CN113234231B - Preparation of metal organic framework material and application of metal organic framework material in algae inhibition - Google Patents
Preparation of metal organic framework material and application of metal organic framework material in algae inhibition Download PDFInfo
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- CN113234231B CN113234231B CN202110551412.4A CN202110551412A CN113234231B CN 113234231 B CN113234231 B CN 113234231B CN 202110551412 A CN202110551412 A CN 202110551412A CN 113234231 B CN113234231 B CN 113234231B
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Abstract
The invention discloses a preparation method of a metal organic framework material and application of the metal organic framework material in the aspect of algae inhibition. The metal organic framework material has good algae inhibiting effect, can obviously inhibit the growth of algae in a relatively low dosage and relatively short time when being used as an algae inhibiting agent, can greatly reduce the economic cost, shorten the treatment period, can quickly control or eliminate harmful algae, is suitable for controlling the occurrence of algal bloom, is beneficial to the management of the environment, and has very high economic benefit.
Description
Technical Field
The invention relates to the technical field of water treatment, in particular to a preparation method of a metal organic framework material and application of the metal organic framework material in the aspect of algae inhibition.
Background
In an aquatic ecosystem, the phenomenon of water bloom outbreak of harmful blue algae caused by water pollution and environmental destruction is more and more common, and the outbreak of the harmful blue algae can destroy the ecology in a water area, so that the ecosystem is unbalanced, and serious environmental, economic and social problems are caused. For example, algae floating on water surface affect the landscape and have an unpleasant odor, causing the water to emit an odor; the water quality is putrefacted, so that some aquatic organisms such as fishes are suffocated and die, and the aquaculture industry suffers from great economic loss; the filtration devices of waterworks are clogged with algae; during the water treatment process, the algae cells with flagella easily pass through the flocculating constituent, thereby destroying the flocculation process; the algal toxins produced by blue algae can seriously threaten the life safety of human beings through the biological amplification effect of a food chain, wherein the predominant species of freshwater bloom which is most concerned is microcystis aeruginosa which is photoautotrophic prokaryotes, the produced microcystis toxins have extremely strong hepatoma causing property and influence the self health of human beings through the food chain, including causing diseases or death of human beings, causing great harm, and the human poisoning events caused by the algal toxins occur every year around the world, and causing great economic loss and seriously threatening the safety problem of drinking water sources when more serious algae outbreaks.
These problems put great pressure on water workers, and the continuous search for better algae inhibiting substances becomes the target of water workers. Allelochemicals have long development history in the field of inhibiting the growth of algae, obtain good algae inhibiting performance, and have the advantages of degradability, environmental friendliness and the like. However, most allelochemicals have limited algae inhibition effect, often need a large amount to obtain certain algae inhibition effect, and are not suitable for large water areas with large outbreaks of harmful algal blooms.
Accordingly, the prior art is yet to be improved and developed.
Disclosure of Invention
In view of the defects of the prior art, the invention aims to provide a preparation method of a metal organic framework material and an application of the metal organic framework material in the aspect of algae inhibition, and aims to solve the problem that the existing algae inhibition substance has limited algae inhibition effect.
The technical scheme of the invention is as follows:
in a first aspect of the present invention, there is provided a metal-organic framework material, wherein the metal-organic framework material comprises ferulic acid and zinc ions, and the ferulic acid is combined with the zinc ions in a coordination bond manner.
Optionally, the hydroxyl group in the ferulic acid forms a coordinate bond with the zinc ion.
Optionally, the molar ratio of the ferulic acid to the zinc ion is (0.8-1.2): (0.8-1.2).
In a second aspect of the present invention, there is provided a method for preparing the metal organic framework material, comprising the steps of:
dissolving zinc salt in a first organic solvent to obtain a first solution;
dissolving ferulic acid in a second organic solvent to obtain a second solution;
under the condition of stirring, mixing the first solution and the second solution, and carrying out coordination reaction to obtain a third solution;
and drying the third solution to obtain the metal organic framework material.
Alternatively, the ratio of the zinc salt to the first organic solvent is (0.1 ± 0.005) mmol:1 mL;
and/or the ratio of the ferulic acid to the second organic solvent is (0.1 +/-0.005) mmol:1 mL.
