CN114539542B - Metal organic framework material for tumor microwave thermal-dynamic treatment and preparation method and application thereof - Google Patents

Metal organic framework material for tumor microwave thermal-dynamic treatment and preparation method and application thereof Download PDF

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CN114539542B
CN114539542B CN202011356812.1A CN202011356812A CN114539542B CN 114539542 B CN114539542 B CN 114539542B CN 202011356812 A CN202011356812 A CN 202011356812A CN 114539542 B CN114539542 B CN 114539542B
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framework material
organic framework
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nickel
metal
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CN114539542A (en
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吴琼
孟宪伟
谭龙飞
任湘菱
付长慧
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Technical Institute of Physics and Chemistry of CAS
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
    • C08G83/008—Supramolecular polymers
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K41/00—Medicinal preparations obtained by treating materials with wave energy or particle radiation ; Therapies using these preparations
    • A61K41/0052—Thermotherapy; Hyperthermia; Magnetic induction; Induction heating therapy
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K41/00—Medicinal preparations obtained by treating materials with wave energy or particle radiation ; Therapies using these preparations
    • A61K41/0057—Photodynamic therapy with a photosensitizer, i.e. agent able to produce reactive oxygen species upon exposure to light or radiation, e.g. UV or visible light; photocleavage of nucleic acids with an agent
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
    • A61P35/00—Antineoplastic agents

Abstract

The invention discloses a metal organic framework material for tumor microwave thermal-power treatment, a preparation method and application thereof, wherein the central metal ion of the metal organic framework material is nickel ion and cobalt ion. The metal organic framework material can be used for tumor microwave thermal therapy sensitization and microwave power treatment, and can realize good tumor treatment effect.

Description

Metal organic framework material for tumor microwave thermal-dynamic treatment and preparation method and application thereof
Technical Field
The invention relates to a preparation technology of a metal organic framework material and the field of biological application thereof, in particular to a metal organic framework material for tumor microwave thermal-power treatment and a preparation method and application thereof.
Background
Cancer (malignancy) is becoming one of the major public health problems that severely threatens human health (CA Cancer J Clin 2018, 68, 394-424). Recent statistics in the national cancer center show that cancer incidence has been increased by about 3.9% per year and mortality has been increased by about 2.5% per year for more than 10 years (Chin J Cancer Res 2018, 30 (1), 1-12,Chin J Cancer Res 2019, 31 (1), 99-116). Death of the resident caused by cancer accounts for about 23.91% of all causes of death, and the incidence and death of cancer are in a continuous rising situation in recent decades, and medical cost caused by cancer exceeds 2200 hundred million each year. Cancer has seriously affected the healthy and happy life of people in China and even worldwide, and brings great pain and challenges to human society. Therefore, the prevention and control of cancer is severe.
At present, the clinical application and treatment modes of cancers mainly comprise: surgery, radiation therapy, chemotherapy, thermal therapy, biological therapy, traditional Chinese medicine therapy, molecular targeted therapy, etc. (Biomaterials 2018, 158,1-9, acs Nano 2017, 11 (7), 7006-7018,Nat Commun2017,8 (1), 1343). But the most common in clinic are the traditional treatments, namely surgery, chemotherapy and radiotherapy, and biological and tumor hyperthermia, which are now known as fourth and fifth modes of treatment (New Engl J Med 2005, 352 (10), 987-996,Nat Commun2017,8 (1), 902). Among them, tumor hyperthermia (hyperthermia) is a tumor treatment method that heats tumor tissue by heating with physical energy of non-ionizing radiation to reach an effective treatment temperature. Tumor hyperthermia is a purely physical treatment, and its physical energy heat sources include infrared rays, ultrasonic waves, high-frequency electromagnetic waves, etc., which can effectively kill tumor cells (Nat Rev Cancer 2014, 14 (3), 199-208,Acs Nano 2015,9 (6), 6626-6633). In recent years, the tumor hyperthermia has made a lot of great progress, has developed rapidly in clinical application, and can not only kill cancer cells directly, so as to treat tumor effectively; the composition can be used as an auxiliary treatment method to improve the effect of radiotherapy and chemotherapy, thereby increasing the sensitivity of the radiotherapy and chemotherapy, and simultaneously reducing the side effects of the radiotherapy and chemotherapy, so that the composition is called a fifth tumor treatment method (Chem Rev 2015, 115 (19), 10637-89,Nanoscale 2017,9 (33), 11888-11901) except for surgery, chemotherapy, radiotherapy and biological treatment, and has important position in tumor treatment.
