CN110975894A - Visible light response type efficient and stable nano CsPbBr3/TiO2Composite photocatalyst and preparation method thereof - Google Patents

Visible light response type efficient and stable nano CsPbBr3/TiO2Composite photocatalyst and preparation method thereof Download PDF

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CN110975894A
CN110975894A CN201911311806.1A CN201911311806A CN110975894A CN 110975894 A CN110975894 A CN 110975894A CN 201911311806 A CN201911311806 A CN 201911311806A CN 110975894 A CN110975894 A CN 110975894A
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cspbbr
tio
nano
composite photocatalyst
preparation
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CN110975894B (en
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孟哈日巴拉
郭祖安
张博文
付乌有
曹建亮
李彦伟
王晓东
孙广
张战营
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Henan University of Technology
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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
    • B01J27/06—Halogens; Compounds thereof
    • B01J27/135—Halogens; Compounds thereof with titanium, zirconium, hafnium, germanium, tin or lead
    • B01J35/39—
    • 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
    • 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
    • C02F2101/34—Organic compounds containing oxygen
    • 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
    • C02F2101/36—Organic compounds containing halogen
    • 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
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W10/00—Technologies for wastewater treatment
    • Y02W10/30—Wastewater or sewage treatment systems using renewable energies
    • Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy

Abstract

The invention provides a visible light response type efficient and stable nano CsPbBr3/TiO2The preparation method of the composite photocatalyst comprises the following steps: weighing cesium bromide and lead bromide according to the proportion to prepare CsPbBr3A precursor solution; adding toluene, sealing and stirring to obtain CsPbBr3A nanocrystal suspension; adding the toluene solution containing tetrabutyl titanate into CsPbBr under stirring3Stirring the nano-crystalline suspension in air to obtain Ti (OH)4Coated CsPbBr3Mixed suspension of nano crystalFloating liquid; finally, the precipitate is put into a reaction kettle, heated and kept warm, cooled and then centrifugally separated, and the precipitate is dried to obtain the nano CsPbBr3/TiO2A composite photocatalyst is provided. The composite photocatalyst prepared by the invention has higher catalytic activity and high recycling rate, can quickly degrade organic pollutants in an aqueous solution, has good water resistance, and can stably work in a water system for a long time.

Description

Visible light response type efficient and stable nano CsPbBr3/TiO2Composite photocatalyst and preparation method thereof
Technical Field
The invention belongs to the technical field of visible light response type photocatalysis, and particularly relates to a visible light response type efficient and stable nano CsPbBr3/TiO2A composite photocatalyst and a preparation method thereof.
Background
The research on organic-inorganic hybrid perovskite and all-inorganic perovskite solar cells is broken through, a favorable result is obtained, the efficiency of a single-section perovskite solar cell is high, the perovskite material has high extinction coefficient, excellent bipolar charge migration, smaller exciton binding energy, adjustable band gap and other excellent performances, can be used for researching and developing high-efficiency solar cells, can also be used in the fields of electroluminescence, photoluminescence, sensing, catalysis, photocatalysis and the like, and has huge potential application prospects.
Recent studies found that CsPbBr3In the preparation process of the quantum dot, after titanium hydroxide is coated by in-situ hydrolyzed tetrabutyl titanate, the core-shell structure CsPbBr is obtained by heat treatment at 300 ℃ under the protection of argon3/TiO2A composite material. TiO 22Protection of the shell to CsPbBr3/TiO2The composite material has certain water resistance, potential application in the field of luminescence is verified, and the requirement on later-stage preparation operation is strict.
TiO2As an oxide semiconductor photocatalytic material with no toxicity, good biocompatibility and high stability, the material is widely applied to the fields of environmental pollutant degradation, water photolysis for hydrogen production and the like. However, due to TiO2Belongs to a wide-bandgap semiconductor, needs ultraviolet light for excitation, can utilize the narrow wavelength range of sunlight, and is difficult to be served as a visible light response type photocatalyst.
Therefore, it is necessary to provide an improved solution to the above-mentioned deficiency of the performance of the single photocatalytic material.
Disclosure of Invention
The invention aims to provide a visible light response type efficient and stable nano CsPbBr3/TiO2Composite photocatalyst and preparation method thereof, and CsPbBr is utilized3Has strong absorption property of visible light in wide wavelength range and TiO2The amorphous TiO is prepared by adopting a simple liquid phase method2Coated nano CsPbBr3Composite photocatalyst (CsPbBr)3/TiO2) For overcoming the defects of the existing single photocatalytic material, such as CsPbBr3Readily soluble in water, TiO2The light absorption range of (2) is narrow.
