CN112264060A - Ag3PO4-Bi2WO6Preparation method and application of visible light photocatalyst - Google Patents

Ag3PO4-Bi2WO6Preparation method and application of visible light photocatalyst Download PDF

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CN112264060A
CN112264060A CN202011137275.1A CN202011137275A CN112264060A CN 112264060 A CN112264060 A CN 112264060A CN 202011137275 A CN202011137275 A CN 202011137275A CN 112264060 A CN112264060 A CN 112264060A
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visible light
solution
preparation
photocatalyst
washing
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许琦
朱瑜瑜
葛艳
韩粉女
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Yancheng Institute of Technology
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    • B01J35/39
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D53/00Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34Chemical or biological purification of waste gases
    • B01D53/74General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86Catalytic processes
    • B01D53/864Removing carbon monoxide or hydrocarbons
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D53/00Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34Chemical or biological purification of waste gases
    • B01D53/74General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86Catalytic processes
    • B01D53/8678Removing components of undefined structure
    • B01D53/8687Organic components
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/14Phosphorus; Compounds thereof
    • B01J27/186Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J27/188Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2257/00Components to be removed
    • B01D2257/70Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
    • B01D2257/708Volatile organic compounds V.O.C.'s
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02ATECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A50/00TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
    • Y02A50/20Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters

Abstract

The invention discloses Ag3PO4‑Bi2WO6Preparation method and application of visible light catalyst, wherein the preparation method comprises the step of preparing Bi by hydrothermal method2WO6Followed by impregnation of different amounts of Ag3PO4Loaded to Bi2WO6Washing and drying after reaction, and finally grinding to obtain Ag3PO4‑Bi2WO6A visible light photocatalyst. The preparation method disclosed by the invention is simple to operate and nontoxic, combines the advantages of the two, can form a heterojunction after being compounded, enhances the light absorption range, promotes the effective separation of electrons and holes, and greatly improves the light absorption rangeThe capability of degrading VOCs by photocatalysis is improved. With Bi alone2WO6Compared with the photocatalyst, the photocatalyst has higher photocatalytic activity.