Microwave hyperthermia is an emerging green therapy, has the advantages of noninvasive or minimally invasive, high heating efficiency, wide treatment range, large penetration depth and the like, and plays an important role in clinical tumor treatment. However, with the increasing development of basic research and clinical application, the limitation of the microwave hyperthermia is gradually revealed, and the microwave hyperthermia technology cannot realize specific heating, that is, the microwave hyperthermia cannot limit the heating range to the tumor part, so that the temperature difference between the tumor part and normal tissues is not large, the thermal effect of the microwave hyperthermia on the tumor area is insufficient, the residual of tumor cells is caused, and the tumor recurs. The development of nano technology provides a solution to the problem, and the specificity of microwave thermal therapy can be improved and the microwave ablation area can be enlarged by utilizing the high permeation and long retention (EPR) effect of nano materials in the tumor area. However, basic research shows that although the nano material is introduced as the microwave sensitizer, the problem of nonspecific heating of the microwave hyperthermia can be solved, and the microwave hyperthermia curative effect can be improved. However, the temperature drops rapidly at the edges of the tumor remote from the microwave source, resulting in insufficient heat and thus difficulty in thoroughly killing the tumor cells. However, the tumor cells in the sublethal state may be revived by self-repair, so that the tumor area still has local focus residues after microwave hyperthermia, and the tumor is caused to relapse locally. Therefore, single microwave sensitization thermotherapy still can not meet the requirement of complex and changeable microenvironment of tumors, and can not thoroughly kill the tumors.
Therefore, how to prepare the nano material for microwave power therapy at the same time of microwave thermal therapy, and the specificity of the tumor microwave thermal therapy is effectively increased and the tumor cells are killed by combining the microwave thermal therapy sensitization and the microwave power effect; meanwhile, microwave hyperthermia is assisted by microwave power therapy to effectively kill residual local focus of a tumor area after microwave hyperthermia so as to thoroughly kill tumors, thereby achieving good in-vivo and in-vitro microwave thermo-dynamic effects and realizing effective microwave thermo-dynamic treatment of tumors.
Disclosure of Invention
In order to solve the technical problems, the invention provides a metal-organic framework material for tumor microwave thermo-dynamic treatment, wherein the central metal ion of the metal-organic framework material is nickel ion (Ni 2+ ) And cobalt ion (Co) 2+ )。
According to an embodiment of the invention, the metal organic framework material is obtained by reacting a nickel salt and a cobalt salt with an organic ligand.
According to an embodiment of the present invention, the nickel and cobalt salts are, for example, at least one of nickel and cobalt nitrate, chloride, sulfate, acetate and carbonate; nitrate and chloride of nickel and cobalt are preferred.
According to an exemplary embodiment of the present invention, the central metal ion nickel ion (Ni 2+ ) Various divalent nickel salts may be selected, includingBut are not limited to, at least one of nickel nitrate, nickel chloride, and nickel acetate; nickel nitrate is preferred.
According to an exemplary embodiment of the invention, the central metal ion cobalt ion (Co 2+ ) A variety of divalent cobalt salts may be selected including, but not limited to, at least one of cobalt nitrate, cobalt chloride, and cobalt acetate. Cobalt nitrate is preferred.
According to an embodiment of the invention, the organic ligand in the metal organic framework material is an imidazole ligand. For example, at least one of 2-methylimidazole, 2-ethylimidazole and imidazole; preferably selected from 2-methylimidazole.
According to an embodiment of the invention, the metal-organic framework material has a diameter of 40-500nm.
Preferably, the diameter of the metal organic framework material is 40-100nm and 45-95nm.
The invention also provides a preparation method of the metal organic framework material for the tumor microwave thermo-dynamic treatment, which comprises the steps of dispersing nickel salt and cobalt salt in a solvent, and then reacting with an organic ligand to obtain the metal organic framework material.
