CN113856732A - Lamellar flower-shaped Mn (VO)3)2Composite g-C3N4Photocatalyst and preparation method and application thereof - Google Patents

Lamellar flower-shaped Mn (VO)3)2Composite g-C3N4Photocatalyst and preparation method and application thereof Download PDF

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CN113856732A
CN113856732A CN202111312343.8A CN202111312343A CN113856732A CN 113856732 A CN113856732 A CN 113856732A CN 202111312343 A CN202111312343 A CN 202111312343A CN 113856732 A CN113856732 A CN 113856732A
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lamellar
flower
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张涵
徐乐瑶
闫军锋
雷晓艺
张云尧
戴扬
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Northwest University
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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
    • B01J27/24—Nitrogen compounds
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16—Catalysts 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
    • B01J23/32—Manganese, technetium or rhenium
    • B01J23/34—Manganese
    • B01J35/39—
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B01J37/10—Heat treatment in the presence of water, e.g. steam
    • 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
    • C02F2101/38—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
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C02F2101/40—Organic compounds containing sulfur
    • 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

Abstract

The invention discloses a lamellar flower-shaped Mn (VO)3)2Composite g-C3N4A photocatalyst and a preparation method and application thereof; the preparation method comprises the following steps: (1) respectively preparing a manganese acetate solution and an ammonium metavanadate solution by taking deionized water as a solvent, then mixing the manganese acetate solution and the ammonium metavanadate solution, and uniformly stirring to obtain a mixed solution A; (2) adjusting the pH value of the mixed solution A to the value of5.2-5.6, and continuously stirring for 2-3h to obtain a precursor solution; (3) adding g-C to the precursor solution3N4Stirring the powder for 3-4h, transferring the powder into an autoclave with a polytetrafluoroethylene lining, and carrying out closed reaction for 17-20h at the temperature of 170-; (4) after the reaction is finished and the solution is cooled to room temperature, pouring out the upper solution to obtain a black-brown deposit, fully washing the black-brown deposit by deionized water and ethanol, and drying the black-brown deposit to obtain lamellar flower-shaped Mn (VO)3)2Composite g-C3N4A photocatalyst. The invention adopts a one-step hydrothermal method, has simple preparation process, is suitable for batch production, lays a good foundation for application research, and has good prospect in the field of photocatalysis.

Description

Lamellar flower-shaped Mn (VO)3)2Composite g-C3N4Photocatalyst and preparation method and application thereof
Technical Field
The invention belongs to the technical field of photocatalysis, and particularly relates to lamellar flower-shaped Mn (VO)3)2Composite g-C3N4A photocatalyst and a preparation method and application thereof.
Background
In the current research in the field of photocatalysis, some oxide semiconductor materials (e.g., TiO)2ZnO), however, titanium dioxide has a relatively large band gap energy (Eg ═ 3.2ev), and electron transition can occur under the irradiation of ultraviolet light, but the ultraviolet light in natural light is less than 5%, so that the utilization rate of sunlight is very low, i.e. the photocatalytic degradation efficiency under sunlight is relatively low. With the continuous and deep understanding of people on photocatalysis, semiconductor materials are deeply developed in the field of photocatalysis.
Metal vanadates are a class of excellent functional materials. Recent research shows that certain vanadate has great application potential in the field of photocatalysis and is a novel high-activity photocatalyst. In manganese vanadate, vanadium and manganese atoms have good optical properties due to special structures.
The form and the preparation method of the material are also key factors influencing the physical and chemical properties of the material, and when the size of the material reaches the nanometer level, the surface effect, the quantum size and other effects of the material can cause the properties of the nano material to be obviously superior to those of a corresponding block material, so that different physical and chemical properties are shown, and therefore, the preparation of manganese vanadate nano materials with different forms by different methods has important research significance for the application of the manganese vanadate nano material. Secondly, an effective measure for improving the photocatalytic activity of the catalyst is to improve the separation-combination probability of the photoproduction electrons and the photoproduction holes. Research shows that binary or multicomponent semiconductor compounding technology can reach the aim, and the compounded material can regulate the performance of single material effectively and produce many new photochemical and photophysical characteristics.
