Metal-based organic new material, preparation method and application thereof

Abstract

The application provides a metal-based organic new material and a preparation method and application thereof, and relates to the technical fields of materials, chemical engineering and environmental protection. The preparation method comprises the following steps: uniformly mixing a metal salt solution and an organic ligand solution to obtain a mixed solution; adding an alkaline solution into the mixed solution, performing mixing reaction, discarding supernatant after centrifugation, washing and re-centrifugation, and drying to obtain the metal-based organic new material. The metal-based organic new material (MOs) is prepared by using a metal salt, an organic ligand and an alkaline solution. The method has the advantages of convenient and easily obtained reactants, mild reaction conditions, safe and rapid reaction process, and solves the problems of harsh synthesis conditions of MOs in the prior art. The MOs synthesized by the method can effectively remove blue algae, and the removal effect is better than that of hydrogen peroxide which is widely used.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical fields of materials, chemical industry and environmental protection, in particular, relates to a metal-based organic new material and a preparation method and application thereof. BACKGROUND

[0002] The spread of microcystis bloom is a major global environmental challenge, and predictions show that this problem will intensify in the future. The spread of these blooms has harmful effects on water quality, aquatic plants and animals, and human health. Metal-based organic materials are a kind of porous nanocrystalline materials composed of metal ions and polydentate organic ligands, which have the advantages of large specific surface area, high porosity, good thermal stability, controllable physicochemical properties, etc. Therefore, metal-based organic materials have been widely used in catalysis, adsorption, optics, electricity, magnetism, environment and many other fields. In the field of algae removal, metal-based organic materials also show high inhibitory capacity for cyanobacterial cells in a short time, which provides a new way to solve the problem of cyanobacterial bloom.

[0003] The synthesis method of metal-based organic materials mostly needs to be carried out in high temperature and high pressure, organic solvent [Rubio-Martinez et al., Chem. Soc. Rev. 2017; Kumar et al., Coordin. Chem. Rev. 2020], and the reactants are difficult to obtain and expensive. These conditions are not conducive to the industrial synthesis and large-scale application of metal-based organic materials in the field of cyanobacterial bloom control. It is particularly important to develop a synthesis method of metal-based organic new materials with easily available raw materials, suitable price and mild reaction conditions, and to obtain a metal-based organic new material that can be applied to the application scenario of cyanobacterial bloom control. SUMMARY

[0004] The purpose of the present application is to provide a metal-based organic new material and a preparation method thereof and its application as an algicide in inhibiting the growth of cyanobacteria. The preparation method is simple and easy to operate, and the reaction can be completed quickly at room temperature. The metal-based organic new material prepared has a remarkable effect on inhibiting the growth of cyanobacteria.

[0005] To solve the above technical problems, the technical scheme adopted by the present application is:

[0006] In a first aspect, the present application provides a preparation method of a metal-based organic new material, comprising the following steps:

[0007] S1, configuring a metal salt solution and an organic ligand solution;

[0008] S2, adding a basic solution to the above metal salt solution, mixing and uniformly adding the organic ligand solution to react, discarding the supernatant after centrifugation, washing and centrifugation again, and drying to obtain the metal-based organic new material.

[0009] In a second aspect, the application provides a metal-based organic new material prepared by the above method, and the apparent form of the metal-based organic new material is milky white powder after drying.

[0010] In a third aspect, the application provides an application of the metal-based organic new material as an algicide in the field of inhibiting growth of blue algae. The blue algae are selected from at least one of Microcystis aeruginosa, Oscillatoria, and Nostoc, Anabaena and Lyngbya.

[0011] Compared with the prior art, the embodiments of the application have at least the following advantages or beneficial effects:

[0012] 1. The metal-based organic new material is prepared by using a metal salt, an organic ligand and an alkaline solution. The method is convenient and low in cost, and the reaction conditions are mild and safe and fast. The method solves the problem of harsh conditions for synthesizing the metal-based organic new material in the prior art.