According to an embodiment of the invention, co in the metal organic framework material 2+ 、Ni 2+ The molar usage ratio of (2) is 1: (0.5-2), exemplary 1:0.5, 1:1, 1:2; preferably 1:1.
according to an embodiment of the invention, the mass concentration of the central metal ion of the metal-organic framework material is 10-200mg/mL; preferably 20-100mg/mL; exemplary are 10mg/mL, 20mg/mL, 40mg/mL, 60mg/mL, 80mg/mL, 100mg/mL, 200mg/mL, or any point value between any two combinations of the above.
According to an embodiment of the invention, the organic ligand in the metal organic framework material is an imidazole ligand. For example, the imidazole-based ligand may be selected from at least one of 2-methylimidazole, 2-ethylimidazole and imidazole; preferably selected from 2-methylimidazole.
According to an embodiment of the invention, the mass concentration of the imidazole ligand is 20-1600mg/mL; preferably 80-1000mg/mL; exemplary are 20mg/mL, 40mg/mL, 80mg/mL, 100mg/mL, 200mg/mL, 300mg/mL, 400mg/mL, 500mg/mL, 600mg/mL, 700mg/mL, 800mg/mL, 900mg/mL, 1000mg/mL, 1200mg/mL, 1500mg/mL, 1600mg/mL, or any point in between any two combinations of the foregoing.
According to an embodiment of the invention, the solvent is selected from methanol, ethanol and water.
According to the embodiment of the invention, the preparation method further comprises the process of carrying out solid-liquid separation on the reaction system after the reaction is finished to obtain a reaction product. For example, the solid-liquid separation may employ means known in the art, such as centrifugation. Preferably, the rotational speed of the centrifugation is in the range of 5000-10000rpm, such as 6000-9000rpm. Further, the centrifugation time is, for example, 5 to 10 minutes. Under the centrifugal condition, the metal organic framework material with excellent performance for tumor microwave thermal-power treatment can be obtained.
According to an embodiment of the present invention, the preparation method further comprises washing the reaction product obtained by the solid-liquid separation. For example, the reaction product is washed with a solvent capable of dissolving the metal-organic framework material. Preferably, the solvent may be absolute ethanol. As another example, the number of washes may be one, two or more, preferably two.
According to an embodiment of the invention, the preparation method further comprises drying the washed reaction product. For example, freeze drying is used.
According to an embodiment of the invention, the preparation method comprises the steps of:
1) Ultrasonically dispersing nickel salt and cobalt salt in methanol;
2) Dispersing 2-methylimidazole in methanol by ultrasonic waves;
3) Adding the solution in the step 2) into the solution in the step 1), and stirring at room temperature;
4) Centrifuging the product obtained in the step 3), washing with ethanol, and finally freeze-drying the sample to obtain a powdery product.
According to an embodiment of the invention, in step 3), the stirring time is 0.5 to 12 hours; preferably 1 to 10 hours.
The invention also provides application of the metal organic framework material in tumor microwave thermal-power treatment. The invention has the beneficial effects that:
(1) The metal organic framework material is applied to the fields of tumor microwave thermal therapy sensitization and microwave power treatment for the first time, ions in the environment can be recruited based on the high specific surface area and the porous structure, strong inelastic collision is generated through a finite field effect under microwave irradiation, and a large amount of friction heat generated by collision can cause death of tumor cells. Meanwhile, the metal organic framework material adopted by the invention can generate heat and free radicals under microwave irradiation, can be used as a microwave sensitizer, and can effectively generate active oxygen (ROS) with cytotoxicity by a special microwave power effect to assist microwave hyperthermia, thereby further killing residual tumors and realizing a good tumor treatment effect. Therefore, the treatment efficiency of cancer treatment can be obviously improved, and the method has good clinical application value.
(2) The preparation method of the metal organic framework material for tumor microwave hyperthermia technology and microwave power treatment is simple, no special equipment is needed, the reaction raw materials are easy to obtain, the cost is low, and the metal organic framework material prepared by the method has uniform size and good monodispersity.
