Water body purification material and preparation method thereof

Abstract

The preparation method is characterized by comprising the following steps: S1, adding potassium permanganate and manganese sulfate into deionized water / glycerol, and stirring to obtain a mixed solution; polyvinylpyrrolidone is added into the mixed solution; the preparation method comprises the following steps: uniformly mixing the raw materials, putting the mixture into a microwave reactor, reacting at 165-180 DEG C for 0.5-2 hours to obtain a precipitate, and alternately washing the obtained precipitate with deionized water and ethanol for 3 times; s2, adding the precipitate obtained in the step S1 into a tert-butyl alcohol solvent, continuously adding cerous nitrate into the solvent, uniformly mixing, putting the mixture into a microwave reactor, reacting at 160-180 DEG C for 0.5-2 hours to obtain a precipitate, and continuously alternately washing the obtained precipitate with deionized water and ethanol for 3 times; the MnO2-CeO2 photocatalytic material is obtained.

Description

Technical Field

[0001] The invention belongs to the technical field of sewage purification, and specifically relates to a water purification composite material and a preparation method thereof and application in water purification. Background Art

[0002] With the acceleration of the global industrialization process, there are more and more organic matter in the water, which leads to the deterioration of water environment quality, endangers the survival of aquatic organisms, and threatens the health of humans and animals. The methods for removing organic matter in industry include adsorption, biochemical method and coagulation sedimentation method. The photocatalytic degradation method started in 1972 and is a new sewage treatment method developed in the past 30 years. Since the late 1970s, there have been a lot of reports on the research of using photocatalytic degradation to treat various pollutants in wastewater. For example, CN115350702A discloses a high-efficiency photocatalyst mullite-type bismuth manganate and its preparation method and application. The preparation method comprises: adding a manganese source and a bismuth source to ethylene glycol and stirring to obtain a mixed solution, adding polyvinyl pyrrolidone and urea and mixing, then adding deionized water and mixing, placing in an autoclave and sealing it at 175-200 ° C for 10-15h, collecting the precipitate and washing and drying it. The present invention provides a process for preparing mullite-type bismuth manganate by a one-step hydrothermal method, which is simple in process and has no toxic emissions; the prepared Bi2Mn4O 10 The morphology is spherical, the purity is high, and the particle size is between 50-85nm; the prepared Bi2Mn4O 10 When added to the untreated sewage containing organic pollutants, the degradation rate can reach up to 88% after 3 hours of light degradation, and the degradation rate drops to less than 10% after being recycled for 4 times, which is suitable for industrial application. CN114345391A discloses a carbon nitride / graphene / manganese dioxide bifunctional catalyst and its preparation method and application, the preparation comprising: step 1, calcining and acidifying a carbon nitride precursor to obtain protonated carbon nitride; step 2, preparing manganese dioxide and then using a silane coupling agent to react to obtain amination manganese dioxide; step 3, filtering the graphene dispersion and the amination manganese dioxide dispersion and then hydrothermally reacting to obtain a graphene / manganese dioxide material; then filtering the protonated carbon nitride dispersion towards the graphene layer, and reacting to obtain the carbon nitride / graphene / manganese dioxide bifunctional catalyst. CN112264107A discloses a visible light catalytic material and a preparation method and application thereof. The preparation method comprises the following steps: (1) dissolving isopropyl titanate in ethyl acetoacetate to obtain liquid A, dissolving nickel stearate in another ethyl acetoacetate solution to obtain liquid B, mixing liquid A and liquid B to obtain a mixed solution, and heating and stirring; (2) dissolving β-cyclodextrin in a mixed solvent consisting of water and isopropanol to obtain a β-cyclodextrin solution; (3) adding the mixed solution in step (1) to the β-cyclodextrin solution and performing a hydrothermal reaction; (4) washing the reactants and vacuum drying to obtain cyclodextrin-induced NiO-doped TiO2-x Visible light catalytic materials. Photocatalytic degradation can degrade a variety of organic matter and mineralize them into carbon dioxide, water or less toxic organic matter. It can completely destroy organic matter and achieve the requirements of harmless treatment. It is gradually becoming an important method for controlling organic pollution. How to prepare photocatalytic materials with stable structure, simple process and strong degradation ability is the core and focus of current photocatalytic technology research. Summary of the invention

[0003] The technical problem to be solved by the present invention is to overcome the deficiencies of the prior art and provide a composite photocatalyst with a stable structure, a simple preparation process and a strong ability to degrade organic pollutants.