In order to achieve the above purpose, the invention provides the following technical scheme:
visible light response type efficient and stable nano CsPbBr3/TiO2The preparation method of the composite photocatalyst comprises the following steps:
the method comprises the following steps: weighing cesium bromide and lead bromide as raw materials in a first container according to a ratio, adding N, N-dimethylformamide, oleic acid and oleylamine, and stirring under a sealed condition until the raw materials are completely dissolved to obtain CsPbBr3A precursor solution;
step two: adding toluene into a second container, and adding the CsPbBr obtained in the step one under the condition of stirring3The precursor solution is continuously stirred under the sealing condition to obtain CsPbBr3A nanocrystal suspension;
step three: adding toluene into a third container, adding tetrabutyl titanate under the stirring condition, and continuously stirring under the sealing condition to obtain a toluene solution containing tetrabutyl titanate;
step four: adding the toluene solution of tetrabutyl titanate obtained in the third step into CsPbBr obtained in the second step under the condition of stirring3Stirring the nano-crystalline suspension in an open air atmosphere for a period of time to obtain Ti (OH)4Coated CsPbBr3Mixing the nano-crystalline mixed suspension;
step five: mixing the Ti (OH) obtained in step four4Coated CsPbBr3Putting the mixed suspension of the nano-crystals into a high-pressure reaction kettle, heating and preserving heat, then cooling to room temperature, washing and centrifugally separating for many times, and drying the precipitate to obtain the nano-CsPbBr3/TiO2A composite photocatalyst is provided.
The visible light response type efficient and stable nano CsPbBr3/TiO2The preparation method of the composite photocatalyst is a preferable scheme, and the volume ratio of the tetrabutyl titanate to the toluene in the step three is 1: 10.
The visible light response type highly effective stable nanometerCsPbBr3/TiO2In the preparation method of the composite photocatalyst, as a preferable scheme, the quantity ratio of the cesium bromide to the lead bromide in the step one is 1: 1.
The visible light response type efficient and stable nano CsPbBr3/TiO2The preparation method of the composite photocatalyst is preferably characterized in that CsPbBr is adopted in the step one3The mass concentration of the precursor solution is 0.02-0.05 mol/L.
The visible light response type efficient and stable nano CsPbBr3/TiO2According to the preparation method of the composite photocatalyst, as a preferable scheme, in the first step, the volume ratio of the N, N-dimethylformamide to the oleic acid to the oleylamine is (9-15): 1:0.5.
The visible light response type efficient and stable nano CsPbBr3/TiO2The preparation method of the composite photocatalyst is preferably that the toluene and the CsPbBr are mixed in the step two3The volume ratio of the precursor liquid is (8-12): 1.
the visible light response type efficient and stable nano CsPbBr3/TiO2Preferably, in the fourth step, after the composite photocatalyst is stirred for a period of time in an air atmosphere, Ti (OH) is obtained4Coated CsPbBr3And (3) mixing the nanocrystalline mixed suspension, wherein the humidity of the air atmosphere is 20% -60%, and the stirring time is 2-10 h.
The visible light response type efficient and stable nano CsPbBr3/TiO2And as an optimal scheme, in the fifth step, heating and heat preservation are carried out, wherein the heating temperature is 120-200 ℃, and the heat preservation time is 4-12 hours.
The visible light response type efficient and stable nano CsPbBr3/TiO2According to the preparation method of the composite photocatalyst, as a preferable scheme, in the fifth step, the precipitate is dried, the drying temperature is 60 ℃, and the drying time is 24 hours.
The visible light response type efficient and stable nano CsPbBr3/TiO2Visible light response type efficient and stable nano CsPbBr prepared by preparation method of composite photocatalyst3/TiO2A composite photocatalyst is provided.
Compared with the closest prior art, the technical scheme provided by the invention has the following excellent effects:
(1) in the invention, CsPbBr with strong absorption performance of visible light in wide wavelength range3With TiO having a high degree of stability2Combined, a simple liquid phase method is adopted to prepare the nano CsPbBr with the nano visible light response type, high efficiency and stability3/TiO2The composite photocatalyst has simple preparation process and low manufacturing cost, is operated in natural air atmosphere, does not need a glove box and inert gas protection measures, does not relate to high-temperature heat treatment in the later preparation stage, and can meet the requirement of large-scale industrial production.
(2) Nano CsPbBr prepared in the invention3/TiO2The composite photocatalyst is nano CsPbBr under the irradiation of visible light3/TiO2The composite photocatalyst has higher catalytic activity and high recycling rate, can rapidly degrade organic pollutants in an aqueous solution, has the rate constant of degrading the organic pollutants by photocatalysis higher than that of a commercial P25 titanium dioxide photocatalyst by about 7 times, and is nano CsPbBr3/TiO2The composite photocatalyst has great application prospect in the field of environmental management of sewage treatment and the aspect of degrading organic pollutants by utilizing solar light irradiation.
