CN115350719A - Photocatalytic film and preparation method and application thereof - Google Patents
Photocatalytic film and preparation method and application thereof Download PDFInfo
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- CN115350719A CN115350719A CN202211018156.3A CN202211018156A CN115350719A CN 115350719 A CN115350719 A CN 115350719A CN 202211018156 A CN202211018156 A CN 202211018156A CN 115350719 A CN115350719 A CN 115350719A
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- 230000001699 photocatalysis Effects 0.000 title claims abstract description 174
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 239000000463 material Substances 0.000 claims abstract description 115
- 238000012986 modification Methods 0.000 claims abstract description 67
- 230000004048 modification Effects 0.000 claims abstract description 67
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 42
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 40
- 239000000758 substrate Substances 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 21
- 229910002367 SrTiO Inorganic materials 0.000 claims abstract description 19
- 239000011248 coating agent Substances 0.000 claims abstract description 7
- 238000000576 coating method Methods 0.000 claims abstract description 7
- 239000000243 solution Substances 0.000 claims description 101
- 238000001035 drying Methods 0.000 claims description 69
- 239000007788 liquid Substances 0.000 claims description 40
- 239000006185 dispersion Substances 0.000 claims description 39
- 238000002156 mixing Methods 0.000 claims description 25
- 238000006243 chemical reaction Methods 0.000 claims description 21
- 239000011258 core-shell material Substances 0.000 claims description 20
- 239000002245 particle Substances 0.000 claims description 19
- UWCPYKQBIPYOLX-UHFFFAOYSA-N benzene-1,3,5-tricarbonyl chloride Chemical compound ClC(=O)C1=CC(C(Cl)=O)=CC(C(Cl)=O)=C1 UWCPYKQBIPYOLX-UHFFFAOYSA-N 0.000 claims description 18
- 239000002131 composite material Substances 0.000 claims description 17
- 238000005406 washing Methods 0.000 claims description 17
- 239000011259 mixed solution Substances 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 12
- 101100496858 Mus musculus Colec12 gene Proteins 0.000 claims description 12
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 12
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 12
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 12
- 230000001678 irradiating effect Effects 0.000 claims description 10
- 239000004743 Polypropylene Substances 0.000 claims description 7
- 239000003513 alkali Substances 0.000 claims description 7
- -1 polypropylene Polymers 0.000 claims description 7
- 229920001155 polypropylene Polymers 0.000 claims description 7
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 6
- 239000002585 base Substances 0.000 claims description 6
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 6
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- 238000000151 deposition Methods 0.000 abstract 1
- 239000010408 film Substances 0.000 description 153
- 230000000052 comparative effect Effects 0.000 description 20
- AXDJCCTWPBKUKL-UHFFFAOYSA-N 4-[(4-aminophenyl)-(4-imino-3-methylcyclohexa-2,5-dien-1-ylidene)methyl]aniline;hydron;chloride Chemical group Cl.C1=CC(=N)C(C)=CC1=C(C=1C=CC(N)=CC=1)C1=CC=C(N)C=C1 AXDJCCTWPBKUKL-UHFFFAOYSA-N 0.000 description 16
- VEALVRVVWBQVSL-UHFFFAOYSA-N strontium titanate Chemical compound [Sr+2].[O-][Ti]([O-])=O VEALVRVVWBQVSL-UHFFFAOYSA-N 0.000 description 13
- 229940052223 basic fuchsin Drugs 0.000 description 12
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- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 3
- 238000001338 self-assembly Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
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- 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 1
- 238000002835 absorbance Methods 0.000 description 1
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- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
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- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/20—Carbon compounds
- B01J27/232—Carbonates
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0205—Impregnation in several steps
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
- B01J37/344—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of electromagnetic wave energy
- B01J37/345—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of electromagnetic wave energy of ultraviolet wave energy
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
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Abstract
The invention relates to a photocatalytic film and a preparation method and application thereof, wherein the photocatalytic film comprises a film substrate and at least two modification layers coated on the outer surface of the film substrate; the modification layer comprises a first photocatalytic material layer, a graphene oxide layer and a second photocatalytic material layer which are alternately connected from inside to outside in sequence; the photocatalytic material comprises SrSO 4 A kernel coated with the SrSO 4 SrCO of the outer surface of the inner core 3 And coating the SrCO 3 SrTiO of outer surface 3 . The preparation method comprises the step of depositing a photocatalytic material layer and a graphene oxide layer in sequence by adopting ultraviolet light to obtain the photocatalytic film. The photocatalytic film provided by the invention has excellent photocatalytic activity by the mutual matching of the photocatalytic material and the graphene oxide. The preparation method provided by the invention is simple in process and can be applied industrially.
Description
Technical Field
The invention relates to the technical field of photocatalytic materials, in particular to a photocatalytic film and a preparation method and application thereof.
Background
The enrichment of organic matters in water body will cause serious influence on water quality, wherein, the organic matters which are difficult to degrade are difficult to biodegrade due to strong stability, and the conventional treatment process can not effectively remove the organic matters, such as polycyclic aromatic hydrocarbon and the like. At present, the treatment modes of refractory organic matters mainly comprise a reinforced biological treatment process, a Biological Aerated Filter (BAF) process and other treatment processes, and the outstanding problems are low treatment efficiency, complex process, high cost and the like. Especially for natural water, the concentration of the refractory organic matters is low, the distribution is wide, the long-time enrichment is easy, and an effective treatment technology is lacked. The photocatalytic degradation technology is one of degradation ways of organic matters in a plurality of water bodies because of the characteristics of environmental protection, high efficiency, long degradation duration and the like. Researches show that when 313nm and 366nm light is used for irradiating polycyclic aromatic hydrocarbon solution taking pure water as a solvent, a plurality of organic molecules are destroyed and degraded, but the efficiency of directly degrading organic matters by the light is very slow, and the polycyclic aromatic hydrocarbon solution has no practical application value. Compared with the traditional water treatment technology, the perovskite semiconductor photocatalytic material has unique advantages in the decomposition treatment of organic pollutants, for example, only solar energy is utilized in the whole degradation process, the degradation effect is excellent, organic matters can be directly degraded into water and carbon dioxide, the preparation process is simple, and the like, and the development concept of a new green energy-saving material is met. Strontium titanate (SrTiO) 3 STO) is a typical ABO 3 Perovskite-type composite oxides have been widely studied in the field of photocatalysis. Its indirect band gap value is 3.25eV, and it can only absorb and utilize UV light, so that its photocatalytic performance is greatly limited, and at the same time, the photoproduction electron and hole are easily combined, and its photocatalytic efficiency is seriously affected.
