CN110975894B - Visible light response type efficient and stable nano CsPbBr 3 /TiO 2 Composite photocatalyst and preparation method thereof - Google Patents

Visible light response type efficient and stable nano CsPbBr 3 /TiO 2 Composite photocatalyst and preparation method thereof Download PDF

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CN110975894B
CN110975894B CN201911311806.1A CN201911311806A CN110975894B CN 110975894 B CN110975894 B CN 110975894B CN 201911311806 A CN201911311806 A CN 201911311806A CN 110975894 B CN110975894 B CN 110975894B
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cspbbr
tio
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composite photocatalyst
stirring
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CN110975894A (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 CsPbBr 3 /TiO 2 The preparation method of the composite photocatalyst comprises the following steps: weighing cesium bromide and lead bromide according to the proportion to prepare CsPbBr 3 A precursor solution; adding toluene, sealing and stirring to obtain CsPbBr 3 A nanocrystal suspension; adding the toluene solution containing tetrabutyl titanate into CsPbBr under stirring 3 Stirring in the air to obtain Ti (OH) 4 Coated CsPbBr 3 Mixing the nano-crystalline mixed suspension; finally, the precipitate is put into a reaction kettle, heated and insulated, cooled and centrifugally separated, and the precipitate is dried to obtain the nano CsPbBr 3 /TiO 2 A 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 CsPbBr 3 /TiO 2 Composite lightCatalyst 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 CsPbBr 3 /TiO 2 A composite photocatalyst and a preparation method thereof.
Background
Since 2009 research on organic-inorganic hybrid perovskite materials is tried to be applied to the photovoltaic field to obtain primary results, the hot trend of research on lead-halogen perovskite materials is raised. The research on organic-inorganic hybrid perovskite and all-inorganic perovskite solar cells is broken through all the time, favorable results are obtained, and the efficiency of a single perovskite solar cell is high. The perovskite material has excellent performances of high extinction coefficient, excellent bipolar charge migration, smaller exciton binding energy, adjustable band gap and the like, 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 prospect. However, lead-halide perovskite materials are typically low-valent ionic crystals, which are easily dissolved in water and polar organic solvents, limiting their extended applications, and thus scientists have extensively explored and sought various protection techniques and methods for lead-halide perovskite materials, such as: wrapping a bismuth indium tin alloy layer to avoid direct contact between the perovskite layer and the aqueous solution; embedding perovskite in polystyrene; the water resistance of the lead-halogen perovskite material is improved to a certain extent by embedding perovskite with sulfobutyl ether-beta-cyclodextrin (SBE-beta-CD) and other technologies.
Recent studies have found that CsPbBr 3 In 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 argon 3 /TiO 2 A composite material. TiO 2 2 Protection of the shell to CsPbBr 3 /TiO 2 The composite material has certain water resistance, and the potential application in the field of luminescence is verified, but the later preparation operation requirement is strict.
TiO 2 Has no toxicity, good biocompatibility and stabilityHigh oxide semiconductor photocatalytic materials have been widely used in the fields of environmental pollutant degradation, photolysis of water to produce hydrogen, and the like. However, due to TiO 2 Belongs 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 CsPbBr 3 /TiO 2 Composite photocatalyst and preparation method thereof, and CsPbBr is utilized 3 Has strong absorption performance of visible light in wide wavelength range and TiO 2 The high stability of the method is combined, and amorphous TiO is prepared by adopting a simple liquid phase method 2 Coated nano CsPbBr 3 Composite photocatalyst (CsPbBr) 3 /TiO 2 ) For overcoming the defects of the existing single photocatalytic material, such as CsPbBr 3 Readily soluble in water, tiO 2 The 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 CsPbBr 3 /TiO 2 The 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 ratio in a first container, adding N, N-dimethylformamide, oleic acid and oleylamine, and stirring under a sealed condition until the raw materials are completely dissolved to obtain CsPbBr 3 A precursor solution;
step two: adding toluene into a second container, and adding the CsPbBr obtained in the step one under the condition of stirring 3 The precursor solution is continuously stirred under the sealing condition to obtain CsPbBr 3 A 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 stirring 3 Stirring the nano-crystalline suspension in an open air atmosphere for a period of time to obtain Ti (OH) 4 Coated CsPbBr 3 Mixing the nano-crystalline mixed suspension;
step five: the Ti (OH) obtained in the fourth step 4 Coated CsPbBr 3 Filling the mixed suspension of the nanocrystal into a high-pressure reaction kettle, heating and preserving heat, then cooling to room temperature, cleaning and centrifugally separating for multiple times, and drying the precipitate to obtain the nano CsPbBr 3 /TiO 2 A composite photocatalyst is provided.