(3) Nano CsPbBr prepared in the invention3/TiO2The composite photocatalyst has good water resistance and can stably work in a water system for a long time.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this application, illustrate embodiments of the invention and, together with the description, serve to explain the invention and not to limit the invention. Wherein:
FIG. 1 shows the CsPbBr nanoparticles prepared in the embodiment of the present invention3/TiO2Composite lightTransmission electron micrograph of catalyst;
FIG. 2 shows the CsPbBr nanoparticles prepared in the embodiment of the present invention3/TiO2High-resolution transmission electron microscope photographs of the composite photocatalyst;
FIG. 3 shows the CsPbBr nanoparticles prepared in the embodiment of the present invention3/TiO2Ultraviolet-visible absorption spectrum of the composite photocatalyst and the P25 titanium dioxide;
FIG. 4 shows the CsPbBr nanoparticles prepared in the embodiment of the present invention3/TiO2The light absorption curve diagram of the composite photocatalyst at different moments when the rhodamine B aqueous solution is degraded under the irradiation of simulated sunlight is shown;
FIG. 5 shows the CsPbBr nanoparticles prepared in the embodiment of the present invention3/TiO2A photodegradation rate graph of the composite photocatalyst and P25 titanium dioxide on the rhodamine B water solution under the irradiation of simulated sunlight;
FIG. 6 shows CsPbBr nanoparticles prepared in an embodiment of the present invention3/TiO2A cycle degradation rate diagram of the composite photocatalyst on a rhodamine B aqueous solution under simulated sunlight irradiation;
FIG. 7 shows the CsPbBr nanoparticles prepared in the embodiment of the present invention3/TiO2And (3) a degradation rate graph of the composite photocatalyst on a rhodamine B aqueous solution before and after soaking in water for 45 days.
Detailed Description
The technical solutions in the embodiments of the present invention will be described clearly and completely below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments that can be derived by one of ordinary skill in the art from the embodiments given herein are intended to be within the scope of the present invention.
The present invention will be described in detail below with reference to the embodiments with reference to the attached drawings. It should be noted that the embodiments and features of the embodiments may be combined with each other without conflict.
The invention provides a visible light response type efficient and stable nano CsPbBr3/TiO2Composite photocatalyst andthe preparation method adopts a simple and mild liquid phase method to prepare CsPbBr with strong absorption performance of visible light in a wide wavelength range3With TiO having a high degree of stability2Combining to prepare the nano CsPbBr3/TiO2The composite photocatalyst is visible light response type, has high catalytic activity under the irradiation condition of visible light, can quickly degrade organic pollutants in an aqueous solution, has good water resistance, and can stably work in a water system for a long time.
The invention provides a visible light response type efficient and stable nano CsPbBr3/TiO2The preparation method of the composite photocatalyst comprises the following steps:
the method comprises the following steps: weighing cesium bromide and lead bromide as raw materials in a first container according to a ratio, adding N, N-dimethylformamide, oleic acid and oleylamine, and stirring under a sealed condition until the raw materials are completely dissolved to obtain CsPbBr3A precursor solution;
in an embodiment of the invention, the ratio of the amount of cesium bromide to lead bromide species in step one is 1: 1.
In an embodiment of the present invention, CsPbBr is used in the first step3The mass concentration of the precursor solution is 0.02-0.05 mol/L (such as 0.02mol/L, 0.022mol/L, 0.024mol/L, 0.026mol/L, 0.028mol/L, 0.03mol/L, 0.032mol/L, 0.034mol/L, 0.036mol/L, 0.038mol/L, 0.04mol/L, 0.042mol/L, 0.044mol/L, 0.046mol/L, 0.048mol/L, 0.05 mol/L).
In the specific embodiment of the invention, the volume ratio of the N, N-dimethylformamide to the oleic acid to the oleylamine in the first step is (9-15): 1:0.5 (e.g., 9:1:0.5, 10:1:0.5, 11:1:0.5, 12:1:0.5, 13:1:0.5, 14:1:0.5, 15:1: 0.5).
Step two: adding toluene into a second container, and adding the CsPbBr obtained in the step one under the condition of stirring3The precursor solution is continuously stirred under the sealing condition to obtain CsPbBr3And (3) a nanocrystal suspension.
In a specific embodiment of the present invention, toluene and CsPbBr are used in step two3The volume ratio of the precursor liquid is(8-12): 1 (e.g., 8:1, 8.5:1, 9:1, 9.5:1, 10:1, 10.5:1, 11:1, 11.5:1, 12: 1).
Step three: and (3) adding toluene into a third container, adding tetrabutyl titanate under the stirring condition, and continuously stirring under the sealing condition to obtain a toluene solution containing tetrabutyl titanate.
In the specific embodiment of the invention, the volume ratio of tetrabutyl titanate to toluene in the step three is 1: 10.
Step four: adding the toluene solution of tetrabutyl titanate obtained in the third step into CsPbBr obtained in the second step under the condition of stirring3Stirring the nano-crystalline suspension in an open air atmosphere for a period of time to obtain Ti (OH)4Coated CsPbBr3The nanocrystal is mixed with the suspension.
In the embodiment of the invention, after stirring for a period of time in the air atmosphere in the fourth step, Ti (OH) is obtained4Coated CsPbBr of3And (3) mixing the nanocrystalline mixed suspension, wherein the humidity of the air atmosphere is 20-60% (such as 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%), and the stirring time is 2-10 h (such as 2h, 2.5h, 3h, 3.5h, 4h, 4.5h, 5h, 5.5h, 6h, 6.5h, 7h, 7.5h, 8h, 8.5h, 9h, 9.5h, and 10 h).
Step five: mixing the Ti (OH) obtained in step four4Coated CsPbBr3Putting the mixed suspension of the nano-crystals into a high-pressure reaction kettle, heating and preserving heat, then cooling to room temperature, washing and centrifugally separating for many times, and drying the precipitate to obtain the nano-CsPbBr3/TiO2A composite photocatalyst is provided.