CN104383906A discloses a preparation method of a photocatalyst, which takes PEG series surfactants with different molecular weights as pore-forming agents and adopts a sol-gel method to synthesize a porous strontium titanate photocatalyst. With the addition of PEG, the strontium titanate powder is refined, the porosity and the specific surface area are increased, and the porous strontium titanate powder has higher adsorption capacity.
CN113968591A discloses a method for preparing porous hollow single-crystal strontium titanate, which utilizes abundant functional groups on the surface of a carbon sphere template to adsorb a large amount of precursor ions, hydrothermally grows single-crystal strontium titanate coated with a specific crystal face and exposed on the surface of the carbon sphere template, and removes the template through heat treatment to obtain the porous hollow single-crystal strontium titanate material.
The strontium titanate catalyst can only absorb and utilize ultraviolet light, has very limited visible light response range and low photocatalytic activity.
Therefore, the photocatalytic material with excellent catalytic performance and the preparation method thereof have important significance.
Disclosure of Invention
In view of the above problems, an object of the present invention is to provide a photocatalytic film, and a preparation method and use thereof, wherein compared with the prior art, the photocatalytic material adopted by the photocatalytic film provided by the present invention has a multiple heterojunction structure, and the photocatalytic film is formed by performing chemical deposition and self-assembly with graphene oxide, such that the photocatalytic activity is substantially improved.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a photocatalytic film, comprising a film substrate and at least two modification layers coated on an outer surface of the film substrate; the modification layer comprises a first photocatalytic material layer, a graphene oxide layer and a second photocatalytic material layer which are alternately connected from inside to outside in sequence; the photocatalytic material comprises SrSO 4 A kernel coated with the SrSO 4 Srco of the outer surface of the inner core 3 And coating the SrCO 3 SrTiO of outer surface 3 。
The photocatalytic film provided by the invention adopts SrSO 4 、SrCO 3 And SrTiO 3 The formed photocatalytic material with the ternary core-shell structure forms multiple heterojunctions and can cooperate quicklyThe photoelectrons and the cavities are quickly separated and led out, excellent photo-oxidation-reduction efficiency is achieved, on the basis, the modification layers are formed by the photocatalytic material and the graphene oxide in an alternating mode, the modification layers are at least two layers, the heterojunction structure and the graphene oxide can be matched with each other, and the photocatalytic degradation efficiency of the photocatalytic material is further improved through the high carrier migration capacity of the graphene oxide.
The modifying layer is at least two layers, for example, 2, 4, 6, 10, 15, 19, 20 or 23 layers, but not limited to the recited values, and other values within the range are equally applicable.
Preferably, in the photocatalytic material, srSO 4 、SrCO 3 And SrTiO 3 The mass ratio is (70-80): (1-4): (10-20), and can be, for example, 70.
Preferably, in the photocatalytic film, the mass ratio of the photocatalytic material to the graphene oxide is (0.01-0.1): 100, and may be, for example, 0.01.
According to the invention, the mass ratio of the photocatalytic material to the graphene oxide is preferably controlled within a specific range, so that the catalytic activity of the photocatalytic film can be further improved.
Preferably, the number of modifying layers is 15-23, such as 15, 16, 17, 18, 19, 20, 21, 22 or 23, but not limited to the recited values, and other values not recited in the range of values are equally applicable.
The invention preferably controls the number of the modification layers within a specific range, and can further improve the catalytic activity of the photocatalytic film.
In a second aspect, the present invention provides a method for preparing a photocatalytic film according to the first aspect, comprising the steps of:
(1) Immersing the film base material into a polyvinyl alcohol solution, and then drying to obtain a pretreatment film:
(2) Immersing the pretreated film obtained in the step (1) into a trimesoyl chloride solution for first modification, then immersing into a dispersion liquid of a photocatalytic material for second modification, and then washing and drying to obtain a first film;
(3) Immersing the first film obtained in the step (2) into a trimesoyl chloride solution for third modification, and then drying to obtain a second film;
(4) Immersing the second film obtained in the step (3) into graphene oxide dispersion liquid for fourth modification, and then drying to obtain a third film;
(5) Immersing the third film obtained in the step (4) into a dispersion liquid of a photocatalytic material for fifth modification, and then drying to obtain a fourth film;
(6) And (3) repeating the operations of the steps (3) to (5) on the fourth film obtained in the step (5) to obtain a composite film material, and then irradiating the composite film material by adopting ultraviolet light to obtain the photocatalytic film.
The preparation method provided by the invention realizes SrTiO by using an ultraviolet light source 3 /SrCO 3 /SrSO 4 The photocatalytic material and the two-dimensional graphene oxide are subjected to layer-by-layer chemical grafting self-assembly on the film substrate to prepare the photocatalytic film, and the photocatalytic degradation efficiency of the photocatalytic film is greatly improved due to the heterojunction structure and the high carrier mobility of the graphene oxide.
Preferably, the film substrate of step (1) comprises a polypropylene film.
Preferably, the polyvinyl alcohol solution in step (1) has a polyvinyl alcohol content of 1-2% by mass, for example, 1%, 1.2%, 1.4%, 1.6%, 1.8% or 2%, but not limited to the recited values, and other values not recited in the range of values are also applicable.
Preferably, the drying temperature in step (1) is 50-80 ℃, for example 50 ℃, 52 ℃, 55 ℃, 58 ℃, 60 ℃, 62 ℃, 65 ℃, 68 ℃, 70 ℃, 72 ℃, 75 ℃, 78 ℃ or 80 ℃, but not limited to the recited values, and other values not recited in the range of values are equally applicable.
Preferably, the drying time in step (1) is 1 to 3 hours, for example 1 hour, 1.2 hours, 1.4 hours, 1.6 hours, 1.8 hours, 2 hours, 2.2 hours, 2.5 hours, 2.8 hours or 3 hours, but is not limited to the recited values, and other values not recited in the range of values are equally applicable.
Preferably, the content of trimesoyl chloride in the trimesoyl chloride solution in steps (2) and (3) is 0.1-0.5% by mass, for example 0.1%, 0.2%, 0.3%, 0.4% or 0.5% by mass, but not limited to the recited values, and other values not recited in the numerical range are also applicable.
Preferably, the amount of the photocatalytic material in the dispersion of photocatalytic material in step (2) and step (5) is 0.2-2mg/mL, for example, 0.2mg/mL, 0.6mg/mL, 0.8mg/mL, 1mg/mL, 1.2mg/mL, 1.4mg/mL, 1.6mg/mL, 1.8mg/mL or 2mg/mL, but not limited to the values listed, and other values not listed in the range of values are equally applicable.
