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CN112371113A - Bi2WO6Preparation method and application of-rGO visible light catalyst - Google Patents

Bi2WO6Preparation method and application of-rGO visible light catalyst Download PDF

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CN112371113A
CN112371113A CN202011412818.6A CN202011412818A CN112371113A CN 112371113 A CN112371113 A CN 112371113A CN 202011412818 A CN202011412818 A CN 202011412818A CN 112371113 A CN112371113 A CN 112371113A
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rgo
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distilled water
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朱瑜瑜
许琦
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Changzhou University
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00Catalysts, in general, characterised by their form or physical properties
    • B01J35/30Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/39Photocatalytic properties
    • 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
    • B01J23/00Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/24Chromium, molybdenum or tungsten
    • B01J23/31Chromium, molybdenum or tungsten combined with bismuth
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2257/00Components to be removed
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    • 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

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Abstract

The invention discloses a Bi2WO6-rGO visible light catalyst preparation method and application, the preparation method comprises the following steps: dissolving bismuth nitrate, sodium tungstate and hexadecyl trimethyl ammonium bromide in 80ml of distilled water, stirring the solution for 1 hour under magnetic stirring, and uniformly stirring the solution; transferring the product obtained in the step S1 to a reaction kettle, carrying out hydrothermal reaction at 160 ℃ for 24 hours, after the reaction is finished, centrifuging and washing, and then placing the product in a drying box for drying treatment to obtain Bi2WO6(ii) a Bi prepared from S22WO6Dissolving GO in 100ml of distilled water, dissolving GO in 20ml of distilled water, and respectively carrying out ultrasonic treatment for 1 h; slowly dripping GO solution into Bi2WO6In solutionStirring the mixed solution for 1 hour; according to the weight percentage of hydrazine hydrate: adding hydrazine hydrate into the mixed solution according to the mass ratio of 7:10 of GO, and stirring for 12 hours at 95 ℃; cooling the solution, centrifuging, washing and drying to obtain the Bi2WO6-rGO visible light photocatalyst. According to the preparation method disclosed by the invention, Bi is improved by adjusting the content of GO2WO6-rGO photocatalytic degradation of toluene capability.

