CN114539542A - Metal organic framework material for microwave thermal-dynamic tumor treatment and preparation method and application thereof - Google Patents
Metal organic framework material for microwave thermal-dynamic tumor treatment and preparation method and application thereof Download PDFInfo
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- 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
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Abstract
The invention discloses a metal organic framework material for microwave thermal-dynamic tumor treatment, and a preparation method and application thereof. The metal organic framework material can be used for tumor microwave thermotherapy sensitization and microwave dynamic therapy, and can realize good tumor therapy effect.
Description
Technical Field
The invention relates to the field of preparation technology and biological application of metal organic framework materials, in particular to a metal organic framework material for tumor microwave thermal-dynamic therapy and a preparation method and application thereof.
Background
Cancer (malignancy) is increasingly becoming one of the major public health problems that severely threaten human health (CA Cancer J Clin 2018, 68, 394-. Recent statistics by the national Cancer center show that over the last 10 years, Cancer incidence has remained on the order of 3.9% and mortality has remained on the order of 2.5% per year (Chin J Cancer Res 2018, 30(1), 1-12, Chin J Cancer Res 2019, 31(1), 99-116). Cancer-related deaths account for about 23.91% of all deaths of residents, and cancer-related deaths have been on the rise in recent decades, with medical costs exceeding 2200 billions per year. Cancer has severely affected the healthy and happy lives of china and even people all over the world, and has brought enormous pain and challenge to human society. Therefore, the prevention and control of cancer is serious.
Currently, the clinical application of cancer treatment modes mainly include: surgery, radiotherapy, chemotherapy, thermotherapy, biotherapy, traditional Chinese medicine therapy, molecular targeted therapy, etc. (Biomaterials 2018, 158, 1-9, ACS Nano 2017, 11(7), 7006-. However, the most common clinical treatments are surgery, chemotherapy and radiotherapy, and the fourth and fifth therapeutic modalities known today as biological therapy and tumor hyperthermia (New Engl J Med 2005, 352(10), 987-. Among them, the tumor thermotherapy (hyperthermia) is a tumor treatment method in which the physical energy of non-ionizing radiation is used for heating tumor tissue to raise the temperature of the tumor tissue, thereby achieving an effective treatment temperature. Tumor hyperthermia is a pure physical therapy, and the physical energy heat source of the hyperthermia comprises infrared rays, ultrasonic waves, high-frequency electromagnetic waves and the like, and can effectively kill tumor cells (Nat Rev Cancer 2014, 14(3), 199-. In recent years, the tumor thermotherapy has made great progress, and is rapidly developed in the aspect of clinical application, and the tumor thermotherapy can directly kill cancer cells so as to directly and effectively treat tumors; moreover, the compound can be used as an auxiliary treatment method to improve the effect of radiotherapy and chemotherapy, thereby increasing the sensitivity of radiotherapy and chemotherapy and simultaneously reducing the side effect of radiotherapy and chemotherapy, so the compound is called as a fifth tumor treatment method (Chem Rev 2015, 115(19), 10637-89, Nanoscale 2017, 9(33), 11888-11901) besides surgery, chemotherapy, radiotherapy and biological treatment, and has an important position in tumor treatment.
Microwave thermotherapy, as a new green therapy, has the advantages of non-invasive or minimally invasive, high heating efficiency, wide treatment range, large penetration depth and the like, and occupies an important position in clinical tumor treatment. However, with the development of basic research and clinical application, the limitations of microwave thermotherapy begin to be gradually revealed, and the microwave thermotherapy cannot realize specific heating, that is, the microwave thermotherapy cannot limit the heating range to the tumor region, so the temperature difference between the tumor region and the normal tissue is not large, which causes the microwave thermotherapy to have insufficient thermal effect on the tumor region, and the tumor cells remain, causing the recurrence of the tumor. The development of the nanometer technology provides a solution for the problem, and the specificity of microwave thermotherapy can be improved and the microwave ablation area can be enlarged by utilizing the high-permeability and long-retention (EPR) effect of the nanometer material in the tumor area. However, basic research finds that the problem of non-specific heating of microwave thermotherapy can be improved and the curative effect of microwave thermotherapy can be improved by introducing the nano material as a microwave sensitizer. However, the temperature drops rapidly at the tumor margins away from the microwave source, resulting in insufficient heat and thus difficulty in completely killing the tumor cells. However, these tumor cells in the sub-lethal state may be restored by self-repair, so that the tumor area still has local lesion residues after microwave thermotherapy, resulting in local tumor recurrence. Therefore, the single microwave sensitization thermotherapy can not meet the requirements of complicated and changeable micro-environments of the tumor and can not thoroughly kill the tumor.