Preferably, the time of the first modification in step (2) is 1-5min, such as 1min, 2min, 3min, 4min or 5min, but not limited to the recited values, and other values not recited in the numerical range are also applicable.
Preferably, the time of the second modification in step (2) is 1-5min, such as 1min, 2min, 3min, 4min or 5min, but not limited to the recited values, and other values not recited in the numerical range are also applicable.
Preferably, the drying temperature in step (2) is 50-80 deg.C, such as 50 deg.C, 52 deg.C, 55 deg.C, 58 deg.C, 60 deg.C, 62 deg.C, 65 deg.C, 68 deg.C, 70 deg.C, 72 deg.C, 75 deg.C, 78 deg.C or 80 deg.C, but not limited to the recited values, and other values not recited in the range of values are equally applicable.
Preferably, the drying time in step (2) is 1 to 2 hours, for example, 1 hour, 1.2 hours, 1.4 hours, 1.6 hours, 1.8 hours or 2 hours, but not limited to the recited values, and other values not recited in the range of values are also applicable.
Preferably, the time of the third modification in step (3) is 1-2min, such as 1min, 1.2min, 1.4min, 1.6min, 1.8min or 2min, but not limited to the recited values, and other values not recited in the numerical range are also applicable.
Preferably, the drying time in step (3) is 5-20s, for example, 5s, 6s, 8s, 10s, 12s, 14s, 16s, 18s or 20s, but not limited to the recited values, and other values not recited in the range of values are also applicable.
Preferably, the mass percentage content of the graphene oxide in the graphene oxide dispersion liquid in the step (4) is 0.1-0.2%, for example, 0.1%, 0.12%, 0.14%, 0.16%, 0.18%, or 0.2%, but not limited to the recited values, and other values in the range of the values are also applicable.
Preferably, the time of the fourth modification in step (4) is 1-2min, such as 1min, 1.2min, 1.4min, 1.6min, 1.8min or 2min, but not limited to the recited values, and other values not recited in the numerical range are also applicable.
Preferably, the drying time in step (4) is 5-20s, for example, 5s, 6s, 8s, 10s, 12s, 14s, 16s, 18s or 20s, but not limited to the recited values, and other values not recited in the range of values are also applicable.
Preferably, the time for the fifth modification in step (5) is 1-2min, such as 1min, 1.2min, 1.4min, 1.6min, 1.8min or 2min, but not limited to the values listed, and other values not listed in the range of values are equally applicable.
Preferably, the drying time in step (5) is 5-20s, for example, 5s, 6s, 8s, 10s, 12s, 14s, 16s, 18s or 20s, but not limited to the recited values, and other values not recited in the range of values are also applicable.
Preferably, the number of repetitions of step (6) is 14-22, and may be, for example, 14, 15, 16, 17, 18, 19, 20, 21 or 22, but is not limited to the recited values, and other values not recited within the range of values are equally applicable.
Preferably, the power of the ultraviolet light in step (6) is 150-300W, such as 150W, 160W, 180W, 200W, 220W, 240W, 260W, 280W or 300W, but not limited to the recited values, and other values in the range of values not recited are also applicable.
Preferably, the irradiation in step (6) is carried out for a period of time of 0.2 to 1 hour, for example 0.2 hour, 0.4 hour, 0.5 hour, 0.8 hour or 1 hour, but is not limited to the recited values, and other values not recited in the range of values are equally applicable.
Preferably, the preparation method of the photocatalytic material dispersion liquid in the step (2) comprises: and mixing the photocatalytic material and the solvent to obtain the photocatalytic material dispersion liquid.
Preferably, the solvent comprises n-hexane.
Preferably, the preparation method of the photocatalytic material comprises the following steps:
(a) Mixed SrSO 4 Carrying out a first reaction on the solution and a carbonate solution, and then sequentially carrying out solid-liquid separation, washing and drying to obtain the SrSO with the core-shell structure 4 /SrCO 3 A particle;
(b) Mixing the SrSO of the core-shell structure obtained in step (a) 4 /SrCO 3 And carrying out a second reaction on the particles, the Ti-containing solution, the Sr-containing solution and the alkali assistant, and then sequentially carrying out solid-liquid separation, washing and drying to obtain the photocatalytic material.
In the present invention, the solid-liquid separation method is not particularly limited, and may be, for example, filtration or centrifugation.
Preferably, the SrSO of step (a) 4 The concentration of the solution is 0.5 to 1mol/L, and may be, for example, 0.5mol/L, 0.6mol/L, 0.7mol/L, 0.8mol/L, 0.9mol/L or 1mol/L, but is not limited to the values listed, and other values not listed in the numerical range are also applicable.
Preferably, the carbonate solution comprises (NH) 4 ) 2 CO 3 And (3) solution.
Preferably, the carbonate solution has a concentration of 0.5 to 1mol/L, which may be, for example, 0.5mol/L, 0.6mol/L, 0.7mol/L, 0.8mol/L, 0.9mol/L or 1mol/L, but is not limited to the values recited, and other values not recited in the numerical ranges are equally applicable.
Preferably, the first reaction comprises a metathesis reaction.
Preferably, the first stirring is performed during the first reaction.
Preferably, the first stirring rate is 200-500r/min, such as 200r/min, 250r/min, 300r/min, 350r/min, 400r/min, 450r/min or 500r/min, but not limited to the values recited, and other values not recited in the range of values are equally applicable.
Preferably, the time of the first reaction is 20 to 60min, for example, 20min, 25min, 30min, 35min, 40min, 45min, 50min, 55min or 60min, but is not limited to the recited values, and other values not recited in the numerical range are also applicable.
Preferably, the temperature of the first reaction is 25-40 ℃, for example, 25 ℃, 26 ℃, 28 ℃, 30 ℃, 32 ℃, 34 ℃, 36 ℃, 38 ℃ or 40 ℃, but not limited to the recited values, and other values not recited in the range of values are equally applicable.
Preferably, the drying temperature in step (a) is 60-80 ℃, for example 60 ℃, 62 ℃, 64 ℃, 66 ℃, 68 ℃, 70 ℃, 72 ℃, 74 ℃, 76 ℃, 78 ℃ or 80 ℃, but not limited to the recited values, and other values not recited in the range of values are equally applicable.
Preferably, the drying time in step (a) is 1 to 2 hours, for example 1 hour, 1.2 hours, 1.4 hours, 1.6 hours, 1.8 hours or 2 hours, but not limited to the recited values, and other values not recited in the range of values are equally applicable.
Preferably, the mixing of step (b) comprises: mixing a Ti-containing solution and a Sr-containing solution, performing second stirring to obtain a mixed solution, and then mixing the mixed solution and the SrSO with the core-shell structure obtained in the step (1) 4 /SrCO 3 Granules and an alkali assistant.