Huang et al successfully prepared manganese vanadate nanoribbons by a hydrothermal method, but the preparation method takes too long time and has high preparation cost. The patent with the application number of 201410400470.7 and the name of 'a manganese vanadate self-cleaning coating with a nano needle structure' discloses a manganese vanadate nano needle structure. ZnO/Mn (VO) prepared by Sandeep Kaushal et al by hydrothermal method3)2The composite photocatalyst shows good photocatalytic degradation effect under ultraviolet light and visible light. Pu et al prepared Ag by surface chemical precipitation2O/g-C3N4Photocatalyst, Ag2The photocatalytic performance of O is improved. Yu et al prepared direct z form g-C3N4/Ag2WO4The photocatalyst shows higher photocatalytic performance on the degradation of organic pollutants. Based on the above related research progress and the influence of different morphologies, different compounds and preparation methods on the material performance, research on the material of the manganese vanadate compound in the field of photocatalysis needs to be overcome.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide lamellar flower-shaped Mn (VO) with simple preparation process, low cost and excellent catalytic performance3)2Composite g-C3N4A photocatalyst and a preparation method and application thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
lamellar flower-shaped Mn (VO)3)2Composite g-C3N4The preparation method of the photocatalyst comprises the following steps:
(1) respectively preparing a manganese acetate solution and an ammonium metavanadate solution by taking deionized water as a solvent, and then mixing the manganese acetate solution and the ammonium metavanadate solution according to a molar ratio of manganese acetate to ammonium metavanadate of 1: (2-3) mixing, and uniformly stirring to obtain a mixed solution A;
(2) adjusting the pH value of the mixed solution A to 5.2-5.6 by adopting an acetic acid solution, and continuously stirring for 2-3h to obtain a precursor solution;
(3) manganese acetate with g-C3N4In a molar ratio of 1: (0.5-2), adding g-C to the precursor solution3N4Stirring the powder for 3-4h, transferring the powder into an autoclave with a polytetrafluoroethylene lining, and carrying out closed reaction for 17-20h at the temperature of 170-;
(4) after the reaction is finished and the solution is cooled to room temperature, pouring out the upper solution to obtain a black-brown deposit, fully washing the black-brown deposit by deionized water and ethanol, and drying the black-brown deposit to obtain lamellar flower-shaped Mn (VO)3)2Composite g-C3N4A photocatalyst.
Further, the concentration of manganese acetate in the mixed liquor A in the step (1) is 0.02-0.03 mol/L.
Further, the concentration of the acetic acid in the acetic acid solution in the step (2) is 1-3 mol/L.
Further, in the step (4), the drying temperature is 60-80 ℃, and the drying time is 10-15 h.
The invention also relates to lamellar flower-shaped Mn (VO) prepared by the method3)2Composite g-C3N4Photocatalyst, said lamellar flower-like Mn (VO)3)2Composite g-C3N4The microstructure of the photocatalyst is in a lamellar flower shape with attached cloud-like lamellar substances, wherein the cloud-like lamellar substances are g-C3N4。
The invention also relates to the lamellar flower-shaped Mn (VO)3)2Composite g-C3N4Application of photocatalyst in organic pollutant degradation.
Compared with the prior art, the invention has the following technical effects:
1. the invention combines manganese vanadate monomer and two-dimensional metal-free polymer graphite carbon nitride (g-C) with excellent photophysical property3N4) The band gap value is reduced by recombination, and the light excitation is more favorable for generating electron-hole pairsThe separation probability of photoproduction electrons and photoproduction holes of the monomer is improved, and in addition, Mn (VO)3)2And g-C3N4The establishment of the p-n heterojunction between the two layers effectively promotes the migration of carriers through an internal electric field, so that the prepared lamellar flower-shaped Mn (VO)3)2Composite g-C3N4The photocatalyst has good photocatalytic performance.