[0013] 2. The metal-based organic new material synthesized by the method can be combined with blue algae cells through electrostatic action, inhibit photosynthesis of blue algae cells and inhibit synthesis of ribosomes of blue algae cells, and at the same time, cause strong oxidative stress of blue algae, so as to finally cause death of the blue algae. Therefore, the metal-based organic new material can effectively remove the blue algae as an algicide, and the removal effect is better than that of hydrogen peroxide which is widely used. In addition, the metal-based organic new material is safe and efficient, and environmentally friendly, and has the potential to be applied to the treatment of blue-green algae blooms. BRIEF DESCRIPTION OF DRAWINGS

[0014] In order to more clearly illustrate the technical solutions of the embodiments of the application, the following will briefly introduce the drawings needed to be used in the embodiments. It should be understood that the following drawings only show some embodiments of the application, and therefore should not be regarded as a limitation on the scope, and for those skilled in the art, other related drawings can also be obtained without creative labor on the basis of these drawings.

[0015] Figure 1 X-ray powder diffraction patterns of the metal-based organic new materials MO1, MO2, MO3 and MO4 prepared in the embodiments;

[0016] Figure 2 Effect diagram of the metal-based organic new material MO1 of the application for removing blue algae. DETAILED DESCRIPTION

[0017] In order to make the purposes, technical solutions, and advantages of the embodiments of the present application clearer, the technical solutions in the embodiments of the present application will be clearly and completely described in the following. The specific conditions are not indicated in the embodiments, and the conventional conditions or the conditions suggested by the manufacturers are adopted. The reagents or instruments used are not indicated by the manufacturers, and are all conventional products that can be purchased in the market.

[0018] It should be noted that the embodiments in the present application and the features in the embodiments can be combined with each other without conflict. The present application will be described in detail below with reference to specific embodiments.

[0019] A preparation method of a metal-based organic new material, comprising the following steps:

[0020] S1, configuring a metal salt solution and an organic ligand solution;

[0021] S2, adding an alkaline solution to the metal salt solution, mixing and uniformly mixing, then adding the organic ligand solution to react, discarding the supernatant after centrifugation, washing, and centrifugation again, and drying to obtain the metal-based organic new material.

[0022] In some embodiments of the present application, the metal salt in the above S1 step is at least one of zinc salt, copper salt, cobalt salt, and nickel salt, and the salt is one or more of chloride salt, acetate salt, sulfate salt, nitrate salt, gluconate salt, lactate salt, and citrate salt.

[0023] In some embodiments of the present application, the metal-based organic new material in the above S1 step is one or more of 1,2,4-triazolin-3-one, 5-methyl-1H-benzotriazole, 5-benzylthiotetrazole, 5-ethylthiotetrazole, and derivatives thereof.

[0024] In some embodiments of the present application, the molar ratio of the metal salt solution to the organic ligand solution in the above S1 step is 1:(2-10).

[0025] In some embodiments of the present application, the alkaline solution in the above S2 step is one or more of sodium hydroxide solution, potassium hydroxide solution, ammonia solution, sodium carbonate solution, and sodium bicarbonate solution.

[0026] In some embodiments of the present application, the volume ratio of the alkaline solution to the metal salt solution is (1-10):200.

[0027] In some embodiments of the present application, the mixing reaction time in the above S2 step is 10-30 min, the stirring rate of mixing is 40-80 rpm, the centrifugation is performed twice, the rate of each centrifugation is 5000-8000 rpm, and the centrifugation time is 3-6 min.

[0028] In some embodiments of the present application, the temperature of the drying in the above S2 step is 40-80℃, and the drying time is 12-72h.

[0029] A metal-based organic new material prepared by the above method, which has an apparent morphology of ivory white powder and a micro-morphology of one of nanorod, nanoflower, spherical and filamentous morphology.

