Visible light catalytic material capable of synchronously removing heavy metals and antibiotics and preparation method of visible light catalytic material

Abstract

The invention particularly relates to a visible light catalytic material for synchronously removing heavy metals and antibiotics and a preparation method. The preparation method comprises the following steps: carrying out alkalization treatment on foamy copper by using a mixed solution of alkali liquor, a persulfate solution and ammonia water to construct a nano array, soaking in a dopamine solution to generate a polydopamine film, adsorbing Fe3O4 nano particles on the surface of the nano array, and finally preparing the Fe3O4 / CuO nano array / foamy copper composite material. The one-dimensional nano array heterostructure not only enhances the absorption and utilization capability of the blocky foamy copper on visible light, but also remarkably improves the separation and migration efficiency of photogenerated charges, and the visible light catalytic adsorption material has good visible light catalytic reduction and degradation capability on Cr (VI) and antibiotics. The preparation method of the photocatalytic material is simple in process, environment-friendly, low in cost and suitable for batch production; the Fe3O4 / CuO nano array / foamy copper composite material prepared by the method belongs to a blocky material, and does not have the problems of high recovery difficulty and easiness in causing secondary pollution; the nanometer array film layer on the surface of the Fe3O4 / CuO nanometer array / foamy copper composite material is regular and ordered in structure, has good visible light catalytic reduction and degradation capacity on Cr (VI) and antibiotics, and has wide application prospects in the aspect of treating waste liquid containing heavy metal and antibiotics at the same time.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of nanomaterial preparation, and particularly relates to a preparation method of a visible light catalytic adsorption material for simultaneously removing heavy metals and antibiotics. BACKGROUND

[0002] Heavy metal pollution and antibiotic pollution in water sources have become global pollution problems that need to be solved urgently. Chromium is one of the five key heavy metal pollutants in wastewater, mainly existing in the form of Cr(III) and Cr(VI). Cr(VI) is about 100 times more toxic than Cr(III) and is not easy to degrade under natural conditions. In the past few decades, the overuse and unregulated disposal of antibiotics in the medical industry and the livestock industry and other human activities have introduced a large amount of antibiotics into the water environment, posing a major threat to human health. At present, common removal methods for Cr(VI) and antibiotics include membrane separation, adsorption, chemical precipitation, electrolysis, and photocatalytic degradation. However, most removal studies only focus on the removal effect of a single pollutant in water, and only a small number of studies report the application of adsorption in antibiotic and heavy metal combined pollution. Among them, adsorption and photocatalytic degradation are more widely used in the removal of Cr(VI) and antibiotics. However, adsorption is widely used due to its low cost and high efficiency, but adsorption only plays a fixing role, and Cr(VI) still poses a potential threat. Semiconductor-based photocatalytic technology can achieve the reduction of Cr(VI) and is considered a new green technology. Existing photocatalytic reduction can effectively reduce Cr(VI) to Cr(III), but Cr(III) may be oxidized again in the aquatic environment. Only by reducing Cr(VI) to elemental Cr can the environmental pollution problem be effectively reduced. In view of the shortcomings of the existing materials, there is an urgent need to develop a composite material that can simultaneously reduce Cr(VI) and remove antibiotics.

[0003] The water-sliding-lithium-based Bi2O2CO3 / MgAlBi-LDHs adsorption-photocatalytic composite material described in the existing patent "A composite environmental purification material and a preparation method thereof (CN 114180700 A)" synergistically degrades Cr(VI) and tetracycline TC (a typical antibiotic) under visible light excitation, making Cr(VI) be reduced to non-toxic Cr(III), further improving the removal capacity of Cr(VI) and TC. However, the hydrotalcite powder used in this preparation technology is easy to cause secondary pollution, and it is difficult to recover. In addition, Cr(III) also has certain toxicity, and there is still a threat of Cr elements to the environment.

[0004] The biochar-based CoFe2O4 / Fe2O3 composite heterojunction structure described in the prior art "Construction of CoFe2O4 / Fe2O3 S-type heterojunctions on biochar for activating peroxymonosulfate towards simultaneous removal of TC and Cr(VI) (Separation and Purification Technology 354(2025)129157)" can effectively remove Cr(VI) and TC under visible light irradiation. However, this preparation technology is still based on biomass powder raw materials, and also has the problems of difficult recovery and easy secondary pollution. It also does not solve the problem of reducing Cr(VI) to elemental Cr.

[0005] Therefore, how to prepare a reusable and easily recyclable visible light catalytic adsorption material for simultaneous removal of heavy metals and antibiotics for wastewater treatment becomes particularly important. SUMMARY

[0006] The present application aims to overcome the defects of the prior art, and the purpose is to provide a preparation method of photocatalytic adsorption material with simple process, environmental friendliness and low cost; the surface nano array film layer structure of the foam copper prepared by the method is regular and ordered, firmly combined with the substrate, and has excellent photocatalytic reduction and degradation performance.