2. The invention adopts a one-step hydrothermal method, has simple preparation process, low cost, short time consumption and controllable conditions, and the obtained product has uniform appearance and size, is suitable for batch production, lays a good foundation for application research, and has good prospects in the field of photocatalysis.
3. In the synthesis process, any surfactant or organic template agent is not needed, nontoxic manganese acetate, ammonium metavanadate and the like are adopted, and the raw materials and the preparation process meet the industrial production direction of environmental protection requirements.
4. Lamellar flower-shaped Mn (VO) prepared by the invention3)2Composite g-C3N4The photocatalyst can effectively degrade organic pollutants.
Drawings
FIG. 1 shows lamellar flower-like Mn (VO) prepared in example 1 of the present invention3)2Composite g-C3N4XRD pattern of photocatalyst;
FIG. 2 shows lamellar flower-like Mn (VO) prepared in example 2 of the present invention3)2Composite g-C3N4XRD pattern of photocatalyst;
FIG. 3 shows lamellar flower-like Mn (VO) prepared in example 5 of the present invention3)2Composite g-C3N4XRD pattern of photocatalyst;
FIG. 4 shows lamellar flower-like Mn (VO) prepared in example 5 of the present invention3)2Composite g-C3N4SEM image of photocatalyst;
FIG. 5 shows lamellar flower-like Mn (VO) prepared in comparative example 1 of the present invention3)2XRD pattern of photocatalyst;
FIG. 6 shows lamellar flower-like Mn (VO) prepared in comparative example 1 of the present invention3)2SEM image of photocatalyst;
FIG. 7 shows lamellar flower-like Mn (VO) prepared in example 5 of the present invention3)2Composite g-C3N4A photocatalytic degradation diagram of sulfamethoxazole by the photocatalyst;
FIG. 8 shows lamellar flower-like Mn (VO) prepared according to comparative example of the present invention3)2And (3) a photocatalytic degradation diagram of sulfamethoxazole by a photocatalyst.
Detailed Description
The present invention will be explained in further detail with reference to examples.
The embodiment relates to a lamellar flower-shaped Mn (VO)3)2Composite g-C3N4The preparation method of the photocatalyst comprises the following steps:
(1) respectively preparing a manganese acetate solution and an ammonium metavanadate solution by taking deionized water as a solvent, and then mixing the manganese acetate solution and the ammonium metavanadate solution according to a molar ratio of manganese acetate to ammonium metavanadate of 1: (2-3) mixing, and uniformly stirring to obtain a mixed solution A;
(2) adjusting the pH value of the mixed solution A to 5.2-5.6 by adopting an acetic acid solution, and continuously stirring for 2-3h to obtain a precursor solution;
(3) manganese acetate with g-C3N4In a molar ratio of 1: (0.5-2), adding g-C to the precursor solution3N4Stirring the powder for 3-4h, transferring the powder into an autoclave with a polytetrafluoroethylene lining, and carrying out closed reaction for 17-20h at the temperature of 170-;
(4) after the reaction is finished and the solution is cooled to room temperature, pouring out the upper solution to obtain a black-brown deposit, fully washing the black-brown deposit by deionized water and ethanol, and drying the black-brown deposit to obtain lamellar flower-shaped Mn (VO)3)2Composite g-C3N4A photocatalyst.
The embodiment also relates to lamellar flower-shaped Mn (VO) prepared by the method3)2Composite g-C3N4Photocatalyst, said lamellar flower-like Mn (VO)3)2Composite g-C3N4The microstructure of the photocatalyst is in a lamellar flower shape with attached cloud-like lamellar substances, wherein the cloud-like lamellar substances are g-C3N4。
This example also relates to the lamellar flower-like Mn (VO) described above3)2Composite g-C3N4Application of photocatalyst in organic pollutant degradation.