The visible light response type efficient and stable nano CsPbBr 3 /TiO 2 According to the preparation method of the composite photocatalyst, as a preferable scheme, the volume ratio of the tetrabutyl titanate to the toluene in the step three is 1.
The visible light response type efficient and stable nano CsPbBr 3 /TiO 2 In the preparation method of the composite photocatalyst, as a preferable scheme, the ratio of the cesium bromide to the lead bromide in the first step is 1.
The visible light response type efficient and stable nano CsPbBr 3 /TiO 2 The preparation method of the composite photocatalyst is preferably characterized in that CsPbBr is adopted in the step one 3 The mass concentration of the precursor solution is 0.02-0.05 mol/L.
The visible light response type efficient and stable nano CsPbBr is adopted 3 /TiO 2 Preferably, in the step one, 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 CsPbBr is adopted 3 /TiO 2 The preparation method of the composite photocatalyst is preferably that the toluene and the CsPbBr are mixed in the step two 3 The volume ratio of the precursor solution is (8-12): 1.
the visible light responsive member as described aboveStable-effect nano CsPbBr 3 /TiO 2 Preferably, in the fourth step, the composite photocatalyst is prepared by stirring in an air atmosphere for a period of time to obtain Ti (OH) 4 Coated CsPbBr 3 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 CsPbBr 3 /TiO 2 And as a preferred scheme, the preparation method of the composite photocatalyst comprises the fifth step of heating and heat preservation, 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 CsPbBr 3 /TiO 2 And as a preferred scheme, in the fifth step, the precipitate is dried, wherein the drying temperature is 60 ℃, and the drying time is 24 hours.
The visible light response type efficient and stable nano CsPbBr is adopted 3 /TiO 2 Visible light response type efficient and stable nano CsPbBr prepared by preparation method of composite photocatalyst 3 /TiO 2 A 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 range 3 With TiO having a high degree of stability 2 In combination, the nano-scale visible light response type efficient and stable nano CsPbBr is prepared by adopting a simple liquid phase method 3 /TiO 2 The 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 period, and can meet the requirement of large-scale industrial production.
(2) Nano CsPbBr prepared in the invention 3 /TiO 2 The composite photocatalyst is nano CsPbBr under the irradiation of visible light 3 /TiO 2 The composite photocatalyst has higher catalytic activity and can be recycledThe rate is high, the organic pollutants in the aqueous solution can be rapidly degraded, the rate constant of the photocatalytic degradation of the organic pollutants is about 7 times higher than that of the organic pollutants degraded by a commercial P25 titanium dioxide photocatalyst, and the nano CsPbBr is 3 /TiO 2 The 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 irradiation.