Optionally, the zinc salt is selected from one or more of zinc nitrate, zinc sulfate, and zinc acetate.
Optionally, the first organic solvent is selected from one or two of dimethylformamide and dimethylacetamide; and/or the second organic solvent is selected from one or two of ethanol and methanol.
Optionally, the temperature of the coordination reaction is 20-30 ℃, and the time of the coordination reaction is 10-30 min;
and/or the drying temperature is 100 +/-5 ℃, and the drying time is 24 +/-1 h.
In a third aspect of the invention, the invention provides an application of the metal organic framework material in inhibiting the growth of freshwater algae.
Optionally, the method of applying comprises the steps of:
providing a sterile BG-11 medium solution;
adding the metal organic framework material into the sterile BG-11 culture medium solution to prepare a metal organic framework material stock solution;
culturing the microcystis aeruginosa to obtain microcystis aeruginosa in logarithmic growth period;
and mixing the microcystis aeruginosa in the logarithmic growth phase with the sterile BG-11 culture medium solution, and then adding the metal-organic framework material storage solution to inhibit the growth of the microcystis aeruginosa in the logarithmic growth phase.
Has the advantages that: the metal organic framework material provided by the invention can slowly release the algae-inhibiting substance ferulic acid and metal zinc ions to inhibit the growth of fresh water algae, so that the synthesized metal organic framework material has the algae inhibiting effects of the algae-inhibiting substance ferulic acid and the metal zinc ions, has a synergistic algae inhibiting effect which is higher than the simple superposition effect of the zinc ions and the ferulic acid, can obviously inhibit the growth of algae in a lower dosage and shorter time as an algae inhibitor, can greatly reduce the economic cost, shorten the treatment period, can quickly control or eliminate harmful algae, is suitable for controlling the occurrence of algal bloom, is beneficial to environmental management, and has high economic benefit.
Drawings
FIG. 1 is a flow chart of the preparation of the metal organic framework material according to the embodiment of the present invention.
FIG. 2 is a powder diffraction pattern of the metal organic framework material in example 1 of the present invention.
FIG. 3 is a graph comparing a powder diffraction pattern and a standard powder diffraction pattern of the metal organic framework material in example 1 of the present invention.
FIG. 4 is a SEM image of the metal-organic framework material of example 1, wherein (a) is a 1000-fold magnification SEM image and (b) is a 150000-fold magnification SEM image.
Detailed Description
The invention provides a preparation method of a metal organic framework material and application thereof in algae inhibition, and the invention is further described in detail below in order to make the purpose, technical scheme and effect of the invention clearer and clearer. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The embodiment of the invention provides a metal-organic framework material, wherein the metal-organic framework material comprises ferulic acid and zinc ions, and the ferulic acid and the zinc ions are combined in a coordinate bond mode.
Ferulic acid (also known as 3-methoxy-4-hydroxycinnamic acid) with a structural formula
Is the most common allelochemicals in terrestrial species, can be isolated from many plants, is susceptible to oxidation, and produces O during oxidation2 ·-The zinc ion inhibitor can interfere the metabolic function of algae cells to inhibit the growth of the algae cells, and the inventor finds that most algae have strong sensitivity to metal zinc which can inhibit the growth and the propagation of the algae cells, so that the inventor combines the allelochemicals ferulic acid and metal zinc for the first time to prepare the zinc ion (Zn)2+) Is a metal ionThe metal organic framework material takes ferulic acid as an organic ligand, zinc ions in the metal organic framework material are combined with hydroxyl groups in the ferulic acid in a coordination bond mode, and the chemical formula of the metal organic framework material is { [ Zn ]2(fer)2]}nIt belongs to the monoclinic system, has a space group of C2/C and a crystal size (mm) of 0.31X 0.12X 0.07, and is characterized by { [ Zn ]2(fer)2]}nThe metal organic framework material can be used as the algistat to be applied to inhibiting the growth of the fresh water algae, in addition, the ferulic acid and the zinc ions in the metal organic framework material can also generate a synergistic algistatic effect, the generated algistatic effect is higher than the simple additive effect of the zinc ions and the ferulic acid, and the growth of the algae can be obviously inhibited in a lower dosage and shorter time. The metal organic framework material has the advantages of easiness in degradation of allelochemicals, environmental friendliness and the like, has a stronger inhibition effect than the allelochemicals ferulic acid and metal zinc ions, can effectively inhibit the growth of freshwater algae, and obtains a better inhibition effect.
