CN110841649B - Preparation method of copper-cerium bimetal Fenton catalytic material, prepared catalytic material and application thereof - Google Patents

Preparation method of copper-cerium bimetal Fenton catalytic material, prepared catalytic material and application thereof Download PDF

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CN110841649B
CN110841649B CN201910985936.7A CN201910985936A CN110841649B CN 110841649 B CN110841649 B CN 110841649B CN 201910985936 A CN201910985936 A CN 201910985936A CN 110841649 B CN110841649 B CN 110841649B
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catalytic material
cerium
copper
fenton
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CN110841649A (en
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方战强
张暖钦
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South China Normal 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
    • 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
    • B01J23/83—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 rare earths or actinides
    • 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
    • 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
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C02F2101/38—Organic compounds containing nitrogen

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Abstract

The invention discloses a preparation method of a copper-cerium bimetal Fenton catalytic material, the prepared catalytic material and application thereof, wherein the preparation method comprises the following steps: s1, preparation of a precursor: adding a precipitator into a solution containing copper ions and cerium ions, adjusting the pH value of the system to be alkaline, adding a glucose solution, and continuously stirring to obtain a blue precursor; s2, hydrothermal reaction: and (3) placing the precursor prepared in the step (S1) in a hydrothermal reaction kettle, carrying out solid-liquid separation on the product after the reaction is finished, and collecting the solid phase part to obtain the catalytic material. The catalytic material provided by the scheme of the invention has high catalytic activity, and can rapidly catalyze Fenton reaction to degrade organic pollutants in water, especially for azole antifungal drugs.

