 The photocatalytic film is prepared by the preparation method.
The novel domain-limited inorganic perovskite Cs 3 Bi 2 Br 9 Use of a photocatalytic film in photocatalysis.
The photocatalysis is preferably the photocatalytic removal of NO.
Compared with the prior art, the invention has the following advantages and effects:
(1) The novel domain-limited inorganic perovskite Cs 3 Bi 2 Br 9 The photocatalytic film takes mesoporous silicon dioxide SBA-15 (∈) as a finite field framework, and Cs is filtered by a simple suction filtration method 3 Bi 2 Br 9 Filtering to obtain a finite field photocatalytic film in an SBA-15 (T) pore canal, and effectively exposing active sites and inhibiting Cs by utilizing the finite field effect of the pore canal structure 3 Bi 2 Br 9 The nano-crystal is agglomerated and denatured, so that Cs is promoted 3 Bi 2 Br 9 Catalytic activity and stability of (a).
Drawings
FIG. 1 is a finite field inorganic perovskite Cs prepared according to example 1 of the present invention 3 Bi 2 Br 9 X-ray diffraction pattern of photocatalytic film.
FIG. 2 is a finite field inorganic perovskite Cs prepared according to example 1 of the present invention 3 Bi 2 Br 9 Ultraviolet visible absorbance plot of the photocatalytic film.
FIG. 3 is a finite field inorganic perovskite Cs prepared according to example 1 of the present invention 3 Bi 2 Br 9 Transmission electron microscopy of photocatalytic films.
FIG. 4 is a finite field inorganic perovskite Cs prepared according to example 1 of the present invention 3 Bi 2 Br 9 Photocatalytic membranes and unconfined Cs 3 Bi 2 Br 9 Is a comparison of photocatalytic NO removal activity.
FIG. 5 is a finite field inorganic perovskite Cs prepared according to example 1 of the present invention 3 Bi 2 Br 9 Long-time photocatalytic NO removal activity for photocatalytic filmsA drawing.
FIG. 6 is a finite field inorganic perovskite Cs prepared according to example 1 of the present invention 3 Bi 2 Br 9 Photocatalytic film photocatalytic removal of NO activity pattern under different humidity conditions.
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but embodiments of the present invention are not limited thereto.
Example 1
Novel domain-limited inorganic perovskite Cs 3 Bi 2 Br 9 The preparation method of the photocatalytic film comprises the following steps:
(1) Preparation of mesoporous silica SBA-15 (∈): weighing 0.7g of polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer (PEO-PPO-PEO, triblock copolymer P123), putting into a beaker, adding 50mL of deionized water, stirring for 1h in a water bath at 45 ℃, adding 0.75g of cetyl trimethyl ammonium bromide and 1g of sodium dodecyl sulfonate, and continuously stirring for 1h in the water bath at 45 ℃ to obtain a mixed solution; then pouring the mixed solution into 150mL of sodium silicate aqueous solution with the concentration of 80.0mmol/L, pH approximately equal to 5.0, then closing stirring and standing for 12 hours at 45 ℃, washing the filtered filter cake with distilled water for 3 times, drying at 60 ℃, then placing the filter cake into a muffle furnace for roasting at 600 ℃ for 6 hours to obtain mesoporous silica SBA-15 (cavity) powder material, and detecting that the BET specific surface area of the mesoporous silica SBA-15 (cavity) powder material is 400-1000 m 2 /g；
(2)Cs 3 Bi 2 Br 9 Preparation of nanocrystals: 51.1mg CsBr (0.24 mmol) and 71.8mg BiBr were weighed out 3 (0.16 mmol) dissolved in 10mL dimethyl sulfoxide to form Cs 3 Bi 2 Br 9 A precursor solution; then rapidly injecting the prepared precursor solution into 200mL of isopropanol under rapid stirring, and stirring for 1 minute to obtain a mixed solution; centrifuging the mixture at 4000rpm for 5min, and removing precipitate to obtain yellow supernatant as homogeneously dispersed Cs 3 Bi 2 Br 9 The grain size of the nanocrystalline is 3-5 nm after detection;