In one embodiment, the molar ratio of the ferulic acid to the zinc ion is (0.8-1.2): (0.8-1.2).
In one embodiment, the molar ratio of ferulic acid to zinc ion is 1: 1.
the embodiment of the present invention further provides a method for preparing a metal organic framework material, as shown in fig. 1, where the method includes the steps of:
s11, dissolving zinc salt in a first organic solvent to obtain a first solution;
s12, dissolving ferulic acid in a second organic solvent to obtain a second solution;
s13, mixing the first solution and the second solution under the stirring condition, and performing coordination reaction to obtain a third solution;
and S14, drying the third solution to obtain the metal organic framework material.
In this embodiment, the first solution contains a first organic solvent and a zinc salt dissolved in the first organic solvent, the second solution contains a second organic solvent and ferulic acid dissolved in the second organic solvent, and the third solution mainly contains crystals of a metal-organic framework material, the first organic solvent and the second organic solvent, and may contain unreacted zinc salt or ferulic acid.
The preparation method in the embodiment is simple and high in yield, and the prepared metal organic framework material can be used as an algae inhibitor and has good algae inhibiting effect.
In step S11, in one embodiment, the ratio of the zinc salt to the first organic solvent is (0.1 ± 0.005) mmol:1 mL. That is, the ratio was (0.1. + -. 0.005) mmol:1mL of zinc salt is mixed with the first organic solvent such that the zinc salt is dissolved in the first organic solvent to obtain a first solution.
In one embodiment, the zinc salt may be selected from one or more of zinc nitrate, zinc sulfate, and zinc acetate, but is not limited thereto.
In one embodiment, the first organic solvent may be selected from one or both of dimethylformamide and dimethylacetamide, but is not limited thereto.
In step S12, in one embodiment, the ratio of the ferulic acid to the second organic solvent is (0.1 ± 0.005) mmol:1 mL. That is, the ratio was (0.1. + -. 0.005) mmol: mixing 1mL of ferulic acid with a second organic solvent to dissolve ferulic acid in the second organic solvent to obtain a second solution.
In one embodiment, the second organic solvent may be selected from one or two of ethanol and methanol, but is not limited thereto.
In step S13, in one embodiment, the coordination reaction temperature is 20-30 deg.C, and the coordination reaction time is 10-30min, wherein the coordination reaction between zinc ion and ferulic acid is performed at 20-30 deg.C for 10-30 min.
In this embodiment, the zinc ion and ferulic acid undergo a coordination reaction, wherein the zinc ion and hydroxyl in ferulic acid form a coordination bond, thereby obtaining the metal-organic framework material.
In step S14, in one embodiment, the drying temperature is 100 ± 5 ℃ and the drying time is 24 ± 1 h. In this step, when the third solution contains only the metal-organic framework material and the first and second organic solvents, the obtained third solution, i.e., the solution containing the metal-organic framework material, is dried at a temperature of 100 ± 5 ℃ for 24 ± 1h to obtain the metal-organic framework material.
In one embodiment, in the step S14, when the third solution contains unreacted ferulic acid or zinc ions, the method may further include filtering and washing the third solution, and then drying the washed mixture to obtain the metal-organic framework material.
The embodiment of the invention also provides application of the metal organic framework material in inhibiting the growth of freshwater algae.
In one embodiment, the method of applying comprises the steps of:
s21, providing a sterile BG-11 culture medium solution;
s22, adding the metal organic framework material into the aseptic BG-11 culture medium solution to prepare a metal organic framework material stock solution;
s23, culturing the microcystis aeruginosa to obtain microcystis aeruginosa in log augmentation period;
s24, mixing the microcystis aeruginosa in the logarithmic growth phase with the aseptic BG-11 culture medium solution, and then adding the metal organic framework material stock solution to inhibit the growth of the microcystis aeruginosa in the logarithmic growth phase.