Therefore, how to prepare the nano material for microwave power therapy while performing microwave thermotherapy is to combine the sensitization of the microwave thermotherapy and the microwave power effect to effectively increase the specificity of the microwave thermotherapy of the tumor and kill the tumor cells; meanwhile, the microwave power therapy is used for assisting the microwave thermotherapy to effectively kill residual local focus in a tumor area after the microwave thermotherapy so as to thoroughly kill the tumor, thereby achieving good microwave heat-power effect inside and outside the body and realizing effective microwave heat-power treatment of the tumor.
Disclosure of Invention
In order to improve the technical problem, the invention provides a metal organic framework material for tumor microwave thermal-dynamic therapy,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 salt and cobalt salt are, for example, at least one of nitrate, chloride, sulfate, acetate and carbonate of nickel and cobalt; nitrates, chlorides of nickel and cobalt are preferred.
According to an exemplary embodiment of the invention, the central metal ion nickel ion (Ni) of the metal-organic framework material2+) A variety of divalent nickel salts may be selected, including but not limited to at least one of nickel nitrate, nickel chloride, and nickel acetate; preferably nickel nitrate.
According to an exemplary embodiment of the invention, the central metal ion of the metal-organic framework material is cobalt ion (Co)2+) Various 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 present invention, the organic ligands in the metal-organic framework material are imidazole ligands. 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 40-500 nm.
Preferably, the diameter of the metal organic framework material is 40-100nm and 45-95 nm.
The invention also provides a preparation method of the metal organic framework material for the microwave thermal-dynamic tumor 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 is present in the metal-organic framework material2+、Ni2+The molar use ratio of (1): (0.5-2), illustratively 1:0.5, 1:1, 1: 2; preferably 1: 1.
according to an embodiment of the present invention, the mass concentration of the central metal ion of the metal-organic framework material is 10-200 mg/mL; preferably 20-100 mg/mL; exemplary is 10mg/mL, 20mg/mL, 40mg/mL, 60mg/mL, 80mg/mL, 100mg/mL, 200mg/mL, or any combination of any two of the foregoing.
According to an embodiment of the present invention, the organic ligands in the metal-organic framework material are imidazole ligands. For example, the imidazole ligand may be at least one selected from the group consisting of 2-methylimidazole, 2-ethylimidazole and imidazole; preferably selected from 2-methylimidazole.
According to the embodiment of the invention, the mass concentration of the imidazole ligand is 20-1600 mg/mL; preferably 80-1000 mg/mL; exemplary is 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 combination of any two 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 step 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 be by means known in the art, such as centrifugation. Preferably, the rotation speed of the centrifugation is 5000-. Further, the time for the centrifugation is, for example, 5 to 10 min. Under the centrifugal condition, the metal organic framework material with excellent performance for the microwave thermal-dynamic tumor 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 washing may be one, two or more, preferably two.
According to an embodiment of the present invention, the preparation method further comprises drying the washed reaction product. For example, freeze drying is employed.
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) ultrasonically dispersing 2-methylimidazole in methanol;
3) adding the solution obtained in the step 2) into the solution obtained 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 present 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-dynamic therapy. The invention has the beneficial effects that:
(1) the metal organic framework material is applied to the fields of tumor microwave thermotherapy sensitization and microwave dynamic therapy for the first time, ions in the environment can be recruited and generate strong inelastic collision through a limited domain effect under microwave irradiation based on the high specific surface area and the porous structure of the metal organic framework material, and a large amount of frictional heat generated by collision can cause tumor cells to die. 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 by itself, and can effectively generate Reactive Oxygen Species (ROS) with cytotoxicity by the specific microwave dynamic effect to assist microwave thermotherapy, so that residual tumors can be further killed, and a good tumor treatment effect can be realized. Therefore, the treatment efficiency of cancer treatment can be obviously improved, and the preparation method has good clinical application value.