(3) Limited domain Cs 3 Bi 2 Br 9 Preparation of the photocatalytic film: 40mg of the aboveThe SBA-15 (∈) powder material synthesized by the method is dispersed in 8mL of isopropanol by ultrasonic to form SBA-15 (∈) solution; commercial Polyethersulfone (PES) membranes (StarTech) at 0.2 μm pore size were then used TM Vanadium Tai research Innovative Co., ltd.) as a carrier, 1mL SBA-15 (. T.) solution and 1mL Cs 3 Bi 2 Br 9 Dispersion, 1mL SBA-15 (∈) solution, 2mL Cs 3 Bi 2 Br 9 Sequentially carrying out suction filtration on the dispersion liquid into a PES film, and vacuum drying the obtained composite porous film at 25 ℃ for 3-5 min to obtain SBA-15 (∈) limit Cs immobilized on the PES film 3 Bi 2 Br 9 The composite membrane is the finite field inorganic perovskite Cs 3 Bi 2 Br 9 Photocatalytic film (Cs) 3 Bi 2 Br 9 @SBA-15 (∈)) and detected to have a BET specific surface area of 400-1000 m 2 /g。
The confined inorganic perovskite Cs prepared in example 1 of the present invention 3 Bi 2 Br 9 The X-ray diffraction pattern, the ultraviolet visible absorbance pattern and the transmission electron microscope pattern of the photocatalytic film are respectively shown in fig. 1-3. As can be seen from FIG. 1, the diffraction peaks of the product are Cs except for the amorphous broad peak of SBA-15 (∈) 3 Bi 2 Br 9 No excessive impurity phase peak appears, and the product is proved to be Cs of SBA-15 (∈) limited domain 3 Bi 2 Br 9 A material. As can be seen from FIG. 2, the product has strong absorption capacity to ultraviolet light and visible light, and the product has photoresponsive capacity. As can be seen from the transmission electron microscope image of FIG. 3, the product has an ordered pore canal domain structure.
Example 2
Novel domain-limited inorganic perovskite Cs 3 Bi 2 Br 9 The preparation method of the photocatalytic film comprises the following steps:
(1) Preparation of mesoporous silica SBA-15 (∈): weighing 2g of polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer (PEO-PPO-PEO, triblock copolymer P123), putting into a beaker, adding 50mL of deionized water, stirring for 1h in a water bath at 45 ℃, adding 0.75g of cetyl trimethyl ammonium bromide and 1g of sodium dodecyl sulfonate, and continuously stirring for 1h in the water bath at 45 ℃ to obtain a mixed solution; then willPouring the mixed solution into 150mL of sodium silicate aqueous solution with the concentration of 80.0mmol/L, pH approximately equal to 5.0, then closing stirring, standing for 24 hours at the temperature of 45 ℃, washing a filtered filter cake with distilled water for 3 times, drying at the temperature of 60 ℃, putting into a muffle furnace, roasting at the temperature of 600 ℃ for 6 hours to obtain mesoporous silica SBA-15 (∈) powder material, and detecting that the BET specific surface area of the mesoporous silica SBA-15 (∈) powder material is 400-1000 m 2 /g；
(2)Cs 3 Bi 2 Br 9 Preparation of nanocrystals: 51.1mg CsBr (0.24 mmol) and 71.8mg BiBr were weighed out 3 (0.16 mmol) dissolved in 10mL dimethyl sulfoxide to form Cs 3 Bi 2 Br 9 A precursor solution; then rapidly injecting the prepared precursor solution into 200mL of isopropanol under rapid stirring, and stirring for 1 minute to obtain a mixed solution; centrifuging the mixture at 5000rpm for 5min, and removing precipitate to obtain yellow supernatant as uniformly dispersed Cs 3 Bi 2 Br 9 The grain size of the nanocrystalline is 3-5 nm after detection;
(3) Limited domain Cs 3 Bi 2 Br 9 Preparation of the photocatalytic film: taking 40mg of SBA-15 (∈T) synthesized by the method, and ultrasonically dispersing in 8mL of isopropanol to form SBA-15 (∈T) solution; commercial Polyethersulfone (PES) membranes (StarTech) at 0.5 μm pore size were then used TM vanadium-Tai Innovative Co., ltd.) as a carrier, 1mL SBA-15 (. T.) solution and 2mL Cs 3 Bi 2 Br 9 Dispersion, 1mL SBA-15 (∈) solution, 2mL Cs 3 Bi 2 Br 9 Sequentially carrying out suction filtration on the dispersion liquid into a PES film, and vacuum drying the obtained composite porous film at 25 ℃ for 3-5 min to obtain SBA-15 (∈) limit Cs immobilized on the PES film 3 Bi 2 Br 9 The composite membrane is the finite field inorganic perovskite Cs 3 Bi 2 Br 9 The BET specific surface area of the photocatalytic film is 400-1000 m after detection 2 /g。
Application example 1
Confined inorganic perovskite Cs prepared by comparison with example 1 of the present invention 3 Bi 2 Br 9 Photocatalytic film and non-limiting Cs prepared in step (2) of example 1 3 Bi 2 Br 9 The activity of NO is removed by photocatalysis,the effect of the confinement effect on the catalytic performance was studied.
