Preparation method and application of a modified diatomite loaded organic photovoltaic material photocatalyst for removing manganese, copper, cadmium and lead

Abstract

This invention discloses a method for preparing and applying a modified diatomaceous earth-supported organic photovoltaic photocatalyst for removing manganese, copper, cadmium, and lead. The preparation method includes the following steps: A) mixing diatomaceous earth with deionized water; B) adding epichlorohydrin (ECH) as a crosslinking agent to the mixture in step A; C) adding an amino-rich material to the mixture in step B in an ice bath environment and stirring for 1 hour; D) filtering, washing, and drying the solution after the reaction in step C to obtain the modified diatomaceous earth material; E) mixing the organic photovoltaic material with chloroform; F) uniformly coating the mixture in step E onto the modified diatomaceous earth material and drying to obtain the modified diatomaceous earth-supported organic photovoltaic photocatalyst for removing manganese, copper, cadmium, and lead. The photocatalyst obtained by this invention can achieve efficient and rapid removal of Mn(II), Cu(II), Cd(II), and Pb(II) simultaneously, and is reusable, solving the problems of photocatalyst loading process and recycling, and providing a truly green, environmentally friendly, and pollution-free treatment method for heavy metal removal.

Description

Technical Field

[0001] This invention relates to the field of functional materials preparation technology, specifically a method for preparing and applying a photocatalyst for modified diatomaceous earth-supported organic photovoltaic materials to remove manganese, copper, cadmium, and lead. Background Technology

[0002] Water is the source of life, and water resources play a vital role in human production and development. However, this important resource has been severely polluted by industrial development in recent decades. In particular, both surface water and groundwater have been contaminated with heavy metals to varying degrees. Industries such as electroplating, ceramics, glass, mining, and battery manufacturing are considered major sources of heavy metals such as lead in waterways. High levels of industrialization lead to higher levels of lead and other heavy metals (such as cadmium, manganese, and copper) in local waterways, posing a significant threat to public health.

[0003] Common methods for treating heavy metals include chemical precipitation, membrane filtration, ion exchange, alum coagulation, and adsorption. These are the most frequently used methods for treating and disposing of water containing metals. Among them, adsorption is considered a particularly economical and effective method for removing low concentrations of heavy metals.

[0004] Diatomaceous earth (SiO2·nH2O) is a soft, lightweight rock primarily composed of silica microfossils of aquatic single-celled algae, varying in shape and size. It is highly porous, containing up to 80-90% voids in its structure. It is used in many industrial applications, such as as a filter medium for various beverages, inorganic and organic chemicals, and as an adsorbent for pet waste and oil spills. Despite its unique physical and chemical properties, its application as an adsorbent in wastewater treatment has not been widely adopted. This is because raw diatomaceous earth often contains metal oxides and organic components that clog its pores and occupy its active sites, leading to a decrease in specific surface area and reduced adsorption capacity.

[0005] There are also studies on the adsorption of heavy metal ions using diatomaceous earth, but most of them explore the influence of external factors on the adsorption effect, and do not study how to reduce the toxicity of the heavy metal ions themselves, and they cannot be recycled.

[0006] Therefore, there is a need to develop a photocatalyst preparation method that is highly biosafe, recyclable, and capable of secondary purification of water while removing Mn(II), Cu(II), Cd(II) and Pb(II). Summary of the Invention

[0007] The technical problem to be solved by this invention is to provide a method for preparing a photocatalyst for removing manganese, copper, cadmium and lead from a modified diatomaceous earth-supported organic photovoltaic material and its application. The photocatalyst obtained by this method can achieve efficient removal of Mn(II), Cu(II), Cd(II) and Pb(II) simultaneously, and can be reused. This solves the problems of photocatalyst loading process and recycling, and provides a truly green, environmentally friendly and pollution-free treatment method for the removal of manganese, copper, cadmium and lead ions.

[0008] The present invention solves the above-mentioned technical problems by means of the following technical solution:

[0009] This invention discloses a method for preparing a photocatalyst for removing manganese, copper, cadmium, and lead from a modified diatomaceous earth-supported organic photovoltaic material, comprising the following steps:

[0010] Step A: Mix diatomaceous earth with deionized water to obtain mixed solution A, wherein the ratio of diatomaceous earth to deionized water is: 5g diatomaceous earth and 50ml deionized water.

[0011] Step B: Add crosslinking agent epichlorohydrin (ECH) to mixed solution A, and stir mechanically to obtain mixed solution B. The amount of epichlorohydrin added is 2-8% of the weight of mixed solution A.