(2) The preparation method of the metal organic framework material for tumor microwave thermotherapy and microwave dynamic therapy 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 TEM image of the metal-organic framework material obtained in example 1 for microwave thermotherapy and dynamic microwave treatment of tumor;
FIG. 2 is a scanning electron microscope photograph of the metal-organic framework material for microwave thermotherapy and microwave-powered therapy of tumor obtained in example 1;
FIG. 3 is the size distribution of the metal-organic framework material for microwave thermotherapy and microwave-powered therapy of tumor obtained in example 1 under the SEM photograph;
FIG. 4 is the hydrated particle size distribution of the metal-organic framework material for microwave thermotherapy and microwave-powered therapy of tumor obtained in example 1;
FIG. 5 shows the microwave heating effect of the metal-organic framework material for microwave thermotherapy and microwave-powered therapy of tumor in example 1;
FIG. 6 shows the microwave power effect of the metal-organic framework material for microwave thermotherapy and microwave-powered therapy of tumor in example 1;
FIG. 7 is a microwave heating graph monitored by a near-infrared thermal imaging instrument in an in-vivo microwave thermal-dynamic combined treatment experiment of the metal organic framework material for tumor microwave thermotherapy and microwave dynamic therapy obtained in example 1;
FIG. 8 is the TEM image of the metal-organic framework material obtained in example 2 for microwave thermotherapy and microwave-powered treatment of tumor;
FIG. 9 shows the microwave heating effect of the metal-organic framework material for microwave thermotherapy and microwave-powered therapy of tumor in example 2;
FIG. 10 shows the microwave power effect of the metal-organic framework material for microwave thermotherapy and microwave-powered therapy of tumor in example 2;
FIG. 11 is the TEM image of the metal-organic framework material obtained in example 3 for microwave thermotherapy and microwave-powered treatment of tumor;
FIG. 12 shows the microwave heating effect of the metal-organic framework material for microwave thermotherapy and microwave-powered therapy of tumor in example 3;
FIG. 13 shows the microwave power effect of the metal-organic framework material for microwave thermotherapy and microwave-powered therapy of tumor obtained in example 3.
Detailed Description
The technical solution of the present invention will be further described in detail with reference to specific embodiments. It is to be understood that the following examples are only illustrative and explanatory of the present invention and should not be construed as limiting the scope of the present invention. All the technologies realized based on the above-mentioned contents of the present invention are covered in the protection scope of the present invention.
Unless otherwise indicated, the raw materials and reagents used in the following examples are all commercially available products or can be prepared by known methods.
Example 1
100mg of Ni (NO)3)2·6H2O and 100mg of Co (NO)3)2·6H2Placing the O in a glass bottle, and ultrasonically dispersing by using 5mL of methanol; placing 400mg of 2-methylimidazole in a glass bottle, carrying out ultrasonic dispersion by using 5mL of methanol, adding the obtained solution into the obtained solution, uniformly mixing, and carrying out magnetic stirring at room temperature for 6 hours; and then putting the obtained product into a centrifuge tube for centrifugation, washing twice by using ethanol, and finally freeze-drying the sample to obtain a powdery product.
The transmission electron micrograph, the scanning electron micrograph, the size distribution under the scanning electron micrograph, and the hydrated particle size distribution of the metal organic framework material prepared in example 1 are shown in fig. 1 to 4, respectively. 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, so that the metal organic framework material can be applied to the fields of tumor microwave thermotherapy sensitization and microwave dynamic therapy, realizes good tumor therapy effect, remarkably improves the therapy efficiency of cancer therapy and has good clinical application value.
Example 2
100mg of NiCl2·6H2O and 100mg CoCl2·6H2Placing the O in a glass bottle, and ultrasonically dispersing by using 5mL of methanol; placing 400mg of 2-methylimidazole in a glass bottle, carrying out ultrasonic dispersion by using 5mL of methanol, adding the obtained solution into the obtained solution, uniformly mixing, and carrying out magnetic stirring at room temperature for 6 hours; and then putting the obtained product into a centrifuge tube for centrifugation, washing twice by using ethanol, and finally freeze-drying the sample to obtain a powdery product.
The transmission electron micrograph of the metal organic framework material prepared in example 2 is shown in fig. 8. As can be seen from the figure, 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.
Example 3
100mg of Ni (CH)3COO)2And 100mg of Co (CH)3COO)2Placing the mixture in a glass bottle, and ultrasonically dispersing the mixture by using 5mL of methanol; placing 400mg of 2-methylimidazole in a glass bottle, carrying out ultrasonic dispersion by using 5mL of methanol, adding the obtained solution into the obtained solution, uniformly mixing, and carrying out magnetic stirring at room temperature for 6 hours; and then putting the obtained product into a centrifuge tube for centrifugation, washing twice by using 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 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.
Example 4
The metal organic framework materials prepared in examples 1 to 3 were subjected to an in vitro microwave heating experiment, and the microwave power effect, the microwave thermotherapy for in vivo tumor and the microwave power treatment effect were evaluated.
