CN115138369A - Molybdenum trioxide composite material and preparation method and application thereof - Google Patents

Molybdenum trioxide composite material and preparation method and application thereof Download PDF

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CN115138369A
CN115138369A CN202210943139.4A CN202210943139A CN115138369A CN 115138369 A CN115138369 A CN 115138369A CN 202210943139 A CN202210943139 A CN 202210943139A CN 115138369 A CN115138369 A CN 115138369A
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molybdenum trioxide
composite material
molybdenum
trioxide composite
cobalt
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CN115138369B (en
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曾庆意
谭晶
刘益林
高贝贝
张清彦
傅喜军
郭陆林
张超
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University of South China
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    • 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
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/85—Chromium, molybdenum or tungsten
    • B01J23/88—Molybdenum
    • B01J23/882—Molybdenum and cobalt
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B01J37/082—Decomposition and pyrolysis
    • B01J37/088—Decomposition of a metal salt
    • 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
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/722—Oxidation by peroxides
    • 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
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
    • 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
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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    • C02F2101/34—Organic compounds containing oxygen
    • C02F2101/345—Phenols
    • 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
    • C02F2305/02—Specific form of oxidant
    • C02F2305/023—Reactive oxygen species, singlet oxygen, OH radical
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    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W10/00—Technologies for wastewater treatment
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    • Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy

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Abstract

The invention belongs to the technical field of organic pollutant treatment, and particularly relates to a molybdenum trioxide composite material and a preparation method and application thereof. The invention provides a molybdenum trioxide composite material, which comprises a molybdenum trioxide matrix and cobalt doped in the molybdenum trioxide matrix; the molybdenum trioxide composite material has a perovskite-like structure. The molybdenum trioxide composite material provided by the invention has a perovskite-like structure, has higher charge transfer performance and is beneficial to interface charge transfer; co is doped in MoO at the same time 3 Can further improve the molybdenum trioxide composite material to persulfateThe activation effect of the catalyst, and further the degradation efficiency of the organic pollutants is improved.

Description

Molybdenum trioxide composite material and preparation method and application thereof
Technical Field
The invention belongs to the technical field of organic pollutant treatment, and particularly relates to a molybdenum trioxide composite material and a preparation method and application thereof.
Background
With the development of modern industry and agriculture, a large amount of artificially synthesized organic matters, such as medicines, antibiotics, endocrine disruptors, pesticides, persistent organic pollutants and the like, are directly discharged into the environment, so that the water body is polluted. For the treatment of wastewater containing organic pollutants, conventional methods include microbial degradation, activated carbon adsorption, membrane filtration, etc., but the above methods have the drawback of low treatment efficiency.
The advanced oxidation technology is a treatment method which has high-efficiency degradation capability on organic pollutants at present, and mainly adopts hydrogen peroxide as an oxidant to generate hydroxyl radicals through activation so as to degrade the organic pollutants. However, in the practical application process, the dosage of hydrogen peroxide is large, the effective utilization rate is low, a large amount of oxidant remains in the solution obtained by treatment, subsequent treatment is required, and the operation cost is increased.
In recent years, the persulfate advanced oxidation technology based on sulfate radicals is mature day by day, and compared with hydroxyl radicals, sulfate radicals have higher oxidation-reduction potential and higher catalytic efficiency, and have the characteristics of long service life, good water solubility and difficult volatilization, so that the persulfate oxidation technology can more effectively degrade organic pollutants.
Currently, sulfate radicals are generated primarily by activating persulfates, and commonly used activation methods include photoactivation, thermal activation, or transition metal ion activation. The light activation and the heat activation need additional energy supply, and the energy consumption is low; in contrast, the transition metal ion activation does not need to provide energy to the system, and is more suitable for industrial application.
Common transition metal ions include Fe 2+ 、Fe 3+ 、Mn 2+ However, the above transition metal ions still have the defect of low activation efficiency, which results in low degradation efficiency of organic pollutants.
Disclosure of Invention
The invention aims to provide a molybdenum trioxide composite material, and a preparation method and application thereof.
In order to achieve the above purpose, the invention provides the following technical scheme:
the invention provides a molybdenum trioxide composite material, which comprises a molybdenum trioxide matrix and cobalt doped in the molybdenum trioxide matrix;
the molybdenum trioxide composite material has a perovskite-like structure.
Preferably, the doping percentage of the cobalt is 1-20%.
The invention also provides a preparation method of the molybdenum trioxide composite material in the technical scheme, which comprises the following steps:
and mixing a molybdenum source and a cobalt source, and calcining to obtain the molybdenum trioxide composite material.
Preferably, the molybdenum source comprises one or more of molybdenum pentachloride, molybdenum acetate, molybdenum acetylacetonate, ammonium molybdate, ammonium dimolybdate and ammonium heptamolybdate;
the cobalt source comprises one or more of cobalt nitrate, cobalt chloride, cobalt oxide and cobalt acetate;
the molar ratio of the molybdenum source to the cobalt source is 100:0.5 to 1.5.
