Synthesis method of borate cluster
By controlling the ratio of metal salt and boric acid in a specific solvent to react, a stable metal-borate network structure is formed, solving the problem of complex synthesis steps in existing borate clusters. This results in borate clusters with high conductivity and high ion adsorption rate, broadening their application range.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- NORTHEAST NORMAL UNIVERSITY
- Filing Date
- 2025-11-24
- Publication Date
- 2026-04-14
AI Technical Summary
Existing methods for preparing borate clusters are complex and require strict synthesis conditions, making it difficult to meet the requirements for high conductivity and high ion adsorption rate, thus limiting their widespread application.
Metal salts and boric acid are mixed in a specific solvent and reacted under controlled temperature in a high-pressure reactor through mechanical stirring to form a stable metal-borate network structure. By controlling the ratio of metal ions to borate ions, ordered covalent and coordinate bonds are formed, resulting in borate clusters with porous structures.
It achieves high conductivity and high ion adsorption rate, enhances the mechanical strength and chemical stability of the material, provides good electrical conductivity and ion adsorption performance, and broadens its application prospects.
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Abstract
Description
Technical Field
[0001] This invention relates to the field of borate materials, and more specifically to a method for synthesizing borate clusters. Background Technology
[0002] In today's society, materials with high electrical conductivity and excellent ion adsorption performance show broad application prospects in many fields, such as energy conversion, electrochemical sensors, and battery materials. Among them, borate clusters have attracted widespread attention in these fields due to their unique structure and excellent performance. However, existing methods for preparing borate clusters often suffer from complex synthesis steps and strict requirements for synthesis conditions, making it difficult for the prepared borate coordination metal clusters to meet the requirements of high electrical conductivity and high ion adsorption rate, thus limiting their wider application and development.
[0003] Therefore, developing a synthetic method for borate clusters is of significant practical importance. Summary of the Invention
[0004] To overcome the aforementioned technical problems, the present invention aims to provide a method for synthesizing borate clusters, which solves the problem that existing methods for preparing borate clusters often involve complex synthesis steps and strict synthesis conditions, resulting in borate coordination metal clusters that cannot meet the requirements for high conductivity and high ion adsorption rate, thus limiting their wider application and development.
[0005] The objective of this invention can be achieved through the following technical solutions: In a first aspect, this application provides a method for synthesizing borate clusters, comprising the following steps: Step 1: Dissolve the metal salt in the first solvent to prepare a metal salt solution, thus obtaining solution A; Step 2: Dissolve boric acid in a second solvent to prepare a boric acid solution, thus obtaining solution B; Step 3: Add solution A to solution B and stir mechanically until homogeneous to obtain a mixed solution of A / B; Step 4: Add the A / B mixed solution to the high-pressure reactor, control the temperature for reaction, and after the reaction is completed, cool the high-pressure reactor to room temperature. Then filter, collect the filter cake, wash the filter cake with water, and then dry it to obtain borate clusters.
[0006] In a preferred embodiment of the present invention, the metal salt in step one is a mixture of cobalt nitrate and modified metal salt in a mass ratio of 10:0.5-1.5.
[0007] In a preferred embodiment of the present invention, the modified metal salt in step one is one of ferric nitrate, nickel nitrate, and copper nitrate.
[0008] In a preferred embodiment of the present invention, the first solvent in step one includes, but is not limited to, methanol, ethanol, acetonitrile, tetrahydrofuran, dichloromethane, chloroform, N,N-dimethylformamide, N,N-dimethylacetamide, and triethylamine.
[0009] In a preferred embodiment of the present invention, the concentration of solution A in step one is 1-200 mg / mL.
[0010] In a preferred embodiment of the present invention, the second solvent in step two includes, but is not limited to, deionized water, acetonitrile, chloroform, and ethanol.
[0011] In a preferred embodiment of the present invention, the concentration of solution B in step two is 1-800 mg / mL.
[0012] In a preferred embodiment of the present invention, the volume ratio of solution A to solution B in step three is 1:1-20.
[0013] In a preferred embodiment of the present invention, the volume ratio of solution A to solution B is 1:1-8.
[0014] In a preferred embodiment of the present invention, the mechanical stirring conditions in step three are a stirring time of 0.5-10h and a stirring speed of 60-2000r / min.
[0015] In a preferred embodiment of the present invention, the mechanical stirring conditions are a stirring time of 1-6 hours and a stirring speed of 200-1800 r / min.
[0016] In a preferred embodiment of the present invention, the temperature-controlled reaction conditions in step four are: a reaction temperature of 140-280℃ and a reaction time of 2-10 days; the number of times the water is washed is 1-8 times; and the drying conditions are: a drying temperature of 50-110℃ and a drying time of 10-20 hours.