Drawings
FIG. 1 is a transmission electron micrograph of the metal-organic framework material for tumor microwave hyperthermia technology and microwave kinetic treatment obtained in example 1;
FIG. 2 is a scanning electron micrograph of the metal-organic framework material obtained in example 1 for use in tumor microwave hyperthermia techniques and microwave kinetic therapy;
FIG. 3 shows the size distribution of the metal-organic framework material obtained in example 1 under a scanning electron microscope photograph for tumor microwave hyperthermia technology and microwave power treatment;
FIG. 4 shows the hydrated particle size distribution of the metal organic framework material for tumor microwave hyperthermia technology and microwave power treatment obtained in example 1;
FIG. 5 shows the microwave heating effect of the metal-organic framework material for tumor microwave hyperthermia technology and microwave power treatment obtained in example 1;
FIG. 6 shows the microwave kinetic effects of the metal-organic framework material for tumor microwave hyperthermia technology and microwave kinetic treatment obtained in example 1;
FIG. 7 is a diagram showing the temperature rise of the microwave obtained by monitoring the near infrared thermal imager in the experiment of microwave thermal-power combined treatment of the metal organic framework material for tumor microwave thermal therapy technology and microwave power treatment obtained in example 1;
FIG. 8 is a transmission electron micrograph of the metal-organic framework material for tumor microwave hyperthermia technology and microwave kinetic treatment obtained in example 2;
FIG. 9 shows the microwave heating effect of the metal-organic framework material for tumor microwave hyperthermia technology and microwave power treatment obtained in example 2;
FIG. 10 shows the microwave kinetic effects of the metal-organic framework material for tumor microwave hyperthermia technology and microwave kinetic treatment obtained in example 2;
FIG. 11 is a transmission electron micrograph of the metal-organic framework material for tumor microwave hyperthermia technology and microwave kinetic treatment obtained in example 3;
FIG. 12 shows the microwave heating effect of the metal-organic framework material for tumor microwave hyperthermia technology and microwave power treatment obtained in example 3;
fig. 13 shows the microwave power effect of the metal organic framework material for tumor microwave hyperthermia technology and microwave power treatment obtained in example 3.
Detailed Description
The technical scheme of the invention will be further described in detail below with reference to specific embodiments. It is to be understood that the following examples are illustrative only and are not to be construed as limiting the scope of the invention. All techniques implemented based on the above description of the invention are intended to be included within the scope of the invention.
Unless otherwise indicated, the starting materials and reagents used in the following examples were either commercially available or may be prepared by known methods.
Example 1
100mg of Ni (NO) 3 ) 2 ·6H 2 O and 100mg of Co (NO) 3 ) 2 ·6H 2 Placing O in a glass bottle, and performing ultrasonic dispersion by using 5mL of methanol; 400mg of 2-methylimidazole is placed in a glass bottle, 5mL of methanol is also used for ultrasonic dispersion, the mixture is added into the solution and uniformly mixed, and magnetic stirring is carried out for 6 hours at room temperature; and then putting the obtained product into a centrifuge tube for centrifugation, washing twice with ethanol, and finally freeze-drying the sample to obtain a powdery product.
The transmission electron microscope photograph, the scanning electron microscope photograph, the size distribution and the hydration particle size distribution of the metal organic framework material prepared in the example 1 are respectively shown in fig. 1-4. It can be seen from the figure that the diameter of the metal organic framework material prepared by the embodiment is 40-500nm, preferably in the particle size range of 40-100nm, the metal organic framework material has high specific surface area and porous structure, uniform size and good monodispersity, and therefore, the metal organic framework material can be applied to the fields of tumor microwave hyperthermia sensitization and microwave power treatment, realizes good tumor treatment effect, obviously improves the treatment efficiency of cancer treatment, and has good clinical application value.
Example 2
100mg of NiCl 2 ·6H 2 O and 100mg CoCl 2 ·6H 2 Placing O in a glass bottle, and performing ultrasonic dispersion by using 5mL of methanol; 400mg of 2-methylimidazole is placed in a glass bottle, 5mL of methanol is also used for ultrasonic dispersion, the mixture is added into the solution and uniformly mixed, and magnetic stirring is carried out for 6 hours at room temperature; and then putting the obtained product into a centrifuge tube for centrifugation, washing twice with ethanol, and finally freeze-drying the sample to obtain a powdery product.
The transmission electron microscope photograph of the metal organic framework material prepared in example 2 is shown in fig. 8. As can be seen from the figure, the metal organic framework material prepared by the embodiment has the diameter of 40-500nm, preferably 40-100nm, a high specific surface area and a porous structure, uniform size and good monodispersity.