Preferably, the calcining temperature is 400-550 ℃; the heating rate of heating to the calcining temperature is less than or equal to 10 ℃/min; the heat preservation time is 2-40 h.
The invention also provides the application of the molybdenum trioxide composite material or the molybdenum trioxide composite material prepared by the preparation method in the technical scheme in degrading organic pollutants.
Preferably, the application comprises the following steps:
mixing the molybdenum trioxide composite material, persulfate and waste water containing organic pollutants, and carrying out catalytic degradation.
Preferably, the persulfate salt comprises a peroxymonosulfate salt and/or a peroxydisulfate salt.
Preferably, the concentration of the organic pollutants in the wastewater containing the organic pollutants is 10-50 mg/L;
the mass ratio of the organic pollutants to the persulfate in the wastewater containing the organic pollutants is 1:5 to 100;
the mass ratio of the organic pollutants in the wastewater containing the organic pollutants to the molybdenum trioxide composite material is 1:1 to 30.
Preferably, the temperature of the catalytic degradation is 20-45 ℃, and the time is 10-30 min.
The invention provides a molybdenum trioxide composite material, which comprises a molybdenum trioxide matrix and cobalt doped in the molybdenum trioxide matrix; the molybdenum trioxide composite material has a perovskite-like structure. The molybdenum trioxide composite material provided by the invention has a perovskite-like structure, has higher charge transfer performance and is beneficial to interface charge transfer; co is doped in MoO at the same time 3 In the crystal lattice, the activation effect of the molybdenum trioxide composite material on persulfate can be further improved, and the degradation efficiency of organic pollutants is further improved.
Drawings
FIG. 1 is an SEM photograph of a molybdenum trioxide composite obtained in example 12;
FIG. 2 is an XRD pattern of the molybdenum trioxide composite material obtained in example 12;
FIG. 3 is an XPS plot of the molybdenum trioxide composite obtained in example 12;
FIG. 4 shows hydroxyl radicals (OH. Cndot.) and sulfate radicals (SO) 4 - ·) electron paramagnetic resonance spectrum;
FIG. 5 shows superoxide radical (O) 2 - ·) electron paramagnetic resonance spectrum;
FIG. 6 is a graph showing the catalytic degradation efficiency in applications 1 to 4, comparative example 2 and comparative example 3;
FIG. 7 is a graph showing the catalytic degradation efficiency of application examples 5 to 7;
FIG. 8 is a graph showing the catalytic degradation efficiency of application examples 8 to 12;
FIG. 9 is a graph of catalytic degradation efficiency at different pH values for 30 min;
FIG. 10 is a graph of catalytic degradation efficiency at different temperatures;
FIG. 11 is a graph of the catalytic degradation efficiency of a composite material catalytically activated peroxymonosulfate to degrade bisphenol A with different catalyst concentrations;
FIG. 12 is a graph of the catalytic degradation efficiency of different amounts of permonosulfate for the catalytic activation of the permonosulfate to degrade bisphenol A in the composite material;
FIG. 13 is a graph of catalytic degradation efficiency at 30min in application example 13;
FIG. 14 is a graph of the cycle performance of activated peroxymonosulfate of the molybdenum trioxide composite material provided by the present invention.
Detailed Description
The invention provides a molybdenum trioxide composite material, which comprises a molybdenum trioxide matrix and cobalt doped in the molybdenum trioxide matrix;
the molybdenum trioxide composite material has a perovskite-like structure.
In the present invention, the molybdenum trioxide composite is preferably a nanoprism structure; the aspect ratio of the nanoprism structure is preferably 2 to 2.5:1.
in the present invention, the doping percentage of cobalt is preferably 1 to 20%, more preferably 5 to 15%, and still more preferably 8 to 12%.
The invention also provides a preparation method of the molybdenum trioxide composite material in the technical scheme, which comprises the following steps:
and mixing a molybdenum source and a cobalt source, and calcining to obtain the molybdenum trioxide composite material.
In the present invention, all the starting materials for the preparation are commercially available products known to those skilled in the art unless otherwise specified.
In the present invention, the molybdenum source preferably includes one or more of molybdenum pentachloride, molybdenum acetate, molybdenum acetylacetonate, ammonium molybdate, ammonium dimolybdate and ammonium heptamolybdate; when the molybdenum source is two or more selected as described above, the ratio of the specific substances in the present invention is not particularly limited, and the molybdenum source may be mixed in any ratio. In a particular embodiment of the invention, the ammonium molybdate is preferably added in the form of ammonium molybdate tetrahydrate.
In the invention, the cobalt source preferably comprises one or more of cobalt nitrate, cobalt chloride, cobalt oxide and cobalt acetate; when the cobalt source is two or more selected as described above, the ratio of the specific substances in the present invention is not particularly limited, and the specific substances may be mixed in any ratio. In a particular embodiment of the invention, the cobalt chloride is preferably added in the form of cobalt chloride hexahydrate.