In this embodiment, the growth of microcystis aeruginosa in log growth stage is inhibited by mixing microcystis aeruginosa in log growth stage with the aseptic BG-11 culture medium solution and then adding the metal organic framework material stock solution. The inhibition effect of the metal organic framework material on the growth of the microcystis aeruginosa can be evaluated by periodically measuring the content of chlorophyll a in a mixed solution of the metal organic framework material, the microcystis aeruginosa and a sterile BG-11 culture medium solution, and the method specifically comprises the following steps: chlorophyll a is the most important component of primary producers and indirectly reflects the growth status and biomass of algae. Because the microcystis aeruginosa contains chlorophyll a which is an indispensable substance for maintaining the life of the microcystis aeruginosa, the metal organic framework material, the microcystis aeruginosa and the sterile BG-11 culture medium solution are mixed to obtain a mixed solution, the content of the chlorophyll a in the mixed solution is regularly measured, the life condition of the algae can be judged, the content of the chlorophyll a is reduced, and the content of the microcystis aeruginosa is reduced, so that the algae inhibiting effect of the metal organic framework material can be evaluated.
Experiments show that the metal organic framework material provided by the embodiment of the invention has good algae inhibiting effect, and obtains long and obvious algae inhibiting effect in a short time at low dosage.
The invention is further illustrated by the following specific examples.
Example 1
Adding Zn (NO)3)2·4H2O (0.297g,1mmol) was dissolved in 5mL dimethylformamide to give Zn (NO)3)2Dissolving ferulic acid (0.194g,1.0mmol) in 5mL ethanol to obtain ethanol solution of ferulic acid; the two are mixed and reacted for 30min at room temperature, and then baked in an oven for 24 hours at 100 ℃ to prepare 0.249g of the metal organic framework material, wherein the total yield is 90% calculated by Zn.
Performing characterization test on the prepared metal organic framework material
(1) XRD test
The prepared metal organic framework material is ground into superfine powder and pressed into tablets, the powder is detected by an XRD device, the test results are shown in figures 2 and 3, figure 2 is a powder diffraction pattern of the metal organic framework material, figure 3 is a powder diffraction pattern and a standard powder diffraction pattern of the metal organic framework material, and as can be seen from figure 3, the prepared metal organic framework material and { [ Zn ]2(fer)2]}nThe characteristic peaks of the standard powder diffraction pattern are matched, which indicates that the zinc ion is obtained by the preparationThe metal-organic framework material takes metal ions and ferulic acid as an organic ligand and has a chemical formula of { [ Zn { [2(fer)2]}n。
(2) SEM test
The metal organic framework material powder is directly pasted on the electrocoagulation adhesive, and is placed under SEM for scanning detection, the test result is shown in figure 4, when the magnification is 1000 times, the figure 4 (a) shows, the metal organic framework material has a rod-shaped structure, the sizes are different, when the magnification is 150000 times, the figure 4 (b) shows that the metal organic framework material has a net-shaped porous structure.
(3)Zn2+Dissolution test
Dissolving the metal organic framework material in water to prepare an aqueous solution of the metal organic framework material with the concentration of 1mg/L, and measuring Zn by ICP/MS2+Measured as Zn in an aqueous solution of a metal organic framework material of 1mg/L2+The concentration of (B) was 0.214 mg/L.
(4) Algal inhibition assay
Preparing 8 parts of metal organic framework material stock solution with the same concentration, wherein the preparation method of each part comprises the following steps: adding 10mg of metal organic framework material into 10mL of normal-temperature sterile BG-11 culture medium solution to prepare a metal organic framework material stock solution with the concentration of 1000 mg/L;
the microcystis aeruginosa is cultured for about 7 days to be in logarithmic growth phase, and the method specifically comprises the following steps: the cyanobacteria strain is Microcystis aeruginosa (Microcystis aeruginosa) provided by Wuhan aquatic organism research institute of Chinese academy of sciences, and is cultured in a light-irradiation incubator by using BG-11 culture medium. The culture conditions were: light intensity of about 30. mu. mol. (m)2·s)-1The temperature is 26 +/-1 ℃, the light-dark ratio is 12 h: 12h, and the shaking is carried out for 1-2 times every day at regular time.