Preferably, the Ti-containing solution comprises TiCl 4 And (3) solution.
Preferably, the Ti-containing solution has a concentration of 0.1 to 0.5mol/L, which may be, for example, 0.1mol/L, 0.2mol/L, 0.3mol/L, 0.4mol/L or 0.5mol/L, but is not limited to the values recited, and other values not recited in the numerical ranges are equally applicable.
Preferably, the Sr-containing solution includes SrCl 2 And (3) solution.
Preferably, the Sr containing solution has a concentration of 0.1 to 0.5mol/L, which may be, for example, 0.1mol/L, 0.2mol/L, 0.3mol/L, 0.4mol/L or 0.5mol/L, but is not limited to the values recited, and other values not recited in the numerical ranges are equally applicable.
Preferably, the base adjuvant comprises a LiOH solution.
Preferably, the concentration of the alkali builder is 1 to 3mol/L, and may be, for example, 1mol/L, 1.5mol/L, 2mol/L, 2.5mol/L or 3mol/L, but is not limited to the recited values, and other values not recited in the numerical range are also applicable.
Preferably, the volume of the base adjuvant is 10 to 30mL, for example 10mL, 15mL, 20mL, 25mL or 30mL, but is not limited to the values recited, and other values not recited within the range of values are equally applicable.
Preferably, the second reaction comprises a hydrothermal reaction.
Preferably, the temperature increase rate of the second reaction is 1 to 5 deg.C/min, and may be, for example, 1 deg.C/min, 2 deg.C/min, 3 deg.C/min, 4 deg.C/min, or 5 deg.C/min, but is not limited to the recited values, and other values not recited within the range of values are also applicable.
Preferably, the end temperature of the second reaction is 175 to 185 ℃, for example 175 ℃, 176 ℃, 178 ℃, 180 ℃, 182 ℃, 184 ℃ or 185 ℃, but not limited to the recited values, and other values not recited in the range of values are equally applicable.
Preferably, the incubation time for the second reaction is 24-28h, for example 24h, 25h, 26h, 27h or 28h, but is not limited to the recited values, and other values not recited in the range of values are equally applicable.
Preferably, the drying temperature in step (b) is 60-90 ℃, for example 60 ℃, 65 ℃, 70 ℃, 75 ℃, 80 ℃, 85 ℃ or 90 ℃, but not limited to the recited values, and other values not recited in the range of values are equally applicable.
Preferably, the drying time in step (b) is 1 to 2 hours, for example 1 hour, 1.2 hours, 1.4 hours, 1.6 hours, 1.8 hours or 2 hours, but not limited to the recited values, and other values not recited in the range of values are equally applicable.
As a preferred embodiment of the second aspect of the present invention, the preparation method comprises the steps of:
(1) Immersing the film base material into a polyvinyl alcohol solution with the mass percentage of 1-2%, and then drying for 1-3h at 50-80 ℃ to obtain a pretreated film:
(2) Immersing the pretreated film obtained in the step (1) into a trimesoyl chloride solution with the mass percentage of 0.1-0.5% for first modification for 1-5min, then immersing into a photocatalytic material dispersion liquid with the mass percentage of 0.2-2mg/mL for second modification for 1-5min, then washing, and drying at the temperature of 50-80 ℃ for 1-2h to obtain a first film;
(3) Immersing the first film obtained in the step (2) into a trimesoyl chloride solution with the mass percentage of 0.1-0.5% for third modification for 1-2min, and then drying for 5-20s to obtain a second film;
(4) Immersing the second film obtained in the step (3) into graphene oxide dispersion liquid with the mass percentage of 0.1-0.2% for fourth modification for 1-2min, and then drying for 5-20s to obtain a third film;
(5) Immersing the third film obtained in the step (4) into a dispersion liquid of a photocatalytic material for fifth modification for 1-2min, and then drying for 5-20s to obtain a fourth film;
(6) Repeating the operation of the steps (3) to (5) on the fourth film obtained in the step (5) for 18 to 22 times to obtain a composite film material, and then irradiating the composite film material with ultraviolet light of 150 to 300W for 0.2 to 1 hour to obtain the photocatalytic film;
the preparation method of the photocatalytic material dispersion liquid comprises the following steps:
(a) Mixing 0.5-1mol/L SrSO 4 Solution and 0.5-1mol/L of (NH) 4 ) 2 CO 3 Carrying out double decomposition reaction on the solution at the temperature of 25-40 ℃ for 20-60min, carrying out first stirring at the speed of 200-500r/min, then sequentially filtering and washing,drying at 60-80 deg.C for 1-2h to obtain SrSO with core-shell structure 4 /SrCO 3 Particles;
(b) Mixing 0.1-0.5mol/L TiCl 4 Solution and 0.1-0.5mol/L SrCl 2 Performing second stirring on the solution to obtain a mixed solution, and then mixing the mixed solution and the SrSO with the core-shell structure obtained in the step (1) 4 /SrCO 3 Heating the particles and 10-30mL of 1-3mol/L LiOH solution at 1-5 ℃/min to 175-185 ℃ for carrying out hydrothermal reaction for 24-28h, then sequentially filtering and washing, and drying at 60-90 ℃ for 1-2h to obtain the photocatalytic material;
(c) And mixing the photocatalytic material and n-hexane to obtain the photocatalytic material dispersion liquid.
In a third aspect, the present invention provides a use of the catalytic membrane according to the first aspect of the present invention, wherein the photocatalytic membrane is used for oxidation-reduction reaction of pollutants in a water body.
The photocatalytic film provided by the invention is used for oxidation-reduction reaction of pollutants in water, such as catalytic decomposition of basic fuchsin and oxidation-reduction reaction of Co element.
Compared with the prior art, the invention has the following beneficial effects:
(1) The photocatalytic film provided by the invention adopts SrSO 4 、SrCO 3 And SrTiO 3 The formed ternary core-shell structure photocatalytic material forms multiple heterojunctions, and on the basis, the photocatalytic material and the graphene oxide are alternately used for forming a modification layer, so that the heterojunction structure and the high carrier mobility of the graphene oxide can be matched with each other, photoelectrons and holes can be rapidly separated and led out in a synergetic mode, and the photooxidation-reduction efficiency is excellent.
(2) The preparation method of the photocatalytic film provided by the invention utilizes an ultraviolet light source to realize layer-by-layer chemical grafting self-assembly of the photocatalytic material and the two-dimensional graphene oxide on the film substrate to prepare the photocatalytic film, and the preparation method is simple and can be applied industrially.