To further illustrate the technical solution of the present invention, the following detailed description is given with reference to specific examples.
Example 1
2.5mmol of NH4VO3And 1mmol Mn (CH)3COOH)2·4H2O is respectively dissolved in 22ml of deionized water, and Mn (CH) is added under the action of magnetic stirring3COOH)2·4H2O solution is mixed to NH4VO3Stirring the solution for 10min to obtain a mixed solution A, and adding 1.5mol/L of CH3Adjusting the pH value of the mixed solution A to 5.5 by using the COOH solution, continuously stirring for 3h to obtain a precursor solution, and adding 1.8mmol g-C into the precursor solution3N4Stirring was continued for 4h, then transferred to an autoclave with a teflon liner, sealed and placed in a thermostat and reacted at 180 ℃ for 18 h. After the reaction is finished and the temperature is cooled to room temperature, pouring out the upper solution to obtain a black-brown deposit, washing the deposit for a plurality of times by deionized water (DI), washing the deposit for 2 times by ethanol, and drying the deposit for 12 hours at 60 ℃ to obtain lamellar flower-shaped Mn (VO)3)2Composite g-C3N4A photocatalyst.
FIG. 1 shows lamellar flower-like Mn (VO) prepared in this example3)2Composite g-C3N4The XRD pattern of the photocatalyst shows that diffraction peaks exist at 27.42 degrees, 28.401 degrees, 29.655 degrees, 32.908 degrees and 38.957 degrees of 2 theta, and the diffraction peaks correspond to Mn (VO) in sequence3)2The (110), (002), (201), (-210) and (211) crystal planes of (1), wherein g-C3N4Diffraction Peak at 28.3 ℃ 2. theta. with Mn (VO)3)2(002) The diffraction peaks of the crystal planes overlap; mn (VO) is included in the figure3)2And g-C3N4Shows Mn (VO)3)2And g-C3N4Coexisting in the heterojunction. Mn (VO)3)2And g-C3N4After mixing, the crystallinity is higherGood, the basic structure of the matrix is not changed, different g-C are correspondingly added according to different diffraction peak strengths3N4The amount of (c).
Example 2
2mmol of NH4VO3And 1mmol Mn (CH)3COOH)2·4H2O is respectively dissolved in 17ml of deionized water, and Mn (CH) is added under the action of magnetic stirring3COOH)2·4H2O solution is mixed to NH4VO3Stirring the solution for 10min to obtain a mixed solution A, and adding 2mol/L of CH3Adjusting the pH value of the mixed solution A to 5.6 by the COOH solution, continuously stirring for 2.5h to obtain a precursor solution, and adding 1mmol g-C into the precursor solution3N4Stirring was continued for 3.5h, then transferred to an autoclave with a teflon liner, sealed and placed in a thermostat to react at 180 ℃ for 19 h. After the reaction is finished and the temperature is cooled to room temperature, pouring out the upper solution to obtain a black-brown deposit, washing the deposit for a plurality of times by deionized water (DI), washing the deposit for 2 times by ethanol, and drying the deposit for 15 hours at 60 ℃ to obtain lamellar flower-shaped Mn (VO)3)2Composite g-C3N4A photocatalyst.
FIG. 2 shows lamellar flower-like Mn (VO) prepared in this example3)2Composite g-C3N4The XRD pattern of the photocatalyst shows that diffraction peaks exist at 27.42 degrees, 28.401 degrees, 29.655 degrees, 32.908 degrees and 38.957 degrees of 2 theta, and the diffraction peaks correspond to Mn (VO) in sequence3)2The (110), (002), (201), (-210) and (211) crystal planes of (1), wherein g-C3N4Diffraction Peak at 28.3 ℃ 2. theta. with Mn (VO)3)2(002) The diffraction peaks of the crystal planes overlap; mn (VO) is included in the figure3)2And g-C3N4Shows Mn (VO)3)2And g-C3N4Coexisting in the heterojunction. Mn (VO)3)2And g-C3N4The crystallinity is better after mixing, the basic structure of the matrix is not changed, and different g-C are added corresponding to different diffraction peak strengths3N4The amount of (c).