In the embodiment of the invention, in the fifth step, the heating and heat preservation are carried out, the heating temperature is 120-200 ℃ (such as 120 ℃, 125 ℃, 130 ℃, 135 ℃, 140 ℃, 145 ℃, 150 ℃, 155 ℃, 160 ℃, 165 ℃, 170 ℃, 175 ℃, 180 ℃, 185 ℃, 190 ℃, 195 ℃, 200 ℃), and the heat preservation time is 4-12 h (such as 4h, 4.5h, 5h, 5.5h, 6h, 6.5h, 7h, 7.5h, 8h, 8.5h, 9h, 9.5h, 10h, 10.5h, 11h, 11.5h, 12 h).
In the embodiment of the invention, the precipitate is dried in the fifth step, wherein the drying temperature is 60 ℃ and the drying time is 24 hours.
Example 1
The embodiment provides a visible light response type efficient and stable nano CsPbBr3/TiO2The preparation method of the composite photocatalyst comprises the following steps:
the method comprises the following steps: weighing 0.2556g of cesium bromide and 0.4404g of lead bromide as raw materials in a beaker with the volume of 100ml, adding 36ml of N, N-dimethylformamide, 3.0ml of oleic acid and 1.5ml of oleylamine (the volume ratio of the N, N-dimethylformamide to the oleic acid to the oleylamine is 12:1:0.5), sealing the opening of the beaker with a preservative film, and stirring by magnetic force until the raw materials are completely dissolved to obtain CsPbBr3A precursor solution;
step two: adding 360ml of toluene into a beaker with the volume of 1000ml, and adding the CsPbBr obtained in the step one under the condition of magnetic stirring3The precursor solution is continuously stirred under the sealing condition to obtain CsPbBr3And (3) a nanocrystal suspension.
Step three: adding 30ml of toluene into a 100ml beaker, adding 3ml of tetrabutyl titanate under the stirring condition, sealing the opening of the beaker by using a preservative film, and magnetically stirring for 5min to obtain a toluene solution containing tetrabutyl titanate.
Step four: adding the toluene solution of tetrabutyl titanate obtained in the third step into CsPbBr obtained in the second step3In the nanocrystalline suspension, stirring for 6h in an open air under the natural air condition that the air humidity is 40%, and slowly hydrolyzing tetrabutyl titanate by water vapor in the air to obtain Ti (OH)4Coated CsPbBr3The nanocrystal is mixed with the suspension.
Step five: the Ti (OH) obtained in the fourth step4Coated CsPbBr3Filling the mixed suspension of the nano-crystalline into a 500ml high-pressure reaction kettle, heating to 150 ℃, preserving the heat for 8 hours, and adding the nano CsPbBr into the reaction kettle3Coated Ti (OH)4Conversion to TiO by dehydration2Then cooling to room temperature, centrifugally separating the precipitate, washing the precipitate with toluene, and drying the centrifugally separated precipitate in a constant-temperature drying oven at 60 ℃ for 24 hours to obtain the nano CsPbBr3/TiO2A composite photocatalyst is provided.
This detailed descriptionNano CsPbBr prepared in example3/TiO2The characterization result of the composite photocatalyst is as follows:
as shown in FIG. 1, the CsPbBr nanoparticles prepared in this example are3/TiO2Transmission electron micrograph of the composite photocatalyst shows that CsPbBr is observed in the micrograph3The shape of the nano crystal is similar to a sphere, CsPbBr3The diameter of the nano-crystal is distributed in the range of 8-17 nm, and the average diameter is 13 nm; there are several or several tens of CsPbBr3The nanocrystalline is coated on the TiO with irregular morphology2Inside, nano CsPbBr is formed3/TiO2A composite material.
As shown in FIG. 2, the CsPbBr nanoparticles prepared in this example are3/TiO2The high-resolution transmission electron microscope photo of the composite photocatalyst can clearly show that CsPbBr is added in the photo3The measured interplanar spacing of the regularly stacked stripes of (1) is 0.57nm, and the attribute is CsPbBr3The (001) plane of (a), however, no surface coating with TiO was observed2Regular stripes of (i.e. identifying TiO)2Is in an amorphous state.
As shown in FIG. 3, the CsPbBr prepared in the embodiment of the present invention is a nano-CsPbBr3/TiO2Ultraviolet-visible absorption spectra of the composite photocatalyst and P25 titanium dioxide, wherein P25 titanium dioxide is a commercial nano titanium dioxide photocatalyst with an average particle size of 25 nm. From the ultraviolet-visible absorption spectrogram, the light absorption band edge of the P25 titanium dioxide is less than 400nm, and the sunlight utilization rate is low, however, the CsPbBr prepared in the embodiment is low3/TiO2The composite photocatalyst has a wide light absorption band, covers the wavelength range with the strongest sunlight irradiation, has the light absorption band edge expanded to 533nm, has high absorbance and has the characteristic of being excited by sunlight to work.
In order to evaluate the photocatalytic activity of the catalyst, simulated sunlight with the atmospheric quality of AM1.5G given by a sunlight simulator is used as a light source, and the light power is 100mW/cm2Selecting rhodamine B as a simulated pollutant, and testing the nano CsPbBr3/TiO2Composite photocatalystThe photocatalytic degradation rate of the rhodamine B water solution.