(3) Nano CsPbBr prepared in the invention 3 /TiO 2 The 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 invention 3 /TiO 2 A transmission electron microscope photograph of the composite photocatalyst;
FIG. 2 shows the CsPbBr nanoparticles prepared in the embodiment of the present invention 3 /TiO 2 High-resolution transmission electron microscope photos of the composite photocatalyst;
FIG. 3 shows the CsPbBr nanoparticles prepared in the embodiment of the present invention 3 /TiO 2 Ultraviolet-visible absorption spectrogram of the composite photocatalyst and the P25 titanium dioxide;
FIG. 4 shows the CsPbBr nanoparticles prepared in the embodiment of the present invention 3 /TiO 2 The light absorption curve diagram of the composite photocatalyst at different moments of degrading rhodamine B aqueous solution under the irradiation of simulated sunlight;
FIG. 5 shows the CsPbBr nanoparticles prepared in the embodiment of the present invention 3 /TiO 2 A photodegradation rate graph of the composite photocatalyst and P25 titanium dioxide to rhodamine B water solution under the irradiation of simulated sunlight;
FIG. 6 shows CsPbBr nanoparticles prepared in an embodiment of the present invention 3 /TiO 2 Cyclic degradation rate of composite photocatalyst to rhodamine B aqueous solution under simulated sunlight irradiationDrawing;
FIG. 7 shows the CsPbBr nanoparticles prepared in the embodiment of the present invention 3 /TiO 2 And (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 of the embodiments. All other embodiments, which can be derived from the embodiments of the present invention by a person skilled in the art, are within the scope of the present invention.
The present invention will be described in detail below with reference to the accompanying drawings in conjunction with embodiments. 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 CsPbBr 3 /TiO 2 The composite photocatalyst is prepared by adopting a simple and mild liquid phase method and enabling CsPbBr with strong absorption performance of visible light in a wide wavelength range to be used 3 With TiO having high stability 2 Combining to prepare the nano CsPbBr 3 /TiO 2 The 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 CsPbBr 3 /TiO 2 The 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 CsPbBr 3 A precursor solution;
in an embodiment of the invention, the ratio of the amount of cesium bromide to lead bromide in step one is 1.
In an embodiment of the present invention, csPbBr is used in the first step 3 The amount concentration of the precursor solution is 0.02 to 0.05mol/L (e.g., 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 present invention, the volume ratio of N, N-dimethylformamide, oleic acid and oleylamine in the first step is (9 to 15): 1.
Step two: adding toluene into a second container, and adding the CsPbBr obtained in the step one under the condition of stirring 3 The precursor solution is continuously stirred under the sealing condition to obtain CsPbBr 3 And (3) a nanocrystal suspension.
In a specific embodiment of the present invention, toluene and CsPbBr are used in step two 3 The volume ratio of the precursor solution is (8-12): 1 (such as 8.
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.
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 stirring 3 Stirring the nano-crystalline suspension in an open air atmosphere for a period of time to obtain Ti (OH) 4 Coated CsPbBr 3 The nanocrystal is mixed with the suspension.
In the embodiment of the present invention, after stirring in air atmosphere for a certain period of time in step four, ti (OH) is obtained 4 Coated CsPbBr of 3 Mixing the nano-crystalline mixed suspension with air atmosphere of 20-60% (such as 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%) and stirring for 2%10h (e.g., 2h, 2.5h, 3h, 3.5h, 4h, 4.5h, 5h, 5.5h, 6h, 6.5h, 7h, 7.5h, 8h, 8.5h, 9h, 9.5h, 10 h).
Step five: mixing the Ti (OH) obtained in the fourth step 4 Coated CsPbBr 3 Filling the mixed suspension of the nanocrystal into a high-pressure reaction kettle, heating and preserving heat, then cooling to room temperature, cleaning and centrifugally separating for multiple times, and drying the precipitate to obtain the nano CsPbBr 3 /TiO 2 A 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 ℃ and 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 and 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 CsPbBr 3 /TiO 2 The 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 three is 12 3 A 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 stirring 3 The precursor solution is continuously stirred under the sealing condition to obtain CsPbBr 3 And (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 step 3 In 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) 4 Coated CsPbBr 3 The nanocrystal is mixed with the suspension.
Step five: ti (OH) obtained in the fourth step 4 Coated CsPbBr 3 Filling 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 kettle 3 Coated Ti (OH) 4 Conversion to TiO by dehydration 2 Then 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 CsPbBr 3 /TiO 2 A composite photocatalyst is provided.