In the present invention, the molar ratio of the molybdenum source to the cobalt source is preferably 100:0.5 to 1.5, more preferably 100:0.8 to 1.3, more preferably 100:1.0 to 1.2.
The mixing process is not particularly limited in the present invention, as long as the raw materials can be uniformly mixed.
In the present invention, the temperature of the calcination is preferably 400 to 550 ℃, more preferably 420 to 520 ℃, and still more preferably 450 to 500 ℃; the heating rate of the temperature rise to the calcination temperature is preferably less than or equal to 10 ℃/min, and is further preferably 2-5 ℃/min; the holding time is preferably 2 to 40 hours, more preferably 5 to 35 hours, and still more preferably 10 to 30 hours. In the present invention, the calcination is preferably performed under an air atmosphere. In the present invention, the calcination is preferably carried out in a muffle furnace.
After the calcination is completed, the present invention also preferably includes cooling and grinding the resulting product. In the present invention, the cooling method is preferably natural cooling. The process of the present invention is not particularly limited, and those skilled in the art will be familiar with the process of the present invention.
The preparation method provided by the invention is simple, high in yield, good in stability and repeatability, and suitable for industrial production.
The invention also provides application of the molybdenum trioxide composite material or the molybdenum trioxide composite material prepared by the preparation method in the technical scheme in degradation of organic pollutants.
In the present invention, the application preferably comprises the steps of:
mixing the molybdenum trioxide composite material, persulfate and waste water containing organic pollutants, and carrying out catalytic degradation.
In the present invention, the persulfate preferably includes a peroxymonosulfate and/or peroxydisulfate; further preferred is a peroxymonosulfate salt. In the present invention, the salt of monopersulfate preferably includes a potassium hydrogen peroxymonosulfate complex salt. In the invention, the chemical composition of the potassium hydrogen peroxymonosulfate composite salt is preferably 2KHSO 5 ·KHSO 4 ·K 2 SO 4 . In the present invention, the peroxodisulfate preferably comprises K 2 S 2 O 8 And/or Na 2 S 2 O 8 。
In the present invention, the organic contaminants in the wastewater containing organic contaminants preferably include one or more of dyes, antibiotics, personal care products, pesticides, and endocrine disruptors. In a specific embodiment of the present invention, the organic contaminant is specifically bisphenol a, rhodamine B, ciprofloxacin, dichlorophenol, p-nitrophenol, adriamycin, aureomycin, oxytetracycline, or tetracycline.
In the present invention, the concentration of the organic contaminant in the wastewater containing the organic contaminant is 10 to 50mg/L, more preferably 15 to 45mg/L, and still more preferably 20 to 40mg/L. In the present invention, the mass ratio of the organic pollutant to the persulfate in the wastewater containing the organic pollutant is preferably 1:5 to 100, more preferably 1:10 to 90, more preferably 1:20 to 80.
In the present invention, the mass ratio of the organic pollutant to the molybdenum trioxide composite material in the wastewater containing the organic pollutant is preferably 1:1 to 30, more preferably 1:5 to 25, more preferably 1:10 to 20.
In the present invention, the mixing process is preferably:
mixing the molybdenum trioxide composite material and wastewater containing organic pollutants at a first stage, and standing to obtain a first-stage mixed solution;
and carrying out secondary mixing on the primary mixed solution and persulfate.
The process of the first mixing is not particularly limited, and may be performed by a process known to those skilled in the art. In the present invention, the time for the standing is preferably 10min. In the invention, the adsorption of the molybdenum trioxide composite material can reach the balance by standing.
In the present invention, the secondary mixing is preferably performed under stirring. The stirring speed and time are not particularly limited in the present invention, and may be performed as is well known to those skilled in the art.
In the invention, the temperature of the catalytic degradation is preferably 20-45 ℃, and more preferably 25-40 ℃; the time is preferably 30-35 ℃; the time is preferably 10 to 30min, more preferably 12 to 28min, and still more preferably 15 to 25min.
In the present invention, the catalytic degradation is preferably carried out under stirring conditions; the rotation speed of the stirring is not particularly limited in the present invention, and those known to those skilled in the art can be used.
In the present invention, during the catalytic degradation, the mixed system is preferably sampled, and then the concentration of the organic pollutants in the sample is detected by using an ultraviolet-visible spectrophotometer. The sampling and detection process is not particularly limited in the present invention and may be performed in a manner well known to those skilled in the art.
According to the invention, the Co is adopted to dope the molybdenum trioxide, so that the catalytic activity of the composite material can be further improved; meanwhile, as Co is doped in the crystal lattice of molybdenum trioxide, the dissolution of Co can be reduced and secondary pollution can be prevented in the actual application process.