[0004] A method for preparing a water purification material comprises the following steps:

[0005] S1: adding potassium permanganate and manganese sulfate to deionized water / glycerol and stirring to obtain a mixed solution; adding polyvinyl pyrrolidone to the mixed solution; after mixing evenly, placing it in a microwave reactor, reacting at 165-180° C. for 0.5-2 h to obtain a precipitate, and washing the obtained precipitate with deionized water and ethanol alternately for 3 times;

[0006] S2: adding the precipitate obtained in step S1 to tert-butanol solvent, adding cerium nitrate to the solvent, mixing evenly, placing it in a microwave reactor, reacting at 160°C-180°C for 0.5-2h to obtain a precipitate, and then washing the obtained precipitate with deionized water and ethanol alternately for 3 times; obtaining a MnO2-CeO2 composite material.

[0007] During the experiment, by controlling the proportion of solvents in the microwave reaction and adding polyvinyl pyrrolidone, highly dispersed nano-spherical β-MnO2 was synthesized, and its particle size could be uniformly controlled between 50-100 nanometers. Using tert-butyl alcohol as a solvent, microwave reaction controlled the production of CeO2 micro-nano sheets coated on the outside of nano-spherical manganese dioxide.

[0008] Preferably, the concentration ratio of potassium permanganate:manganese sulfate is 2:3;

[0009] Preferably, the volume ratio of deionized water to glycerol is (1-2):(5-8);

[0010] Preferably, the MnO2-CeO2 composite material is a flower-like structure in which CeO2 nanosheets are coated on the periphery of 50-100nm MnO2;

[0011] Preferably, the mass ratio of potassium permanganate:polyvinyl pyrrolidone is 1:(0.2-0.4);

[0012] The technical effects achieved by this application are:

[0013] In the experiment of this application, CeO2 micro-nano sheets are coated on the outside of nano-spherical manganese dioxide. This structure can fully improve the utilization rate of light energy. The combination of the two improves the degradation efficiency of the material for many organic pollutants. The heterojunction structure of MnO2-CeO2 is beneficial to improving the electron-hole pair separation efficiency of the material. BRIEF DESCRIPTION OF THE DRAWINGS

[0014] The drawings constituting a part of this application are used to provide a further understanding of the present invention. The illustrative embodiments of the present invention and their descriptions are used to explain the present invention and do not constitute improper limitations on the present invention.

[0015] Figure 1 The XRD pattern of MnO2 in this application shows that its crystal structure is β-MnO2;

[0016] Figure 2 This is a scanning electron microscope image of MnO2-CeO2 of the present application. DETAILED DESCRIPTION

[0017] The present invention is further described in detail below through specific examples. The following examples are only illustrative and not restrictive, and the protection scope of the present invention cannot be limited thereto.

[0018] Example 1

[0019] S1: adding 2mmol of potassium permanganate and 3mmol of manganese sulfate to 100ml of deionized water / glycerol and stirring to obtain a mixed solution, wherein the volume of deionized water is 20ml and the volume of glycerol is 80ml; adding polyvinyl pyrrolidone to the mixed solution; wherein the mass ratio of potassium permanganate to polyvinyl pyrrolidone is 1:0.3; after mixing evenly, placing it in a microwave reactor (power is 1000w), reacting at 165°C for 0.5h to obtain a precipitate, and washing the obtained precipitate with deionized water and ethanol alternately;

[0020] S2: Add the precipitate obtained in step S1 to 100 ml of tert-butanol solvent, continue to add 1 mmol of cerium nitrate to the solvent, mix well, place it in a microwave reactor (power is 1000 w), react at 160° C. for 0.5 h to obtain a precipitate, and continue to wash the obtained precipitate with deionized water and ethanol alternately for 3 times; obtain a MnO2-CeO2 composite material.