(3) The photocatalytic film provided by the invention can be used for oxidation-reduction reaction of pollutants in water body and has excellent catalysisActivating and photo-redox efficiency to catalytically decompose basic fuchsin and Co 2+ For example, in the catalytic decomposition of basic fuchsin test, the decomposition rate of basic fuchsin can reach more than 65%, and under better conditions, the decomposition rate of basic fuchsin can reach more than 89%; in the photo-oxidation reduction of Co 2+ In the test, co 3+ The proportion of (A) can reach more than 53 percent, and can reach more than 72 percent under better conditions.
Drawings
FIG. 1 shows SrSO having a core-shell structure according to embodiment 1 of the present invention 4 /SrCO 3 SEM images of the particles;
FIG. 2 is an SEM image of the photocatalytic material described in example 1 of the present invention.
Detailed Description
The technical solution of the present invention is further described below by way of specific embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
The embodiment provides a photocatalytic film, which comprises a film substrate and 20 modification layers coated on the outer surface of the film substrate; the modifying layer comprises a first photocatalytic material layer, a graphene oxide layer and a second photocatalytic material layer which are alternately connected from inside to outside in sequence; the photocatalytic material comprises SrSO 4 A kernel coated with the SrSO 4 SrCO of the outer surface of the inner core 3 And coating the SrCO 3 SrTiO of outer surface 3 (ii) a In the photocatalytic material, srSO 4 、SrCO 3 And SrTiO 3 The mass ratio of (1) to (3) is 75.
The embodiment also provides a preparation method of the photocatalytic film, which comprises the following steps:
(1) Immersing a polypropylene film substrate into a polyvinyl alcohol solution with the mass percentage of 1.5%, and then drying at 75 ℃ for 2h to obtain a pretreated film:
(2) Immersing the pretreated film obtained in the step (1) into a trimesoyl chloride solution with the mass percentage content of 0.3% for carrying out first modification for 3min, then immersing into a photocatalytic material dispersion liquid with the mass percentage content of 1mg/mL for carrying out second modification for 3min, then washing, and drying at 75 ℃ for 1.5h to obtain a first film;
(3) Immersing the first film obtained in the step (2) into a trimesoyl chloride solution with the mass percentage of 0.3% for third modification for 1.5min, and then drying for 10s to obtain a second film;
(4) Immersing the second film obtained in the step (3) into graphene oxide dispersion liquid with the mass percentage of 0.15% for fourth modification for 1.5min, and then drying for 10s to obtain a third film;
(5) Immersing the third film obtained in the step (4) into the dispersion liquid of the photocatalytic material for fifth modification for 1.5min, and then drying for 10s to obtain a fourth film;
(6) Repeating the operation of the steps (3) to (5) on the fourth film obtained in the step (5) for 19 times to obtain a composite film material, and then irradiating the composite film material for 0.6h by using 200W ultraviolet light to obtain the photocatalytic film;
the preparation method of the photocatalytic material dispersion liquid comprises the following steps:
(a) Mixing 0.7mol/L SrSO 4 Solution and 0.7mol/L of (NH) 4 ) 2 CO 3 Solution of said SrSO 4 SrSO in solution 4 Molar amount of (C) and (NH) 4 ) 2 CO 3 In solution (NH) 4 ) 2 CO 3 The molar ratio of (a) to (b) is 21, carrying out a metathesis reaction at 32 ℃ for 40min, carrying out first stirring at 350r/min, then sequentially filtering, washing, and drying at 70 ℃ for 1h to obtain core-shell SrSO 4 /SrCO 3 Particles;
(b) Mixing 0.3mol/L TiCl 4 Solution and 0.3mol/L SrCl 2 Solution of said TiCl 4 TiCl in solution 4 With SrCl 2 SrCl in solution 2 Is 1:1, performing second stirring to obtain a mixed solution, and then mixing the mixed solution and the core-shell structure SrSO obtained in the step (1) 4 /SrCO 3 Particles and 20mL of 2mol/L LiOH solution, wherein the SrTiO solution is contained in the mixed solution 3 Molar amount of (A) with SrSO 4 /SrCO 3 SrSO in particles 4 The molar weight ratio of the component (a) to the component (b) is 0.27/1, heating to 180 ℃ at 3 ℃/min to perform hydrothermal reaction for 26h, then sequentially performing filtration and washing, and drying at 75 ℃ for 1.5h to obtain the photocatalytic material;
(c) And mixing the photocatalytic material and n-hexane to obtain the photocatalytic material dispersion liquid.
The obtained SrSO with a core-shell structure 4 /SrCO 3 The SEM image of the particles is shown in FIG. 1, and it can be seen from FIG. 1 that SrSO 4 /SrCO 3 The particles are of a core-shell structure comprising SrSO 4 An inner core and a coating on the SrSO 4 Srco of the outer surface of the inner core 3 。
The SEM image of the obtained photocatalytic material is shown in FIG. 2, and as can be seen from FIG. 2, the SrSO with the core-shell structure 4 /SrCO 3 The surface of the particles is coated with SrTiO 3 。
Example 2
The embodiment provides a photocatalytic film, which comprises a film substrate and 15 modification layers coated on the outer surface of the film substrate; the modification layer comprises a first photocatalytic material layer, a graphene oxide layer and a second photocatalytic material layer which are alternately connected from inside to outside in sequence; the photocatalytic material comprises SrSO 4 A kernel coated with SrSO 4 Srco of the outer surface of the inner core 3 And coating the SrCO 3 SrTiO of outer surface 3 (ii) a In the photocatalytic material, srSO 4 、SrCO 3 And SrTiO 3 The mass ratio of (1) to (10) is from 0.01.