[0012] Step C: In an ice bath environment, amino-rich material is slowly added dropwise to mixed solution B and then mechanically stirred for 1 hour to obtain mixed solution C. The amount of amino-rich material added is 5-10% of the weight of mixed solution B.

[0013] Step D: After filtering, washing, and drying the mixed solution C, the modified diatomaceous earth material is obtained.

[0014] Step E: Mix the organic photovoltaic material with chloroform in the following weight ratio: 0.005-0.015g organic photovoltaic material: 10-15ml chloroform, to obtain an organic photocatalyst mixed solution; the organic photovoltaic material is P3HT:PCBM.

[0015] Step F: The organic photocatalyst mixed solution obtained in step E is uniformly coated onto the modified diatomaceous earth material and dried for 24 hours to obtain a modified diatomaceous earth-supported organic photovoltaic material photocatalyst for removing manganese, copper, cadmium and lead.

[0016] In step B of this invention, the mechanical stirring rate is 200-600 r / min, and the stirring time is 15 min.

[0017] In step C of this invention, the mechanical stirring rate is 300-500 r / min.

[0018] In step C of this invention, the water temperature of the ice bath environment is 2-10℃.

[0019] In step C of this invention, the amino-rich material is polyaniline or polyethyleneamine.

[0020] In step D of this invention, the filtration is performed by collecting diatomaceous earth using filter paper with a diameter of 0.1 to 1 μm; the washing is performed by rinsing the collected diatomaceous earth 3 to 5 times with deionized water; and the drying is performed by drying in an oven at a temperature of 60°C for 24 hours.

[0021] In step F of this invention, the amount of the organic photocatalyst mixed solution and the modified diatomaceous earth material is in a weight ratio of 1:5000 to 10000.

[0022] In step E of this invention, the P3HT:PCBM is a mixture of P3HT and PCBM in a weight ratio of 1:1.

[0023] Application of the photocatalyst prepared by the method of this invention: The photocatalyst is used for the removal of heavy metal ions such as manganese, copper, cadmium and lead from wastewater.

[0024] The present invention has the following beneficial effects:

[0025] (1) The photocatalyst obtained by the method of the present invention can achieve efficient removal of Mn(II), Cu(II), Cd(II) and Pb(II) by modified diatomaceous earth material at the same time, and the removal effect is very good, with a removal rate of up to 100%, and it can be reused.

[0026] (2) Compared with inorganic catalysts, the photocatalyst obtained by the method of the present invention has unique advantages in wastewater purification: rapid and effective exciton dissociation, tunable energy level, wide absorption spectrum and excellent chemical stability, etc., which enable it to generate a large number of superoxide radicals and electrons with strong reducing properties in water, which can reduce Mn(II), Cu(II), Cd(II) and Pb(II) to metal elements or sparingly soluble salts, and can also completely remove them through electrostatic adsorption and complexation reaction of modified diatomaceous earth materials.

[0027] (3) The matrix material used in this invention is diatomaceous earth, a natural product, which has many excellent properties such as hydrophilicity, greenness, high porosity and large specific surface area. Furthermore, organic optoelectronic materials can be loaded onto the matrix material for repeated use and are biodegradable, thus achieving true green friendliness and environmental pollution-free, which is in line with the national key research and development plan for low-carbon, environmentally friendly and green "renewable energy technology" development concept. Attached Figure Description

[0028] Figure 1 This is a test chart showing the stability of the photocatalyst for degrading manganese, copper, cadmium, and lead ions obtained in Example 1 of this invention. Detailed Implementation

[0029] The technical solution of the present invention will be further described below with reference to specific embodiments, but this does not limit the present invention.

[0030] Example 1

[0031] The present invention discloses a method for preparing a photocatalyst for removing manganese, copper, cadmium, and lead from modified diatomaceous earth-supported organic photovoltaic materials, which is carried out according to the following steps:

[0032] A. Put 5g of diatomaceous earth into a high-speed blender and grind it for 45 seconds;

[0033] B. Add 5g of crushed diatomaceous earth to 50ml of deionized water to obtain a mixed solution;

[0034] C. Add 4.4g of crosslinking agent epichlorohydrin (ECH) to 55g of the mixed solution from step B, and mechanically stir at 300r / min for 15min;

[0035] D. In an ice bath environment (water temperature 2℃), add 5.94g of polyethyleneamine to 59.4g of the mixture obtained in step C.