Description

Preparation method of copper-cerium bimetal Fenton catalytic material, prepared catalytic material and application thereof
Technical Field
The invention relates to the technical field of Fenton-like catalysts, in particular to a preparation method of a copper-cerium bimetal Fenton-like catalytic material, the prepared catalytic material and application thereof.
Background
With the increasing clinical application of immunosuppressants, the incidence rate of fungal infection is also rising year by year, and azole drugs (including imidazole and triazole derivatives) are a class of antifungal drugs with better prospects and are widely applied clinically. In addition, such drugs are also widely used in agricultural production and personal care products. However, since such drugs are difficult to degrade, they have been recognized as a new class of environmental pollutants in recent years. However, as most conventional wastewater treatment plants do not consider how to remove such emerging pollutants, large amounts of the azole antifungal drugs, which are not degraded, may be discharged directly into the environmental water body. Research has shown that such pollutants, when introduced into the environment, have a negative impact on both aquatic life and plants. In addition, its widespread presence in the environment can lead to the emergence of drug-resistant fungal species and may pose potential health risks to humans. Therefore, it is of great significance to develop a high-efficiency removal technology for such contaminants.
The fenton oxidation process is considered to be one of the most effective methods for removing nonbiodegradable organic contaminants from water. Under the excitation of catalyst, the hydrogen peroxide can generate hydroxyl radical with strong oxidizing property, and no difference existsRespectively oxidizing various organic pollutants. The principle of the Fenton oxidation process comprises a homogeneous Fenton method and a heterogeneous Fenton method, and the homogeneous Fenton method has the defects that the pH application range is narrow (generally between 3 and 5), the catalyst is difficult to recover, a large amount of iron mud is generated, secondary pollution is caused, and the like, so that the research in recent years is mainly turned to the heterogeneous Fenton method. Among many transition metals, copper is the most abundant element in earth resources, and the standard reduction potential of Cu (II)/Cu (I) is low, so that Fenton reaction is more easily triggered, and therefore, the copper-based Fenton catalyst is considered to have better industrial application prospect. However, the heterogeneous fenton-like catalysts in the prior art generally have the problems of low activity, slow catalytic reaction rate and the like, so that the application range of the heterogeneous fenton-like catalysts is greatly limited. Therefore, there is a need for improvement of the conventional heterogeneous Fenton-like materials, and the chemical properties of the surface of the heterogeneous Fenton-like catalyst strongly influence H 2 O 2 Dissociation and OH related reactions, therefore, improving catalyst surface properties is considered a new strategy to increase the efficiency of contaminant degradation. Therefore, the development of the modified copper-based heterogeneous Fenton-like material is expected to solve the problem of high-efficiency removal of azole antifungal drugs.
Disclosure of Invention
The present invention is directed to solving at least one of the problems of the prior art. Therefore, the invention provides a preparation method of the copper-cerium bimetal Fenton catalytic material, and the prepared catalytic material can realize the efficient removal of azole antifungal drugs.
The invention also provides a catalytic material prepared by the method.
The invention also provides an application of the catalytic material.
The preparation method according to the embodiment of the first aspect of the invention comprises the following steps:
s1, preparing a precursor: adding a precipitator into an aqueous solution containing copper ions and cerium ions, adjusting the pH value of the system to be alkaline, adding a glucose solution, and continuously stirring to obtain a blue precursor;
s2, hydrothermal reaction: and (3) placing the precursor prepared in the step (S1) in a hydrothermal reaction kettle, carrying out solid-liquid separation on the product after the reaction is finished, and collecting the solid phase part to obtain the catalytic material.
The preparation method provided by the embodiment of the invention has at least the following beneficial effects: the preparation raw materials of the scheme of the invention have low price, are green and pollution-free, have mild reaction conditions, can react under normal pressure, do not need to use a surfactant and other organic solvents, reduce the manufacturing cost, and reduce the pollution generated in the preparation process; the glucose is used for partially reducing metal ions, the operation is simple and convenient, and the prepared catalytic material has high catalytic activity and can rapidly catalyze the Fenton reaction to degrade organic pollutants in water.
According to some embodiments of the invention, the molar ratio of cerium ions in the copper ions and cerium ions is less than 15%.
According to some embodiments of the invention, the molar ratio of cerium ions is between (2.5 and 10)%.
According to some embodiments of the invention, the molar proportion of cerium ions is between (2.5 and 7.5)%.