The embodiment also provides a preparation method of the photocatalytic film, which comprises the following steps:
(1) Immersing a polypropylene film substrate into a polyvinyl alcohol solution with the mass percentage of 1%, and then drying at 80 ℃ for 1h to obtain a pretreated film:
(2) Immersing the pretreated film obtained in the step (1) into a trimesoyl chloride solution with the mass percentage content of 0.1% for first modification for 5min, then immersing into 2mg/mL of photocatalytic material dispersion liquid for second modification for 1min, then washing, and drying for 1h at 80 ℃ to obtain a first film;
(3) Immersing the first film obtained in the step (2) into a trimesoyl chloride solution with the mass percentage of 0.5% for third modification for 1min, and then drying for 20s to obtain a second film;
(4) Immersing the second film obtained in the step (3) into graphene oxide dispersion liquid with the mass percentage of 0.1% for fourth modification for 2min, and then drying for 5s to obtain a third film;
(5) Immersing the third film obtained in the step (4) into a dispersion liquid of a photocatalytic material for fifth modification for 2min, and then drying for 5s to obtain a fourth film;
(6) Repeating the operations of the steps (3) - (5) for 14 times on the fourth film obtained in the step (5) to obtain a composite film material, and then irradiating the composite film material for 1h by adopting 150W ultraviolet light to obtain the photocatalytic film;
the preparation method of the photocatalytic material dispersion liquid comprises the following steps:
(a) Mixed with 0.5mol/L SrSO 4 Solution and 0.5mol/L of (NH) 4 ) 2 CO 3 Solution of said SrSO 4 SrSO in solution 4 Molar amount of (C) and (NH) 4 ) 2 CO 3 In solution (NH) 4 ) 2 CO 3 The molar ratio of (b) is 57, carrying out a metathesis reaction at 25 ℃ for 60min, carrying out first stirring at 200r/min, then sequentially filtering, washing, and drying at 80 ℃ for 1h to obtain core-shell SrSO 4 /SrCO 3 Particles;
(b) Mixing 0.1mol/L TiCl 4 Solution and 0.1mol/L SrCl 2 Solution of said TiCl 4 TiCl in solution 4 Molar amount of (a) with SrCl 2 SrCl in solution 2 Is 1:1, performing second stirring to obtain a mixed solution, and then mixing the mixed solution and the core-shell structure SrS obtained in the step (1)O 4 /SrCO 3 Particles and 10mL,1mol/L LiOH solution, wherein the mixed solution contains SrTiO 3 With SrSO 4 /SrCO 3 SrSO in the particles 4 The molar weight ratio of the components is 0.18, the temperature is raised to 185 ℃ at the speed of 5 ℃/min to carry out hydrothermal reaction for 24 hours, then the filtration and the washing are carried out in sequence, and the drying is carried out for 1 hour at the temperature of 60 ℃ to obtain the photocatalytic material;
(c) And mixing the photocatalytic material and n-hexane to obtain the photocatalytic material dispersion liquid.
Example 3
The embodiment provides a photocatalytic film, which comprises a film substrate and 23 modification layers wrapping the outer surface of the film substrate; the modifying layer comprises a first photocatalytic material layer, a graphene oxide layer and a second photocatalytic material layer which are alternately connected from inside to outside in sequence; the photocatalytic material comprises SrSO 4 A kernel coated with SrSO 4 Srco of the outer surface of the inner core 3 And coating the SrCO 3 SrTiO of outer surface 3 (ii) a In the photocatalytic material, srSO 4 、SrCO 3 And SrTiO 3 The mass ratio of (a) to (b) is 80.
The embodiment also provides a preparation method of the photocatalytic film, which comprises the following steps:
(1) Immersing a polypropylene film substrate into a polyvinyl alcohol solution with the mass percentage of 1%, and then drying at 50 ℃ for 3h to obtain a pretreated film:
(2) Immersing the pretreated film obtained in the step (1) into a trimesoyl chloride solution with the mass percentage of 0.5% for carrying out first modification for 1min, then immersing into a photocatalytic material dispersion liquid with the mass percentage of 0.2mg/mL for carrying out second modification for 5min, then washing, and drying at 50 ℃ for 2h to obtain a first film;
(3) Immersing the first film obtained in the step (2) into a trimesoyl chloride solution with the mass percentage of 0.1% for carrying out third modification for 2min, and then drying for 5s to obtain a second film;
(4) Immersing the second film obtained in the step (3) into graphene oxide dispersion liquid with the mass percentage of 0.2% for fourth modification for 1min, and then drying for 20s to obtain a third film;
(5) Immersing the third film obtained in the step (4) into a dispersion liquid of a photocatalytic material for fifth modification for 1min, and then drying for 20s to obtain a fourth film;
(6) Repeating the operations of the steps (3) - (5) for 22 times on the fourth film obtained in the step (5) to obtain a composite film material, and then irradiating the composite film material by adopting 300W ultraviolet light for 0.2h to obtain the photocatalytic film;
the preparation method of the photocatalytic material dispersion liquid comprises the following steps:
(a) Mixing 1mol/L SrSO 4 Solution and 1mol/L of (NH) 4 ) 2 CO 3 Solution of said SrSO 4 SrSO in solution 4 Molar amount of (C) and (NH) 4 ) 2 CO 3 In solution (NH) 4 ) 2 CO 3 Is 46 at 40 ℃, and is subjected to a first stirring at 500r/min, then sequentially filtered, washed, and dried at 60 ℃ for 2 hours to obtain the core-shell SrSO 4 /SrCO 3 A particle;
(b) Mixing 0.5mol/L TiCl 4 Solution and 0.5mol/L SrCl 2 Solution of said TiCl 4 TiCl in solution 4 Molar amount of (a) with SrCl 2 SrCl in solution 2 Is 17, performing second stirring to obtain a mixed solution, and then mixing the mixed solution and the core-shell structure SrSO obtained in step (1) to obtain a mixture solution 4 /SrCO 3 Particles and 30mL,3mol/L LiOH solution, the mixed solution being SrTiO 3 Molar amount of (A) with SrSO 4 /SrCO 3 SrSO in particles 4 The molar weight ratio of the components is 0.3, the temperature is raised to 175 ℃ at the speed of 1 ℃/min, the hydrothermal reaction is carried out for 28h, then the filtration and the washing are carried out in sequence, and the drying is carried out for 2h at the temperature of 90 ℃ to obtain the photocatalytic material;
(c) And mixing the photocatalytic material and n-hexane to obtain the photocatalytic material dispersion liquid.
Example 4
This example provides a photocatalytic film that differs from example 1 only in that the number of modification layers is 5.
Example 5
This example provides a photocatalytic film that differs from example 1 only in that the number of modification layers is 50.
Example 6
This example provides a photocatalytic film, which is different from example 1 only in that the mass ratio of the photocatalytic material to the graphene oxide in the photocatalytic film is 0.005.
Example 7
This example provides a photocatalytic film, which is different from example 1 only in that the mass ratio of the photocatalytic material to the graphene oxide in the photocatalytic film is 0.5.
Comparative example 1
The present comparative example provides a photocatalytic thin film, which is different from example 1 only in that the photocatalytic material layer is replaced by a strontium titanate layer, that is, the photocatalytic thin film comprises a thin film substrate and 20 modification layers coated on the outer surface of the thin film substrate; the modification layer comprises a first strontium titanate layer, a graphene oxide layer and a second strontium titanate layer which are alternately connected from inside to outside in sequence.
This comparative example provides a method of preparing the above photocatalytic film, differing from example 1 only in that the photocatalytic material dispersion was replaced with a strontium titanate dispersion having a concentration of 1mg/mL.