The specific test method comprises the following steps:
taking 100ml of the solution in a 250ml beaker with the concentration of 3.0X 10-5Adding 100mg of nano CsPbBr into mol/L rhodamine B water solution3/TiO2Stirring the composite photocatalyst (or P25 titanium dioxide) in the dark for 10min, after adsorption equilibrium is reached, starting timing under the irradiation of a solar simulator, continuing stirring, taking out 10mL of reaction liquid every 3min, centrifugally separating by using a high-speed centrifuge, taking out supernatant, testing an absorption spectrum in the range of 450-650 nm by using an ultraviolet visible spectrophotometer, determining the absorbance of the reaction liquid at 553nm, comparing the absorbance with a standard working curve, and calculating the concentration of a rhodamine B aqueous solution, thereby calculating the photocatalytic degradation rate of the rhodamine B aqueous solution.
As shown in FIG. 4, the CsPbBr prepared in the embodiment of the present invention is a nano-CsPbBr3/TiO2The light absorption curve diagrams of the composite photocatalyst at different moments of degrading the rhodamine B aqueous solution under the irradiation of simulated sunlight show that the absorbance of the rhodamine B aqueous solution is rapidly reduced along with the prolonging of the illumination time.
As shown in FIG. 5, the CsPbBr prepared in the embodiment of the present invention is a nano-CsPbBr3/TiO2The light degradation rate of the composite photocatalyst and P25 titanium dioxide to the rhodamine B aqueous solution under the sunlight simulation irradiation is shown in the figure, when the simulated sunlight is continuously irradiated for 15min, the degradation rate of the P25 titanium dioxide to the rhodamine B aqueous solution can only reach 35.44%; nano CsPbBr3/TiO2The degradation rate of the composite photocatalyst on rhodamine B reaches 98.05 percent, and the rhodamine B is basically and completely degraded.
To further verify the nano CsPbBr3/TiO2The composite photocatalyst has the recycling performance, after the photocatalytic degradation of the rhodamine B aqueous solution is finished, the catalyst is separated out by centrifugation, washed for 3 times by deionized water, and then 100ml of the catalyst with the concentration of 3.0 multiplied by 10 is added-5And (3) simulating sunlight irradiation of the rhodamine B water solution of mol/L for photodegradation again, and repeating for 2 times.
FIG. 6 shows the nano-particles prepared in the example of the present inventionRice CsPbBr3/TiO2The composite photocatalyst is a circular degradation rate diagram of a rhodamine B aqueous solution under simulated sunlight irradiation, when the illumination time is 15min, the second degradation rate of rhodamine B reaches 96.93%, the third degradation rate of rhodamine B reaches 93.45%, the degradation rate is reduced compared with the first degradation rate, the suspension property of the nano catalyst in the aqueous solution is good, the nano catalyst is not completely settled during washing and centrifugal separation, a small amount of catalyst is lost, and the high degradation rate is still maintained.
CsPbBr3The nano CsPbBr prepared in the embodiment is ineffective by rapidly dissolving into ions after entering water3/TiO2After the composite photocatalyst is placed in water and soaked for 45 days, centrifugal separation is carried out, and then photocatalytic activity is investigated. FIG. 7 shows the CsPbBr nanoparticles prepared in the examples of the present invention3/TiO2And (3) a degradation rate graph of the composite photocatalyst on a rhodamine B aqueous solution before and after soaking in water for 45 days. As can be seen from the figure, the nano CsPbBr after soaking in water for 45 days3/TiO2When the composite photocatalyst is irradiated for 15min by simulated sunlight, the degradation rate of rhodamine B still reaches 92.23%, that is to say, amorphous TiO2The coating greatly improves CsPbBr3Water resistance of (1), namely the nano CsPbBr provided in this embodiment3/TiO2The composite photocatalyst has good water resistance and can be used in a water system for a long time.
Example 2
The embodiment provides a visible light response type efficient and stable nano CsPbBr3/TiO2The preparation method of the composite photocatalyst is different from the preparation method in the example 1 in that in the fourth step, the tetrabutyl titanate is slowly hydrolyzed by the water vapor in the air to obtain Ti (OH) under the condition that the open stirring is carried out for 7 hours under the natural air condition that the air humidity is 30 percent4Coated CsPbBr3The nanocrystal is mixed with the suspension.
Other steps are the same as embodiment 1 and are not described herein again.
The nano-particles prepared in this example were mixedCsPbBr3/TiO2The composite photocatalyst takes simulated sunlight with atmospheric mass of AM1.5G given by a sunlight simulator as a light source, and the luminous power is 100mW/cm2Selecting rhodamine B as a simulated pollutant, and illuminating for 15min by using the nano CsPbBr3/TiO2The photocatalytic degradation rate of the composite photocatalyst to rhodamine B water solution reaches 97.36%.