In the invention, the molybdenum trioxide composite material is adopted to activate persulfate, SO that hydroxyl free radicals (OH) and sulfate free radicals (SO) can be generated simultaneously 4 - A) and singlet oxygen: ( 1 O 2 ) And further the redox capability of the system is greatly improved, therefore forThe organic pollutants have higher degradation efficiency. Meanwhile, the molybdenum trioxide composite material obtained by the invention belongs to a solid catalyst, is convenient to separate from wastewater and recycle.
For further illustration of the present invention, the following detailed description of the molybdenum trioxide composite material and the preparation method and application thereof are provided in conjunction with the drawings and examples, which should not be construed as limiting the scope of the present invention.
Example 1
Mixing 6.18g of ammonium molybdate tetrahydrate and 0.024g of cobalt chloride hexahydrate, placing the mixture in a muffle furnace, heating to 500 ℃ at the heating rate of 5 ℃/min in the air atmosphere, calcining, and keeping the temperature for 4 hours; and after the calcination is finished, naturally cooling and grinding to obtain the molybdenum trioxide composite material.
Example 2
Mixing 6.18g of ammonium molybdate tetrahydrate and 0.060g of cobalt chloride hexahydrate, placing the mixture in a muffle furnace, heating to 500 ℃ at the heating rate of 5 ℃/min in the air atmosphere, calcining, and keeping the temperature for 4 hours; and after the calcination is finished, naturally cooling and grinding to obtain the molybdenum trioxide composite material.
Example 3
Mixing 6.18g of ammonium molybdate tetrahydrate and 0.119g of cobalt chloride hexahydrate, placing the mixture in a muffle furnace, heating to 500 ℃ at a heating rate of 5 ℃/min in an air atmosphere, calcining, and keeping the temperature for 4 hours; and after the calcination is finished, naturally cooling and grinding to obtain the molybdenum trioxide composite material.
Example 4
Mixing 6.18g of ammonium molybdate tetrahydrate and 0.179g of cobalt chloride hexahydrate, placing the mixture in a muffle furnace, heating to 500 ℃ at a heating rate of 5 ℃/min in an air atmosphere, calcining, and keeping the temperature for 4 hours; and after the calcination is finished, naturally cooling and grinding to obtain the molybdenum trioxide composite material.
Example 5
Mixing 6.18g of ammonium molybdate tetrahydrate and 0.119g of cobalt chloride hexahydrate, placing the mixture in a muffle furnace, heating to 400 ℃ at a heating rate of 5 ℃/min in an air atmosphere, calcining, and keeping the temperature for 4 hours; and after the calcination is finished, naturally cooling and grinding to obtain the molybdenum trioxide composite material.
Example 6
Mixing 6.18g of ammonium molybdate tetrahydrate and 0.119g of cobalt chloride hexahydrate, placing the mixture in a muffle furnace, heating to 450 ℃ at a heating rate of 5 ℃/min in an air atmosphere, calcining, and keeping the temperature for 4 hours; and after the calcination is finished, naturally cooling and grinding to obtain the molybdenum trioxide composite material.
Example 7
Mixing 6.18g of ammonium molybdate tetrahydrate and 0.119g of cobalt chloride hexahydrate, placing the mixture in a muffle furnace, heating to 550 ℃ at a heating rate of 5 ℃/min in an air atmosphere, calcining, and keeping the temperature for 4 hours; and after the calcination is finished, naturally cooling and grinding to obtain the molybdenum trioxide composite material.
Example 8
Mixing 6.18g of ammonium molybdate tetrahydrate and 0.119g of cobalt chloride hexahydrate, placing the mixture in a muffle furnace, heating to 450 ℃ at a heating rate of 5 ℃/min in an air atmosphere, calcining, and keeping the temperature for 2 hours; and after the calcination is finished, naturally cooling and grinding to obtain the molybdenum trioxide composite material.
Example 9
Mixing 6.18g of ammonium molybdate tetrahydrate and 0.119g of cobalt chloride hexahydrate, placing the mixture in a muffle furnace, heating to 450 ℃ at a heating rate of 5 ℃/min in an air atmosphere, calcining, and keeping the temperature for 10 hours; and after the calcination is finished, naturally cooling and grinding to obtain the molybdenum trioxide composite material.
Example 10
Mixing 6.18g of ammonium molybdate tetrahydrate and 0.119g of cobalt chloride hexahydrate, placing the mixture in a muffle furnace, heating to 450 ℃ at a heating rate of 5 ℃/min in an air atmosphere, calcining, and keeping the temperature for 20 hours; and after the calcination, naturally cooling and grinding to obtain the molybdenum trioxide composite material.
Example 11
Mixing 6.18g of ammonium molybdate tetrahydrate and 0.119g of cobalt chloride hexahydrate, placing the mixture in a muffle furnace, heating to 450 ℃ at a heating rate of 5 ℃/min in an air atmosphere, calcining, and keeping the temperature for 30 hours; and after the calcination is finished, naturally cooling and grinding to obtain the molybdenum trioxide composite material.