Comparative example 2
The comparative example provides a photocatalytic film, which is different from the photocatalytic film in example 1 only in that a photocatalytic material layer is removed, and the photocatalytic film comprises a film substrate and 20 modification layers coated on the outer surface of the film substrate; the modification layer is a graphene oxide layer.
This comparative example provides a method for preparing the above photocatalytic film, which is different from example 1 only in that the method for preparing the photocatalytic film comprises the steps of:
(1) Immersing a polypropylene film substrate into a polyvinyl alcohol solution with the mass percentage of 1.5%, and then drying at 75 ℃ for 2h to obtain a pretreated film:
(2) Immersing the pretreated thin film obtained in the step (1) into a trimesoyl chloride solution with the mass percentage content of 0.3% for second modification for 1.5min, and then drying for 10s to obtain a first thin film;
(3) Immersing the first film obtained in the step (2) into graphene oxide dispersion liquid with the mass percentage of 0.15% for third modification for 1.5min, and then drying for 10s to obtain a second film;
(4) Repeating the operations of the steps (2) to (3) on the second film obtained in the step (3) for 19 times to obtain a composite film material, and then irradiating the composite film material for 0.6h by using 200W ultraviolet light to obtain the photocatalytic film.
Comparative example 3
The present comparative example provides a photocatalytic thin film, which is different from example 1 only in that a graphene oxide layer is removed, and which includes a thin film substrate and 20 modification layers coated on an outer surface of the thin film substrate; the modification layer is a photocatalytic material layer.
This comparative example provides a method for preparing the above photocatalytic film, which is different from example 1 only in that the method for preparing the photocatalytic film comprises the steps of:
(1) Immersing a polypropylene film substrate into a polyvinyl alcohol solution with the mass percentage of 1.5%, and then drying at 75 ℃ for 2h to obtain a pretreated film:
(2) Immersing the pretreated thin film obtained in the step (1) into a trimesoyl chloride solution with the mass percentage of 0.3% for first modification for 1.5min, and then drying for 10s to obtain a first thin film;
(3) Soaking the first film obtained in the step (2) into the dispersion liquid of the photocatalytic material for second modification for 1.5min, and then drying for 10s to obtain a second film;
(4) Repeating the operations of the steps (2) to (3) on the second film obtained in the step (3) for 19 times to obtain a composite film material, and then irradiating the composite film material for 0.6h by using 200W ultraviolet light to obtain the photocatalytic film.
The photocatalytic films of examples 1-7 and comparative examples 1-3 were subjected to a catalytic decomposition of basic fuchsin test by: the decomposition rate of basic magenta, which was obtained by placing 1.5g of the photocatalytic film prepared in the above examples and comparative examples in an aqueous basic magenta solution having a concentration of 0.5g/L, irradiating the film with 366nm ultraviolet light for 1 hour, and measuring the concentration of basic magenta in the solution after the reaction by measuring the absorbance of the basic magenta solution at 665nm, was calculated as shown in Table 1.
Photo-oxidation-reduction of Co was performed on the photocatalytic films of examples 1 to 7 and comparative examples 1 to 3 2+ The test method comprises the following steps: first, a photocatalytic film (3X 3cm in size) was placed on the bottom of a light-transmitting container containing 100mL of distilled water; then, co (NO) was prepared at a concentration of 2mg 2mg/mL 3 ) 2 ·6H 2 An aqueous solution of O; finally, 2mL Co (NO) was added by magnetic stirring 3 ) 2 ·6H 2 The aqueous O solution was added to the aqueous dispersion where the photocatalytic film was placed, and the resulting mixture was irradiated with a xenon lamp (300W, full arc) for 30min, and the mixture was heated on a hot water bath until dried. XPS test of the photocatalytic film sample to detect Co 2+ And Co 3+ Content of (C), calculating Co 3+ The results are shown in Table 1, based on the ratios of all Co elements.
The photocatalytic film provided by the invention can be used for treating basic fuchsin and Co 2+ And the method can also be used for pollutants in other water bodies, and the experiment is only used for proving the effect of the photocatalytic film.
TABLE 1
| Alkaline productDecomposition rate of Red/%) | Co 3+ Is a fraction of% | |
| Example 1 | 92％ | 79％ |
| Example 2 | 91％ | 76％ |
| Example 3 | 89％ | 72％ |
| Example 4 | 75％ | 67％ |
| Example 5 | 80％ | 70％ |
| Example 6 | 65％ | 53％ |
| Example 7 | 72％ | 61％ |
| Comparative example 1 | 60％ | 35％ |
| Comparative example 2 | 26％ | 5％ |
| Comparative example 3 | 58％ | 46％ |
From table 1, the following points can be seen:
(1) As can be seen from the data of examples 1-7, when the photocatalytic film provided by the invention is used for a test of catalytically decomposing basic fuchsin, the decomposition rate of the basic fuchsin can reach more than 65%, and under a better condition, the decomposition rate of the basic fuchsin can reach more than 89%; the photocatalytic film is used for photo-oxidation reduction of Co 2+ Test, co 3+ Can reach over 53 percent, and can reach over 72 percent under better conditions.
(2) As can be seen by comparing the data of examples 1 and 4-5, the number of layers of the modified layer was 20 in example 1, and the decomposition rate of basic fuchsin and the Co decomposition rate were higher in example 1 than in examples 4-5, which were 5 and 50, respectively 3+ The ratio of (a) to (b) is higher than that in examples 4 to 5, and therefore, the number of layers of the modification layer is preferably controlled in the invention, and the catalytic effect of the photocatalytic film can be further improved.
(3) As can be seen by comparing the data of example 1 and examples 6 to 7 together, the mass ratio of the photocatalytic material to the graphene oxide in example 1 is 0.06 3+ The ratio of (b) is higher than that in examples 6 to 7, so that the mass ratio of the photocatalytic material to the graphene oxide is preferably controlled, and the catalytic effect of the photocatalytic film can be further improved.
(4) Comparing the data of example 1 and comparative examples 1 to 3 together, it can be seen that comparative example 1 differs from example 1 only in that the photocatalytic material layer is replaced with a strontium titanate layer, comparative example 2 differs from example 1 only in that the photocatalytic material layer is removed, comparative example 3 differs from example 1 only in that the graphene oxide layer is removed,basic fuchsin decomposition rate and Co in example 1 3+ The ratios of (A) to (B) are higher than those of comparative examples 1 to 3, so that the photocatalytic film and the preparation method thereof provided by the invention have excellent catalytic effect.