Example 3
The embodiment provides a visible light response type efficient and stable nano CsPbBr3/TiO2The preparation method of the composite photocatalyst is different from the preparation method in the example 1 in that in the fourth step, the tetrabutyl titanate is slowly hydrolyzed by the water vapor in the air under the natural air condition that the air humidity is 20 percent by stirring for 10h in an open way to obtain Ti (OH)4Coated CsPbBr3The nanocrystal is mixed with the suspension.
Other steps are the same as embodiment 1 and are not described herein again.
The nano CsPbBr prepared in the example3/TiO2The composite photocatalyst takes simulated sunlight with atmospheric mass of AM1.5G given by a sunlight simulator as a light source, and the luminous power is 100mW/cm2Selecting rhodamine B as a simulated pollutant, and illuminating for 15min by using the nano CsPbBr3/TiO2The photocatalytic degradation rate of the composite photocatalyst to the rhodamine B water solution reaches 97.54%.
Example 4
The embodiment provides a visible light response type efficient and stable nano CsPbBr3/TiO2The preparation method of the composite photocatalyst is different from the preparation method in the example 1 in that in the fourth step, the tetrabutyl titanate is slowly hydrolyzed by the water vapor in the air to obtain Ti (OH) under the condition that the open stirring is carried out for 5 hours under the natural air condition that the air humidity is 50 percent4Coated CsPbBr3The nanocrystal is mixed with the suspension.
Other steps are the same as embodiment 1 and are not described herein again.
The nano CsPbBr prepared in the example3/TiO2Composite photocatalyst, EtherThe sunlight simulator gives simulated sunlight with the atmospheric mass of AM1.5G as a light source and the luminous power of 100mW/cm2Selecting rhodamine B as a simulated pollutant, and illuminating for 15min by using the nano CsPbBr3/TiO2The photocatalytic degradation rate of the composite photocatalyst to rhodamine B water solution reaches 97.86%.
Example 5
The embodiment provides a visible light response type efficient and stable nano CsPbBr3/TiO2The preparation method of the composite photocatalyst is different from the preparation method in the example 1 in that in the fourth step, under the condition that natural air is obtained under the air humidity of 60%, the mixture is stirred for 3h in an open way, and water vapor in the air slowly hydrolyzes tetrabutyl titanate to obtain Ti (OH)4Coated CsPbBr3The nanocrystal is mixed with the suspension.
Other steps are the same as embodiment 1 and are not described herein again.
The nano CsPbBr prepared in the example3/TiO2The composite photocatalyst takes simulated sunlight with atmospheric mass of AM1.5G given by a sunlight simulator as a light source, and the luminous power is 100mW/cm2Selecting rhodamine B as a simulated pollutant, and illuminating for 15min by using the nano CsPbBr3/TiO2The photocatalytic degradation rate of the composite photocatalyst to rhodamine B water solution reaches 97.12%.
Example 6
The embodiment provides a visible light response type efficient and stable nano CsPbBr3/TiO2The preparation method of the composite photocatalyst is different from the preparation method in the embodiment 1 in that in the step one, 30ml of N, N-dimethylformamide, 3.0ml of oleic acid and 1.5ml of oleylamine (the volume ratio of the N, N-dimethylformamide to the oleic acid to the oleylamine is 9:1:0.5) are added, a beaker mouth is sealed by a preservative film, and the mixture is magnetically stirred until the raw materials are completely dissolved to obtain CsPbBr3A precursor liquid.
Other steps are the same as embodiment 1 and are not described herein again.
The nano CsPbBr prepared in the example3/TiO2The composite photocatalyst adopts a sunlight simulator to give simulated sunlight with the atmospheric quality of AM1.5GLight source with luminous power of 100mW/cm2Selecting rhodamine B as a simulated pollutant, and illuminating for 15min by using the nano CsPbBr3/TiO2The photocatalytic degradation rate of the composite photocatalyst to the rhodamine B water solution reaches 96.83%.
Example 7
The embodiment provides a visible light response type efficient and stable nano CsPbBr3/TiO2The preparation method of the composite photocatalyst is different from the preparation method in the embodiment 6 in that in the fifth step, the heating temperature is 200 ℃, and the heat preservation is carried out for 4 hours.
The other steps are the same as those in embodiment 6, and are not described herein again.
The nano CsPbBr prepared in the example3/TiO2The composite photocatalyst takes simulated sunlight with atmospheric mass of AM1.5G given by a sunlight simulator as a light source, and the luminous power is 100mW/cm2Selecting rhodamine B as a simulated pollutant, and illuminating for 15min by using the nano CsPbBr3/TiO2The photocatalytic degradation rate of the composite photocatalyst to rhodamine B water solution reaches 97.12%.
Example 8
The embodiment provides a visible light response type efficient and stable nano CsPbBr3/TiO2The preparation method of the composite photocatalyst is different from the preparation method in the embodiment 1 in that in the step one, 51.42ml of N, N-dimethylformamide, 5.72ml of oleic acid and 2.86ml of oleylamine (the volume ratio of the N, N-dimethylformamide to the oleic acid to the oleylamine is 9:1:0.5) are added, a beaker mouth is sealed by a preservative film, and the mixture is magnetically stirred until the raw materials are completely dissolved to obtain CsPbBr3A precursor solution; in the second step, 360ml of toluene is added into a beaker with the volume of 1000ml, and the CsPbBr obtained in the first step is added under the condition of magnetic stirring345ml of precursor solution is continuously stirred under the sealing condition to obtain CsPbBr3And (3) a nanocrystal suspension.