Description

Ag3PO4-Bi2WO6Preparation method and application of visible light photocatalyst
Technical Field
The invention belongs to the technical field of chemical catalysis, and particularly relates to Ag3PO4-Bi2WO6A preparation method and application of a visible light photocatalyst.
Background
The rapid development of economy makes the environment face a severe examination, and for the development of industrial production, the two characteristics of persistent existence and accumulation of VOCs which are discharged in large quantity in the production process have serious threat to the ecological environment, so that the control and treatment of the VOCs become important. In 2020, the ecological environment department requires the combination of precise enforcement and scientific management and control, mainly in the industries of petrifaction, chemical engineering, industrial coating and the like, and the control of VOCs substances with strong photochemical reaction activity is comprehensively enhanced. Nowadays, a plurality of visible light response semiconductor photocatalytic materials are widely applied to the degradation of pollutants, and Bi2WO6The photocatalyst which has been developed in recent years has an appropriate energy gap and is composed of (Bi)2O2)2+And (WO)6)2-The unique layered structure of perovskite layer oxide formed by mutually and alternately stacking octahedrons improves the separation efficiency of photon-generated carriers. Thus Bi2WO6The catalytic material opens up a new way for degrading volatile organic compounds.
Ag3PO4Has a body-centered cubic structure and is composed of regular isolated tetrahedrons PO4 3-Form a body-centered cubic structure of 6 Ag+Distributed on 12 doubly symmetrical positions, Ag atoms are combined with 4 surrounding O atoms to form covalent bonds, P atoms are also combined with 4 surrounding O atoms, and the O atoms are coordinated and combined with 1 surrounding P atom and 3 surrounding Ag atoms. Ag3PO4The forbidden band width is about 2.36eV, the solar light with the wavelength less than 530nm can be absorbed, the photocatalytic oxidation capability under visible light is extremely strong, and the quantum efficiency is as high as more than 90%. The material has the characteristics of high-efficiency visible light catalytic activity, extremely strong photocatalytic oxidation capability, high quantum yield, small band gap, low toxicity and the like, and is an ideal research material in the field of photocatalysis at present.
However Bi prepared by the prior art2WO6When the catalyst is used for degrading VOCs in a photocatalytic manner, the technical problems of small visible light response range and easy recombination of electrons and holes exist. And to Bi2WO6And Ag3PO4The methods for compounding are rarely reported.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides Ag3PO4-Bi2WO6The preparation method and the application of the visible-light-driven photocatalyst are combined, and the advantages of the visible-light-driven photocatalyst and the visible-light-driven photocatalyst are combined, so that a heterojunction can be formed by compounding the visible-light-driven photocatalyst and the visible-light-driven photocatalyst, the light absorption range is enhanced, the effective separation of electrons and holes is promoted, and the capability of degrading VOCs by photocatalysis is greatly improved.
The invention is realized by the following technical scheme:
ag3PO4-Bi2WO6The preparation method of the visible light photocatalyst comprises the following steps:
step 1) dissolving bismuth nitrate, sodium tungstate and hexadecyl trimethyl ammonium bromide in 80mL of distilled water, stirring the solution for 1h under magnetic stirring, uniformly stirring the solution, transferring the solution into a reaction kettle, carrying out hydrothermal reaction at 160 ℃ for 24h, after the reaction is finished, centrifuging and washing the product, and then carrying out freeze drying to obtain Bi2WO6
Step 2) AgNO3Dissolved in 50mL of distilled water, and NH was added dropwise3·H2O solution, then 1M HNO is dropped3Solution, adjusting the pH of the solution to be neutral, and adding the Bi prepared in the step 1)2WO6Adding into the solution, and stirring for 30 min;
step 3) adding Na2HPO4·12H2O was dissolved in 20mL of distilled water, and Na was added2HPO4·12H2Dripping O solution into the solution prepared in the step 2), stirring, centrifuging, washing, freeze drying, and finally grinding to obtain the Ag3PO4-Bi2WO6A visible light photocatalyst.
Preferably, the molar ratio of the bismuth nitrate to the sodium tungstate in the step 1) is 2:1, and the content of the hexadecyl trimethyl ammonium bromide is 0.05 g.
Preferably, the centrifugation and washing steps in step 1) are as follows: the centrifugation rate was 10000rpm/min, and the washing was carried out three times each by exchanging ethanol with distilled water.
Preferably, the AgNO of step 2)3And Bi2WO6The molar ratio of (a) to (b) is 1:1 to 1: 3.
Preferably, step 2) said NH3·H2The concentration of O was 2 wt%.
Preferably, said Na of step 3)2HPO4·12H2The dropping speed of the O solution is 20-30 drops/min.
Preferably, the speed of centrifugation in step 3) is 10000 rpm/min.
Ag prepared by the preparation method3PO4-Bi2WO6The application of the visible light catalyst in the catalytic degradation of VOCs under the condition of visible light.
Preferably, the light source is a 1000W xenon lamp, which is 10cm above the reaction system.
The invention has the following beneficial effects:
the preparation method of the invention changes Ag3PO4And Bi2WO6Molar ratio for preparing Ag3PO4-Bi2WO6The visible light catalyst is simple to operate and non-toxic, combines the advantages of the visible light catalyst and the VOCs, can form a heterojunction after being compounded, enhances the light absorption range, promotes the effective separation of electrons and holes, and greatly improves the capability of degrading VOCs by photocatalysis. With Bi alone2WO6Compared with the photocatalyst, the photocatalyst has higher photocatalytic activity. The experimental result shows that when n (Ag)3PO4:Bi2WO6) The best effect is obtained when the ratio is 1: 2.
Drawings