[0036] In the solution, the reaction was carried out with mechanical stirring at 500 r / min for 1 h;

[0037] E. The mixed solution obtained in step D is filtered (i.e., diatomaceous earth is collected using filter paper with a diameter of 0.1 to 1 μm), washed 5 times with deionized water, and dried in an oven at 60°C for 24 hours to obtain modified diatomaceous earth material.

[0038] F. Mix 0.01 g of P3HT:PCBM with 13 ml of chloroform to obtain a mixed solution of organic photocatalyst, wherein...

[0039] P3HT:PCBM is obtained by mixing P3HT and PCBM in a weight ratio of 1:1.

[0040] G. The organic photocatalyst mixture obtained in step F is uniformly coated onto the modified diatomaceous earth material and dried for 24 hours to obtain a modified diatomaceous earth-supported organic photovoltaic material photocatalyst for removing manganese, copper, cadmium and lead, wherein the weight ratio of the organic photocatalyst mixture to the modified diatomaceous earth material is 1:7500.

[0041] The photocatalyst prepared in this example was used for the adsorption and degradation of manganese, copper, cadmium and lead in wastewater. The removal rate was 100% in 15 minutes. It achieved efficient removal of Mn(II), Cu(II), Cd(II) and Pb(II) simultaneously, and the removal effect was very good.

[0042] Example 2

[0043] The present invention discloses a method for preparing a photocatalyst for removing manganese, copper, cadmium, and lead from modified diatomaceous earth-supported organic photovoltaic materials, which is carried out according to the following steps:

[0044] A. Put 5g of diatomaceous earth into a high-speed blender and grind it for 45 seconds;

[0045] B. Add 5g of crushed diatomaceous earth to 50ml of deionized water to obtain a mixed solution;

[0046] C. Add 1.1g of crosslinking agent epichlorohydrin (ECH) to 55g of the mixed solution from step B, and mechanically stir at 400r / min for 15min;

[0047] D. In an ice bath environment (water temperature 6℃), add 2.805g of polyaniline to 56.1g of the mixed solution obtained in step C.

[0048] In the liquid, the mixture was mechanically stirred at 300 r / min for 1 h.

[0049] E. The mixed solution obtained in step D is filtered (i.e., the diatomaceous earth material is collected using filter paper with a diameter of 0.1 to 1 μm), washed three times with deionized water, and dried in an oven at 60°C for 24 hours to obtain the modified diatomaceous earth material.

[0050] F. Mix 0.005 g of P3HT:PCBM with 10 ml of chloroform to obtain a mixed solution of organic photocatalyst, wherein...

[0051] P3HT:PCBM is obtained by mixing P3HT and PCBM in a weight ratio of 1:1.

[0052] G. The organic photocatalyst mixture obtained in step F is uniformly coated onto the modified diatomaceous earth material and dried for 24 hours to obtain a modified diatomaceous earth-supported organic photovoltaic material photocatalyst for removing manganese, copper, cadmium and lead, wherein the weight ratio of the organic photocatalyst mixture to the modified diatomaceous earth material is 1:5000.

[0053] The photocatalyst prepared in this example was used for the adsorption and degradation photocatalysis of manganese, copper, cadmium and lead. The removal rate was 99.8% after 15 minutes. It achieved efficient removal of Mn(II), Cu(II), Cd(II) and Pb(II) at the same time, and the removal effect was very good.

[0054] Example 3

[0055] The present invention discloses a method for preparing a photocatalyst for removing manganese, copper, cadmium, and lead from modified diatomaceous earth-supported organic photovoltaic materials, which is carried out according to the following steps:

[0056] A. Put 5g of diatomaceous earth into a high-speed blender and grind it for 45 seconds;

[0057] B. Add 5g of crushed diatomaceous earth to 50ml of deionized water to obtain a mixed solution;

[0058] C. Add 2.75g of crosslinking agent epichlorohydrin (ECH) to 55g of the mixed solution from step B, and mechanically stir at 500r / min for 15min;

[0059] D. In an ice bath environment (water temperature 10℃), add 4.33g of polyethyleneamine to 57.75g of the mixture obtained in step C.

[0060] The mixture was stirred mechanically at 400 r / min for 1 h in the combined solution;

[0061] E. The mixed solution from step D is filtered (i.e., the diatomaceous earth material is collected using filter paper with a diameter of 0.1 to 1 μm), washed four times with deionized water, and dried in an oven at 60°C for 24 hours to obtain the modified diatomaceous earth material.