Example 3
Adding 3mmol of NH4VO3And 1mmol Mn (CH)3COOH)2·4H2O is respectively dissolved in 25ml of deionized water, and Mn (CH) is added under the action of magnetic stirring3COOH)2·4H2O solution is mixed to NH4VO3Stirring the solution for 10min to obtain a mixed solution A, and adding 3mol/L CH3Adjusting the pH value of the mixed solution A to 5.3 by using the COOH solution, continuously stirring for 2h to obtain a precursor solution, and adding 2mmol g-C into the precursor solution3N4Stirring was continued for 3h, then transferred to an autoclave with a teflon liner, sealed and placed in a thermostat to react at 190 ℃ for 17 h. After the reaction is finished and the temperature is cooled to room temperature, pouring out the upper solution to obtain a black-brown deposit, washing the black-brown deposit with deionized water (DI) for 3 times, washing the black-brown deposit with ethanol for 3 times, and drying the black-brown deposit at 80 ℃ for 10 hours to obtain lamellar flower-shaped Mn (VO)3)2Composite g-C3N4A photocatalyst.
Example 4
2.5mmol of NH4VO3And 1mmol Mn (CH)3COOH)2·4H2Dissolving O in 21ml deionized water respectively, and stirring Mn (CH) under the action of magnetic force3COOH)2·4H2O solution is mixed to NH4VO3Stirring the solution for 10min to obtain a mixed solution A, and adding 1mol/L CH3Adjusting the pH value of the mixed solution A to 5.2 by using the COOH solution, continuously stirring for 3h to obtain a precursor solution, and adding 0.7mmol g-C into the precursor solution3N4Stirring was continued for 4h, then transferred to an autoclave with a teflon liner, sealed and placed in a thermostat and reacted at 170 ℃ for 20 h. After the reaction is finished and the temperature is cooled to room temperature, pouring out the upper solution to obtain a black-brown deposit, washing the black-brown deposit for a plurality of times by deionized water (DI), washing the black-brown deposit for 3 times by ethanol, and drying the black-brown deposit for 12 hours at 70 ℃ to obtain lamellar flower-shaped Mn (VO)3)2Composite g-C3N4A photocatalyst.
Example 5
2mmol of NH4VO3And 1mmol Mn (CH)3COOH)2·4H2O is respectively dissolved in 20ml of deionized water and stirred by magnetic forceUnder the action of Mn (CH)3COOH)2·4H2O solution is mixed to NH4VO3Stirring the solution for 10min to obtain a mixed solution A, and adding 1.5mol/L of CH3Adjusting the pH value of the mixed solution A to 5.4 by the COOH solution, continuously stirring for 2.5h to obtain a precursor solution, and adding 0.5mmol g-C into the precursor solution3N4Stirring was continued for 3.5h, then it was transferred to a 50ml autoclave with a teflon liner, which was sealed and placed in a thermostat and reacted at 180 ℃ for 18 h. After the reaction is finished and the temperature is cooled to room temperature, pouring out the upper solution to obtain a black-brown deposit, washing the deposit for a plurality of times by deionized water (DI), washing the deposit for 2 times by ethanol, and drying the deposit for 12 hours at 60 ℃ to obtain lamellar flower-shaped Mn (VO)3)2Composite g-C3N4A photocatalyst.