[0007] To achieve the above purpose, the technical scheme adopted by the present application is: a preparation method of visible light catalytic adsorption material, characterized in that it comprises the following steps:

[0008] 1) : The foam copper is sequentially cleaned with ethanol and deionized water for 30 min, and then subjected to alkalization treatment in a mixed solution of lye, persulfate solution and ammonia water for 10-60 min. After taking out and rinsing with deionized water, it is dried in an oven at 50°C for 1-6 h to obtain a CuO nano array / foam copper material.

[0009] 2) : The CuO nano array / foam copper material obtained in step 1) is soaked in a dopamine solution for 1-12 h, and then soaked in a Fe3O4 dispersion liquid for 0.5-12 h. After taking out and rinsing with deionized water, it is dried in an oven at 50°C for 1-6 h to obtain a Fe3O4 / CuO nano array / foam copper composite material.

[0010] The alkali liquor is one or both of sodium hydroxide and potassium hydroxide solution, and the concentration of the alkali liquor is 0.05-3 mol / L; the persulfate solution is one or both of ammonium persulfate, sodium persulfate and potassium persulfate solution, and the concentration of the persulfate solution is 0.01-1 mol / L; and the volume fraction of the ammonia water is 1-5 vol.%.

[0011] The dopamine solution is mixed with Tris-HCl 10-40 mM buffer and 1-4 mg / mL hydrochloric acid dopamine at pH 8-8.5.

[0012] The concentration of the Fe3O4 dispersion liquid is 0.001-1 g / L, the particle size of Fe3O4 in the dispersion liquid is 10-150 nm, and the temperature of the dispersion liquid is-5-50 DEG C.

[0013] Compared with the prior art, the application has the following advantages:

[0014] 1) The preparation process of the application can be carried out at room temperature, and the production process is simple, the energy consumption is small, the required instrument equipment investment is small, the raw material price is low, the utilization rate is high, there is no environmental pollution, and it is suitable for batch production.

[0015] 2) The foamed copper used in the application belongs to block material, and there is no problem of difficult recovery and easy secondary pollution.

[0016] 3) The Fe3O4 / CuO nanometer array / foamed copper composite material prepared by the application has a nanometer array structure on the surface, which significantly increases the specific surface area of the foamed copper material and enhances the absorption and utilization of visible light;

[0017] 4) The Fe3O4 / CuO nanometer array / foamed copper composite material prepared by the application has a Fe3O4 / CuO heterojunction structure, which not only further enhances the absorption and utilization of visible light, but also reduces the recombination of photoelectron hole pairs at the interface, promotes the separation and migration of carriers;

[0018] 5) The Fe3O4 / CuO nanometer array / foamed copper composite material prepared by the application has a reduction rate of Cr of more than 95% and a decomposition rate of antibiotic of more than 99% under visible light irradiation; through analysis, after visible light irradiation for 2h, the proportion of elemental Cr in the Cr(VI) reduction product prepared by the application is more than 50%, which significantly reduces the threat of Cr(VI) and Cr(III) to the environment. The results show that the Fe3O4 / CuO nanometer array / foamed copper composite material prepared by the application has good photocatalytic reduction and degradation capacity for Cr(VI) and antibiotics.

[0019] Therefore, the preparation method of the photocatalytic material is simple, environment-friendly and low in cost, and is suitable for batch production; the Fe3O4 / CuO nanometer array / foamed copper composite material prepared by the method belongs to a blocky material, and does not have problems of great recovery difficulty and easy secondary pollution; the surface nanometer array film layer structure of the Fe3O4 / CuO nanometer array / foamed copper composite material is regular and orderly, has good visible light catalytic reduction and degradation capacity on Cr(VI) and antibiotics, and has a wide application prospect in treatment of waste liquid containing heavy metals and antibiotics at the same time. BRIEF DESCRIPTION OF DRAWINGS

[0020] In order to more clearly illustrate the specific embodiments of the present application or the technical solutions in the prior art, the drawings needed to be used in the specific embodiments or the prior art description will be briefly introduced as follows. Obviously, the drawings in the following description are some embodiments of the present application, and other drawings can also be obtained by those skilled in the art without creative labor on the basis of these drawings.

