阅读说明：本技术 一种用于降解废水有机污染物的材料 (Material for degrading organic pollutants in wastewater ) 是由 李伟 于 2021-08-09 设计创作，主要内容包括：本发明公开了一种用于降解废水有机污染物的材料,采用如下方法制备:称取硝酸镍和高锰酸钾溶于乙二醇-水的混合液中,随后加入柠檬酸铵,将混合液转移到高压水热釜中,随后将移至微波超声水热合成仪中反应,干燥得到海胆状NiMnO-(3)；将海胆状的NiMnO-(3)溶于去离子水中,随后加入Co盐和镍盐、硫代乙酰胺,将混合溶液采用400～800W微波加热至100～220℃,保持恒温进行微波水热合成反应2～10h；得到的产物于空气气氛下进行热处理,得到产物NiMnO-(3)/NiCo-(2)S-(4),复合材料比表面积高,物理吸附性能强,能够有效抑制电子与空穴的复合,提高光催化剂降解污染物的效率。(The invention discloses a material for degrading organic pollutants in wastewater, which is prepared by the following steps of weighing nickel nitrate and potassium permanganate, dissolving the nickel nitrate and the potassium permanganate in a mixed solution of glycol and water, adding ammonium citrate, transferring the mixed solution into a high-pressure hydrothermal kettle, transferring the mixed solution into a microwave ultrasonic hydrothermal synthesizer for reaction, and drying to obtain echinoid NiMnO 3 (ii) a Mixing NiMnO in the shape of sea urchin 3 Dissolving in deionized water, then adding Co salt, nickel salt and thioacetamide, heating the mixed solution to 100-220 ℃ by adopting 400-800W microwaves, and keeping the temperature constant to perform microwave hydrothermal synthesis reaction for 2-10 h; obtainedThe product is subjected to heat treatment in the air atmosphere to obtain a NiMnO product 3 /NiCo 2 S 4 The composite material has high specific surface area and strong physical adsorption performance, can effectively inhibit the recombination of electrons and holes, and improves the efficiency of degrading pollutants by the photocatalyst.)

1. A material for degrading organic pollutants in wastewater is characterized by being prepared by the following steps:

(1) weighing nickel nitrate and potassium permanganate, dissolving in mixed solution of ethylene glycol and water, wherein the volume ratio of the ethylene glycol to the water is 1: (0.5-1), adding ammonium citrate, transferring the mixed solution into a high-pressure hydrothermal kettle, transferring the high-pressure hydrothermal kettle into a microwave ultrasonic hydrothermal synthesizer for reaction, and drying to obtain echinoid NiMnO₃(ii) a The temperature of the ultrasonic hydrothermal reaction is 150-;

(2) mixing NiMnO in the shape of sea urchin₃Dissolving the load carrier in deionized water, adding Co salt, nickel salt and thioacetamide, heating the mixed solution to 100-220 ℃ by adopting 400-800W microwaves, and keeping constant temperature to perform microwave hydrothermal synthesis reaction for 2-10 h;

(3) carrying out heat treatment on the product obtained in the step (2) in the air atmosphere to obtain a NiMnO product₃/NiCo₂S₄Nanoscale NiCo₂S₄Loaded in NiMnO₃In the pores of (a).

2. The material for degrading organic pollutants in wastewater as claimed in claim 1, wherein the molar ratio of the nickel nitrate to the potassium permanganate is 1: 1.

3. The material for degrading organic pollutants in wastewater as claimed in claim 1, wherein the heat treatment temperature is 300 ℃ to 400 ℃, and the reaction time is 1-2 h.

Technical Field

The invention belongs to the field of sewage treatment, and particularly relates to a catalyst for degrading organic pollutants in sewage by natural light and a preparation method thereof.

Background

In recent years, antibiotics are widely applied to the fields of agriculture, aquaculture and the like, so that the antibiotics in lakes, rivers and oceans are accumulated and enriched continuously, the natural water environment is seriously polluted, and pollutants in water enter human bodies and directly and seriously harm the health of the human bodies. At present, photocatalytic degradation of organic pollutants in sewage by using a photocatalytic material is considered to be one of pollution treatment approaches with the most potential and research value.

Titanium dioxide is one of the most important photocatalytic materials in the world due to its strong oxidizing ability, stable chemical properties and no toxicity, however, TiO₂Due to the inherent wide band gap, the material can only absorb ultraviolet light, and electrons and holes generated by light excitation are easy to recombine, so that the quantum efficiency is low. Therefore, the development of a novel photocatalyst has important practical significance.

Disclosure of Invention

Aiming at the technical problems in the prior art, the invention provides a composite photocatalyst and a preparation method thereof, and the prepared composite photocatalyst can efficiently degrade antibiotics.