FIGS. 3 and 4 are graphs showing lamellar flower-like Mn (VO) prepared in this example3)2Composite g-C3N4XRD and SEM images of the photocatalyst; it can be seen from FIG. 3 that there are diffraction peaks at 27.42 °, 28.401 °, 29.655 °, 32.908 ° and 38.957 ° 2 θ, which correspond to Mn (VO) in order3)2The (110), (002), (201), (-210) and (211) crystal planes of (1), wherein g-C3N4Diffraction Peak at 28.3 ℃ 2. theta. with Mn (VO)3)2(002) The diffraction peaks of the crystal planes overlap; mn (VO) is included in the figure3)2And g-C3N4Shows Mn (VO)3)2And g-C3N4Coexisting in the heterojunction. Mn (VO)3)2And g-C3N4The crystallinity is better after mixing, the basic structure of the matrix is not changed, and different g-C are added corresponding to different diffraction peak strengths3N4The amount of (c); from FIG. 4, it can be seen that the lamellar flower-like Mn (VO) synthesized in this example3)2Composite g-C3N4The microstructure of the photocatalyst is in a lamellar flower shape with attached cloud-like lamellar substances, wherein the cloud-like lamellar substances are g-C3N4。
Comparative example
2mmol of NH4VO3And 1mmol Mn (CH)3COOH)2·4H2O is respectively dissolved in 20ml of deionized water, and Mn (CH) is added under the action of magnetic stirring3COOH)2·4H2O solution is mixed to NH4VO3Stirring the solution for 10min to obtain a mixed solution A, and adding 1.5mol/L of CH3And adjusting the pH value of the mixed solution A to 5.4 by using the COOH solution, continuously stirring for 2.5h to obtain a precursor solution, transferring the precursor solution into a 50ml autoclave with a polytetrafluoroethylene lining, sealing, placing the autoclave in a constant temperature cabinet, and reacting for 18h at 180 ℃. After the reaction is finished and the temperature is cooled to room temperature, pouring out the upper solution to obtain a black-brown deposit, washing the black-brown deposit for a plurality of times by deionized water (DI), washing the black-brown deposit for 2 times by ethanol, and drying the black-brown deposit for 12 hours at 60 ℃ to obtain lamellar flower-shaped Mn (VO)3)2A photocatalyst.
FIGS. 5 and 6 are respectively the lamellar flower-like Mn (VO) prepared in this comparative example3)2XRD and SEM images of the photocatalyst; it can be seen from FIG. 5 that there are diffraction peaks at 27.42 °, 28.401 °, 29.655 °, 32.908 ° and 38.957 ° 2 θ, which correspond to Mn (VO) in order3)2The (110), (002), (201), (210) and (211) crystal planes of the crystal lattice, and Mn (VO) is contained in the graph3)2All diffraction peaks of (a); from FIG. 6, it can be seen that the lamellar flower-like Mn (VO) synthesized in this example3)2The microstructure of the photocatalyst is a lamellar flower-like structure.
The lamellar flower-like Mn (VO) provided for fully illustrating the present invention3)2Composite g-C3N4Application of photocatalyst in degradation of organic pollutants, taking organic pollutants Sulfamethoxazole (SMX) as an example, lamellar flower-like Mn (VO) prepared in comparative example 5 is examined by the photodegradation of sulfamethoxazole under the irradiation of visible light at room temperature3)2Composite g-C3N4Photocatalyst and lamellar flower-shaped Mn (VO) prepared by comparative example3)2The photocatalyst has the catalytic action in the degradation process of sulfamethoxazole.
The application adopts a 500w long-arc xenon lamp and an AM 1.5 optical filter (100mW cm)-2) Simulating visible light.
50mg of lamellar flower-like Mn (VO) prepared in example 53)2Composite g-C3N4The photocatalyst was uniformly dispersed in 50ml of SMX solution (SMX ═ 5mg/L) and placed in a dark environment with continuous stirring for 30min to ensure adsorption-desorption equilibrium; the cells were then exposed to visible light for degradation and 5ml of the suspension was removed every 15min and analyzed by UV1901PC UV-visible spectrophotometer, the results of which are shown in FIG. 7.