The nano CsPbBr prepared in the embodiment 3 /TiO 2 The characterization result of the composite photocatalyst is as follows:
as shown in FIG. 1, the CsPbBr nanoparticles prepared in this example are 3 /TiO 2 Transmission electron micrograph of the composite photocatalyst shows that CsPbBr is observed in the micrograph 3 The appearance of the nanocrystal is similar to a sphere, csPbBr 3 The diameter of the nano-crystal is distributed in the range of 8-17 nm, and the average diameter is 13nm; there are several or several tens of CsPbBr 3 The nanocrystalline is coated on the TiO with irregular morphology 2 Inside, nano CsPbBr is formed 3 /TiO 2 A composite material.
As shown in FIG. 2, the CsPbBr nanoparticles prepared in this example are 3 /TiO 2 The high-resolution transmission electron microscope photo of the composite photocatalyst can clearly show that CsPbBr is added in the photo 3 The spacing between crystal faces of the stripes regularly stacked on the crystal faces is 0.57nm through testing, and the stripes are assigned as CsPbBr 3 The (001) plane of (a), however, no surface coating with TiO was observed 2 Regular stripes of (i.e. identifying TiO) 2 Is in an amorphous state.
As shown in FIG. 3, the CsPbBr is prepared in the embodiment of the present invention 3 /TiO 2 A composite photocatalyst and a UV-visible absorption spectrum of P25 titanium dioxide, wherein the P25 titanium dioxide is a commercial nano titanium dioxide photocatalyst with an average particle size of 25nm. 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 low 3 /TiO 2 The 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/cm 2 Selecting rhodamine B as a simulated pollutant, and testing the nano CsPbBr 3 /TiO 2 The photocatalytic degradation rate of the composite photocatalyst to the rhodamine B water solution is improved.
The specific test method comprises the following steps:
taking 100ml in a 250ml beaker with a concentration of 3.0X 10 -5 Adding 100mg of nano CsPbBr into mol/L rhodamine B water solution 3 /TiO 2 Stirring 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 within 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 so as to calculate 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-CsPbBr 3 /TiO 2 The light absorption curve diagram of the composite photocatalyst at different moments of degrading rhodamine B aqueous solution under the irradiation of simulated sunlight shows that rhodamine B is dissolved in water along with the extension of illumination timeThe absorbance of the solution decreased rapidly.
As shown in FIG. 5, the CsPbBr prepared in the embodiment of the present invention is a nano-CsPbBr 3 /TiO 2 The light degradation rate of the composite photocatalyst and P25 titanium dioxide to the rhodamine B aqueous solution under sunlight simulation irradiation is shown in the figure, and 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 CsPbBr 3 /TiO 2 The degradation rate of the composite photocatalyst on rhodamine B reaches 98.05%, and the rhodamine B is basically and completely degraded.
To further verify the nano CsPbBr 3 /TiO 2 The 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 -5 And (3) simulating sunlight irradiation of the rhodamine B water solution of mol/L for photodegradation again, and repeating for 2 times.
As shown in FIG. 6, the CsPbBr is prepared in the embodiment of the present invention 3 /TiO 2 The 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%, and compared with the first degradation rate, the degradation rate is reduced, 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.
CsPbBr 3 The nano CsPbBr prepared in the embodiment is ineffective by rapidly dissolving into ions after entering water 3 /TiO 2 After the composite photocatalyst is placed in water for soaking for 45 days, centrifugal separation is carried out, and the photocatalytic activity is investigated. FIG. 7 shows the CsPbBr nanoparticles prepared in the examples of the present invention 3 /TiO 2 And (3) a degradation rate graph of the composite photocatalyst on 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 days 3 /TiO 2 Composite photocatalyst for simulating sunlightWhen the irradiation is carried out for 15min, the degradation rate of rhodamine B still reaches 92.23 percent, namely, amorphous TiO 2 The coating greatly improves CsPbBr 3 Water resistance of (1), namely the nano CsPbBr provided in this embodiment 3 /TiO 2 The 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 CsPbBr 3 /TiO 2 The 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 water vapor in the air to obtain Ti (OH) under the condition of natural air with the air humidity of 30 percent and open stirring for 7 hours 4 Coated CsPbBr 3 The 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 example 3 /TiO 2 The 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/cm 2 Selecting rhodamine B as a simulated pollutant, and irradiating for 15min with the nano CsPbBr 3 /TiO 2 The 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 CsPbBr 3 /TiO 2 The 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 of natural air with the air humidity of 20 percent and is stirred for 10 hours in an open way 4 Coated CsPbBr 3 The nanocrystal mixes the suspension.