Preparing 8 parts of mixed liquor containing microcystis aeruginosa in logarithmic growth phase and normal-temperature aseptic BG-11 culture medium solution, wherein the preparation method of each group of mixed liquor comprises the following steps: 100mL of room temperature sterile BG-11 medium solution was added to a 250mL Erlenmeyer flask and 10mL of Microcystis aeruginosa cell suspension in logarithmic phase was added, with the same initial concentration of Microcystis aeruginosa in each aliquot.
6 parts of the mixture are added inRespectively adding a certain amount of 1000mg/L metal-organic framework material stock solution into a mixed solution of the microcystis aeruginosa in the logarithmic growth period and the normal-temperature sterile BG-11 culture medium solution to ensure that the final concentration of the metal-organic framework material in each part is 0, 0.5, 1, 2, 4 and 8mg/L, respectively marking the obtained mixture as a blank control group, a 1 st group, a 2 nd group, a 3 rd group, a 4 th group and a 5 th group, respectively adding a certain amount of Zn (NO) into the remaining 2 parts of mixed solution containing the microcystis aeruginosa in the logarithmic growth period and the normal-temperature sterile BG-11 culture medium solution3)2·4H2O and ferulic acid, Zn2+The concentration in the mixed solution was 0.214mg/L (via Zn)2+The dissolution test shows that Zn is contained in the aqueous solution of the metal organic framework material of 1mg/L2+Was 0.214mg/L, thus, as a comparative group, Zn was caused here2+The concentration in the mixed solution is 0.214mg/L) is recorded as a group 6, so that the concentration of the ferulic acid in the mixed solution is 1mg/L and is recorded as a group 7; then the eight groups of mixed liquid samples are placed at normal temperature.
On days 1, 2, 3, 4, 5, 6, and 7 of the experiment, 2mL of microcystis aeruginosa cell suspension was taken from each mixed solution sample and placed in a measuring cup for chlorophyll a (Chl-a) concentration determination using a phytoplankton fluorescence classifier (Phyto-PAM).
The Chl-a concentrations in the microcystis aeruginosa cell suspensions at days 1, 2, 3, 4, 5, 6 and 7 after being treated with 0, 0.5, 1, 2, 4 and 8mg/L (respectively referred to as blank control group, 1 st group, 2 nd group, 3 rd group, 4 th group and 5 th group) of the metal-organic framework material are shown in table 1.
TABLE 1 Chl-a concentration (μ g/L) in Microcystis aeruginosa cell suspensions of different concentration metal organic framework material treatment groups
As is apparent from Table 1, the growth potential of Microcystis aeruginosa in the blank control group (i.e., the concentration of the metal-organic framework material is 0mg/L) is good and meets the growth characteristics of Microcystis aeruginosa. The growth of the microcystis aeruginosa in the group 1, namely the growth of the microcystis aeruginosa treated by the metal-organic framework material with the concentration of 0.5mg/L, is inhibited to a certain extent compared with a blank control group, and the highest inhibition rate of about 31 percent is reached on the 6 th day of the experiment. In the groups 2 and 3, when the concentration of the metal organic framework material is increased to 1mg/L and 2mg/L, the growth of microcystis aeruginosa is inhibited to a great extent compared with that of a blank control group, and the algae inhibiting effect which can be achieved only by 6 days after the metal organic framework material of 0.5mg/L is treated is achieved by the 3 rd day of the experiment. After the 4mg/L metal-organic framework material in the group 4 is treated, the growth of the microcystis aeruginosa is more obviously influenced than that of a blank control group, the inhibition rate is about 35% in the 2 nd day of the experiment, the inhibition rate is more than 60% in the 3 rd day of the experiment, the complete inhibition of the microcystis aeruginosa is realized in the 6 th day of the experiment, and the metal-organic framework material has strong inhibition effect on the growth of the microcystis aeruginosa. In the group 5, the concentration of the metal organic framework material is 8mg/L at most, the inhibition rate of more than 90% is reached on the 4 th day of the experiment, and the microcystis aeruginosa cells are completely killed on the 5 th day, which shows that the metal organic framework material can effectively inhibit the growth of the microcystis aeruginosa in a short time. Moreover, no sign of growth recovery of the microcystis aeruginosa in the groups 4 and 5 is shown after the microcystis aeruginosa is inhibited by 4mg/L and 8mg/L of metal-organic framework materials.