Example 12
Mixing 6.18g of ammonium molybdate tetrahydrate and 0.119g of cobalt chloride hexahydrate, placing the mixture in a muffle furnace, heating to 450 ℃ at a heating rate of 5 ℃/min in an air atmosphere, calcining, and keeping the temperature for 40 hours; and after the calcination is finished, naturally cooling and grinding to obtain the molybdenum trioxide composite material.
Application example 1
Mixing 10mg of the molybdenum trioxide composite material obtained in example 1 with 50mL of a bisphenol A aqueous solution (pH value is 4.04) with the concentration of 20mg/L, standing for 10min, and obtaining a mixed solution after adsorption equilibrium; adding 17mg of potassium monopersulfate composite salt (PMS) into the mixed solution, stirring at 30 ℃ for catalytic degradation, sampling every five minutes in the catalytic degradation process, and measuring the concentration of bisphenol A in a sample by adopting an ultraviolet-visible light photometer. The test results are shown in FIG. 6 (in example 1/PMS).
Application example 2
Mixing 10mg of the molybdenum trioxide composite material obtained in the example 2 with 50mL of a bisphenol A aqueous solution (pH value is 4.04) with the concentration of 20mg/L, standing for 10min, and obtaining a mixed solution after adsorption equilibrium; adding 17mg of potassium hydrogen peroxymonosulfate composite salt (PMS) into the mixed solution, stirring at 30 ℃ for catalytic degradation, sampling every five minutes in the catalytic degradation process, and measuring the concentration of bisphenol A in a sample by adopting an ultraviolet-visible light photometer. The test results are shown in FIG. 6 (expressed as example 2/PMS).
Application example 3
Mixing 10mg of the molybdenum trioxide composite material obtained in the example 3 with 50mL of a bisphenol A aqueous solution (pH value is 4.04) with the concentration of 20mg/L, standing for 10min, and obtaining a mixed solution after adsorption equilibrium; adding 17mg of potassium hydrogen peroxymonosulfate composite salt (PMS) into the mixed solution, stirring at 30 ℃ for catalytic degradation, sampling every five minutes in the catalytic degradation process, and measuring the concentration of bisphenol A in a sample by adopting an ultraviolet-visible light photometer. The test results are shown in FIG. 6 (expressed as example 3/PMS).
Application example 4
Mixing 10mg of the molybdenum trioxide composite material obtained in the example 4 with 50mL of a bisphenol A aqueous solution (pH value is 4.04) with the concentration of 20mg/L, standing for 10min, and obtaining a mixed solution after adsorption equilibrium; adding 17mg of potassium hydrogen peroxymonosulfate composite salt (PMS) into the mixed solution, stirring at 30 ℃ for catalytic degradation, sampling every five minutes in the catalytic degradation process, and measuring the concentration of bisphenol A in a sample by adopting an ultraviolet-visible light photometer. The test results are shown in FIG. 6 (expressed as example 4/PMS).
Application example 5
Mixing 10mg of the molybdenum trioxide composite material obtained in the example 5 with 50mL of a bisphenol A aqueous solution (pH value is 4.04) with the concentration of 20mg/L, standing for 10min, and obtaining a mixed solution after adsorption equilibrium; adding 17mg of potassium hydrogen peroxymonosulfate composite salt (PMS) into the mixed solution, stirring at 30 ℃ for catalytic degradation, sampling every five minutes in the catalytic degradation process, and measuring the concentration of bisphenol A in a sample by adopting an ultraviolet-visible light photometer. The test results are shown in FIG. 7 (expressed as example 5/PMS).
Application example 6
Mixing 10mg of the molybdenum trioxide composite material obtained in example 6 with 50mL of a bisphenol A aqueous solution (pH value of 4.04) with a concentration of 20mg/L, standing for 10min, and obtaining a mixed solution after adsorption equilibrium; adding 17mg of potassium monopersulfate composite salt (PMS) into the mixed solution, stirring at 30 ℃ for catalytic degradation, sampling every five minutes in the catalytic degradation process, and measuring the concentration of bisphenol A in a sample by adopting an ultraviolet-visible light photometer. The test results are shown in FIG. 7 (expressed as example 6/PMS).
Application example 7
Mixing 10mg of the molybdenum trioxide composite material obtained in example 7 with 50mL of a bisphenol A aqueous solution (pH value of 4.04) with a concentration of 20mg/L, standing for 10min, and obtaining a mixed solution after adsorption equilibrium; adding 17mg of potassium monopersulfate composite salt (PMS) into the mixed solution, stirring at 30 ℃ for catalytic degradation, sampling every five minutes in the catalytic degradation process, and measuring the concentration of bisphenol A in a sample by adopting an ultraviolet-visible light photometer. The test results are shown in FIG. 7 (expressed as example 7/PMS).