According to some embodiments of the present invention, the total concentration of the copper ion and the cerium ion in the reaction system is (0.01 to 0.2) mol/L, and the concentration of the glucose is (3 to 60) g/L.
According to some embodiments of the invention, the precipitant is an alkaline solution (which may include at least one of sodium hydroxide, potassium hydroxide, sodium carbonate, and ammonium carbonate).
According to some embodiments of the invention, the pH is 7.0 to 12.0.
According to some embodiments of the present invention, in the step S2, the temperature of the hydrothermal reaction is 100 to 150 ℃ and the reaction time is (8 to 15) hours.
According to the copper-cerium bimetal Fenton catalytic material of the embodiment of the second aspect of the invention, the catalytic material is prepared by the method.
The catalytic material according to the embodiment of the invention has at least the following beneficial effects: cerium is introduced into the surface of the copper-based material to improve the surface characteristic of the copper-based material, so that the catalytic efficiency of the copper-based material is higher.
According to a third aspect of the present invention, there is provided a method of treating wastewater, comprising the steps of: the catalytic material is put into an aqueous solution containing organic pollutants, and hydrogen peroxide is added.
According to some embodiments of the invention, after adding hydrogen peroxide, the entire system is reacted at 20 to 40 ℃.
According to some embodiments of the invention, the organic contaminant comprises at least one of an azole antifungal, a dye, an antibiotic, an endocrine disruptor, or an industrial feedstock phenol.
According to some embodiments of the invention, the organic contaminant comprises at least one of fluconazole, rhodamine B, phenol, bisphenol a, norfloxacin or tetracycline.
Additional aspects and advantages of the invention will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the invention.
Drawings
FIG. 1 is a scanning electron microscope image of the Cu-Ce bimetallic Fenton catalytic material of example 1 according to the present invention;
FIG. 2 is a scanning electron microscope image of the Cu-Ce bimetallic Fenton catalytic material of example 2 according to the present invention;
FIG. 3 is a graph showing the influence of different stoichiometric ratios of Cu-Ce bimetallic Fenton-like catalytic materials on the catalytic oxidation of Fluconazole (FLC) in the embodiment of the present invention;
FIG. 4 is a bar graph of the degradation rate of the catalytic material of example 3 of the present invention for different organic pollutants.
Detailed Description
In order to explain technical contents, achieved objects, and effects of the present invention in detail, the following description is made with reference to the accompanying drawings in combination with the embodiments.
The first embodiment of the invention is as follows: a preparation method of a copper-cerium bimetal Fenton catalytic material comprises the following steps:
1) Preparing a precursor: dispersing soluble copper salt (97.5 at%) and cerium salt (2.5 at%) in about 80ml of water, and stirring uniformly; adding 4mol/L sodium hydroxide solution, adjusting the pH value of the system to 7.0, adding 20ml 0.15g/ml glucose solution to partially reduce metal ions, and continuously stirring for 1h to obtain a blue precursor.
2) Hydrothermal reaction: placing the obtained precursor in a hydrothermal reaction kettle, and keeping the constant temperature of 100 ℃ for 15 hours; cooling to room temperature, centrifuging to obtain precipitate, washing with water for 3 times, and vacuum drying at 65 deg.C overnight to obtain the catalytic material. The material is characterized by a scanning electron microscope, and the result is shown in figure 1. As can be seen from figure 1, the microscopic morphology of the prepared material is spherical, the particle size is 300-400nm, the particle surface is uneven, and the material has a large specific surface area, many reaction active sites and strong catalytic capability.
The second embodiment of the invention is as follows: a preparation method of a copper-cerium bimetal Fenton catalytic material comprises the following steps:
1) Preparing a precursor: dispersing soluble copper salt (92.5 at%) and cerium salt (7.5 at%) in water, and stirring; adding 4mol/L sodium hydroxide solution, adjusting the pH value of the system to 12.0, adding 20ml 0.15g/ml glucose solution to partially reduce metal ions, and continuously stirring for 1h to obtain a blue precursor.
2) Hydrothermal reaction: placing the obtained precursor in a hydrothermal reaction kettle, and keeping the constant temperature of 150 ℃ for 8 hours; cooling to room temperature, centrifuging to obtain precipitate, washing with water for 3 times, and vacuum drying at 65 deg.C overnight to obtain the final product. The material is characterized by a scanning electron microscope, and the result is shown in fig. 2, and as can be seen from fig. 2, the prepared material has a spherical microstructure and a particle size of 300-400nm, and compared with the catalytic material in example 1, the surface of the material becomes rougher, possibly caused by deposition of cerium on the surface.
The third embodiment of the invention is as follows: the preparation method of the copper-cerium bimetal Fenton catalytic material is different from the first embodiment only in that: during the preparation of the precursor, soluble copper salt (95 at%) and cerium salt (5 at%).