The half-maximal effect concentration (EC50) of the metal-organic framework material in 7 days of the algae inhibition experiment, calculated by software, is shown in table 2.
TABLE 2 EC50 values of MOM materials for Microcystis aeruginosa
The half-maximal effect concentration (EC50) reflects the capability of the metal-organic framework material to inhibit the growth of microcystis aeruginosa, and the results show that the metal-organic framework material can inhibit the growth of microcystis aeruginosa very efficiently, and EC50 is only 1.31mg/L on the 4 th day of the experiment and is only 0.775mg/L on the 7 th day of the experiment. Therefore, the metal organic framework material can achieve a better algae inhibiting effect in a shorter time with a lower dosage, can greatly reduce the economic cost, shorten the treatment period, can quickly control or eliminate harmful algae, is suitable for controlling the occurrence of algal bloom and is beneficial to the control of the environment.
0mg/L of metal organic framework material (blank control group), 1mg/L of metal organic framework material (group 2), 0.214mg/L of Zn (NO)3)2·4H2The Chl-a content and the algal inhibition rate of the microcystis aeruginosa cell suspension in O (group 6) and 1mg/L ferulic acid (group 7) are shown in tables 3 and 4, respectively.
TABLE 3 Metal organic framework materials with the same concentration of Zn2+And Chl-a concentration (μ g/L) in Microcystis aeruginosa cell suspension of the ferulic acid-treated group
TABLE 4 Metal organic framework materials with the same concentration of Zn2+Algal inhibition rate of ferulic acid-treated group
1mg/L of metal organic framework material and 0.214mg/L of Zn (NO)3)2·4H2The Chl-a content (. mu.g/L) and algal inhibition rate of O and 1mg/L ferulic acid-treated Microcystis aeruginosa are shown in tables 3 and 4, respectively. As can be seen from tables 3 and 4, the blank control group of Microcystis aeruginosa showed good growth, and the most significant growth inhibition of Microcystis aeruginosa was 1mg/L metal-organic framework material followed by 0.214mg/L Zn (NO)3)2·4H2O, and finally 1mg/L ferulic acid. 0.214mg/L Zn (NO)3)2·4H2The highest inhibition rates of O and 1mg/L ferulic acid within 7 days of the experiment are respectively 25.7 percent and 17.2 percent, while the highest inhibition rate of 1mg/L metal organic framework material is 63.5 percent and is higher than the sum of the inhibition rates of the other two, thus the algae inhibiting effect of the metal organic framework material is not Zn2+And of ferulic acidAlthough metal zinc ions as a heavy metal have a certain inhibition effect on blue-green algae in a water body and ferulic acid as a phenolic acid allelopathy substance also has an algae inhibition effect, the research result of the invention shows that the algae inhibition effect generated by the metal organic framework material is not a simple superposition effect of the zinc ions and the ferulic acid but a certain synergistic algae inhibition effect, and the generated algae inhibition effect is higher than the simple superposition effect of the zinc ions and the ferulic acid and is higher than the sum of the algae inhibition effects of the zinc ions and the ferulic acid, namely the synergistic algae inhibition effect is generated. And the microcystis aeruginosa inhibited by the metal organic framework material of 1mg/L has no growth state recovery potential within 7 days of the experiment, so that the good algae inhibiting effect of the metal organic framework material can be seen, and the higher algae inhibiting effect can be achieved within a shorter time with lower dosage.