Example 3
100mg of Ni (CH) 3 COO) 2 And 100mg Co (CH) 3 COO) 2 Placing in a glass bottle, and performing ultrasonic dispersion by using 5mL of methanol; 400mg of 2-methylimidazole is placed in a glass bottle, 5mL of methanol is also used for ultrasonic dispersion, the mixture is added into the solution and uniformly mixed, and magnetic stirring is carried out for 6 hours at room temperature; and then putting the obtained product into a centrifuge tube for centrifugation, washing twice with ethanol, and finally freeze-drying the sample to obtain a powdery product.
A transmission electron micrograph of the metal-organic framework material prepared in example 3 is shown in fig. 11. As can be seen from the figure, the metal organic framework material prepared by the embodiment has the diameter of 40-500nm, preferably 40-100nm, a high specific surface area and a porous structure, uniform size and good monodispersity.
Example 4
In-vitro microwave heating experiments are carried out on the metal organic framework materials prepared in the examples 1-3, and the microwave power effect and the in-vivo tumor microwave hyperthermia and microwave power treatment effect are evaluated.
Taking the metal organic framework material samples prepared in the examples 1-3, and carrying out in vitro microwave heating experiments. The specific experimental method is as follows:
the metal organic framework materials prepared in examples 1-3 were respectively taken and ultrasonically dispersed in 1mL of 0.9% physiological saline to form 2mg/mL, 5mg/mL and 10mg/mL solutions, then the solutions were sequentially moved into a microwave heating device, microwave irradiation (0.9W, 450Hz and 5 min) was respectively applied to the solutions, and the real-time temperature of the microwave heating of the three solutions was respectively recorded by a near infrared thermal imager, and the microwave heating results are respectively shown in FIGS. 5,9 and 12. From the figure, it can be seen that the metal-organic framework materials prepared in the embodiments 1-3 have better microwave heating effect, so that the metal-organic framework materials can be applied to microwave hyperthermia and microwave power treatment of tumors in vivo.
Taking metal organic framework material samples prepared in examples 1-3, and evaluating microwave power effect through a fluorescent probe DCFH-DA, wherein the specific experimental method is as follows:
the metal-organic framework materials prepared in examples 1 to 3 were respectively prepared by dispersing 2.5mg, 5mg and 10mg in 2.3mL of phosphate buffer saline (PBS, pH=7.4) by ultrasonic treatment to form solutions, then transferring the solutions into a microwave heating device, respectively adding 200. Mu.L of fluorescent probe DCFH-DA solution for detecting ROS (the fluorescent probe DCFH-DA solution is diluted to 50. Mu.M by PBS with pH=7.4) to form solutions of 1mg/mL, 2mg/mL and 4mg/mL, and then respectively applying microwave irradiation treatment (0.9W, 450Hz and 5 min) to the three solutions. And then, standing for 30min in a dark place, centrifuging to obtain a supernatant, detecting the fluorescence intensity of the system by a fluorescence spectrometer, and analyzing the microwave power effect, wherein the microwave power effect is shown in figures 6, 10 and 13 respectively. As can be seen from the figure, the metal-organic framework materials prepared in the examples 1 to 3 of the present invention can generate Reactive Oxygen Species (ROS) with cytotoxicity, and the content of the generated ROS increases with the increase of the concentration of the metal-organic framework material solution after the microwave irradiation treatment. The microwave dynamic effect of the metal organic framework material on the tumor is obvious.
The microwave heat-power combined treatment experiment in animals is as follows:
5mg of the metal organic framework material prepared in example 1 is dispersed in 1mL of 0.9% physiological saline to form 5mg/mL solution, and the solution is injected into an ICR mouse inoculated with H22 tumor subcutaneously by tail vein injection, and different volumes of the metal organic framework material solution are injected according to different weights of the mice, so that the final injection dose of the ICR mouse inoculated with H22 tumor is 50mg/kg. After 6h of tail vein injection, microwave irradiation (0.9W, 450Hz,5 min) was applied to the tumor site of the mice, and the temperatures of ICR mice at different microwave times were monitored and observed by a near infrared thermal imager, and the results are shown in FIG. 7.