In conclusion, the photocatalytic film provided by the invention can mutually match the heterojunction structure and the high carrier mobility of graphene oxide, can synergistically and rapidly separate and lead out photoelectrons and holes, and has excellent catalytic activity and photo-oxidation-reduction efficiency. The applicant declares that the above description is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be understood by those skilled in the art that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are within the scope and disclosure of the present invention.
Claims (10)
1. The photocatalytic film is characterized by comprising a film substrate and at least two modification layers coated on the outer surface of the film substrate;
the modification layer comprises a first photocatalytic material layer, a graphene oxide layer and a second photocatalytic material layer which are alternately connected from inside to outside in sequence;
the photocatalytic material includes SrSO 4 A kernel coated with the SrSO 4 Srco of the outer surface of the inner core 3 And coating the SrCO 3 SrTiO of outer surface 3 。
2. The photocatalytic film as set forth in claim 1, wherein in the photocatalytic material, srSO 4 、SrCO 3 And SrTiO 3 The mass ratio of (70-80) to (1-4) to (10-20);
preferably, in the photocatalytic film, the mass ratio of the photocatalytic material to the graphene oxide is (0.01-0.1): 100;
preferably, the number of the modifying layers is 15-23.
3. A method for preparing a photocatalytic film according to claim 1 or 2, comprising the steps of:
(1) Immersing the film base material into a polyvinyl alcohol solution, and then drying to obtain a pretreatment film:
(2) Immersing the pretreated film obtained in the step (1) into a trimesoyl chloride solution for first modification, then immersing into a dispersion liquid of a photocatalytic material for second modification, and then washing and drying to obtain a first film;
(3) Immersing the first film obtained in the step (2) into a trimesoyl chloride solution for third modification, and then drying to obtain a second film;
(4) Immersing the second film obtained in the step (3) into graphene oxide dispersion liquid for fourth modification, and then drying to obtain a third film;
(5) Immersing the third film obtained in the step (4) into a dispersion liquid of a photocatalytic material for fifth modification, and then drying to obtain a fourth film;
(6) And (3) repeating the operations of the steps (3) to (5) on the fourth film obtained in the step (5) to obtain a composite film material, and then irradiating the composite film material by adopting ultraviolet light to obtain the photocatalytic film.
4. The method of claim 3, wherein the film substrate of step (1) comprises a polypropylene film;
preferably, the polyvinyl alcohol solution in the step (1) has a polyvinyl alcohol content of 1-2% by mass;
preferably, the temperature of the drying in the step (1) is 50-80 ℃;
preferably, the drying time in step (1) is 1-3h.
5. The method according to claim 3 or 4, wherein the mass percentage of trimesoyl chloride in the trimesoyl chloride solution in the steps (2) and (3) is 0.1-0.5%;
preferably, the content of the photocatalytic material in the photocatalytic material dispersion liquid in the step (2) and the step (5) is 0.2-2mg/mL;
preferably, the time for the first modification in the step (2) is 1-5min;
preferably, the time of the second modification in the step (2) is 1-5min;
preferably, the temperature for drying in the step (2) is 50-80 ℃;
preferably, the drying time in step (2) is 1-2h.
6. The production method according to any one of claims 3 to 5, wherein the time for the third modification in step (3) is 1 to 2min;
preferably, the drying time of the step (3) is 5-20s;
preferably, the mass percentage of the graphene oxide in the graphene oxide dispersion liquid in the step (4) is 0.1-0.2%;
preferably, the time for the fourth modification in the step (4) is 1-2min;
preferably, the drying time of the step (4) is 5-20s;
preferably, the time for the fifth modification in the step (5) is 1-2min;
preferably, the drying time of the step (5) is 5-20s;
preferably, the number of said repetition of step (6) is 14-22;
preferably, the power of the ultraviolet light in the step (6) is 150-300W;
preferably, the irradiation time in step (6) is 0.2-1h.
7. The method according to any one of claims 3 to 6, wherein the method for preparing the photocatalytic material dispersion liquid in step (2) comprises: mixing a photocatalytic material and a solvent to obtain a photocatalytic material dispersion liquid;
preferably, the solvent comprises n-hexane;
preferably, the preparation method of the photocatalytic material comprises the following steps:
(a) Mixed SrSO 4 Solution and carbonate solution, a first reaction, and thenCarrying out solid-liquid separation, washing and drying to obtain the SrSO with the core-shell structure 4 /SrCO 3 Particles;
(b) Mixing the core-shell structure SrSO obtained in step (a) 4 /SrCO 3 And carrying out a second reaction on the particles, the Ti-containing solution, the Sr-containing solution and the alkali assistant, and then sequentially carrying out solid-liquid separation, washing and drying to obtain the photocatalytic material.
8. The method according to claim 7, wherein the SrSO of step (a) 4 The concentration of the solution is 0.5-1mol/L;
preferably, the carbonate solution comprises (NH) 4 ) 2 CO 3 A solution;
preferably, the concentration of the carbonate solution is 0.5-1mol/L;
preferably, the first reaction comprises a metathesis reaction;
preferably, a first stirring is carried out during the first reaction;
preferably, the first stirring speed is 200-500r/min;
preferably, the time of the first reaction is 20-60min;
preferably, the temperature of the first reaction is 25-40 ℃;
preferably, the temperature of the drying in step (a) is 60-80 ℃;
preferably, the drying time of step (a) is 1-2h.
9. The method of claim 7 or 8, wherein the mixing of step (b) comprises: mixing a Ti-containing solution and a Sr-containing solution, performing second stirring to obtain a mixed solution, and then mixing the mixed solution and the SrSO with the core-shell structure obtained in the step (1) 4 /SrCO 3 Granules and an alkali adjuvant;
preferably, the Ti-containing solution comprises TiCl 4 A solution;
preferably, the concentration of the Ti-containing solution is 0.1-0.5mol/L;
preferably, the Sr-containing solutionThe solution comprises SrCl 2 A solution;
preferably, the concentration of the Sr-containing solution is 0.1-0.5mol/L;
preferably, the base builder comprises a LiOH solution;
preferably, the concentration of the alkali assistant is 1-3mol/L;
preferably, the volume of the alkali assistant is 10-30mL;
preferably, the second reaction comprises a hydrothermal reaction;
preferably, the temperature rise rate of the second reaction is 1-5 ℃/min;
preferably, the end temperature of the second reaction is 175-185 ℃;
preferably, the holding time of the second reaction is 24-28h;
preferably, the temperature of the drying in step (b) is 60-90 ℃;
preferably, the drying time of step (b) is 1-2h.
10. Use of a photocatalytic film according to claim 1 or 2 for the oxidation-reduction of pollutants in a body of water.
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