Description

Bi2WO6Preparation method and application of-rGO visible light catalyst
Technical Field
The invention relates to the technical field of chemical catalysis, in particular to Bi2WO6Preparation method of-rGO visible light catalystAnd applications.
Background
With the acceleration of the industrialization process, a large amount of VOCs (volatile organic compounds) are discharged in the production process, and the VOCs deteriorate the air quality by forming chemical fumes and haze. Therefore, the control and treatment of VOCs become important. In recent years, the photocatalytic technology is widely applied to removing pollutants due to its own characteristics, such as simple equipment, no secondary pollution, mild reaction conditions and the like. Typical photocatalyst is TiO2It has the characteristics of good stability, strong oxidation capacity and the like, but only responds to ultraviolet light, and the ultraviolet light only accounts for 3 percent of sunlight, so the utilization rate of the sunlight is very low. Therefore, the search for visible light responsive semiconductor materials becomes the center of gravity of researchers. Bi2WO6In recent years, the application of the organic pollutants in energy conversion has attracted wide attention, and the forbidden band width of the organic pollutants is about 2.7eV, and the organic pollutants are prepared from (Bi)2O2)2+And (WO)6)2-The perovskite layer oxide formed by the alternate stacking of octahedrons has appropriate forbidden band width to enable the perovskite layer oxide to have response under visible light, and the unique layered structure improves the separation efficiency of photon-generated carriers.
However, an ideal photocatalyst should have a broad light absorption range and good separation efficiency of photo-generated electrons-holes. Bi2WO6The practical application of the material is greatly limited by the characteristics of small visible light response range and easy recombination of electron and hole, and pure Bi2WO6Only visible light in the region of < 450nm can be absorbed. Therefore, it is one of effective means to improve the photocatalytic activity by combining it with another semiconductor catalyst.
Reduced graphene oxide (rGO) has a large two-dimensional plane and has good electrical conductivity. At the semiconductor/rGO interface, rGO can act as both an electron acceptor, a transporter and an intermediary to enhance the channel structure due to π*Orbitals and excellent conductivity-induced electron transport, facilitating the separation of photogenerated carriers.
Toluene is one of the VOCs, however Bi prepared in the prior art2WO6When the catalyst is used for degrading toluene in a photocatalytic manner, the visible light response range is small and electricity existsThe easy recombination of the sub-cavity and the hole. And to Bi2WO6The application of rGO in toluene degradation after compounding is only rarely reported.
Disclosure of Invention
The object of the present invention is to provide a Bi2WO6Preparation method and application of-rGO visible light catalyst, and Bi is improved by adjusting GO content2WO6-rGO photocatalytic degradation of toluene capability.
The purpose of the invention can be realized by the following technical scheme:
bi2WO6-a method for preparing a rGO visible light catalyst, the method comprising the steps of:
s1, dissolving bismuth nitrate, sodium tungstate and hexadecyl trimethyl ammonium bromide in 80ml of distilled water, stirring the solution for 1 hour under magnetic stirring, and uniformly stirring the solution;
s2, transferring the product obtained in the step S1 into a reaction kettle, carrying out hydrothermal reaction at 160 ℃ for 24 hours, centrifuging and washing after the reaction is finished, and then placing the product into a drying box for drying treatment to obtain Bi2WO6
S3 preparation of Bi from S22WO6Dissolving GO in 100ml of distilled water, dissolving GO in 20ml of distilled water, and respectively carrying out ultrasonic treatment for 1 h; slowly dripping GO solution into Bi2WO6Adding the mixed solution into the solution, and stirring the mixed solution for 1 hour; according to the weight percentage of hydrazine hydrate: adding hydrazine hydrate into the mixed solution according to the mass ratio of 7:10 of GO, and stirring for 12 hours at 95 ℃; cooling the solution, centrifuging, washing and drying to obtain the Bi2WO6-rGO visible light photocatalyst.
Further, the molar ratio of bismuth nitrate to sodium tungstate in the S1 was 2:1, and the content of cetyltrimethylammonium bromide was 0.05 g.
Further, in the mixed solution of S3, GO and Bi2WO6The mass ratio of (A) is 3-7 wt%.
Further, the dripping speed of the GO solution in the S3 is 20-30 drops/min.
Further, the steps of centrifugation and washing are as follows: the centrifugation rate was 10000rpm/min, and the washing was carried out three times each by exchanging ethanol with distilled water.
Further, the drying treatment is low-temperature freeze drying for 12 hours.
Bi prepared by the preparation method2WO6-application of rGO visible light catalyst in catalytic degradation of toluene under visible light conditions.
Further, a 1000W xenon lamp is adopted as a light source, and the distance is 10cm from the upper part of the reaction system.
The invention has the beneficial effects that:
the invention changes GO and Bi2WO6The mass ratio of the Bi to the GO is reduced to rGO by hydrazine hydrate, and Bi is prepared2WO6the-rGO visible light catalyst is simple and convenient to operate. Combining the advantages of the two, the compounded catalyst effectively promotes the separation of electron-hole, and is combined with pure Bi2WO6Compared with the prior art, the photocatalytic activity is greatly improved. The experimental results show that: GO and Bi2WO6The effect is best when the mass ratio is 5 wt%.
Drawings
The invention will be further described with reference to the accompanying drawings.
FIG. 1 shows Bi obtained in examples 1 to 3 of the present invention2WO6rGO and Bi from comparative example 12WO6XRD contrast pattern of (a);
FIG. 2 shows Bi produced by the present invention 1 to 32WO6rGO and Bi from comparative example 12WO6Performance curve of photocatalytic degradation of toluene under visible light.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, 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 by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
Bi2WO6The preparation method of the-rGO visible light catalyst specifically comprises the following steps:
s1 preparation of 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 lining high-pressure reaction kettle after being magnetically stirred for 1 hour, the solution is heated for 24 hours at 160 ℃, and the solution is naturally cooled to the room temperature. Obtaining Bi through centrifugation (the centrifugation speed is 10000rpm/min), washing (three times of exchange washing by ethanol and distilled water respectively) and low-temperature freeze drying for 12h2WO6
S2 preparation of Bi from S12WO6Dissolved in 100ml of distilled water according to the mass ratio m (GO/Bi)2WO6) Weighing GO with the percentage of 3 percent, dissolving the GO in 20ml of distilled water, and respectively carrying out ultrasonic treatment for 1 h; adding Bi2WO6Transferring the solution to a three-neck flask, slowly adding the GO solution into the three-neck flask at a dropping rate of 20-30 drops/min, and stirring the mixed solution for 1 h; a certain amount of hydrazine hydrate was added to the mixed solution at a mass ratio of m (hydrazine hydrate/GO) of 7:10, and stirred at 95 ℃ for 12 hours. Cooling the solution, centrifuging (the centrifugation speed is 10000rpm/min), washing (three times of exchange washing by ethanol and distilled water respectively), and freeze-drying at low temperature for 12h to obtain Bi2WO6-rGO-3%。
Example 2
Bi2WO6The preparation method of the-rGO visible light catalyst specifically comprises the following steps:
s1 preparation of 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 lining high-pressure reaction kettle after being magnetically stirred for 1 hour, the solution is heated for 24 hours at 160 ℃, and the solution is naturally cooled to the room temperature. Obtaining Bi through centrifugation (the centrifugation speed is 10000rpm/min), washing (three times of exchange washing by ethanol and distilled water respectively) and low-temperature freeze drying for 12h2WO6
S2 preparation of Bi from S12WO6Dissolving in 100ml steamDistilled water according to the mass ratio m (GO/Bi)2WO6) Weighing GO with the concentration of 5% and dissolving in 20ml of distilled water, and performing ultrasonic treatment for 1h respectively; adding Bi2WO6Transferring the solution to a three-neck flask, slowly adding the GO solution into the three-neck flask at a dropping rate of 20-30 drops/min, and stirring the mixed solution for 1 h; a certain amount of hydrazine hydrate was added to the mixed solution at a mass ratio of m (hydrazine hydrate/GO) of 7:10, and stirred at 95 ℃ for 12 hours. Cooling the solution, centrifuging (the centrifugation speed is 10000rpm/min), washing (three times of exchange washing by ethanol and distilled water respectively), and freeze-drying at low temperature for 12h to obtain Bi2WO6-rGO-5%。
Example 3
Bi2WO6The preparation method of the-rGO visible light catalyst specifically comprises the following steps:
s1 preparation of 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 lining high-pressure reaction kettle after being magnetically stirred for 1 hour, the solution is heated for 24 hours at 160 ℃, and the solution is naturally cooled to the room temperature. Obtaining Bi through centrifugation (the centrifugation speed is 10000rpm/min), washing (three times of exchange washing by ethanol and distilled water respectively) and low-temperature freeze drying for 12h2WO6
S2 preparation of Bi from S12WO6Dissolved in 100ml of distilled water according to the mass ratio m (GO/Bi)2WO6) Weighing GO with the concentration of 7%, dissolving in 20ml of distilled water, and performing ultrasonic treatment for 1h respectively; adding Bi2WO6Transferring the solution to a three-neck flask, slowly adding the GO solution into the three-neck flask at a dropping rate of 20-30 drops/min, and stirring the mixed solution for 1 h; a certain amount of hydrazine hydrate was added to the mixed solution at a mass ratio of m (hydrazine hydrate/GO) of 7:10, and stirred at 95 ℃ for 12 hours. Cooling the solution, centrifuging (the centrifugation speed is 10000rpm/min), washing (three times of exchange washing by ethanol and distilled water respectively), and freeze-drying at low temperature for 12h to obtain Bi2WO6-rGO-7%。
Comparative example 1
Bi2WO6The method for preparing the compound (A) is as follows,the preparation method specifically comprises the following steps:
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 lining high-pressure reaction kettle after being magnetically stirred for 1 hour, the solution is heated for 24 hours at 160 ℃, and the solution is naturally cooled to the room temperature. Obtaining Bi through centrifugation (the centrifugation speed is 10000rpm/min), washing (three times of exchange washing by ethanol and distilled water respectively) and low-temperature freeze drying for 12h2WO6And (3) sampling.
Test example 1
As shown in FIG. 1, Bi2WO6Corresponding to an orthorhombic system Bi2WO6(PDF #39-0256), GO has a characteristic peak around 10 deg.. Bi2WO6The characteristic peak position of the catalyst compounded with rGO is still equal to Bi2WO6The consistency is kept, no other diffraction peak is found, but the peak intensity is enhanced, which indicates that the addition of rGO does not change the crystal phase of the catalyst, and the crystallinity of the sample is enhanced.
Bi obtained in example 1-32WO6-rGO sample (Bi)2WO6-rGO-3%、Bi2WO6-rGO-5%、Bi2WO6-rGO-7%) and Bi prepared in comparative example 12WO6The samples are respectively added into a photocatalytic reaction instrument according to the amount of 0.1g, the photocatalytic reaction instrument is placed at a position 10cm below a light source to carry out the performance research of photocatalytic degradation of toluene, and the light source is a 1000W xenon lamp.
FIG. 2 shows Bi obtained in examples 1 to 32WO6-rGO sample (Bi)2WO6-rGO-3%、Bi2WO6-rGO-5%、Bi2WO6-rGO-7%) and Bi prepared in comparative example 12WO6The performance curve of the photocatalytic degradation of toluene under visible light is shown in FIG. 2, Bi2WO6after-rGO-5% is irradiated under a 1000W xenon lamp for 180min, the degradation rate of toluene reaches 80%. Under the same experimental conditions, Bi2WO6、Bi2WO6-rGO-3% and Bi2WO6The degradation rates of-rGO-7% p-toluene were 40%, 55% and 67%, respectively. Thus the best toluene degradation effect is achieved at a GO loading of 5 wt%.
In the description herein, references to the description of "one embodiment," "an example," "a specific example" or the like are intended to mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The foregoing shows and describes the general principles, essential features, and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only to illustrate the principle of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the present invention, which fall within the scope of the invention as claimed.