[0021] Example 2

[0022] S1: adding 2mmol of potassium permanganate and 3mmol of manganese sulfate to 100ml of deionized water / glycerol and stirring to obtain a mixed solution, wherein the volume of deionized water is 20ml and the volume of glycerol is 100ml; adding polyvinyl pyrrolidone to the mixed solution; wherein the mass ratio of potassium permanganate to polyvinyl pyrrolidone is 1:0.3; after mixing evenly, placing it in a microwave reactor (power of 800w), reacting at 165°C for 1h to obtain a precipitate, and washing the obtained precipitate with deionized water and ethanol alternately;

[0023] S2: Add the precipitate obtained in step S1 to 100 ml of tert-butanol solvent, continue to add 1 mmol of cerium nitrate to the solvent, mix well, place it in a microwave reactor (power is 800 w), react at 160° C. for 1 hour to obtain a precipitate, and continue to wash the obtained precipitate with deionized water and ethanol alternately for 3 times; obtain a MnO2-CeO2 composite material.

[0024] Example 3

[0025] S1: adding 2mmol of potassium permanganate and 3mmol of manganese sulfate to 100ml of deionized water / glycerol and stirring to obtain a mixed solution, wherein the volume of deionized water is 20ml and the volume of glycerol is 100ml; adding polyvinyl pyrrolidone to the mixed solution; wherein the mass ratio of potassium permanganate to polyvinyl pyrrolidone is 1:0.4; after mixing evenly, placing it in a microwave reactor (power is 1000w), reacting at 165°C for 40min to obtain a precipitate, and washing the obtained precipitate with deionized water and ethanol alternately;

[0026] S2: Add the precipitate obtained in step S1 to 80 ml of tert-butanol solvent, continue to add 1 mmol of cerium nitrate to the solvent, mix well, place it in a microwave reactor (power is 1000 w), react at 160° C. for 1 hour to obtain a precipitate, and continue to wash the obtained precipitate with deionized water and ethanol alternately for 3 times; obtain a MnO2-CeO2 composite material.

[0027] Comparative Example 1

[0028] S1: Add 2mmol potassium permanganate and 3mmol manganese sulfate to 100ml deionized water / glycerol, stir to obtain a mixed solution, wherein the volume of deionized water is 20ml, and the volume of glycerol is 80ml; add polyvinyl pyrrolidone to the mixed solution; wherein the mass ratio of potassium permanganate:polyvinyl pyrrolidone is 1:0.3; after mixing evenly, place it in a microwave reactor (power is 1000w), react at 165°C for 0.5h to obtain a precipitate, and wash the obtained precipitate alternately with deionized water and ethanol to obtain MnO2.

[0029] Comparative Example 2

[0030] 1 mmol of cerium nitrate was added to 100 ml of tert-butanol solvent, and after mixing evenly, it was placed in a microwave reactor (power of 1000 w), and reacted at 160° C. for 0.5 h to obtain a precipitate. The precipitate was then washed alternately with deionized water and ethanol for 3 times to obtain CeO2.