FIG. 1 shows Ag obtained in example 23PO4-Bi2WO6(n-1: 2) Bi obtained in comparative example 12WO6、Ag3PO4XRD contrast pattern of (a);
FIG. 2 shows Ag obtained in examples 1 to 33PO4-Bi2WO6Bi obtained in comparative example 12WO6、Ag3PO4XRD contrast pattern of (a);
FIG. 3 shows Ag obtained in examples 1 to 33PO4-Bi2WO6Bi obtained in comparative example 12WO6、Ag3PO4Performance curve of photocatalytic degradation of toluene under visible light.
Detailed Description
For a better understanding of the present invention, the following further illustrates the present invention by reference to the accompanying drawings and examples, but the present invention is not limited to the following examples.
Example 1
Ag3PO4-Bi2WO6The preparation method of the visible light photocatalyst comprises the following specific steps:
(1) adding 2mmol of bismuth nitrate (Bi (NO)3)3·5H2O), 1mmol of sodium tungstate (Na)2WO4·2H2O) and 0.05g of cetyltrimethylammonium bromide (CTAB) are dissolved in 80mL of distilled water, the solution is transferred into a polytetrafluoroethylene-lined high-pressure reaction kettle after being magnetically stirred for 1 hour, heated for 24 hours at 160 ℃, and naturally cooled to room temperature. After centrifugation (centrifugation speed is 10000rpm/min), washing (three times of exchange washing by ethanol and distilled water respectively) and drying, Bi is obtained2WO6
(2) Mixing AgNO3Dissolved in 50mL of distilled water, and NH was added dropwise3·H2O solution (concentration 2 wt%), followed by 1M HNO dropwise3Solution, adjusting the pH of the solution to be neutral, and adding Bi2WO6According to n (Ag)3PO4:Bi2WO6) Add to solution at 1:1 and stir for 30 min.
(3) Mixing Na2HPO4·12H2Dissolving O in 20mL of distilled water, then dripping the O into the solution obtained in the step (2) at a dripping speed of 20-30 drops/min, stirring, centrifuging (at a centrifuging speed of 10000rpm/min), washing, freeze-drying, and finally grinding. Obtaining a sample Ag3PO4-Bi2WO6(n=1:1)。
Example 2
Ag3PO4-Bi2WO6The preparation method of the visible light photocatalyst comprises the following specific steps:
(1) 2mmol of Bi: (NO3)3·5H2O,1mmol Na2WO4·2H2Dissolving O and 0.05g CTAB in 80mL of distilled water, magnetically stirring for 1h, transferring to a polytetrafluoroethylene-lined high-pressure reaction kettle, heating at 160 ℃ for 24h, and naturally cooling to room temperature. After centrifugation (centrifugation speed is 10000rpm/min), washing (three times of exchange washing by ethanol and distilled water respectively) and drying, Bi is obtained2WO6
(2) Mixing AgNO3Dissolved in 50mL of distilled water, and NH was added dropwise3·H2O solution (concentration 2 wt%), followed by 1M HNO dropwise3Solution, adjusting the pH of the solution to neutral, Bi2WO6According to n (Ag)3PO4:Bi2WO6) Add to solution at 1:2 and stir for 30 min.
(3) Mixing Na2HPO4·12H2Dissolving O in 20mL of distilled water, then dripping the O into the solution obtained in the step (2) at a dripping speed of 20-30 drops/min, stirring, centrifuging (at a centrifuging speed of 10000rpm/min), washing, freeze-drying, and finally grinding. Obtaining a sample Ag3PO4-Bi2WO6(n=1:2)。
Example 3
Ag3PO4-Bi2WO6The preparation method of the visible light photocatalyst comprises the following specific steps:
(1) 2mmol of Bi (NO)3)3·5H2O,1mmol Na2WO4·2H2Dissolving O and 0.05g CTAB in 80mL of distilled water, magnetically stirring for 1h, transferring to a polytetrafluoroethylene-lined high-pressure reaction kettle, heating at 160 ℃ for 24h, and naturally cooling to room temperature. After centrifugation (centrifugation speed is 10000rpm/min), washing (three times of exchange washing by ethanol and distilled water respectively) and drying, Bi is obtained2WO6
(2) Mixing AgNO3Dissolved in 50mL of distilled water, and NH was added dropwise3·H2O solution (concentration 2 wt%), followed by 1M HNO dropwise3Solution, adjusting the pH of the solution to neutral, Bi2WO6According to n (Ag)3PO4:Bi2WO6) 1:3 toThe solution was stirred for 30 min.
(3) Mixing Na2HPO4·12H2Dissolving O in 20mL of distilled water, then dripping the O into the solution obtained in the step (2) at a dripping speed of 20-30 drops/min, stirring, centrifuging (at a centrifuging speed of 10000rpm/min), washing, freeze-drying, and finally grinding. Obtaining a sample Ag3PO4-Bi2WO6(n=1:3)。
Comparative example 1
Bi2WO6The preparation method comprises the following specific steps:
2mmol of Bi (NO)3)3·5H2O,1mmol Na2WO4·2H2Dissolving O and 0.05g CTAB in 80mL of distilled water, magnetically stirring for 1h, transferring to a polytetrafluoroethylene-lined high-pressure reaction kettle, heating at 160 ℃ for 24h, and naturally cooling to room temperature. After centrifugation (centrifugation speed is 10000rpm/min), washing (three times of exchange washing by ethanol and distilled water respectively) and drying, Bi is obtained2WO6
Test example 1
As shown in FIG. 1, Bi2WO6Corresponding to an orthorhombic system Bi2WO6(PDF#39-0256),Ag3PO4Diffraction peak of (2) and cubic system of Ag3PO4(PDF #06-0505) corresponding to Ag3PO4-Bi2WO6All the diffraction peaks in Bi2WO6(PDF #39-0256) and Ag3PO4(PDF #06-0505) no other peaks were present.
As shown in FIG. 2, in Ag3PO4-Bi2WO6In the composite catalyst, along with Ag3PO4Increase in the amount of Bi2WO6The diffraction peak intensity of (A) is obviously weakened, Ag3PO4The peak intensity is increased, no other miscellaneous peaks exist, and Ag is shown3PO4-Bi2WO6The composite catalyst is successfully prepared and has higher purity.
Ag obtained in examples 1 to 33PO4-Bi2WO6Comparative example 1Bi2WO6、Ag3PO4The materials are respectively added into a photocatalytic reaction instrument in an amount of 0.1g, and the photocatalytic reaction instrument is placed at a position 10cm below a light source to perform performance research of photocatalytic degradation of toluene, wherein the light source is a 1000W xenon lamp.
As shown in FIG. 3, Ag3PO4-Bi2WO6(n-1: 2) the degradation rate of toluene reached 80% after 180min of irradiation under a 1000W xenon lamp. Under the same experimental conditions, Bi2WO6、Ag3PO4、Ag3PO4-Bi2WO6(n-1: 1) and Ag3PO4-Bi2WO6The degradation rates of (n-1: 3) toluene were 40%, 5%, 60% and 55%, respectively. Therefore, when n (Ag)3PO4:Bi2WO6) The best toluene degradation effect is achieved when the ratio is 1: 2.