The fourth embodiment of the invention is as follows: the preparation method of the copper-cerium bimetal Fenton catalytic material only differs from the first embodiment in that: in the precursor preparation process, soluble copper salt (90 at%) and cerium salt (10 at%).
The fifth embodiment of the invention is as follows: the preparation method of the copper-cerium bimetal Fenton catalytic material only differs from the first embodiment in that: during the preparation of the precursor, soluble copper salt (85 at%) and cerium salt (15 at%).
The first comparative example of the invention is as follows: a method for preparing a catalytic material, which is different from the first embodiment in that: during the preparation process of the precursor, no cerium salt is added.
In order to study the influence of the copper-cerium bimetal Fenton catalytic material with different stoichiometric ratios on the catalytic effect, the catalytic oxidation Fluconazole (FLC) is used as an object for verification, and the specific operation is as follows: 0.1g/L (prepared in example 1, examples 3 to 5 and comparative example 1) of the material was weighed into a conical flask containing 100ml of a 20mg/L FLC solution (pH = 5.0), and the material was first adsorbed to saturation and then 50mM H was added 2 O 2 The mixture was reacted at a temperature of 35. + -. 1 ℃ at a rate of 250r/min in a shaker and sampled for analysis at set time points.
The influence relationship diagram of the copper-cerium bimetal Fenton catalytic material with different stoichiometric ratios on catalytic oxidation of Fluconazole (FLC) is shown in fig. 3, and as can be seen from fig. 3, the catalytic activity of the catalytic material prepared in example 3 is the highest among all the materials, the removal rate of pollutants is as high as 94% after catalytic oxidation for 60min, and the removal rate is improved by nearly 20% compared with that of pure cuprous oxide. However, as the content of cerium is continuously increased, the catalytic activity of the catalytic material is reduced, and even when the molar ratio of cerium is increased to 0.15, the catalytic activity of the catalytic material is basically equivalent to or even inferior to that of pure cuprous oxide.
Similarly, the catalytic material obtained in example 2 was subjected to the above degradation experiment, and as a result, it was found that the catalytic activity (removal rate 85%) of the catalytic material obtained in example 2 was superior to that of pure cuprous oxide (removal rate 70%), but had a certain decline compared to that of the catalytic material obtained in example 3.
In addition, the catalytic material prepared in example 3 is applied to the sewage treatment polluted by dye (rhodamine B), industrial raw material phenol, antibiotics (norfloxacin and tetracycline) and endocrine disrupter (bisphenol a), and the result shows that the catalytic material also has good degradation effect, the specific removal rate is shown in fig. 4, and as can be seen from fig. 4, the removal rate of the catalytic material of the scheme of the invention to other organic pollutants reaches more than 90%.
The final concentration of the metal ions in the reaction system in the above examples and comparative examples is 0.1mol/L, and the soluble metal salts in the above examples and comparative examples can be chloride salts, sulfate salts and the like, which have no influence on the performance of the prepared catalyst.
The invention utilizes green and environment-friendly glucose as a reducing agent, adopts a medium-temperature hydrothermal reduction method to prepare a cerium-doped copper-based material, and applies the cerium-doped copper-based material to the catalytic Fenton-like reaction for degrading fluconazole in water.
The atomic number percentage of "at%" in the present specification.
The above description is only an embodiment of the present invention, and not intended to limit the scope of the present invention, and all equivalent changes made by using the contents of the present specification and the drawings, or applied directly or indirectly to the related technical fields, are included in the scope of the present invention.

Claims (2)

1. The application of the copper-cerium bimetal Fenton catalytic material in catalytic oxidation of fluconazole is characterized in that the preparation method of the copper-cerium bimetal Fenton catalytic material comprises the following steps:
s1, preparing a precursor: adding a precipitator into an aqueous solution containing copper ions and cerium ions, adjusting the pH value of the system to 7.0-12.0, adding a glucose solution, and continuously stirring to obtain a blue precursor;
s2, hydrothermal reaction: putting the precursor prepared in the step S1 into a hydrothermal reaction kettle, carrying out solid-liquid separation on the product after the reaction is finished, collecting the solid phase part to obtain the catalytic material,
in the step S2, the temperature of the hydrothermal reaction is 100-150 ℃, the reaction time is (8-15) h,
in the copper ions and the cerium ions, the molar ratio of the cerium ions is between (2.5 and 7.5%),
the micro-morphology of the catalytic material is spherical, and the particle size is 300-400 nm.
2. Use according to claim 1, characterized in that: in the reaction system, the total concentration of copper ions and cerium ions is (0.01 to 0.2) mol/L, and the concentration of glucose is (3 to 60) g/L.
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