The finite field inorganic perovskite Cs prepared in example 1 was subjected to photocatalytic removal of NO using a continuous flow photocatalytic reaction system 3 Bi 2 Br 9 Photocatalytic membranes and unconfined Cs 3 Bi 2 Br 9 Respectively fixing in a sealed fixed bed quartz glass reactor, passing NO gas flow containing 400ppb through the reactor at a gas flow rate of 600mL/min and a gas humidity of 15-80%, adsorbing for 5min in dark state, and using 300W Xe lamp equipped with optical filter as light source (lambda)>420 nm) of the reactor was illuminated by NO X The detector monitors the concentration of the air inlet and the air outlet of the reactor on line and judges the NO removal rate. The method for calculating the NO removal rate comprises the following steps:
NO removal rate (%) = (initial addition amount-NO amount in tail gas)/NO initial addition amount×100%
As shown in FIG. 4, after 30 minutes of reaction, the limited-domain inorganic perovskite Cs obtained in example 1 3 Bi 2 Br 9 NO removal effect of the photocatalytic film is 98%, and Cs is not limited 3 Bi 2 Br 9 The effect of removing NO by photocatalysis is only 14 percent, and the result shows that the finite field inorganic perovskite Cs prepared in the example 1 3 Bi 2 Br 9 The photocatalytic film has excellent photocatalytic effect and is far higher than the non-limiting domain Cs 3 Bi 2 Br 9 。
Application example 2
Domain-limited inorganic perovskite Cs 3 Bi 2 Br 9 The experimental result of long-time photocatalytic removal of NO activity by the photocatalytic film was carried out using the reaction apparatus described in application example 1, and the experimental operation was substantially the same as that of application example 1, except that the reaction time was prolonged to 15 hours, and the long-time catalytic stability was judged.
As a result, FIG. 5 shows that the limited-domain inorganic perovskite Cs obtained in example 1 after 15 hours of reaction 3 Bi 2 Br 9 The NO removal effect of the photocatalytic film is still maintained at 82%. The results show that the limited-domain inorganic perovskite Cs prepared in example 1 3 Bi 2 Br 9 The photocatalytic film has excellent photocatalytic stabilityAnd (5) qualitative property.
Application example 3
Domain-limited inorganic perovskite Cs 3 Bi 2 Br 9 The effect experiment of photocatalytic NO removal activity of the photocatalytic film under different humidity conditions adopts the reaction device described in application example 1, and the experimental operation is basically the same as that of application example 1, except that the air humidity is controlled to be 15-80%, and the specific humidity is 15%, 30%, 60% and 80%, respectively, so that the catalytic performance of the photocatalytic film under different humidity conditions is judged.
As a result, as shown in FIG. 6, the limited-domain inorganic perovskite Cs obtained in example 1 were obtained under conditions in which the air humidity was as high as 80% 3 Bi 2 Br 9 The NO removal effect of the photocatalytic film is still maintained at 88%. The results show that the limited-domain inorganic perovskite Cs prepared in example 1 3 Bi 2 Br 9 The photocatalytic film has excellent moisture resistance characteristics.
The above examples are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above examples, and any other changes, modifications, substitutions, combinations, and simplifications that do not depart from the spirit and principle of the present invention should be made in the equivalent manner, and the embodiments are included in the protection scope of the present invention.