[0031] Comparative Example 3

[0032] S1: adding 2mmol of potassium permanganate and 3mmol of manganese sulfate to 100ml of deionized water / glycerol and stirring to obtain a mixed solution, wherein the volume of deionized water is 80ml and the volume of glycerol is 20ml; adding polyvinyl pyrrolidone to the mixed solution; wherein the mass ratio of potassium permanganate to polyvinyl pyrrolidone is 1:0.3; after mixing evenly, placing it in a microwave reactor (power of 1000w), reacting at 165°C for 0.5h to obtain a precipitate, and washing the obtained precipitate with deionized water and ethanol alternately;

[0033] S2: Add the precipitate obtained in step S1 to 100 ml of tert-butanol solvent, continue to add 1 mmol of cerium nitrate to the solvent, mix well, place it in a microwave reactor (power is 1000 w), react at 160° C. for 0.5 h to obtain a precipitate, and continue to wash the obtained precipitate with deionized water and ethanol alternately for 3 times; obtain a MnO2-CeO2 composite material.

[0034] Comparative Example 4

[0035] S1: 2 mmol of potassium permanganate and 3 mmol of manganese sulfate were added to 100 ml of deionized water / glycerol and stirred to obtain a mixed solution, wherein the volume of deionized water was 20 ml and the volume of glycerol was 80 ml; after being mixed evenly, it was placed in a microwave reactor (power was 1000 w) and reacted at 165° C. for 0.5 h to obtain a precipitate, and the obtained precipitate was washed alternately with deionized water and ethanol;

[0036] S2: Add the precipitate obtained in step S1 to 100 ml of tert-butanol solvent, continue to add 1 mmol of cerium nitrate to the solvent, mix well, place it in a microwave reactor (power is 1000 w), react at 160° C. for 0.5 h to obtain a precipitate, and continue to wash the obtained precipitate with deionized water and ethanol alternately for 3 times; obtain a MnO2-CeO2 composite material.

[0037] 50 mL of organic polluted water containing rhodamine B, tetracycline and methyl orange at a concentration of 50 ppm was prepared respectively, and 30 mg of the material prepared in Examples 1-4 or Comparative Examples 1-4 was added to the simulated sewage. After stirring and mixing for 30 minutes, a 400 W xenon lamp was turned on for photocatalytic reaction. After 3 hours, the removal rates of rhodamine B, tetracycline and methyl orange by the materials prepared in different Examples / Comparative Examples were tested. The results can be seen in the table below.

[0038]

[0039]

[0040] In the above, different catalysts in Examples 1-4 and Comparative Examples 1-4 were used to degrade organic matter. The MnO2-CeO2 in Examples 1-4 showed better catalytic performance overall.

[0041] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions and improvements made within the spirit and principles of the present invention should be included in the protection scope of the present invention.

Claims

1. A method for preparing a water purification material, characterized in that: S1: adding potassium permanganate and manganese sulfate to deionized water / glycerol and stirring to obtain a mixed solution; adding polyvinyl pyrrolidone to the mixed solution; after mixing evenly, placing it in a microwave reactor, reacting at 165-180° C. for 0.5-2 h to obtain a precipitate, and washing the obtained precipitate with deionized water and ethanol alternately for 3 times; S2: adding the precipitate obtained in step S1 to tert-butanol solvent, adding cerium nitrate to the solvent, mixing evenly, placing it in a microwave reactor, reacting at 160°C-180°C for 0.5-2h to obtain a precipitate, and then washing the obtained precipitate with deionized water and ethanol alternately for 3 times; obtaining a MnO2-CeO2 composite material.

2. According to the method for preparing a water purification material according to claim 1, the concentration ratio of potassium permanganate:manganese sulfate is 2:

3.

3. According to the method for preparing a water purification material as described in claim 1, the volume ratio of deionized water to glycerol is (1-2): (5-8).

4. According to the method for preparing a water purification material according to claim 1, the MnO2-CeO2 composite material is a flower-like structure in which CeO2 nanosheets are coated on the periphery of MnO2 nanospheres.

5. The method for preparing a water purification material according to claim 1, wherein the mass ratio of potassium permanganate to polyvinyl pyrrolidone is 1:(0.2-0.4).

6. A water purification material, characterized in that: The invention is prepared by the method according to any one of claims 1 to 5.

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