Other steps are the same as embodiment 1 and are not described herein again.
The nano CsPbBr prepared in the example3/TiO2The composite photocatalyst gives the atmosphere with the mass AM by a sunlight simulator1.5G simulated sunlight is used as a light source, and the light power is 100mW/cm2Selecting rhodamine B as a simulated pollutant, and illuminating for 15min by using the nano CsPbBr3/TiO2The photocatalytic degradation rate of the composite photocatalyst to rhodamine B water solution reaches 92.45%.
Example 9
The embodiment provides a visible light response type efficient and stable nano CsPbBr3/TiO2The preparation method of the composite photocatalyst is different from the preparation method in the embodiment 8 in that in the second step, 360ml of toluene is added into a beaker with the volume of 1000ml, and the CsPbBr obtained in the first step is added under the condition of magnetic stirring330ml of the precursor solution is continuously stirred under the sealing condition to obtain CsPbBr3A nanocrystal suspension; in the fifth step, the heating temperature is 120 ℃, and the temperature is kept for 10 hours.
The other steps are the same as those in embodiment 8, and are not described herein again.
The nano CsPbBr prepared in the example3/TiO2The composite photocatalyst takes simulated sunlight with atmospheric mass of AM1.5G given by a sunlight simulator as a light source, and the luminous power is 100mW/cm2Selecting rhodamine B as a simulated pollutant, and illuminating for 15min by using the nano CsPbBr3/TiO2The photocatalytic degradation rate of the composite photocatalyst to rhodamine B water solution reaches 96.35%.
Comparative example 1
The comparison example provides a visible light response type efficient and stable nano CsPbBr3/TiO2The preparation method of the composite photocatalyst is different from the preparation method in the example 1 in that in the third step, the composite photocatalyst is stirred for 1h in an open manner under the condition of natural air with the air humidity of 80%, and water vapor in the air slowly hydrolyzes tetrabutyl titanate to obtain Ti (OH)4Coated CsPbBr3The nanocrystal is mixed with the suspension. Other steps are the same as embodiment 1 and are not described herein again.
The nano CsPbBr prepared in the comparative example was added3/TiO2The composite photocatalyst adopts a sunlight simulator to give simulated sunlight with the atmospheric quality of AM1.5GLight source with luminous power of 100mW/cm2Selecting rhodamine B as a simulated pollutant, and illuminating for 15min by using the nano CsPbBr3/TiO2The photocatalytic degradation rate of the composite photocatalyst to the rhodamine B water solution reaches 78.43%.
Comparative example 2
The comparison example provides a visible light response type efficient and stable nano CsPbBr3/TiO2The preparation method of the composite photocatalyst comprises the step five of the preparation method in the embodiment 1, wherein the heating temperature is 80 ℃, and the heat preservation is carried out for 8 hours.
Other steps are the same as embodiment 1 and are not described herein again.
The nano CsPbBr prepared in the comparative example was added3/TiO2The composite photocatalyst takes simulated sunlight with atmospheric mass of AM1.5G given by a sunlight simulator as a light source, and the luminous power is 100mW/cm2Selecting rhodamine B as a simulated pollutant, and illuminating for 15min by using the nano CsPbBr3/TiO2The photocatalytic degradation rate of the composite photocatalyst to the rhodamine B water solution reaches 83.26%.
Comparative example 3
The comparison example provides a visible light response type efficient and stable nano CsPbBr3/TiO2The preparation method of the composite photocatalyst is different from the preparation method in the embodiment 1 in that in the step one, 111ml of N, N-dimethylformamide, 6ml of oleic acid and 3ml of oleylamine (the volume ratio of the N, N-dimethylformamide to the oleic acid to the oleylamine is 18.5:1:0.5) are added, a beaker mouth is sealed by a preservative film, and the mixture is magnetically stirred until the raw materials are completely dissolved to obtain CsPbBr3A precursor liquid.
Other steps are the same as embodiment 1 and are not described herein again.
The nano CsPbBr prepared in the comparative example was added3/TiO2The composite photocatalyst takes simulated sunlight with atmospheric mass of AM1.5G given by a sunlight simulator as a light source, and the luminous power is 100mW/cm2Selecting rhodamine B as a simulated pollutant, and illuminating for 15min by using the nano CsPbBr3/TiO2The photocatalytic degradation rate of the composite photocatalyst to the rhodamine B water solution reaches 67.56%.
By comparing the examples with the comparative examples, the nano CsPbBr provided by the invention3/TiO2The composite photocatalyst has higher catalytic activity, and the photocatalytic degradation rate of the rhodamine B aqueous solution is still over 92 percent after the rhodamine B aqueous solution is soaked in water for 45 days; the invention provides a nano CsPbBr3/TiO2The preparation of the composite photocatalyst is slightly influenced by the environment humidity condition, when the air humidity is 20-60%, the hydrolysis reaction time of the tetrabutyl titanate is prolonged when the air humidity is low, and the hydrolysis reaction time of the tetrabutyl titanate is shortened when the air humidity is high, so that the catalyst with high catalytic activity can be obtained.
In conclusion, the invention is prepared by adopting a mild liquid phase method in the natural air atmosphere, the preparation process is simple to operate, and the glove box, the protection of inert gas, the high-temperature heat treatment process and the like are not involved; prepared nano CsPbBr3/TiO2The composite photocatalyst is visible light response type, has high catalytic activity under the condition of simulating sunlight irradiation, and has high recycling rate; the photocatalyst can rapidly degrade organic pollutants in aqueous solution, and the rate constant of photocatalytic degradation of the organic pollutants is about 7 times higher than that of the rate constant of degradation of the organic pollutants of the photocatalyst of commercial P25 titanium dioxide; and can work stably for a long time in a water system, and the nano CsPbBr3/TiO2The composite photocatalyst has great application prospect in the field of environmental management of sewage treatment and the aspect of degrading organic pollutants by utilizing solar light irradiation.
The above description is only exemplary of the invention and should not be taken as limiting the invention, as any modification, equivalent replacement, or improvement made within the spirit and principle of the invention is intended to be covered by the appended claims.

Claims (10)

1. Visible light response type efficient and stable nano CsPbBr3/TiO2The preparation method of the composite photocatalyst is characterized by comprising the following steps:
the method comprises the following steps: weighing cesium bromide and lead bromide as raw materials in a first container according to a ratioAdding N, N-dimethylformamide, oleic acid and oleylamine into a container, stirring under a sealed condition until the raw materials are completely dissolved to obtain CsPbBr3A precursor solution;
step two: adding toluene into a second container, and adding the CsPbBr obtained in the step one under the condition of stirring3The precursor solution is continuously stirred under the sealing condition to obtain CsPbBr3A nanocrystal suspension;
step three: adding toluene into a third container, adding tetrabutyl titanate under the stirring condition, and continuously stirring under the sealing condition to obtain a toluene solution containing tetrabutyl titanate;
step four: adding the toluene solution of tetrabutyl titanate obtained in the third step into CsPbBr obtained in the second step under the condition of stirring3Stirring the nano-crystalline suspension in an open air atmosphere for a period of time to obtain Ti (OH)4Coated CsPbBr3Mixing the nano-crystalline mixed suspension;
step five: mixing the Ti (OH) obtained in step four4Coated CsPbBr3Putting the mixed suspension of the nano-crystals into a high-pressure reaction kettle, heating and preserving heat, then cooling to room temperature, washing and centrifugally separating for many times, and drying the precipitate to obtain the nano-CsPbBr3/TiO2A composite photocatalyst is provided.
2. The visible-light-responsive, highly efficient and stable nano-CsPbBr of claim 13/TiO2The preparation method of the composite photocatalyst is characterized in that the volume ratio of the tetrabutyl titanate to the toluene in the step three is 1: 10.
3. The visible-light-responsive, highly efficient and stable nano-CsPbBr of claim 13/TiO2The preparation method of the composite photocatalyst is characterized in that the mass ratio of the cesium bromide to the lead bromide in the step one is 1: 1.
4. The visible-light-responsive, highly efficient and stable nano-CsPbBr of claim 13/TiO2The preparation method of the composite photocatalyst is characterized in that CsPbBr is adopted in the step one3The mass concentration of the precursor solution is 0.02-0.05 mol/L.
5. The visible-light-responsive, highly efficient and stable nano-CsPbBr of claim 13/TiO2The preparation method of the composite photocatalyst is characterized in that in the first step, the volume ratio of the N, N-dimethylformamide to the oleic acid to the oleylamine is (9-15): 1:0.5.
6. The visible-light-responsive, highly efficient and stable nano-CsPbBr of claim 13/TiO2The preparation method of the composite photocatalyst is characterized in that the toluene and the CsPbBr are used in the step two3The volume ratio of the precursor liquid is (8-12): 1.
7. the visible-light-responsive, highly efficient and stable nano-CsPbBr of claim 13/TiO2The preparation method of the composite photocatalyst is characterized in that in the fourth step, the composite photocatalyst is obtained by stirring for a period of time in an open air atmosphere to obtain Ti (OH)4Coated CsPbBr3And (3) mixing the nanocrystalline mixed suspension, wherein the humidity of the air atmosphere is 20% -60%, and the stirring time is 2-10 h.
8. The visible-light-responsive, highly efficient and stable nano-CsPbBr of claim 13/TiO2The preparation method of the composite photocatalyst is characterized by heating and heat preservation in the fifth step, wherein the heating temperature is 120-200 ℃, and the heat preservation time is 4-12 hours.
9. The visible-light-responsive, highly efficient and stable nano-CsPbBr of claim 13/TiO2The preparation method of the composite photocatalyst is characterized in that the precipitate is dried in the fifth step, the drying temperature is 60 ℃, and the drying time is 24 hours.
10. A method as claimed in any one of claims 1 to 9The visible light response type efficient and stable nano CsPbBr3/TiO2Visible light response type efficient and stable nano CsPbBr prepared by preparation method of composite photocatalyst3/TiO2A composite photocatalyst is provided.
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