[0021] Figure 1 is an EDS spectrum (a) of the sample prepared in Example 2, and the inserted graph is an FESEM graph of the sample, Fe element face scanning graph (b), and Cu element face scanning graph (c);

[0022] Figure 2 is a VSM graph of the Fe3O4 nanoparticles used in Example 1;

[0023] Figure 3 is a removal rate curve graph of the samples prepared in Example 1 and Example 3 on 30mg / L Cr(VI);

[0024] Figure 4 is a removal rate curve graph of the samples prepared in Example 1 and Example 3 in 50mg / L Cr(VI) solution under light and no light conditions. EMBODIMENT

[0025] The present application will be further described below in combination with the specific embodiments, but is not limited to the scope of protection.

[0026] To avoid repetition, the technical parameters involved in the present specific embodiments are described as follows, and will not be repeated in the examples:

[0027] The dopamine solution is mixed by Tris-HCl 10-40mM buffer and 1-4mg / mL hydrochloric acid dopamine with pH of 8-8.5.

[0028] Example 1

[0029] A visible light photocatalytic material for simultaneously removing heavy metals and antibiotics. 1): Copper foam is ultrasonically cleaned sequentially with ethanol and deionized water for 30 min, then alkalized with a mixed solution of alkali, persulfate, and ammonia for 40-60 min. After rinsing with deionized water, it is dried in an oven at 50℃ for 1-6 h to obtain CuO nanoarray / copper foam material. 2): The CuO nanoarray / copper foam material obtained in step 1) is immersed in dopamine solution for 1-5 h, then immersed in Fe3O4 dispersion for 9-12 h. After rinsing with deionized water, it is dried in an oven at 50℃ for 1-6 h to obtain Fe3O4 / CuO nanoarray / copper foam composite material.

[0030] In the mixed solution of alkali, persulfate solution, and ammonia, the alkali is 0.05-0.5 mol / L sodium hydroxide; the persulfate solution is 0.5-1 mol / L ammonium persulfate; and the ammonia has a volume fraction of 1-5 vol%.

[0031] The concentration of the Fe3O4 dispersion is 0.001-0.01 g / L, the particle size of Fe3O4 in the dispersion is 10-50 nm, and the temperature of the dispersion is -5 to 20 °C.

[0032] Depend on Figure 2 and 3 It can be seen that the magnetic attraction proves that the prepared Fe3O4 nanoparticles have strong magnetism, and the material can be separated from the solution by magnetic separation, which provides convenient conditions for the recycling of the material.

[0033] Example 2

[0034] A visible light catalytic material for the simultaneous removal of heavy metals and antibiotics. 1): Copper foam was ultrasonically cleaned with ethanol and deionized water for 30 min in sequence, then alkalized with a mixed solution of alkali, persulfate solution and ammonia for 20-40 min. After rinsing with deionized water, it was dried in an oven at 50℃ for 1-6 h to obtain CuO nanoarray / copper foam material.

[0035] 2): The CuO nanoarray / copper foam material obtained in step 1) is soaked in dopamine solution for 1-12 hours, then soaked in Fe3O4 dispersion for 3-9 hours. After being taken out and rinsed with deionized water, it is dried in an oven at 50°C for 1-6 hours to obtain Fe3O4 / CuO nanoarray / copper foam composite material.

[0036] The mixture of alkaline solution, persulfate solution, and ammonia solution comprises: an alkaline solution of 0.5-1.5 mol / L sodium hydroxide and potassium hydroxide; a persulfate solution of 0.1-0.5 mol / L sodium persulfate and potassium persulfate; and ammonia solution with a volume fraction of 1-5 vol%.

[0037] The concentration of the Fe3O4 dispersion is 0.01-0.1 g / L, the particle size of the Fe3O4 in the dispersion is 50-100 nm, and the temperature of the dispersion is 10-30℃.

[0038] Example 3

[0039] A visible light catalytic material for the simultaneous removal of heavy metals and antibiotics. 1): Copper foam was ultrasonically cleaned with ethanol and deionized water for 30 min in sequence, then alkalized with a mixed solution of alkali, persulfate solution and ammonia for 10-20 min. After rinsing with deionized water, it was dried in an oven at 50℃ for 1-6 h to obtain CuO nanoarray / copper foam material.

[0040] 2): The CuO nanoarray / copper foam material obtained in step 1) is soaked in dopamine solution for 1-12 hours, then soaked in Fe3O4 dispersion for 0.5-3 hours. After being taken out and rinsed with deionized water, it is dried in an oven at 50°C for 1-6 hours to obtain Fe3O4 / CuO nanoarray / copper foam composite material.

[0041] In the mixed solution of alkali, persulfate solution, and ammonia, the alkali is 1.5-3 mol / L potassium hydroxide; the persulfate solution is a mixed solution of 0.01-0.1 mol / L ammonium persulfate and potassium persulfate; and the ammonia has a volume fraction of 1-5 vol%.