A sample of the metal organic framework material obtained in example 1 to 3 was subjected to an in vitro microwave heating test. The specific experimental method is as follows:
2mg, 5mg and 10mg of the metal-organic framework materials prepared in the examples 1 to 3 are respectively ultrasonically dispersed in 1mL of 0.9% physiological saline to form 2mg/mL, 5mg/mL and 10mg/mL solutions, then the solutions are sequentially moved into a microwave heating device, microwave irradiation (0.9W, 450Hz and 5min) is respectively applied to the solutions, the real-time temperature of the microwave heating of the three solutions is respectively recorded by a near-infrared thermal imager, and the microwave heating results are respectively shown in FIGS. 5, 9 and 12. As can be seen from the figure, the metal organic framework materials prepared in the embodiments 1-3 have better microwave temperature raising effect, so that the metal organic framework materials can be applied to microwave thermotherapy and microwave dynamic therapy of tumors in vivo.
A sample of the metal organic framework material prepared in the embodiment 1-3 is taken, and a microwave dynamic effect evaluation is carried out through a fluorescent probe DCFH-DA, wherein the specific experimental method comprises the following steps:
after 2.5mg, 5mg, and 10mg of the metal-organic framework material prepared in examples 1 to 3 were ultrasonically dispersed in 2.3mL of phosphate buffered saline (PBS, pH 7.4) to form solutions, the solutions were transferred to a microwave heating apparatus, 200 μ L of a fluorescence probe DCFH-DA solution for detecting ROS (the fluorescence probe DCFH-DA solution was diluted to 50 μ M with PBS having a pH 7.4) was added to form solutions of 1mg/mL, 2mg/mL, and 4mg/mL, and then microwave irradiation treatment (0.9W, 450Hz, 5min) was applied to each of the three solutions. And then standing for 30min in the dark, centrifuging to obtain a supernatant, detecting the fluorescence intensity of a system by using a fluorescence spectrometer, and analyzing the microwave power effect, wherein the microwave power effect is respectively shown in figures 6, 10 and 13. As can be seen from the figure, the metal-organic framework materials prepared in examples 1-3 of the present invention all generated cytotoxic Reactive Oxygen Species (ROS), and as the concentration of the metal-organic framework material solution increased, the content of the generated cytotoxic Reactive Oxygen Species (ROS) after the microwave irradiation treatment also increased. The microwave dynamic effect of the metal organic framework material on the tumor is obvious.
The microwave thermal-dynamic combined treatment experiment in the animal body is as follows:
5mg of the metal-organic framework material prepared in example 1 was dispersed in 1mL of 0.9% physiological saline to form a 5mg/mL solution, which was injected into ICR mice subcutaneously inoculated with H22 tumor by tail vein injection, and different volumes of the metal-organic framework material solution were injected according to the body weight of the mice, so that the final injection dose of the ICR mice inoculated with H22 tumor was 50 mg/kg. After 6h of tail vein injection, microwave irradiation (0.9W, 450Hz, 5min) was applied to the tumor site of the mice, and the temperature of the ICR mice was monitored and observed at different microwave times by a near-infrared thermal imaging instrument, 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 central part of the tumor of the ICR mouse rapidly reaches over 45 ℃, and the tumor cells are completely killed at the temperature; and further, residual tumor cells at the edge of the tumor are killed by cytotoxic ROS generated by microwave power effect, so that the recurrence of sublethal tumors at the edge of the tumor in a warm area is avoided, and the complete killing of the tumors in the ICR mouse is realized. After observation for about half a month, the ICR mice were found to have fully recovered tumor sites and fully recovered normal skin. Therefore, the metal organic framework material can realize good tumor treatment effect so as to remarkably 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, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. The metal organic framework material for the microwave thermal-dynamic tumor treatment is characterized in that the central metal ions of the metal organic framework material are nickel ions (Ni)2+) And cobalt ion (Co)2+)。
2. The metal-organic framework material for microwave thermo-dynamic treatment of tumors of claim 1, wherein said metal-organic framework material is obtained by reacting nickel salt and cobalt salt with organic ligands.
Preferably, the nickel salt and cobalt salt are, for example, at least one of nitrate, chloride, sulfate, acetate and carbonate of nickel and cobalt; preferably nitrate and chloride of nickel and cobalt.
Preferably, theThe central metal ion nickel ion (Ni) of the metal organic framework material2+) A variety of divalent nickel salts may be selected, including but not limited to at least one of nickel nitrate, nickel chloride, and nickel acetate; preferably nickel nitrate.
Preferably, the central metal ion of the metal-organic framework material is cobalt ion (Co)2+) Various 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.
Preferably, 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.
3. The metal-organic framework material for microwave thermo-dynamic treatment of tumors according to claim 1 or 2, wherein the diameter of the metal-organic framework material is 40-500 nm.