Application example 8
Mixing 10mg of the molybdenum trioxide composite material obtained in example 8 with 50mL of a bisphenol A aqueous solution (pH value of 4.04) with a concentration of 20mg/L, standing for 10min, and obtaining a mixed solution after adsorption equilibrium; adding 17mg of potassium hydrogen peroxymonosulfate composite salt (PMS) into the mixed solution, stirring at 30 ℃ for catalytic degradation, sampling every five minutes in the catalytic degradation process, and measuring the concentration of bisphenol A in a sample by adopting an ultraviolet-visible light photometer. The test results are shown in FIG. 8 (expressed as example 8/PMS).
Application example 9
Mixing 10mg of the molybdenum trioxide composite material obtained in example 9 with 50mL of a bisphenol A aqueous solution (pH value of 4.04) with a concentration of 20mg/L, standing for 10min, and obtaining a mixed solution after adsorption equilibrium; adding 17mg of potassium monopersulfate composite salt (PMS) into the mixed solution, stirring at 30 ℃ for catalytic degradation, sampling every five minutes in the catalytic degradation process, and measuring the concentration of bisphenol A in a sample by adopting an ultraviolet-visible light photometer. The test results are shown in FIG. 8 (in example 9/PMS).
Application example 10
Mixing 10mg of the molybdenum trioxide composite material obtained in example 10 with 50mL of a bisphenol A aqueous solution (pH value of 4.04) with a concentration of 20mg/L, standing for 10min, and obtaining a mixed solution after adsorption equilibrium; adding 17mg of potassium hydrogen peroxymonosulfate composite salt (PMS) into the mixed solution, stirring at 30 ℃ for catalytic degradation, sampling every five minutes in the catalytic degradation process, and measuring the concentration of bisphenol A in a sample by adopting an ultraviolet-visible light photometer. The test results are shown in FIG. 8 (expressed as example 10/PMS).
Application example 11
Mixing 10mg of the molybdenum trioxide composite material obtained in example 11 with 50mL of a bisphenol A aqueous solution (pH 4.04) having a concentration of 20mg/L, standing for 10min, and obtaining a mixed solution after adsorption equilibrium; adding 17mg of potassium monopersulfate composite salt (PMS) into the mixed solution, stirring at 30 ℃ for catalytic degradation, sampling every five minutes in the catalytic degradation process, and measuring the concentration of bisphenol A in a sample by adopting an ultraviolet-visible light photometer. The test results are shown in FIG. 8 (expressed as example 11/PMS).
Application example 12
Mixing 10mg of the molybdenum trioxide composite material obtained in example 12 with 50mL of a bisphenol A aqueous solution (pH 4.04) with a concentration of 20mg/L, standing for 10min, and obtaining a mixed solution after adsorption equilibrium; adding 17mg of potassium monopersulfate composite salt (PMS) into the mixed solution, stirring at 30 ℃ for catalytic degradation, sampling every five minutes in the catalytic degradation process, and measuring the concentration of bisphenol A in a sample by adopting an ultraviolet-visible light photometer. The test results are shown in FIG. 8 (example 12/PMS).
As can be seen from FIGS. 6 to 8, the molybdenum trioxide composite material provided by the invention has a good degradation effect on bisphenol A.
Application example 13
Ciprofloxacin, dichlorophen, p-nitrophenol, rhodamine B, atractyl, aureomycin, terramycin and tetracycline are used as organic pollutants, and the catalytic degradation effect of the activated peroxymonosulfate of the molybdenum trioxide composite material on the organic pollutants is detected;
mixing 10mg of the molybdenum trioxide composite material obtained in the embodiment 2 with 50mL of 20mg/L aqueous solution containing the organic pollutants, standing for 10min, and obtaining a mixed solution after adsorption equilibrium; adding 17mg of potassium monopersulfate composite salt (PMS) into the mixed solution, stirring at 30 ℃ for catalytic degradation, sampling every five minutes in the catalytic degradation process, and testing the concentration of organic pollutants in the sample by adopting liquid chromatography. The degradation rate test result at 30min is shown in fig. 13;
as can be seen from FIG. 13, the molybdenum trioxide composite material provided by the invention has a good catalytic degradation effect on ciprofloxacin, dichlorophenol, p-nitrophenol, rhodamine B, atrazine, aureomycin, oxytetracycline and tetracycline through activation of peroxymonosulfate.
Comparative example 1
Putting 6.24g of ammonium molybdate tetrahydrate in a muffle furnace, heating to 450 ℃ at the heating rate of 5 ℃/min in the air atmosphere, calcining, and keeping the temperature for 40 hours; and after the calcination is finished, naturally cooling and grinding to obtain the molybdenum trioxide.
Comparative example 2
Mixing 10mg of the molybdenum trioxide composite material obtained in the comparative example 1 with 50mL of bisphenol A aqueous solution (the pH value is 4.04) with the concentration of 20mg/L, standing for 10min, and obtaining a mixed solution after adsorption equilibrium; adding 17mg of potassium monopersulfate composite salt (PMS) into the mixed solution, stirring at 30 ℃ for catalytic degradation, sampling every five minutes in the catalytic degradation process, and measuring the concentration of bisphenol A in a sample by adopting an ultraviolet-visible light photometer. The test results are shown in FIG. 6 (expressed for 1/PMS).