In summary, the invention provides a metal organic framework material, and a preparation method and an application thereof. The metal organic framework material takes zinc ions as metal ions and ferulic acid as an organic ligand, can release the allelopathic algae inhibiting substances ferulic acid and metal zinc ions in a sustained-release manner, and both can be used as an algae inhibitor for inhibiting the growth of fresh water algae, so that the metal organic framework material can be used as the algae inhibitor for inhibiting the growth of the fresh water algae. In addition, the algae inhibiting effect of the metal organic framework material is higher than the simple additive effect of zinc ions and ferulic acid, and the algae inhibiting effect is higher than the sum of the algae inhibiting effects of the zinc ions and the ferulic acid, namely, the synergistic algae inhibiting effect is generated. The metal organic framework material has good algae inhibiting effect, can obviously inhibit the growth of algae in a relatively low dosage and relatively short time when being used as an algae inhibiting agent, can greatly reduce the economic cost, shorten the treatment period, can quickly control or eliminate harmful algae, is suitable for controlling the occurrence of algal bloom, is beneficial to the management of the environment, and has very high economic benefit.
It is to be understood that the invention is not limited to the examples described above, but that modifications and variations may be effected thereto by those of ordinary skill in the art in light of the foregoing description, and that all such modifications and variations are intended to be within the scope of the invention as defined by the appended claims.
Claims (9)
1. Use of a metal-organic framework material for inhibiting the growth of freshwater algae, the metal-organic framework material comprising ferulic acid and zinc ions, the ferulic acid being bound to the zinc ions in the form of coordinate bonds, the metal-organic framework material belonging to the monoclinic system, having a space group of C2/C, a crystal size of 0.31mm x 0.12mm x 0.07mm, the metal-organic framework material having a reticulated porous structure.
2. The use of a metal organic framework material according to claim 1 for inhibiting the growth of freshwater algae, wherein hydroxyl groups in the ferulic acid form coordinate bonds with the zinc ions.
3. Use of a metal organic framework material according to claim 1 for inhibiting the growth of freshwater algae, wherein the molar ratio of ferulic acid to zinc ions is (0.8-1.2): (0.8-1.2).
4. The use of the metal-organic framework material according to claim 1 for inhibiting the growth of freshwater algae, wherein the preparation method of the metal-organic framework material comprises the steps of:
dissolving zinc salt in a first organic solvent to obtain a first solution;
dissolving ferulic acid in a second organic solvent to obtain a second solution;
under the condition of stirring, mixing the first solution and the second solution, and carrying out coordination reaction to obtain a third solution;
and drying the third solution to obtain the metal organic framework material.
5. The use of a metal-organic framework material according to claim 4 for inhibiting the growth of freshwater algae, wherein the ratio of the zinc salt to the first organic solvent is (0.1 ± 0.005) mmol:1 mL;
and/or the ratio of the ferulic acid to the second organic solvent is (0.1 +/-0.005) mmol:1 mL.
6. The use of a metal organic framework material according to claim 4 for inhibiting the growth of freshwater algae, wherein the zinc salt is selected from one or more of zinc nitrate, zinc sulfate, and zinc acetate.
7. The use of a metal organic framework material according to claim 4 for inhibiting the growth of freshwater algae, wherein the first organic solvent is selected from one or both of dimethylformamide and dimethylacetamide;
and/or the second organic solvent is selected from one or two of ethanol and methanol.
8. Use of a metal organic framework material according to claim 4 for inhibiting the growth of freshwater algae,
the temperature of the coordination reaction is 20-30 ℃, and the time of the coordination reaction is 10-30 min;
and/or the drying temperature is 100 +/-5 ℃, and the drying time is 24 +/-1 h.
9. Use of a metal organic framework material according to claim 1 for inhibiting the growth of freshwater algae, characterized in that the method of application comprises the steps of:
providing a sterile BG-11 medium solution;
adding the metal organic framework material into the sterile BG-11 culture medium solution to prepare a metal organic framework material stock solution;
culturing the microcystis aeruginosa to obtain microcystis aeruginosa in logarithmic growth period;
and mixing the microcystis aeruginosa in the logarithmic growth phase with the sterile BG-11 culture medium solution, and then adding the metal-organic framework material storage solution to inhibit the growth of the microcystis aeruginosa in the logarithmic growth phase.
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