Claims (9)

1. Ag3PO4-Bi2WO6The preparation method of the visible light photocatalyst is characterized by comprising the following steps: step 1) dissolving bismuth nitrate, sodium tungstate and hexadecyl trimethyl ammonium bromide in 80mL of distilled water, stirring the solution for 1h under magnetic stirring, uniformly stirring the solution, transferring the solution into a reaction kettle, carrying out hydrothermal reaction at 160 ℃ for 24h, after the reaction is finished, centrifuging and washing the product, and then carrying out freeze drying to obtain Bi2WO6
Step 2) AgNO3Dissolved in 50mL of distilled water, and NH was added dropwise3·H2O solution, then 1M HNO is dropped3Solution, adjusting the pH of the solution to be neutral, and adding the Bi prepared in the step 1)2WO6Adding into the solution, and stirring for 30 min; step 3) adding Na2HPO4·12H2O was dissolved in 20mL of distilled water, and Na was added2HPO4·12H2Dripping O solution into the solution prepared in the step 2), stirring, centrifuging, washing, freeze drying, and finally grinding to obtain the Ag3PO4-Bi2WO6A visible light photocatalyst.
2. According to claimAn Ag of claim 13PO4-Bi2WO6The preparation method of the visible light photocatalyst is characterized in that the molar ratio of the bismuth nitrate to the sodium tungstate in the step 1) is 2:1, and the content of the hexadecyl trimethyl ammonium bromide is 0.05 g.
3. Ag according to claim 13PO4-Bi2WO6The preparation method of the visible light photocatalyst is characterized in that the steps of centrifuging and washing in the step 1) are as follows: the centrifugation rate was 10000rpm/min, and the washing was carried out three times each by exchanging ethanol with distilled water.
4. Ag according to claim 13PO4-Bi2WO6The preparation method of the visible light photocatalyst is characterized in that the AgNO in the step 2)3And Bi2WO6The molar ratio of (a) to (b) is 1:1 to 1: 3.
5. Ag according to claim 13PO4-Bi2WO6The preparation method of the visible light catalyst is characterized in that the NH in the step 2)3·H2The concentration of O was 2 wt%.
6. Ag according to claim 13PO4-Bi2WO6The preparation method of the visible light photocatalyst is characterized in that the Na in the step 3) is2HPO4·12H2The dropping speed of the O solution is 20-30 drops/min.
7. Ag according to claim 13PO4-Bi2WO6The preparation method of the visible light photocatalyst is characterized in that the centrifugation speed in the step 3) is 10000 rpm/min.
8. Ag produced by the production method according to any one of claims 1 to 73PO4-Bi2WO6Visible light catalysisApplication of the agent in catalyzing and degrading VOCs under visible light conditions.
9. The use of claim 8, wherein the light source is a 1000W xenon lamp, 10cm above the reaction system.
CN202011137275.1A 2020-10-22 2020-10-22 Ag3PO4-Bi2WO6Preparation method and application of visible light photocatalyst Pending CN112264060A (en)

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Application publication date: 20210126