[0030] Application of a metal-based organic new material as an algicide in the field of inhibiting the growth of blue algae. Further, the blue algae are selected from at least one of Microcystis aeruginosa, Oscillatoria, and Nostoc, fishy algae and filamentous algae.

[0031] The features and performance of the present application are further described in detail below in conjunction with the examples.

[0032] Example 1

[0033] In this example, the type of organic ligand is changed, and MO1-MO4 are synthesized.

[0034] 1.2 mmol of zinc nitrate hexahydrate (357.0 mg) was weighed and dissolved in 14.4 mL of double distilled water (ddH2O) to obtain a zinc nitrate solution;

[0035] About 3.6 mmol of 1,2,4-triazolin-3-one (306.22 mg), 5-methyl-1H-benzotriazole (480.06 mg), 5-benzylthio-tetrazole (692.06 mg), and 5-ethylthio-1H-tetrazole (468.61 mg) were taken and dissolved in 15 mL of ddH2O respectively to obtain organic ligand solutions 1, 2, 3, and 4, forming parallel experiments.

[0036] 0.3 mL of 25% ammonia water was added to the zinc nitrate solution using a rubber bulb dropper, and after mixing, the organic ligand solution was added. The horizontal rotary shaker was rotated at 50 rpm at room temperature for 0.5 h, and the precipitate was recovered by centrifugation at 6000 rpm for 5 min, and washed twice with double distilled water. Finally, the product MO1, MO2, MO3, and MO4 of this example was obtained by drying at 60℃ and grinding, and stored at room temperature.

[0037] In this example, four MOs were synthesized by replacing the organic ligand. As shown in Table 1, the yield ranking is MO1>MO3>MO2>MO4. The XRD pattern is as shown in Figure 1 , and all MOs produced obvious characteristic peaks.

[0038] Table 1 Yield ratio of MOs synthesized by different organic ligands

[0039] Product name Ligand name Product mass / mg Production ratio MO1 1,2,4-triazolin-3-one 231.55 75.62％ MO2 5-methyl-1H-benzotriazole 151.45 31.55％ MO3 5-benzylthiotetrazole 160.62 23.21％ MO4 5-ethylthio-1H tetrazole 67.87 14.48％

[0040] Example 2

[0041] This embodiment changes the type of alkali solution to synthesize MO5 and MO6.

[0042] 1.2 mmol of zinc acetate dihydrate (263.0 mg) was weighed and dissolved in 14.4 mL of double distilled water (ddH2O) to obtain a metal salt solution; about 3.6 mmol of 1,2,4-triazolin-3-one (306.22 mg) was dissolved in 15 mL of ddH2O to obtain a 1,2,4-triazolin-3-one solution.

[0043] 0.3 mL of 25% ammonia water or 3 mL of 20 g / L sodium hydroxide solution was added to the zinc acetate dihydrate solution by using a rubber bulb dropper to obtain alkali solution 1 and alkali solution 2; after mixing, the 1,2,4-triazolin-3-one solution was added to the alkali solution. After shaking at room temperature for 0.5 h on a horizontal rotary shaker at 50 rpm, the precipitate was recovered by centrifugation at 6000 rpm for 5 min, and washed twice with double distilled water. Finally, drying was performed at 65°C and grinding to obtain the products MO5 and MO6 of this embodiment, which were stored at room temperature.

[0044] MO5 and MO6 were used to treat Microcystis aeruginosa, and the change in OD680 and the inhibition rate were recorded. As shown in Table 2, the MO synthesized using sodium hydroxide as the alkali solution had an inhibition rate of Microcystis aeruginosa of more than 85% on the third day, which was better than the MO synthesized using ammonia water as the alkali solution.

[0045] Table 2 Change in OD680 and inhibition rate of Microcystis aeruginosa treated with MO5 and MO6

[0046]

[0047]

[0048] Example 3

[0049] This embodiment changes the type of metal salt solution to synthesize MO7-MO10.

[0050] 1.2 mmol of zinc acetate dihydrate (263.0 mg), zinc chloride (164.0 mg), zinc nitrate (357.0 mg), and zinc sulfate heptahydrate (345.0 mg) were weighed and dissolved in 14.4 mL of double distilled water (ddH2O) to obtain metal salt solution 1, metal salt solution 2, metal salt solution 3, and metal salt solution 4, respectively; about 3.6 mmol of 1,2,4-triazolin-3-one (306.22 mg) was dissolved in 15 mL of ddH2O to obtain a 1,2,4-triazolin-3-one solution.

[0051] A 0.3 mL of 25% ammonia water was added to the zinc salt solution by a rubber bulb dropper, and then the 1,2,4-triazolin-3-one solution was added after mixing. The mixture was shaken at 60 rpm for 0.5 h at room temperature, and then the precipitate was recovered by centrifugation at 6000 rpm for 5 min, and washed twice with water. Finally, the product was dried at 65°C and ground to obtain MO7-MO10 of the example, which was stored at room temperature.

[0052] The OD680 and inhibition rate of Microcystis aeruginosa treated by MO7-MO10 were recorded. As shown in Table 3, it can be seen from Table 3 that MO7, MO9 and MO10 can significantly inhibit the growth of Microcystis aeruginosa on the third day, except that the inhibition ability of MO8 is lower.

[0053] Table 3 OD680 and inhibition rate of Microcystis aeruginosa treated by MO7-MO10

[0054]

[0055]

[0056] Experimental Example 4

[0057] In this example, the ratio of metal salt solution to organic ligand was changed to synthesize MO11-MO14.

[0058] 1.2 mmol of zinc acetate dihydrate (263.0 mg) was weighed and dissolved in 14.4 mL of double distilled water (ddH2O) to obtain a metal salt solution; about 1.2 mmol, 3.6 mmol, 6.0 mmol, 12 mmol, and 24 mmol of 1,2,4-triazolin-3-one were dissolved in 15 mL of ddH2O to obtain 1,2,4-triazolin-3-one solution 1, 1,2,4-triazolin-3-one solution 2, 1,2,4-triazolin-3-one solution 3, 1,2,4-triazolin-3-one solution 4, and 1,2,4-triazolin-3-one solution 5.

[0059] A 0.3 mL of 25% ammonia water was added to the zinc acetate solution by a rubber bulb dropper, and then the 1,2,4-triazolin-3-one solution was added after mixing. The mixture was shaken at 60 rpm for 0.5 h at room temperature, and then the precipitate was recovered by centrifugation at 6000 rpm for 5 min, and washed twice with water. Finally, the product was dried at 65°C and ground to obtain MO11-MO14 of the example, which was stored at room temperature.

[0060] The OD680 and inhibition rate of Microcystis aeruginosa treated by MO10-MO14 were recorded. As shown in Table 4, it can be seen from Table 4 that the ratio of metal salt to ligand has little effect on the algal inhibition ability of the synthesized MOs, and the best ratio of metal salt to organic ligand is 1:3.

[0061] Table 3 OD680 and inhibition rate changes of Microcystis aeruginosa after MO10-MO14 treatment

[0062]

[0063]

[0064] Example 5

[0065] This example compares MO1 with copper sulfate, hydrogen peroxide, Lake Wei oxygen, bleaching powder and other commercial algaecide products.

[0066] Microcystis aeruginosa was treated with MO1, copper sulfate, hydrogen peroxide and bleaching powder at the same concentration, and the changes in OD680 and inhibition rate were recorded. The results are shown in Table 5, and MO1 shows the best algaecide effect, showing its great algaecide potential. The intuitive diagram of the inhibition effect of MO1 and H2O2 on the OD680 of Microcystis aeruginosa is shown in Figure 2 From Figure 2 It can be seen that the effect of MO1 is better than that of H2O2.