From the results in fig. 7, it can be found that: after microwave irradiation is applied to the tumor part of the mouse for 1min, the temperature of the tumor center part of the ICR mouse rapidly reaches more than 45 ℃, and the ICR mouse is completely enough to kill tumor cells at the temperature; and further, the residual tumor cells at the edge of the tumor are killed by the cytotoxic ROS generated by the microwave power effect, so that the recurrence of sublethal tumors at the warm-hot area at the edge of the tumor is avoided, and the complete killing of the tumors in the ICR mice is realized. After observation for about half a month, it was found that the tumor location in ICR mice was completely recovered and the skin was completely restored to normal. Therefore, the metal organic framework material can realize good tumor treatment effect so as to obviously improve the treatment efficiency of cancer diagnosis.
The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiment. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (21)

1. The application of the metal organic framework material in preparing the tumor microwave thermo-dynamic therapeutic agent is characterized in that the central metal ion of the metal organic framework material is nickel ion Ni 2+ And cobalt ion Co 2+ The metal organic framework material is obtained by reacting nickel salt and cobalt salt with an organic ligand, and the organic ligand in the metal organic framework material is at least one of 2-methylimidazole, 2-ethylimidazole and imidazole.
2. The use according to claim 1, wherein the nickel and cobalt salts are at least one of nickel and cobalt nitrate, chloride, sulfate, acetate and carbonate.
3. Use according to claim 2, wherein the nickel and cobalt salts are nickel and cobalt nitrates, chlorides.
4. The use according to claim 1, wherein the metal organic framework material has a central metal ion nickel ion Ni 2+ And selecting a plurality of divalent nickel salts, wherein the divalent nickel salts are at least one of nickel nitrate, nickel chloride and nickel acetate.
5. The use according to claim 4, wherein the divalent nickel salt is nickel nitrate.
6. The use according to claim 1, wherein the metal organic framework material has a central metal ion cobalt ion Co 2+ And selecting a plurality of bivalent cobalt salts, wherein the bivalent cobalt salts are at least one of cobalt nitrate, cobalt chloride and cobalt acetate.
7. The use according to claim 6, wherein the divalent cobalt salt is cobalt nitrate.
8. Use according to claim 1, wherein the organic ligand in the metal organic framework material is selected from 2-methylimidazole.
9. The use according to claim 1, wherein the metal-organic framework material has a diameter of 40-500 a nm a.
10. The use according to claim 9, wherein the metal organic framework material has a diameter of 40-100 a nm a.
11. The use according to claim 9, wherein the metal-organic framework material has a diameter of 45-95nm.
12. The use according to claim 1, wherein the preparation of the metal organic framework material comprises dispersing a nickel salt and a cobalt salt in a solvent and then reacting with an organic ligand to obtain the metal organic framework material.
13. The use according to claim 12, wherein Co in the metal organic framework material 2+ 、Ni 2+ The molar usage ratio of (2) is 1: (0.5-2).
14. The use according to claim 13, wherein Co in the metal organic framework material 2+ 、Ni 2+ The molar ratio of (2) is 1:0.5, 1:1 or 1:2.
15. The use according to claim 12, wherein the metal organic framework material has a mass concentration of central metal ions of 10-200 mg/mL.
16. The use according to claim 15, wherein the metal organic framework material has a mass concentration of central metal ions of 20-100 mg/mL.
17. The use according to claim 12, wherein the mass concentration of the organic ligand is 20-1600mg/mL.
18. The use according to claim 17, wherein the mass concentration of the organic ligand is 80-1000mg/mL.
19. Use according to claim 12, wherein the solvent is selected from methanol, ethanol and water.
20. Use according to any one of claims 12 to 19, wherein the method for preparing the metal-organic framework material comprises the steps of:
1) Ultrasonically dispersing nickel salt and cobalt salt in methanol;
2) Dispersing 2-methylimidazole in methanol by ultrasonic waves;
3) Adding the solution in the step 2) into the solution in the step 1), and stirring at room temperature;
4) Centrifuging the product obtained in the step 3), washing with ethanol, and finally freeze-drying the product to obtain a powdery product.
21. The use according to claim 20, wherein in step 3) the stirring time is between 0.5 and 12 and h.
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