[0042] The concentration of the Fe3O4 dispersion is 0.1-1 g / L, the particle size of Fe3O4 in the dispersion is 100-150 nm, and the temperature of the dispersion is -5 to 20 °C.

[0043] Depend on Figure 1 It can be seen that the Fe3O4 nanoparticles have a uniform particle size, with a diameter of about 120 nm. The spherical nanoparticles have regular shapes, smooth surfaces, and are evenly dispersed.

[0044] Compared with the prior art, the present invention has the following advantages:

[0045] 1) The preparation process of this invention can be carried out at room temperature, the production process is simple and energy consumption is low; the required investment in instruments and equipment is small; the raw materials used are inexpensive, have high utilization rate, and do not cause environmental pollution, making them suitable for mass production.

[0046] 2) The foamed copper used in this invention is a block material, which does not have the problems of difficult recycling or easy secondary pollution.

[0047] 3) The Fe3O4 / CuO nanoarray / copper foam composite material prepared by this invention has a nanoarray structure on its surface that significantly increases the specific surface area of ​​the copper foam material and enhances the absorption and utilization of visible light.

[0048] 4) The Fe3O4 / CuO nanoarray / foamed copper composite material prepared by this invention not only further enhances the absorption and utilization of visible light through its Fe3O4 / CuO heterojunction structure, but also reduces the recombination of photogenerated electron-hole pairs at the interface, thus promoting the separation and migration of charge carriers.

[0049] 5) The Fe3O4 / CuO nanoarray / copper foam composite material prepared in this invention achieves a Cr reduction rate of over 95% and an antibiotic decomposition rate of over 99% under visible light irradiation. Analysis shows that after 2 hours of visible light irradiation, the reduced Cr(VI) products of the prepared photocatalytic material contain over 50% elemental Cr, significantly reducing the environmental threat posed by Cr(VI) and Cr(III). These results demonstrate that the prepared Fe3O4 / CuO nanoarray / copper foam composite material exhibits excellent photocatalytic reduction and degradation capabilities for Cr(VI) and antibiotics.

[0050] Therefore, the photocatalytic material preparation method of this invention is simple, environmentally friendly, and low-cost, and suitable for mass production. The Fe3O4 / CuO nanoarray / copper foam composite material prepared by this method is a bulk material, which does not have the problems of difficult recycling and easy secondary pollution. The nanoarray film structure on the surface of the Fe3O4 / CuO nanoarray / copper foam composite material is regular and orderly, and has good visible light photocatalytic reduction and degradation ability for Cr(VI) and antibiotics. It has broad application prospects in the treatment of waste liquid containing both heavy metals and antibiotics.

Claims

1. A visible light catalytic material for simultaneous removal of heavy metals and antibiotics, characterized in that The material composition structure is Fe3O4 / CuO nanometer array / foam copper.

2. The method for producing a visible light catalytic material according to claim 1, wherein The method comprises the following steps: 1) : The foam copper is sequentially cleaned with ethanol and deionized water for 30 min, and then subjected to alkalization treatment in a mixed solution of lye, persulfate solution and ammonia water for 10-60 min, taken out, washed with deionized water, and dried in an oven at 50 DEG C for 1-6 h to obtain a CuO nanometer array / foam copper material. 2) : The CuO nanometer array / foam copper material obtained in step 1) is soaked in a dopamine solution for 1-12 h, and then soaked in a Fe3O4 dispersion liquid for 0.5-12 h, taken out, washed with deionized water, and dried in an oven at 50 DEG C for 1-6 h to obtain a Fe3O4 / CuO nanometer array / foam copper composite material.

3. The production method according to claim 2, characterized by The lye is one or both of sodium hydroxide and potassium hydroxide solution, and the lye concentration is 0.05-3 mol / L; the persulfate solution is one or both of ammonium persulfate, sodium persulfate and potassium persulfate solution, and the persulfate solution concentration is 0.01-1 mol / L; and the ammonia water volume fraction is 1-5 vol%.

4. The production method according to claim 2, characterized by The dopamine solution is mixed with Tris-HCl 10-40 mM buffer and 1-4 mg / mL hydrochloric acid dopamine at pH 8-8.

5.

5. The production method according to claim 2, wherein The Fe3O4 dispersion liquid has a concentration of 0.001-1 g / L, the Fe3O4 particle size in the dispersion liquid is 10-150 nm, and the dispersion liquid temperature is-5-50 DEG C.

6. The production method according to claim 2, wherein The Fe3O4 / CuO nanometer array / foam copper composite adsorption material is prepared according to the preparation method in any one of claims 1-4.

7. The visible light catalytic material according to claim 1 has wide application prospects in treating waste liquid containing heavy metals and antibiotics.

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