Claims (8)

1. Bi2WO6-a preparation method of rGO visible light catalyst, characterized in that the preparation method comprises the following steps:
s1, dissolving bismuth nitrate, sodium tungstate and hexadecyl trimethyl ammonium bromide in 80ml of distilled water, stirring the solution for 1 hour under magnetic stirring, and uniformly stirring the solution;
s2, transferring the product obtained in the step S1 into a reaction kettle, carrying out hydrothermal reaction at 160 ℃ for 24 hours, centrifuging and washing after the reaction is finished, and then placing the product into a drying box for drying treatment to obtain Bi2WO6
S3 preparation of Bi from S22WO6Dissolving GO in 100ml of distilled water, dissolving GO in 20ml of distilled water, and respectively carrying out ultrasonic treatment for 1 h; slowly dripping GO solution into Bi2WO6Adding the mixed solution into the solution, and stirring the mixed solution for 1 hour; according to the weight percentage of hydrazine hydrate: adding hydrazine hydrate into the mixed solution according to the mass ratio of 7:10 of GO, and stirring for 12 hours at 95 ℃; solution coolingCooling, centrifuging, washing and drying to obtain the Bi2WO6-rGO visible light photocatalyst.
2. The Bi of claim 12WO6The preparation method of the-rGO visible light catalyst is characterized in that the molar ratio of bismuth nitrate to sodium tungstate in S1 is 2:1, and the content of hexadecyl trimethyl ammonium bromide is 0.05 g.
3. The Bi of claim 12WO6The preparation method of the-rGO visible light catalyst is characterized in that GO and Bi are contained in the mixed solution of S32WO6The mass ratio of (A) is 3-7 wt%.
4. The Bi of claim 12WO6The preparation method of the-rGO visible light catalyst is characterized in that the dripping speed of the GO solution in the S3 is 20-30 drops/min.
5. The Bi of claim 12WO6-a process for the preparation of rGO visible photocatalyst, characterized in that the centrifugation and washing steps are as follows: the centrifugation rate was 10000rpm/min, and the washing was carried out three times each by exchanging ethanol with distilled water.
6. The Bi of claim 12WO6The preparation method of the-rGO visible light catalyst is characterized in that the drying treatment is low-temperature freeze drying for 12 hours.
7. Bi produced by the production method according to any one of claims 1 to 62WO6-application of rGO visible light catalyst in catalytic degradation of toluene under visible light conditions.
8. The use of claim 7, wherein the light source is a 1000W xenon lamp, 10cm above the reaction system.
CN202011412818.6A 2020-12-05 2020-12-05 Bi2WO6Preparation method and application of-rGO visible light catalyst Pending CN112371113A (en)

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Cited By (2)

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CN113856661A (en) * 2021-10-11 2021-12-31 盐城工学院 Ag3PO4/Bi2WO6Preparation method and application of/rGO visible light catalyst
CN116283455A (en) * 2023-04-13 2023-06-23 西北大学 Composite propellant energetic particle with low burning rate temperature coefficient and preparation method thereof

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113856661A (en) * 2021-10-11 2021-12-31 盐城工学院 Ag3PO4/Bi2WO6Preparation method and application of/rGO visible light catalyst
CN116283455A (en) * 2023-04-13 2023-06-23 西北大学 Composite propellant energetic particle with low burning rate temperature coefficient and preparation method thereof
CN116283455B (en) * 2023-04-13 2024-03-08 西北大学 Composite propellant energetic particle with low burning rate temperature coefficient and preparation method thereof

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