[0062] F. Mix 0.005 g of P3HT:PCBM with 15 ml of chloroform to obtain a mixed solution of organic photocatalyst, wherein...

[0063] P3HT:PCBM is obtained by mixing P3HT and PCBM in a weight ratio of 1:1.

[0064] G. The organic photocatalyst mixture obtained in step F is uniformly coated onto the modified diatomaceous earth material and dried for 24 hours to obtain a modified diatomaceous earth-supported organic photovoltaic material photocatalyst for removing manganese, copper, cadmium and lead, wherein the weight ratio of the organic photocatalyst mixture to the modified diatomaceous earth material is 1:10000.

[0065] The photocatalyst prepared in this example was used for the adsorption and degradation of manganese, copper, cadmium and lead in wastewater. The removal rate was 100% in 15 minutes. It achieved efficient removal of Mn(II), Cu(II), Cd(II) and Pb(II) simultaneously, and the removal effect was very good.

Claims

1. A method for preparing a photocatalyst for removing manganese, copper, cadmium, and lead from a modified diatomaceous earth-supported organic photovoltaic material, characterized in that... The following steps are included: Step A: Mix diatomaceous earth with deionized water to obtain mixed solution A, wherein the ratio of diatomaceous earth to deionized water is: 5 g diatomaceous earth and 50 mL deionized water. Step B involves adding epichlorohydrin, a crosslinking agent, to mixed solution A and mechanically stirring to obtain mixed solution B. The amount of epichlorohydrin added is 2-8% of the weight of mixed solution A. Step C: In an ice bath environment, amino-rich material is slowly added dropwise to mixed solution B, followed by mechanical stirring and reaction for 1 hour to obtain mixed solution C. The amount of amino-rich material added is 5-10% of the weight of mixed solution B; the amino-rich material is polyaniline or polyethyleneamine. Step D: After filtering, washing, and drying the mixed solution C, the modified diatomaceous earth material is obtained. Step E: Mix the organic photovoltaic material with chloroform in the following weight ratio: 0.005-0.015 g of organic photovoltaic material: 10-15 mL of chloroform to obtain a mixed solution of organic photocatalyst; the organic photovoltaic material is P3HT:PCBM. Step F: The organic photocatalyst mixed solution obtained in step E is uniformly coated onto the modified diatomaceous earth material and dried for 24 hours to obtain a modified diatomaceous earth-supported organic photovoltaic material photocatalyst for removing manganese, copper, cadmium and lead.

2. The method for preparing a photocatalyst for removing manganese, copper, cadmium, and lead from a modified diatomaceous earth-supported organic photovoltaic material according to claim 1, characterized in that, In step B, the mechanical stirring rate is 200-600 r / min, and the stirring time is 15 min.

3. The method for preparing a photocatalyst for removing manganese, copper, cadmium, and lead from a modified diatomaceous earth-supported organic photovoltaic material according to claim 1, characterized in that, In step C, the mechanical stirring rate is 300–500 r / min.

4. The method for preparing a photocatalyst for removing manganese, copper, cadmium, and lead from modified diatomaceous earth-supported organic photovoltaic materials according to claim 1, characterized in that, In step C, the water temperature of the ice bath environment is 2–10 °C.

5. The method for preparing a photocatalyst for removing manganese, copper, cadmium, and lead from a modified diatomaceous earth-supported organic photovoltaic material according to claim 1, characterized in that, In step D, the filtration is performed by collecting diatomaceous earth using filter paper with a diameter of 0.1–1 μm; the washing is performed by rinsing the collected diatomaceous earth 3–5 times with deionized water; and the drying is performed by drying in an oven at a temperature of 60 °C for 24 h.

6. The method for preparing a photocatalyst for removing manganese, copper, cadmium, and lead from a modified diatomaceous earth-supported organic photovoltaic material according to claim 1, characterized in that, In step F, the organic photocatalyst mixed solution and the modified diatomaceous earth material are used in a weight ratio of 1:5000 to 10000.

7. The method for preparing a photocatalyst for removing manganese, copper, cadmium, and lead from a modified diatomaceous earth-supported organic photovoltaic material according to claim 1, characterized in that... In step E, the P3HT:PCBM is a mixture of P3HT and PCBM in a weight ratio of 1:

1.

8. The application of the photocatalyst obtained by any one of the preparation methods according to claims 1 to 7, characterized in that, Photocatalysts were used to remove heavy metal ions such as manganese, copper, cadmium, and lead from wastewater.

Images