Comparative example 3
50mL of a 20mg/L bisphenol A aqueous solution (pH value of 4.1) and 17mg of potassium monopersulfate complex salt (PMS) were mixed, and the mixture was stirred at 30 ℃ to perform catalytic degradation, during which sampling was performed at five-minute intervals, and the concentration of bisphenol A in the sample was measured using an ultraviolet-visible light photometer. The test results are shown in fig. 6 (denoted PMS).
Performance test
Test example 1
Scanning electron microscope test is performed on the molybdenum trioxide composite material obtained in example 12, an SEM image is shown in fig. 1, and it can be seen from fig. 1 that the molybdenum trioxide composite material provided by the present invention has a nanoprism structure, and the aspect ratio is 2 to 2.5:1.
test example 2
When the molybdenum trioxide composite material obtained in example 12 was subjected to an X-ray diffraction test, XRD is shown in fig. 2, and it can be seen from fig. 2 that the crystal structure of the molybdenum trioxide composite material provided by the present invention is a hexagonal phase crystal structure.
Test example 3
An X-ray photoelectron spectroscopy test was performed on the molybdenum trioxide composite material obtained in example 12, and an XPS chart is shown in fig. 3, and the molybdenum trioxide composite material provided by the present invention contains characteristic peaks of three elements, i.e., co, O, and Mo.
Test example 4
The activity of catalyzing potassium Peroxymonosulfate (PMS) by using the molybdenum trioxide composite material obtained in example 12 through an electron paramagnetic resonance spectrometerThe detection of the substance is carried out by using 5, 5-dimethyl-1-pyrroline-N-oxide (DMPO) as the hydroxyl radical (OH. Cndot.) and the sulfate radical (SO) 4 - The free radical trapping agent adopts 2-ethyl-2-hydroxymethyl-1, 3-propanediol (TMP) as a detection reagent to detect singlet oxygen (A) 1 O 2 ) The electron paramagnetic resonance spectrum obtained is shown in fig. 4 and 5;
wherein, FIG. 4 shows hydroxyl radical (OH. Cndot.) and sulfate radical (SO) 4 - Graph, as can be seen from FIG. 4, the molybdenum trioxide composite material provided by the invention activates peroxymonosulfate to produce DMPO-OH and DMPO-SO 4 - Addition of the molybdenum trioxide to the molybdenum trioxide composite material, indicating that the molybdenum trioxide composite material can generate OH and SO by activating peroxymonosulfate 4 - ·；
FIG. 5 shows singlet oxygen ( 1 O 2 ) The spectrum of (A) shows that the molybdenum trioxide composite material can generate singlet oxygen by activating peroxymonosulfate (see figure 5) 1 O 2 )。
Test example 5
The pH of the wastewater containing organic contaminants was tested for its effect on molybdenum trioxide composite activated peroxymonosulfate by catalytic degradation in the manner of application example 12, wherein the pH of the aqueous bisphenol a solution was 3.04, 4.04, 4.97, 6.1, 7.3, 8.0, and 9.0 (adjusted to the desired pH by adding 0.1mmol/L hydrochloric acid solution or 0.1mmol/L NaOH solution), and the test results are shown in fig. 9;
as can be seen from FIG. 9, the molybdenum trioxide composite material provided by the invention can be used for catalyzing and activating peroxymonosulfate to degrade organic pollutants in water well in acidic, neutral or alkaline environments, and has good stability.
Test example 6
Testing the influence of the temperature of catalytic degradation (namely, the ambient temperature) on the activation of peroxymonosulfate by the molybdenum trioxide composite material, and carrying out catalytic degradation according to the mode of the application example 12, wherein the temperatures of catalytic degradation are respectively 21.4 ℃, 25 ℃,30 ℃, 35 ℃, 40 ℃ and 45 ℃, and the test result is shown in fig. 10;
as can be seen from FIG. 10, the molybdenum trioxide composite material provided by the invention has wide adaptability to environmental temperature, and can degrade most organic pollutants in a short time under different temperature conditions.
Test example 7
The influence of the usage amount of the molybdenum trioxide composite material on the organic degradation performance is tested.
The test method comprises the following steps:
respectively mixing 2mg, 5mg, 10mg, 20mg, 40mg and 60mg of the molybdenum trioxide composite material obtained in example 12 with 50mL of bisphenol A aqueous solution with the concentration of 40mg/L, standing for 10min, and obtaining a mixed solution after adsorption equilibrium; 65mg of potassium hydrogen peroxymonosulfate composite salt (PMS) is added into the mixed solution, and the mixed solution is stirred at 30 ℃ for catalytic degradation, wherein the test result is shown in figure 11;
as can be seen from fig. 11, the molybdenum trioxide composite material provided by the invention can activate PMS to degrade organic pollutants, has a good degradation effect under different catalyst usage amounts, and has a correspondingly improved degradation effect with the increase of the catalyst usage amount; when the concentration of the catalyst exceeds 0.8g/L, the degradation effect is slowly improved. The result shows that the molybdenum trioxide composite material provided by the invention can meet the requirements of different catalyst dosage.