Preferably, the diameter of the metal organic framework material is 40-100nm and 45-95 nm.
4. The method for preparing a metal-organic framework material for microwave thermal-dynamic tumor treatment according to any one of claims 1 to 3, wherein the method 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.
5. The method of claim 4, wherein Co is present in the metal-organic framework material2+、Ni2+The molar ratio of (1): (0.5-2), illustratively 1:0.5, 1:1, 1: 2; preferably 1: 1.
6. the method according to claim 4, wherein the mass concentration of the central metal ion of the metal-organic framework material is 10 to 200 mg/mL; preferably 20-100 mg/mL.
7. The method according to any one of claims 4 to 6, wherein the organic ligands in the metal-organic framework material are imidazole ligands; for example, the imidazole ligand is selected from at least one of 2-methylimidazole, 2-ethylimidazole and imidazole; preferably selected from 2-methylimidazole.
Preferably, the mass concentration of the imidazole ligand is 20-1600 mg/mL; preferably 80-1000 mg/mL.
8. The method according to any one of claims 4 to 7, wherein the solvent is selected from methanol, ethanol and water.
9. The method of any one of claims 4 to 8, comprising the steps of:
1) ultrasonically dispersing nickel salt and cobalt salt in methanol;
2) ultrasonically dispersing 2-methylimidazole in methanol;
3) adding the solution obtained in the step 2) into the solution obtained 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.
Preferably, in the step 3), the stirring time is 0.5-12 h.
10. Use of a metal organic framework material according to any of claims 1 to 3 for microwave thermo-dynamic treatment of tumours.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104992848A (en) * | 2015-06-30 | 2015-10-21 | 中国地质大学（武汉） | Binary metal organic framework material applied to super capacitor and preparation method for binary metal organic framework material |
| CN107739023A (en) * | 2017-10-23 | 2018-02-27 | 中国矿业大学 | A kind of polyhedron bimetallic oxide and its production and use |
| CN107803207A (en) * | 2017-10-18 | 2018-03-16 | 中南大学 | A kind of carbon-based double metallic composite material, preparation and its application |
| CN108722460A (en) * | 2018-04-08 | 2018-11-02 | 湖北大学 | NiCo@N-C bi-functional oxygen electrode catalyst based on MOFs and preparation method thereof |
| CN110853937A (en) * | 2019-11-29 | 2020-02-28 | 江苏理工学院 | Preparation method of nickel-cobalt bimetallic selenide/carbon composite for supercapacitor |
| CN111554896A (en) * | 2020-04-27 | 2020-08-18 | 上海工程技术大学 | Cobalt nickel selenide nitrogen doped amorphous carbon nano composite negative electrode material and preparation and application thereof |
| CN111816455A (en) * | 2020-07-17 | 2020-10-23 | 扬州大学 | Bimetallic organic framework nanosheet and application thereof in supercapacitor |
-
2020
- 2020-11-26 CN CN202011356812.1A patent/CN114539542B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104992848A (en) * | 2015-06-30 | 2015-10-21 | 中国地质大学（武汉） | Binary metal organic framework material applied to super capacitor and preparation method for binary metal organic framework material |
| CN107803207A (en) * | 2017-10-18 | 2018-03-16 | 中南大学 | A kind of carbon-based double metallic composite material, preparation and its application |
| CN107739023A (en) * | 2017-10-23 | 2018-02-27 | 中国矿业大学 | A kind of polyhedron bimetallic oxide and its production and use |
| CN108722460A (en) * | 2018-04-08 | 2018-11-02 | 湖北大学 | NiCo@N-C bi-functional oxygen electrode catalyst based on MOFs and preparation method thereof |
| CN110853937A (en) * | 2019-11-29 | 2020-02-28 | 江苏理工学院 | Preparation method of nickel-cobalt bimetallic selenide/carbon composite for supercapacitor |
| CN111554896A (en) * | 2020-04-27 | 2020-08-18 | 上海工程技术大学 | Cobalt nickel selenide nitrogen doped amorphous carbon nano composite negative electrode material and preparation and application thereof |
| CN111816455A (en) * | 2020-07-17 | 2020-10-23 | 扬州大学 | Bimetallic organic framework nanosheet and application thereof in supercapacitor |
Non-Patent Citations (1)
| Title |
|---|
| JIHWA HONG ET AL.: ""Synthesis and electrochemical characterization of nanostructured Ni-Co-MOF/graphene oxide composites as capacitor electrodes"", 《ELECTROCHIMICA ACTA》 * |
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