阅读说明：本技术 一种生态环境修复剂 (Ecological environment restoration agent ) 是由 高琴 于 2020-12-15 设计创作，主要内容包括：本发明涉及一种生态环境修复剂,其制备过程包括如下步骤：(1)称取一定量的镍源、钴源和氨基硫脲、柠檬酸钠和PEG、纳米级别的Fe-3O-4溶于去离子水,超声混合均匀,水热得到花瓣状的NiCo-2S-4-Fe-3O-4；(2)将得到的花瓣状的NiCo-2S-4-Fe-3O-4分散于去离子水中,在该溶液中依次加入SnCl-2·2H-2O、Na-2WO-4·2H-2O,加入一定量氨水调节pH后,转到微波水热合成仪中,水热反应,得NiCo-2S-4-Fe-3O-4-SnWO-4磁性异质结复合材料,三种材料之间形成异质结,协同增强光催化性,花瓣状的结构使其具有更高的比表面积,能够提供更多的催化活性位点,对污染物具有优异的吸附性。(The invention relates to an ecological environment restoration agent, which comprises the following steps: (1) weighing a certain amount of nickel source, cobalt source, thiosemicarbazide, sodium citrate, PEG and nano-grade Fe 3 O 4 Dissolving in deionized water, ultrasonic mixing, and hydrothermal reaction to obtain petal-shaped NiCo 2 S 4 ‑Fe 3 O 4 (ii) a (2) The obtained petal-shaped NiCo 2 S 4 ‑Fe 3 O 4 Dispersing in deionized water, and sequentially adding Sn into the solutionCl 2 ·2H 2 O、Na 2 WO 4 ·2H 2 O, adding a certain amount of ammonia water to adjust the pH value, transferring the mixture into a microwave hydrothermal synthesizer, and carrying out hydrothermal reaction to obtain NiCo 2 S 4 ‑Fe 3 O 4 ‑SnWO 4 The magnetic heterojunction composite material has the advantages that a heterojunction is formed among the three materials, the photocatalysis is cooperatively enhanced, the petal-shaped structure enables the magnetic heterojunction composite material to have a higher specific surface area, more catalytic active sites can be provided, and the magnetic heterojunction composite material has excellent adsorbability on pollutants.)

1. An ecological environment restoration agent, the preparation method comprises the following steps: (1) weighing a certain amount of nickel source, cobalt source and thiosemicarbazide, dissolving in deionized water, stirring, and adding a certain amount of sodium citrate, PEG and nano-grade Fe₃O₄Ultrasonic mixing, hydrothermal obtaining petal-shaped NiCo₂S₄-Fe₃O₄(ii) a (2) The obtained petal-shaped NiCo₂S₄-Fe₃O₄Washing with deionized water and absolute ethyl alcohol for three times, and dispersing in the deionized water to form a suspension; subsequently, SnCl was added to the solution in sequence₂·2H₂O、Na₂WO₄·2H₂O, adding a certain amount of ammonia water to adjust the pH, transferring the mixture into a microwave hydrothermal synthesizer, carrying out hydrothermal reaction, washing and drying the obtained product to obtain petal-shaped NiCo₂S₄-Fe₃O₄-SnWO₄A magnetic heterojunction composite material.

2. The ecological restoration agent according to claim 1, wherein the nickel source and the cobalt source are nitrates of nickel and cobalt, respectively.

3. The ecological environment restoration agent according to claim 1, wherein the hydrothermal reaction temperature is 120-180 ℃.

4. The ecological restoration agent according to claim 1, wherein the molar ratio of the nickel source to the cobalt source is 1: 2.

5. The ecological restoration agent according to claim 1, wherein the Fe is selected from the group consisting of₃O₄The particle size is 50-70 nm.

6. The ecological environment restoration agent according to claim 1, wherein the power of the microwave is 700-800 w.

7. Use of an ecological restoration agent, characterized in that the ecological restoration agent of claims 1 to 6 can be used in the fields of sewage treatment/soil restoration/air purification.

Technical Field

The invention relates to an ecological environment restoration agent, in particular to a photocatalyst which can be used for sewage treatment and soil restoration.

Background

In recent years, with the wide application of antibiotics in many fields such as medical treatment and animal husbandry, a large amount of antibiotics enter the environment because human or animals cannot completely metabolize and absorb the antibiotics. In addition, heavy metal ion pollution is more serious, the heavy metal pollution can be transmitted through a food chain, and the heavy metal pollution has the characteristics of easy enrichment and difficult degradation, and is one of the main problems of world environment treatment at present.

The photocatalytic technology is an organic matter/heavy metal treatment technology which is found to be very promising at present, mainly utilizes visible light as a light source, has the advantages of high efficiency, environmental protection, low cost, easy operation, strong oxidizability and the like, and draws wide attention of researchers. However, the application of the photocatalytic technology is limited due to the defects that the photogenerated carriers of a single material are easy to recombine and the like. Therefore, the construction of a heterojunction catalyst having visible light response and high charge separation efficiency is the key to solve the technical problem.

Another technical means for improving the catalytic activity of the photocatalytic material is to increase the specific surface area of the material, for example, the photodegradation capability of the catalyst can be effectively improved by preparing the photocatalyst into one-dimensional materials such as nano-particles/tubes/fibers, nano-sheet materials and hollow/petal-shaped microsphere structures.

Disclosure of Invention

The invention aims to provide NiCo₂S₄-Fe₃O₄-SnWO₄A magnetic heterojunction composite material, a preparation method and application thereof. The invention is beneficial to the absorption and utilization of the photocatalyst on light by adjusting the shape of the material, and improves the removal efficiency of the photocatalyst on organic pollutants such as antibiotics and heavy metals.

The preparation method of the ecological environment restoration agent is characterized by comprising the following steps: (1) weighing a certain amount of nickel source, cobalt source and thiosemicarbazide, dissolving in deionized water, stirring, and adding a certain amount of sodium citrate, PEG and nano-grade Fe₃O₄Ultrasonic mixing, hydrothermal obtaining petal-shaped NiCo₂S₄-Fe₃O₄(ii) a (2) The obtained petal-shaped NiCo₂S₄-Fe₃O₄Washing with deionized water and absolute ethyl alcohol for three times, and dispersing in the deionized water to form a suspension; subsequently, SnCl was added to the solution in sequence₂·2H₂O、Na₂WO₄·2H₂O, adding a certain amount of ammonia water to adjust the pH, transferring the mixture into a microwave hydrothermal synthesizer, carrying out hydrothermal reaction, washing and drying the obtained product to obtain NiCo₂S₄-Fe₃O₄-SnWO₄A magnetic heterojunction composite material.

Preferably, the nickel source and the cobalt source are nitrates of nickel and cobalt, respectively.

Preferably, the hydrothermal reaction temperature is 120-.

Preferably, the molar ratio of the nickel source to the cobalt source is 1: 2.

Preferably, SnCl₂·2H₂O、Na₂WO₄·2H₂The mass ratio of O is 1: 1;

preferably, said Fe₃O₄The particle size is 50-70 nm.

Preferably, the power of the microwave is 700-.

Technical effects

The petal-shaped NiCo of the invention₂S₄-Fe₃O₄Magnetic composite material as carrier, Fe₃O₄As a nucleus, NiCo₂S₄Is a shell, and then microwave hydrothermal compounding is carried out to obtain nano-scale flower-shaped SnWO₄A heterojunction is formed among the three, the photocatalysis is enhanced cooperatively, and the defect of a single material is overcome; the petal-shaped composite material forms a hierarchical pore structure with rich micropores/mesopores/macropores, has higher specific surface area, can provide more catalytic active sites, improves the adsorbability of pollutants such as heavy metals or organic pollutants, and can be used in the fields of sewage treatment, soil remediation, air purification and the like.

Drawings

FIG. 1 is an SEM image of a composite material of the present application;

Detailed Description

Example 1

Weighing 0.05mol of nickel nitrate, 0.1mol of cobalt nitrate and 0.1mol of thiosemicarbazide were dissolved in 150ml of deionized water and stirred, and then 20mg of sodium citrate and 28mg of PEG, 0.05mol of nano-scale Fe were added₃O₄Ultrasonically mixing uniformly, and performing hydrothermal treatment at 180 ℃ for 12 hours to obtain petal-shaped NiCo₂S₄-Fe₃O₄(ii) a (2) The obtained petal-shaped NiCo₂S₄-Fe₃O₄Washing with deionized water and absolute ethyl alcohol for three times, and dispersing in 150ml of deionized water to form a suspension; subsequently, 0.05mol of SnCl was added to the solution in succession₂·2H₂O、Na₂WO₄·2H₂Adding a plurality of drops of ammonia water into O, transferring the mixture into a microwave hydrothermal synthesizer, carrying out hydrothermal reaction for 5 hours at 180 ℃, washing and drying the obtained product to obtain NiCo₂S₄-Fe₃O₄-SnWO ₄A magnetic heterojunction composite material.

Example 2

0.02mol of nickel nitrate, 0.04mol of cobalt nitrate and 0.3mol of thiosemicarbazide were weighed out and dissolved in 150ml of deionized water and stirred, and then 10mg of sodium citrate and 13mg of PEG, 0.05mol of nano-grade Fe were added₃O₄Ultrasonically mixing uniformly, and performing hydrothermal treatment at 180 ℃ for 18h to obtain petal-shaped NiCo₂S₄-Fe₃O₄(ii) a (2) The obtained petal-shaped NiCo₂S₄-Fe₃O₄Washing with deionized water and absolute ethyl alcohol for three times, and dispersing in 150ml of deionized water to form a suspension; subsequently, 0.05mol of SnCl was added to the solution in succession₂·2H₂O、Na₂WO₄·2H₂Adding a plurality of drops of ammonia water into O, transferring the mixture into a microwave hydrothermal synthesizer, carrying out hydrothermal reaction for 6 hours at 180 ℃, washing and drying the obtained product to obtain NiCo₂S₄-Fe₃O₄-SnWO ₄A magnetic heterojunction composite material.

Example 3

0.03mol of nickel nitrate, 0.06mol of cobalt nitrate and 0.05mol of thiosemicarbazide were weighed out and dissolved in 100ml of deionized water and stirred, and subsequently 15mg of sodium citrate and 18mg of PEG, 0.02mol of thiosemicarbazide were addedOf nano-scale Fe₃O₄Ultrasonically mixing uniformly, and performing hydrothermal treatment at 180 ℃ for 12 hours to obtain petal-shaped NiCo₂S₄-Fe₃O₄(ii) a (2) The obtained petal-shaped NiCo₂S₄-Fe₃O₄Washing with deionized water and absolute ethyl alcohol for three times, and dispersing in 150ml of deionized water to form a suspension; subsequently, 0.05mol of SnCl was added to the solution in succession₂·2H₂O、Na₂WO₄·2H₂Adding a plurality of drops of ammonia water into O, transferring the mixture into a microwave hydrothermal synthesizer, carrying out hydrothermal reaction for 5 hours at 190 ℃, washing and drying the obtained product to obtain NiCo₂S₄-Fe₃O₄-SnWO ₄A magnetic heterojunction composite material.

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 and their equivalents.