A photocatalytic material for degrading organic pollutants is characterized by being prepared by the following method:

(1) weighing nickel nitrate and potassium permanganate, dissolving in mixed solution of ethylene glycol and water, wherein the volume ratio of the ethylene glycol to the water is 1: (0.5-1), adding ammonium citrate, transferring the mixed solution into a high-pressure hydrothermal kettle, transferring the high-pressure hydrothermal kettle into a microwave ultrasonic hydrothermal synthesizer for reaction, and drying to obtain echinoid NiMnO₃(ii) a The temperature of the ultrasonic hydrothermal reaction is 150-;

(2) mixing NiMnO in the shape of sea urchin₃Dissolving in deionized water, then adding Co salt, nickel salt and thioacetamide, heating the mixed solution to 100-220W by adopting 400-800W microwaves, and keeping the constant temperature to perform microwave hydrothermal synthesis reaction for 2-10 h;

(3) carrying out heat treatment on the product obtained in the step (2) in an air atmosphere, wherein the heat treatment temperature is 300-400 ℃, and the reaction time is 1-2h, so as to obtain a product NiMnO₃/NiCo₂S₄。

Preferably, the molar ratio of the nickel nitrate to the potassium permanganate is 1: 1;

preferably, the temperature of the ultrasonic hydrothermal reaction is 160-;

the technical effects are as follows: 1. the invention prepares the sea urchin-shaped NiMnO by an ultrasonic hydrothermal method, adjusting the proportion of a solvent, adding ammonium citrate in the hydrothermal process and finely regulating and controlling the structure of a material₃High specific surface area, strong adsorption to organic matter, excellent photocatalytic performance under irradiation of visible light, and adoption of microwave heating to control NiCo₂S₄NiMnO in the form of nano-scale sea urchin₃Nano NiCo beneficial to post preparation as a load₂S₄In the shape of sea urchin NiMnO₃Uniform dispersion of nanoneedle voids, NiCo₂S₄With NiMnO₃A heterojunction formed between the two, NiCo₂S₄The band gap is narrow, and the electron transfer rate is high, so that the recombination of electrons and holes can be effectively inhibited, and the pollutant degradation efficiency of the photocatalyst is improved.

Drawings

FIG. 1 shows NiMnO of the present application₃SEM picture of (1);

Detailed Description

Example 1

(1) Weighing 5mmol of nickel nitrate and 5mmol of potassium permanganate, and dissolving the nickel nitrate and the potassium permanganate in 80ml of mixed solution of ethylene glycol and water, wherein the volume ratio of the ethylene glycol to the water is 1: 0.6, then adding 20mg of ammonium citrate, transferring the mixed solution into a high-pressure hydrothermal kettle, then transferring the mixed solution into a microwave ultrasonic hydrothermal synthesizer for reaction, and drying to obtain echinoid NiMnO₃(ii) a The temperature of the ultrasonic hydrothermal reaction is 180 ℃, the ultrasonic frequency is 60KHz, and the reaction time is 5 h;

(2) mixing NiMnO in the shape of sea urchin₃Dissolving in deionized water, then adding 4mmol of cobalt nitrate, 2mmol of nickel nitrate and 8mmol of thioacetamide, heating the mixed solution to 200 ℃ by adopting 500W microwaves, and keeping constant temperature to perform microwave hydrothermal synthesis reaction for 10 hours;

(3) carrying out heat treatment on the product obtained in the step (2) in an air atmosphere, wherein the heat treatment temperature is 350 ℃, and the reaction time is 1h, so as to obtain a NiMnO product₃/NiCo₂S₄。

Comparative example 1

(1) Weighing 5mmol of nickel nitrate and 5mmol of potassium permanganate, and dissolving the nickel nitrate and the potassium permanganate in 80ml of mixed solution of ethylene glycol and water, wherein the volume ratio of the ethylene glycol to the water is 1: 0.6, then adding 20mg of ammonium citrate, transferring the mixed solution into a high-pressure hydrothermal kettle, then transferring the mixed solution into a microwave ultrasonic hydrothermal synthesizer for reaction, and drying to obtain echinoid NiMnO₃(ii) a The temperature of the ultrasonic hydrothermal reaction is 180 ℃, the ultrasonic frequency is 60KHz, and the reaction time is 5 h;

(2) carrying out heat treatment on the product obtained in the step (1) in an air atmosphere, wherein the heat treatment temperature is 350 ℃, and the reaction time is 1h, so as to obtain a NiMnO product₃。

Comparative example 2

Heating the mixed solution to 200 ℃ by using 500W microwaves in deionized water with 4mmol of cobalt nitrate, 2mmol of nickel nitrate and 8mmol of thioacetamide, and carrying out microwave hydrothermal synthesis reaction for 10 hours while keeping constant temperature; carrying out heat treatment on the obtained product in an air atmosphere, wherein the heat treatment temperature is 350 ℃, and the reaction time is 1h to obtain the product NiCo₂S₄。

Testing the photocatalytic performance:

50mg of the photocatalyst of example 1 and comparative examples 1-2 was weighed and added to 100mL of a tetracycline antibiotic solution/levofloxacin solution having a concentration of 5mg/L, and a photocatalytic reaction was performed by irradiation with a 300W xenon lamp, and the degradation rate of the antibiotic was measured after 60 min.

TABLE 1

	Degradation rate of tetracycline antibiotics	Degradation rate of levofloxacin
			Example 1	98.6％	96.3％
Comparative example 1	84.3％	82.9％
			Comparative example 1	79.1％	81.2％

Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims.