Novel metal-based organic material as well as preparation method and application thereof

Abstract

The invention provides a novel metal-based organic material and a preparation method and application thereof, and relates to the technical field 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; and adding an alkaline solution into the mixed solution, mixing and reacting, centrifuging, washing, centrifuging again, discarding the supernatant, and drying to obtain the metal-based organic new material. The novel metal-based organic material (MOs) is prepared from the metal salt, the organic ligand and the alkaline solution, reactants in the method are convenient and easy to obtain, reaction conditions are mild, the reaction process is safe and rapid, and the problems that in the prior art, MOs synthesis conditions are harsh and the like are solved. The MOs synthesized by the method can effectively remove blue-green algae, and the removal effect is superior to that of widely used hydrogen peroxide.

Description

Technical Field

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

[0002] The spread of Microcystis blooms is a major global environmental challenge, and predictions indicate that this problem will intensify in the future. The spread of these blooms has a detrimental impact on water quality, aquatic plants and animals, and human health. Metal-based organic materials are porous nanocrystalline materials composed of metal ions and multidentate organic ligands, which have the advantages of large specific surface area, high porosity, good thermal stability, and controllable physical and chemical properties. Therefore, metal-based organic materials have been widely used in many fields such as catalysis, adsorption, optics, electricity, magnetism, and environment. In the field of algae removal, metal-based organic materials also show high inhibition ability on cyanobacterial cells in a short time, which provides a new way to solve the problem of cyanobacterial blooms.

[0003] Most of the synthesis methods of metal-based organic materials need to be carried out at high temperature and high pressure in organic solvents [Rubio-Martinez et al., Chem. Soc. Rev. 2017; Kumar et al., Coordin. Chem. Rev. 2020], and the reactants are difficult to obtain and relatively expensive. These conditions are not conducive to the industrial synthesis of metal-based organic materials and large-scale use in the field of cyanobacteria bloom control. It is particularly important to develop a method for synthesizing a new metal-based organic material with easy-to-obtain raw materials, suitable prices, mild reaction conditions and simple reaction processes, and to obtain a new metal-based organic material that can be applied to the application scenario of cyanobacteria bloom control. Summary of the invention

[0004] The purpose of the present application is to provide a new metal-based organic material and a preparation method thereof and its application as an algaecide 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 prepared new metal-based organic material has a significant effect in inhibiting the growth of cyanobacteria.

[0005] In order to solve the above technical problems, the technical solution adopted in this application is:

[0006] In a first aspect, the present application provides a method for preparing a metal-based organic novel material, comprising the following steps:

[0007] S1. preparing a metal salt solution and an organic ligand solution;

[0008] S2. Add an alkaline solution to the metal salt solution, mix well, then add an organic ligand solution to react, centrifuge, wash, centrifuge again, discard the supernatant, and dry to obtain the metal-based organic new material.

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

[0010] In a third aspect, the present application provides an application of a metal-based organic novel material as an algaecide in the field of inhibiting the growth of cyanobacteria. The cyanobacteria are selected from at least one of Microcystis aeruginosa, Oscillatoria, Nostoc, Anabaena and Aphanizomenon.

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

[0012] 1. The present application utilizes metal salts, organic ligands and alkaline solutions to prepare metal-based organic new materials. This method is convenient and easy to obtain reactants, has low cost, mild reaction conditions, and a safe and rapid reaction process, thus solving the problems of harsh conditions for the synthesis of metal-based organic new materials in the prior art.

[0013] 2. The new metal-based organic material synthesized by this method can combine with cyanobacteria cells through electrostatic action, inhibit the photosynthesis of cyanobacteria cells and the synthesis of ribosomes in cyanobacteria cells, and at the same time cause strong oxidative stress in cyanobacteria, eventually leading to the death of cyanobacteria. Therefore, the new metal-based organic material can be used as an algaecide to effectively remove cyanobacteria, and the removal effect is better than the widely used hydrogen peroxide; in addition, the new metal-based organic material is safe, efficient, and environmentally friendly, and has the potential to be used in the control of cyanobacteria blooms. BRIEF DESCRIPTION OF THE DRAWINGS

[0014] In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings required for use in the embodiments will be briefly introduced below. It should be understood that the following drawings only show certain embodiments of the present application and therefore should not be regarded as limiting the scope. For ordinary technicians in this field, other related drawings can be obtained based on these drawings without paying creative work.

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

[0016] Figure 2 This is a diagram showing the effect of using the new metal-based organic material MO1 in this application to remove cyanobacteria. DETAILED DESCRIPTION

[0017] In order to make the purpose, technical scheme and advantages of the embodiments of the present application clearer, the technical scheme in the embodiments of the present application will be described clearly and completely below. If the specific conditions are not specified in the embodiments, they are carried out according to the conventional conditions or the conditions recommended by the manufacturer. If the manufacturer is not specified for the reagents or instruments used, they are all conventional products that can be purchased commercially.

[0018] It should be noted that, in the absence of conflict, the embodiments and features in the embodiments of the present application can be combined with each other. The present application will be described in detail below with reference to specific embodiments.

[0019] A method for preparing a new metal-based organic material comprises the following steps:

[0020] S1. preparing a metal salt solution and an organic ligand solution;

[0021] S2. Add an alkaline solution to the metal salt solution, mix well, then add an organic ligand solution to react, centrifuge, wash, centrifuge again, discard the supernatant, and dry to obtain the metal-based organic new material.

[0022] In some embodiments of the present application, the metal salt in the above-mentioned step S1 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.

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

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

[0025] In some embodiments of the present application, the alkaline solution in the above step S2 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 step S2 is 10-30 min, the mixing stirring rate is 40-80 rpm; centrifugation is performed twice, each centrifugation rate is 5000-8000 rpm, and the centrifugation time is 3-6 min.

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

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

[0030] A metal-based organic new material is used as an algaecide in the field of inhibiting the growth of cyanobacteria. Further, the cyanobacteria are selected from at least one of Microcystis aeruginosa, Oscillatoria, Nostoc, Anabaena and Aphanizomenon.

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

[0032] Example 1

[0033] In this example, the types of organic ligands were changed to synthesize MO1-MO4.

[0034] Weigh 1.2 mmol of zinc nitrate hexahydrate (357.0 mg) and dissolve it in 14.4 mL of secondary 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-benzylthiotetrazolyl (692.06 mg), and 5-ethylthio-1H-tetrazolyl (468.61 mg) were taken and dissolved in 15 mL of ddH2O respectively to obtain organic ligand solution 1, solution 2, solution 3, and solution 4 to form parallel experiments.

[0036] Use a rubber-tipped dropper to add 0.3 mL of 25% ammonia water to the zinc nitrate solution, mix well, and then add the organic ligand solution. Shake well at room temperature for 0.5 h on a horizontal rotary shaker at 50 rpm, centrifuge at 6000 rpm for 5 min to recover the precipitate, and wash it with water twice. Finally, dry and grind at 60°C to obtain the products MO1, MO2, MO3, and MO4 of this embodiment, which are stored at room temperature.

[0037] In this example, four MOs were synthesized by replacing organic ligands. The yield order is MO1>MO3>MO2>MO4 as shown in Table 1. Figure 1 , MOs all produced obvious characteristic peaks.

[0038] Table 1 Production ratio of MOs synthesized with 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-Benzylthiotetrazolyl 160.62 23.21％ MO4 5-Ethylthio-1H-tetrazolyl 67.87 14.48％

[0040] Example 2

[0041] In this example, the type of alkaline solution was changed to synthesize MO5 and MO6.

[0042] Weigh 1.2 mmol zinc acetate dihydrate (263.0 mg) and dissolve it in 14.4 mL of secondary water (ddH2O) to obtain a metal salt solution; about 3.6 mmol 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] Add 0.3mL of 25% ammonia water or 3mL of 20g / L sodium hydroxide solution to the zinc acetate dihydrate solution with a rubber dropper to obtain alkaline solution 1 and alkaline solution 2; add 1,2,4-triazolin-3-one solution to the alkaline solution after mixing. Shake at room temperature for 0.5h on a horizontal rotary shaker at 50rpm, centrifuge at 6000rpm for 5min to recover the precipitate, and wash it with water twice. Finally, dry and grind at 65℃ to obtain products MO5 and MO6 of this embodiment, which are stored at room temperature.

[0044] MO5 and MO6 were used to treat Microcystis aeruginosa, and the OD680 changes and inhibition rates were recorded. As shown in Table 2, it can be seen that the inhibition of MO synthesized with sodium hydroxide as the alkaline solution on Microcystis aeruginosa was more than 85% on the third day, which was better than MO synthesized with ammonia water as the alkaline solution.

[0045] Table 2 Changes in OD680 and inhibition rate of Microcystis aeruginosa after MO5 and MO6 treatment

[0046]

[0047]

[0048] Example 3

[0049] In this example, the type of metal salt solution is changed to synthesize MO7-MO10.

[0050] Weigh 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), and dissolve them in 14.4 mL of secondary 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] Use a rubber-tipped dropper to add 0.3 mL of 25% ammonia water to the zinc salt solution, mix well, and then add the 1,2,4-triazolin-3-one solution. Shake well at room temperature for 0.5 h on a horizontal rotary shaker at 60 rpm, centrifuge at 6000 rpm for 5 min to recover the precipitate, and wash it with water twice. Finally, dry and grind at 65°C to obtain the product MO7-MO10 of this embodiment, which is stored at room temperature.

[0052] MO7-MO10 were used to treat Microcystis aeruginosa, and the OD680 changes and inhibition rates were recorded. As shown in Table 3, it can be seen from Table 3 that except for MO8 which has a lower inhibition ability, MO7, MO9 and MO10 can significantly inhibit the growth of Microcystis aeruginosa on the third day.

[0053] Table 3 Changes in OD680 and inhibition rate after MO7-MO10 treatment of Microcystis aeruginosa

[0054]

[0055]

[0056] Experimental Example 4

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

[0058] Weigh 1.2 mmol zinc acetate dihydrate (263.0 mg) and dissolve it in 14.4 mL of secondary water (ddH2O) to obtain a metal salt solution; about 1.2 mmol, 3.6 mmol, 6.0 mmol, 12 mmol, and 24 mmol 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] Use a rubber-tipped dropper to add 0.3 mL of 25% ammonia water to the zinc acetate solution, mix well, and then add the 1,2,4-triazolin-3-one solution. Shake well at room temperature for 0.5 h on a horizontal rotary shaker at 60 rpm, centrifuge at 6000 rpm for 5 min to recover the precipitate, and wash it with water twice. Finally, dry and grind at 65°C to obtain the products MO11-MO14 of this embodiment, which are stored at room temperature.

[0060] MO10-MO14 were used to treat Microcystis aeruginosa, and the OD680 changes and inhibition rates 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 algicidal ability of the synthesized MOs, and the optimal metal salt: organic ligand is 1:3.

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

[0062]

[0063]

[0064] Example 5

[0065] This example compares MO1 with commercial algaecide products such as copper sulfate, hydrogen peroxide, lake oxygen, and bleaching powder.

[0066] The same concentration of MO1, copper sulfate, hydrogen peroxide and bleaching powder were used to treat Microcystis aeruginosa, and the OD680 changes and inhibition rates were recorded. The results are shown in Table 5. MO1 showed the best algaecidal effect, showing its great algaecidal potential. The intuitive schematic diagram of the OD680 inhibition effect of MO1 and H2O2 on Microcystis aeruginosa is shown in Table 5. Figure 2 As shown, from Figure 2 It can be seen that the effect of MO1 is better than that of H2O2.

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

[0068]

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

[0070] 1. The present application utilizes metal salts, organic ligands and alkaline solutions to prepare metal-based organic new materials. This method is convenient and easy to obtain reactants, has low cost, mild reaction conditions, and a safe and rapid reaction process, thus solving the problems of harsh conditions for the synthesis of metal-based organic new materials in the prior art.

[0071] 2. The new metal-based organic material synthesized by this method can combine with cyanobacteria cells through electrostatic action, inhibit the photosynthesis of cyanobacteria cells and the synthesis of ribosomes in cyanobacteria cells, and at the same time cause strong oxidative stress in cyanobacteria, eventually leading to the death of cyanobacteria. Therefore, the new metal-based organic material can be used as an algaecide to effectively remove cyanobacteria, and the removal effect is better than the widely used hydrogen peroxide; in addition, the new metal-based organic material is safe, efficient, and environmentally friendly, and has the potential to be used in the control of cyanobacteria blooms.

[0072] The embodiments described above are part of the embodiments of the present application, rather than all of the embodiments. The detailed description of the embodiments of the present application is not intended to limit the scope of the present application for protection, but merely represents the selected embodiments of the present application. Based on the embodiments in the present application, all other embodiments obtained by ordinary technicians in this field without making creative work belong to the scope of protection of the present application.

Claims

1. A method for preparing a new metal-based organic material, characterized in that: The following steps are involved: S1. preparing a metal salt solution and an organic ligand solution; S2. Add an alkaline solution to the metal salt solution, mix well, then add an organic ligand solution to react, centrifuge, wash, centrifuge again, discard the supernatant, and dry to obtain the metal-based organic new material.

2. The method for preparing a new metal-based organic material according to claim 1, characterized in that: In the step S1, 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.

3. The method for preparing a new metal-based organic material according to claim 1, characterized in that: In the step S1, the organic ligand includes one or more of 1,2,4-triazolin-3-one, 5-methyl-1H-benzotriazole, 5-benzylthiotetrazolyl, 5-ethylthiotetrazolyl and their derivatives.

4. The method for preparing a new metal-based organic material according to claim 1, characterized in that: In the step S1, the molar ratio of the metal salt solution to the organic ligand solution is 1:(2-10); the volume ratio of the alkaline solution to the metal salt solution is (1-10):

200.

5. The method for preparing a new metal-based organic material according to claim 1, characterized in that: The alkaline solution in step S2 is one or more of sodium hydroxide solution, potassium hydroxide solution, ammonia solution, sodium carbonate solution and sodium bicarbonate solution.

6. The method for preparing a new metal-based organic material according to claim 1, characterized in that: The mixing reaction time in step S2 is 10-30 min, and the mixing stirring rate is 40-80 rpm; the number of centrifugation is two, and the rate of each centrifugation is 5000-8000 rpm, and the centrifugation time is 3-6 min.

7. The method for preparing a new metal-based organic material according to claim 1, characterized in that: The drying temperature in step S2 is 40-80° C., and the drying time is 12-72 hours.

8. A new metal-based organic material prepared by the method according to any one of claims 1 to 7, characterized in that: The apparent form of the metal-based organic new material is white powder.

9. Use of the new metal-based organic material as claimed in claim 8 as an algaecide in the field of inhibiting the growth of blue algae.

10. The use of the metal-based organic new material according to claim 9 as an algaecide in the field of inhibiting the growth of blue algae, characterized in that: The cyanobacteria is selected from at least one of Microcystis aeruginosa, Oscillatoria, Nostoc, Anabaena and Aphanizomenon.

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