[0067] Table 5 OD680 and inhibition rate changes of Microcystis aeruginosa after treatment with different algaecides

[0068]

[0069] In summary, the metal-based organic new material, its preparation method and application according to the embodiments of the present application have the following advantages:

[0070] 1. The metal-based organic new material is prepared by using metal salt, organic ligand and alkaline solution. The method is convenient and low-cost, the reaction conditions are mild, the reaction process is safe and fast, and the problems of harsh conditions for synthesizing metal-based organic new materials in the prior art are solved.

[0071] 2. The metal-based organic new material synthesized by the method can be combined with cyanobacterial cells through electrostatic interaction and blue-green algae cells, inhibit the photosynthesis of blue-green algae cells and the synthesis of blue-green algae ribosomes, and at the same time cause strong oxidative stress in blue-green algae, ultimately leading to the death of blue-green algae. Therefore, the metal-based organic new material can effectively remove blue-green algae as an algaecide, and the removal effect is better than that of hydrogen peroxide which is widely used. In addition, the metal-based organic new material has the characteristics of safety, high efficiency and environmental friendliness, and has the potential to be applied to the control of blue-green algae blooms.

[0072] The embodiments described above are only part of the embodiments of the present application, rather than all the embodiments. The detailed description of the embodiments of the present application is not intended to limit the scope of the claimed present application, but only represents selected embodiments of the present application. Based on the embodiments in the present application, all other embodiments obtained by those of ordinary skill in the art without creative labor fall within the scope of protection of the present application.

Claims

1. Use of a metal-based organic material as an algicide in the field of inhibiting growth of cyanobacteria, characterized in that, The preparation method of the metal-based organic material comprises the following steps: S1, configuring a metal salt solution and an organic ligand solution; S2, adding a basic solution to the metal salt solution, mixing and uniformly, then adding the organic ligand solution to react, discarding the supernatant after centrifugation, washing and re-centrifugation, and drying to obtain the metal-based organic material; The metal salt is at least one of zinc salt, copper salt, cobalt salt and nickel salt, and the salt is one or more of chloride, acetate, sulfate, nitrate, gluconate, lactate and citrate; The organic ligand comprises one or more of 1,2,4-triazolin-3-ketone, 5-methyl-1H-benzotriazole, 5-benzylthiotetrazole and 5-ethylthiotetrazole; The basic solution is one or more of sodium hydroxide solution, potassium hydroxide solution, ammonia solution, sodium carbonate solution and sodium bicarbonate solution.

2. The use of a metal-based organic material according to claim 1 as an algicide in the field of inhibiting the growth of blue-green algae, characterized in that, The molar ratio of the metal salt solution to the organic ligand solution in the S1 step is 1: (2-10), and the volume ratio of the basic solution to the metal salt solution is (1-10):

200.

3. The use of a metal-based organic material according to claim 1 as an algicide in the field of inhibiting the growth of blue-green algae, characterized in that, The mixing reaction time in the S2 step is 10-30 min, the stirring rate of mixing is 40-80 rpm, the centrifugation frequency is twice, the centrifugation rate of each time is 5000-8000 rpm, and the centrifugation time is 3-6 min.

4. The use of a metal-based organic material according to claim 1 as an algicide in the field of inhibiting the growth of blue-green algae, characterized in that, The drying temperature in the S2 step is 40-80℃, and the drying time is 12-72 h.

5. The use of a metal-based organic material according to claim 1 as an algicide in the field of inhibiting the growth of blue-green algae, characterized in that, The apparent form of the metal-based organic material is white powder.

6. The use of a metal-based organic material according to claim 1 as an algicide in the field of inhibiting the growth of blue-green algae, characterized in that, The cyanobacteria are selected from at least one of Microcystis aeruginosa, Oscillatoria, Nostoc, Anabaena and Aphanizomenon.

Images