Other steps are the same as embodiment 1, and are not described herein again.
The nano CsPbBr prepared in the embodiment is added 3 /TiO 2 Composite photocatalyst and solar simulatorThe simulated sunlight with the atmospheric mass of AM1.5G is taken as a light source, and the luminous power is 100mW/cm 2 Selecting rhodamine B as a simulated pollutant, and irradiating for 15min with the nano CsPbBr 3 /TiO 2 The photocatalytic degradation rate of the composite photocatalyst to rhodamine B water solution reaches 97.54 percent.
Example 4
The embodiment provides a visible light response type efficient and stable nano CsPbBr 3 /TiO 2 The 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 of natural air with the air humidity of 50 percent and stirring for 5h in an open way 4 Coated CsPbBr 3 The 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 embodiment is added 3 /TiO 2 The 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/cm 2 Selecting rhodamine B as a simulated pollutant, and illuminating for 15min by using the nano CsPbBr 3 /TiO 2 The photocatalytic degradation rate of the composite photocatalyst on rhodamine B aqueous solution reaches 97.86%.
Example 5
The embodiment provides a visible light response type efficient and stable nano CsPbBr 3 /TiO 2 The 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 natural air is obtained under the condition that the air humidity is 60 percent and the open stirring is carried out for 3 hours 4 Coated CsPbBr 3 The nanocrystal mixes the suspension.
Other steps are the same as embodiment 1, and are not described herein again.
The nano CsPbBr prepared in the embodiment is added 3 /TiO 2 The composite photocatalyst takes simulated sunlight with atmospheric quality of AM1.5G given by a sunlight simulator as a light source, and the light workThe ratio is 100mW/cm 2 Selecting rhodamine B as a simulated pollutant, and irradiating for 15min with the nano CsPbBr 3 /TiO 2 The 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 CsPbBr 3 /TiO 2 The preparation method of the composite photocatalyst is different from the preparation method in example 1 in that in the step one, 30ml of N, N-dimethylformamide, 3.0ml of oleic acid and 1.5ml of oleylamine (volume ratio of the three is 9 3 A precursor liquid.
Other steps are the same as embodiment 1, and are not described herein again.
The nano CsPbBr prepared in the example 3 /TiO 2 The 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/cm 2 Selecting rhodamine B as a simulated pollutant, and illuminating for 15min by using the nano CsPbBr 3 /TiO 2 The photocatalytic degradation rate of the composite photocatalyst to rhodamine B water solution reaches 96.83 percent.
Example 7
The embodiment provides a visible light response type efficient and stable nano CsPbBr 3 /TiO 2 The 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 time is 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 example 3 /TiO 2 The 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/cm 2 Selecting rhodamine B as a simulated pollutant, and illuminating for 15min by using the nano CsPbBr 3 /TiO 2 The 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 CsPbBr 3 /TiO 2 The preparation method of the composite photocatalyst is different from the preparation method in example 1 in that in the step one, 51.42ml of N, N-dimethylformamide, 5.72ml of oleic acid and 2.86ml of oleylamine (volume ratio of the three is 9 3 A 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 stirring 3 45ml of precursor solution is continuously stirred under the sealing condition to obtain CsPbBr 3 And (3) a nanocrystal suspension.
Other steps are the same as embodiment 1, and are not described herein again.
The nano CsPbBr prepared in the example 3 /TiO 2 The 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/cm 2 Selecting rhodamine B as a simulated pollutant, and illuminating for 15min by using the nano CsPbBr 3 /TiO 2 The 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 CsPbBr 3 /TiO 2 The 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 stirring 3 30ml of precursor solution is continuously stirred under the sealing condition to obtain CsPbBr 3 A 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 example 3 /TiO 2 The composite photocatalyst gives the atmosphere with the mass AM by a sunlight simulator1.5G of simulated sunlight is used as a light source, and the luminous power is 100mW/cm 2 Selecting rhodamine B as a simulated pollutant, and illuminating for 15min by using the nano CsPbBr 3 /TiO 2 The 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 CsPbBr 3 /TiO 2 The preparation method of the composite photocatalyst is different from the preparation method in the example 1 in that in the third step, the tetrabutyl titanate is slowly hydrolyzed by water vapor in the air to obtain Ti (OH) under the condition of natural air with the air humidity of 80 percent and the open stirring for 1h 4 Coated CsPbBr 3 The nanocrystal mixes 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 added 3 /TiO 2 The 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/cm 2 Selecting rhodamine B as a simulated pollutant, and illuminating for 15min by using the nano CsPbBr 3 /TiO 2 The photocatalytic degradation rate of the composite photocatalyst on rhodamine B aqueous solution reaches 78.43 percent.
Comparative example 2
The comparison example provides a visible light response type efficient and stable nano CsPbBr 3 /TiO 2 The 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 added 3 /TiO 2 The 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/cm 2 Selecting rhodamine B as a simulated pollutant, and illuminating for 15min by using the nano CsPbBr 3 /TiO 2 The photocatalytic degradation rate of the composite photocatalyst to rhodamine B water solution reaches 83.26%.
Comparative example 3
The comparison example provides a visible light response type efficient and stable nano CsPbBr 3 /TiO 2 The preparation method of the composite photocatalyst is different from the preparation method in example 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 three is 18.5 3 A 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 added 3 /TiO 2 The 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/cm 2 Selecting rhodamine B as a simulated pollutant, and illuminating for 15min by using the nano CsPbBr 3 /TiO 2 The photocatalytic degradation rate of the composite photocatalyst to the rhodamine B water solution reaches 67.56%.
By comparing the embodiment with the comparative example, the nano CsPbBr provided by the invention 3 /TiO 2 The composite photocatalyst has higher catalytic activity, and the photocatalytic degradation rate of rhodamine B water solution is still up to more than 92% after the composite photocatalyst is soaked in water for 45 days; the invention provides a nano CsPbBr 3 /TiO 2 The 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 CsPbBr 3 /TiO 2 The composite photocatalyst is visible light response type, has high catalytic activity under the condition of simulating sunlight irradiation, and has high recycling rate; can rapidly degrade organic pollutants in aqueous solution and degrade organic matters through photocatalysisThe rate constant of the pollutants is about 7 times higher than that of the rate constant of the commercial P25 titanium dioxide photocatalyst for degrading organic pollutants; can work stably for a long time in a water system, and is nano CsPbBr 3 /TiO 2 The 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 (1)

1. Visible light response type efficient and stable nano CsPbBr 3 /TiO 2 The preparation method of the composite photocatalyst is characterized by comprising 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, then adding 36ml of N, N-dimethylformamide, 3.0ml of oleic acid and 1.5ml of oleylamine, sealing the opening of the beaker by using a preservative film, and stirring by magnetic force until the raw materials are completely dissolved to obtain CsPbBr 3 A 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 stirring 3 The precursor solution is continuously stirred under the sealing condition to obtain CsPbBr 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 in the second step 3 In 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) 4 Coated CsPbBr 3 Mixing the nanocrystal suspension;
step five: ti (OH) obtained in the fourth step 4 Coated CsPbBr 3 Filling 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 kettle 3 Coated Ti (OH) 4 Conversion to TiO by dehydration 2 Then 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 CsPbBr 3 /TiO 2 A composite photocatalyst;
CsPbBr 3 /TiO 2 the composite photocatalyst is used for degrading organic pollutants in an aqueous solution.
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