Test example 8
The influence of different addition amounts of peroxymonosulfate on the organic degradability of the molybdenum trioxide composite material provided by the invention is tested.
The test method comprises the following steps:
mixing 10mg of the molybdenum trioxide composite material obtained in the example 12 with 50mL of a bisphenol A aqueous solution with the concentration of 20mg/L, standing for 10min, and obtaining a mixed solution after adsorption equilibrium; adding potassium peroxymonosulfate composite salt (PMS) into the mixed solution (wherein the addition amounts of the potassium peroxymonosulfate composite salt are 5mg, 10mg, 20mg, 50mg and 100mg respectively), stirring at 30 ℃ for catalytic degradation, and performing five groups of verification tests; the test results are shown in fig. 12;
as can be seen from FIG. 12, the degradation effect increases with the amount of peroxymonosulfate.
Test example 9
Testing the recycling performance of the molybdenum trioxide composite material provided by the invention;
the test method comprises the following steps:
mixing 10mg of the molybdenum trioxide composite material obtained in example 12 with 50mL of a 10mg/L bisphenol A aqueous solution (pH value is adjusted to 3 by adding an appropriate amount of 0.1mmol/L hydrochloric acid solution), standing for 10min, and obtaining a mixed solution after adsorption equilibrium; adding 8mg of potassium peroxymonosulfate composite salt (PMS) into the mixed solution, stirring at 30 ℃ for catalytic degradation, sampling after 30min, measuring the concentration of bisphenol A in a sample by adopting an ultraviolet-visible light photometer, and calculating the degradation rate;
after the catalytic degradation is finished, removing the reaction solution by filtration, and collecting the residual solid; washing the obtained solid by adopting a large amount of ultrapure water, drying at 60-80 ℃ for 4-5 h, and carrying out catalytic degradation reaction by taking the dried solid as a catalyst according to the mode; repeating the process for 6 times, and detecting the recycling performance of the molybdenum trioxide composite material;
the test result is shown in fig. 14, and it can be seen from fig. 14 that after 6 times of recycling, the molybdenum trioxide composite material provided by the invention can still completely degrade bisphenol a within 30 minutes, which indicates that the molybdenum trioxide composite material provided by the invention has excellent recycling performance.
Although the present invention has been described in detail with reference to the above embodiments, it is only a part of the embodiments of the present invention, not all of the embodiments, and other embodiments can be obtained without inventive step according to the embodiments, and all of the embodiments belong to the protection scope of the present invention.

Claims (10)

1. A molybdenum trioxide composite characterized by comprising a molybdenum trioxide matrix and cobalt doped in the molybdenum trioxide matrix;
the molybdenum trioxide composite material has a perovskite-like structure.
2. The molybdenum trioxide composite of claim 1, wherein the cobalt is doped in a percentage of 1-20%.
3. The method for preparing the molybdenum trioxide composite material as claimed in claim 1 or 2, which comprises the steps of:
and mixing a molybdenum source and a cobalt source, and calcining to obtain the molybdenum trioxide composite material.
4. The preparation method according to claim 3, wherein the molybdenum source comprises one or more of molybdenum pentachloride, molybdenum acetate, molybdenum acetylacetonate, ammonium molybdate, ammonium dimolybdate and ammonium heptamolybdate;
the cobalt source comprises one or more of cobalt nitrate, cobalt chloride, cobalt oxide and cobalt acetate;
the molar ratio of the molybdenum source to the cobalt source is 100:0.5 to 1.5.
5. The method according to claim 4, wherein the temperature of the calcination is 400 to 550 ℃; the heating rate of heating to the calcining temperature is less than or equal to 10 ℃/min; the heat preservation time is 2-40 h.
6. Use of the molybdenum trioxide composite material according to claim 1 or 2 or the molybdenum trioxide composite material prepared by the preparation method according to any one of claims 3 to 5 for degrading organic pollutants.
7. The application according to claim 6, characterized in that it comprises the following steps:
mixing the molybdenum trioxide composite material, persulfate and waste water containing organic pollutants, and carrying out catalytic degradation.
8. Use according to claim 7, wherein the persulphate comprises a peroxymonosulphate and/or peroxydisulphate.
9. The use according to claim 7, wherein the concentration of the organic contaminant in the wastewater containing the organic contaminant is 10 to 50mg/L;
the mass ratio of the organic pollutants to the persulfate in the wastewater containing the organic pollutants is 1:5 to 100;
the mass ratio of the organic pollutants in the wastewater containing the organic pollutants to the molybdenum trioxide composite material is 1:1 to 30.
10. Use according to claim 9, wherein the catalytic degradation is carried out at a temperature of 20 to 45 ℃ for a time of 10 to 30min.
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