Similarly, the lamellar flower-like Mn (VO) prepared in comparative example3)2The photocatalyst was uniformly dispersed in 50ml of SMX solution (SMX ═ 5mg/L) and placed in a dark environment with continuous stirring for 30min to ensure adsorption-desorption equilibrium; the cells were then exposed to visible light for degradation and 5ml of the suspension was removed every 15min and analyzed by UV1901PC UV-visible spectrophotometer, the results of which are shown in FIG. 8.
The maximum absorption peak of SMX appears at about 260nm, and comparing FIG. 7 with FIG. 8 shows that lamellar flower-like Mn (VO) is added as the irradiation time increases3)2Composite g-C3N4The SMX absorption peak of the SMX solution of the photocatalyst almost disappears after the SMX solution is irradiated for 90min, which indicates that the SMX is completely degraded; while adding lamellar flower-shaped Mn (VO)3)2The absorption peak of SMX of the photocatalyst is not obviously changed after the SMX solution is irradiated for 90min, which shows that the SMX is not degraded, and proves that g-C is compounded3N4Lamellar flower-like Mn (VO)3)2Composite g-C3N4The photocatalyst can effectively promote the degradation of organic pollutants.

Claims (6)

1. Lamellar flower-shaped Mn (VO)3)2Composite g-C3N4The preparation method of the photocatalyst is characterized by comprising the following steps:
(1) respectively preparing a manganese acetate solution and an ammonium metavanadate solution by taking deionized water as a solvent, and then mixing the manganese acetate solution and the ammonium metavanadate solution according to a molar ratio of manganese acetate to ammonium metavanadate of 1: (2-3) mixing, and uniformly stirring to obtain a mixed solution A;
(2) adjusting the pH value of the mixed solution A to 5.2-5.6 by adopting an acetic acid solution, and continuously stirring for 2-3h to obtain a precursor solution;
(3) in the presence of acetic acidManganese with g-C3N4In a molar ratio of 1: (0.5-2), adding g-C to the precursor solution3N4Stirring the powder for 3-4h, transferring the powder into an autoclave with a polytetrafluoroethylene lining, and carrying out closed reaction for 17-20h at the temperature of 170-;
(4) after the reaction is finished and the solution is cooled to room temperature, pouring out the upper solution to obtain a black-brown deposit, fully washing the black-brown deposit by deionized water and ethanol, and drying the black-brown deposit to obtain lamellar flower-shaped Mn (VO)3)2Composite g-C3N4A photocatalyst.
2. Lamellar flower-like Mn (VO) according to claim 13)2Composite g-C3N4The preparation method of the photocatalyst is characterized in that the concentration of manganese acetate in the mixed solution A in the step (1) is 0.02-0.03 mol/L.
3. Lamellar flower-like Mn (VO) according to claim 13)2Composite g-C3N4The preparation method of the photocatalyst is characterized in that the concentration of acetic acid in the acetic acid solution in the step (2) is 1-3 mol/L.
4. Lamellar flower-like Mn (VO) according to claim 13)2Composite g-C3N4The preparation method of the photocatalyst is characterized in that the drying temperature in the step (4) is 60-80 ℃, and the drying time is 10-15 h.
5. Lamellar flower-shaped Mn (VO) prepared by the method of any one of claims 1 to 43)2Composite g-C3N4Photocatalyst, characterized in that said lamellar flower-like Mn (VO)3)2Composite g-C3N4The microstructure of the photocatalyst is in a lamellar flower shape with attached cloud-like lamellar substances, wherein the cloud-like lamellar substances are g-C3N4。
6. Lamellar flower-like Mn (VO) according to claim 53)2Compoundingg-C3N4Application of photocatalyst in organic pollutant degradation.
CN202111312343.8A 2021-11-08 2021-11-08 Lamellar flower-shaped Mn (VO)3)2Composite g-C3N4Photocatalyst and preparation method and application thereof Pending CN113856732A (en)

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