Claims (9)
1. Limited domain inorganic perovskite Cs 3 Bi 2 Br 9 The preparation method of the photocatalytic film is characterized by comprising the following steps:
(1) Preparation of mesoporous silica SBA-15T: dissolving polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer in water, stirring in water bath, adding cetyl trimethyl ammonium bromide and sodium dodecyl sulfonate, and continuing stirring in water bath to obtain mixed solution; then pouring the mixed solution into sodium silicate aqueous solution, standing, filtering to obtain a filter cake, washing, drying and roasting to obtain mesoporous silica SBA-15T powder material;
（2）Cs 3 Bi 2 Br 9 preparation of nanocrystals: csBr and BiBr are taken 3 Dissolving in dimethyl sulfoxide to form Cs 3 Bi 2 Br 9 A precursor solution; then the prepared precursor solution is rapidly injected into isopropanol under stirring, and mixed solution is obtained after stirring; centrifuging the mixture, removing precipitate to obtain yellow supernatant as uniformly dispersed Cs 3 Bi 2 Br 9 A nanocrystalline;
(3) Limited domain Cs 3 Bi 2 Br 9 Preparation of the photocatalytic film: dissolving the mesoporous silica SBA-15T powder material obtained in the step (1) in an organic solvent to form an SBA-15T solution; then taking a polymer porous membrane as a carrier, and adding SBA-15T solution and Cs 3 Bi 2 Br 9 Sequentially carrying out suction filtration on the dispersion liquid into a PES film, and drying to obtain SBA-15T finite field Cs immobilized on the PES film 3 Bi 2 Br 9 The composite membrane is the finite field inorganic perovskite Cs 3 Bi 2 Br 9 A photocatalytic film;
the polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer, hexadecyl trimethyl ammonium bromide and sodium dodecyl sulfonate in the step (1) are calculated according to the mass ratio of 0.7-2:0.75:1;
the concentration of the sodium silicate aqueous solution in the step (1) is 10.0-100.0 mmol/L;
the mixed solution in the step (1) and the sodium silicate aqueous solution are calculated according to the volume ratio of 1:1-5;
the standing condition in the step (1) is that the standing is carried out for 12-24 hours at 20-60 ℃;
the roasting condition in the step (1) is that the roasting temperature is 500-700 ℃ and the roasting temperature is 5-7 h.
2. The process according to claim 1, wherein the polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer and water in step (1) are calculated in a mass g volume mL ratio of 1:20-100.
3. The method according to claim 1, wherein the conditions of the water bath agitation in step (1) are: stirring in water bath at 30-70 deg.c for 0.5-12. 12 h.
4. The method according to claim 1, wherein,
CsBr and BiBr as described in step (2) 3 Calculated according to a molar ratio of 3:2;
the CsBr and dimethyl sulfoxide in the step (2) are calculated according to the mass ratio of 5-15:1;
the dimethyl sulfoxide and the isopropanol in the step (2) are calculated according to the volume ratio of 1:20-40;
the centrifugation conditions described in step (2) are: the rotating speed is 3000-5000 rpm, and the time is 4-6 minutes.
5. The method according to claim 1, wherein,
the organic solvent in the step (3) is isopropanol;
the polymer porous membrane in the step (3) is a polyethersulfone membrane;
the step of suction filtration in the step (3) is SBA-15T solution and Cs 3 Bi 2 Br 9 Dispersion, SBA-15T solution and Cs 3 Bi 2 Br 9 And (3) a dispersion.
6. The method according to claim 5, wherein,
the aperture of the polyether sulfone membrane is 0.2-0.5 mu m;
the suction filtration comprises the following steps: 1-2 mL SBA-15T solution and 1-2 mL Cs 3 Bi 2 Br 9 Dispersing liquid, 1-2 mL SBA-15T solution and 1-2 mL Cs 3 Bi 2 Br 9 And (3) a dispersion.
7. Limited domain inorganic perovskite Cs 3 Bi 2 Br 9 The photocatalytic film is characterized by being prepared by the preparation method according to any one of claims 1 to 6.
8. The confined inorganic perovskite Cs of claim 7 3 Bi 2 Br 9 Photocatalytic film in photocatalysisIs used in the field of applications.
9. The use according to claim 8, wherein said photocatalytic removal of NO is performed.
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