[0017] The beneficial effects of this invention are: This invention discloses a method for synthesizing borate clusters. The method involves dissolving a metal salt in a first solvent to prepare a metal salt solution (solution A), dissolving boric acid in a second solvent to prepare a boric acid solution (solution B), adding solution A to solution B, and mechanically stirring until homogeneous to obtain an A / B mixed solution. This A / B mixed solution is then added to a high-pressure reactor, and the reaction is carried out under controlled temperature. After the reaction, the reactor is cooled to room temperature, filtered, and the filter cake is collected, washed with water, and then dried to obtain the borate clusters. This synthesis method precisely controls the ratio of metal ions to borate ions during the reaction, forming stable covalent and coordinate bonds, resulting in an ordered metal-borate network structure. This metal-borate network structure, with multiple metal ions as its core, provides excellent electrical conductivity and a stable cluster structure. This not only enhances the mechanical strength and chemical stability of the material but also gives it a porous structure, effectively increasing its contact area with ions and enabling efficient ion adsorption, thereby significantly improving the ion adsorption rate. Therefore, this borate cluster has high conductivity and can be used as a high conductivity material. It also has high ion adsorption rate and can be used as an adsorbent to adsorb anions, showing broad application prospects. Detailed Implementation
[0018] The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention. Example 1:
[0019] This embodiment describes a method for synthesizing borate clusters, comprising the following steps: Step 1: Dissolve the metal salt in the first solvent to prepare a metal salt solution, obtaining solution A with a concentration of 30 mg / mL; the metal salt is a mixture of cobalt nitrate and modified metal salt in a mass ratio of 10:0.5; the modified metal salt is ferric nitrate; the first solvent is N,N-dimethylacetamide; Step 2: Dissolve boric acid in a second solvent to prepare a boric acid solution, obtaining solution B with a concentration of 400 mg / mL; the second solvent is deionized water; Step 3: Add solution A to solution B at a volume ratio of 1:4, and mechanically stir for 1 hour at a stirring speed of 200 r / min until homogeneous to obtain a mixed solution of A / B. Step 4: Add the A / B mixed solution to the high-pressure reactor and carry out the temperature-controlled reaction at a reaction temperature of 140℃ for 2 days. After the reaction is completed, cool the high-pressure reactor to room temperature, then filter and collect the filter cake. Wash the filter cake once with water and then dry it at a drying temperature of 50℃ for 10 hours to obtain borate clusters. Example 2:
[0020] This embodiment describes a method for synthesizing borate clusters, comprising the following steps: Step 1: Dissolve the metal salt in the first solvent to prepare a metal salt solution, obtaining solution A with a concentration of 80 mg / mL; the metal salt is a mixture of cobalt nitrate and modified metal salt in a mass ratio of 10:1; the modified metal salt is nickel nitrate; the first solvent is a mixture of N,N-dimethylformamide and N,N-dimethylacetamide in equal volumes; Step 2: Dissolve boric acid in a second solvent to prepare a boric acid solution, obtaining solution B with a concentration of 200 mg / mL; the second solvent is acetonitrile. Step 3: Add solution A to solution B at a volume ratio of 1:2, and mechanically stir for 3 hours at a stirring speed of 1000 r / min until homogeneous to obtain a mixed solution of A / B. Step 4: Add the A / B mixed solution to the high-pressure reactor and carry out a temperature-controlled reaction at a reaction temperature of 210℃ for 6 days. After the reaction is completed, cool the high-pressure reactor to room temperature, then filter and collect the filter cake. Wash the filter cake with water 4 times, and then dry it at a drying temperature of 80℃ for 15 hours to obtain borate clusters. Example 3:
[0021] This embodiment describes a method for synthesizing borate clusters, comprising the following steps: Step 1: Dissolve the metal salt in the first solvent to prepare a metal salt solution, obtaining solution A with a concentration of 160 mg / mL; the metal salt is a mixture of cobalt nitrate and modified metal salt in a mass ratio of 10:1.5; the modified metal salt is copper nitrate; the first solvent is N,N-dimethylformamide; Step 2: Dissolve boric acid in a second solvent to prepare a boric acid solution, obtaining solution B with a concentration of 800 mg / mL; the second solvent is chloroform. Step 3: Add solution A to solution B at a volume ratio of 1:1, and mechanically stir for 6 hours at a stirring speed of 1800 r / min until homogeneous to obtain a mixed solution of A / B. Step 4: Add the A / B mixed solution to the high-pressure reactor and carry out the temperature-controlled reaction at a reaction temperature of 280℃ for 10 days. After the reaction is completed, cool the high-pressure reactor to room temperature, then filter and collect the filter cake. Wash the filter cake with water 8 times, and then dry it at a drying temperature of 110℃ for 20 hours to obtain borate clusters. Example 4:
[0022] This embodiment describes a method for synthesizing borate clusters, comprising the following steps: Step 1: Dissolve the metal salt in the first solvent to prepare a metal salt solution, obtaining solution A with a concentration of 100 mg / mL; the metal salt is a mixture of cobalt nitrate and modified metal salt in a mass ratio of 10:0.5; the modified metal salt is ferric nitrate; the first solvent is a mixture of N,N-dimethylformamide and N,N-dimethylacetamide in an equal volume ratio; Step 2: Dissolve boric acid in a second solvent to prepare a boric acid solution, obtaining solution B with a concentration of 400 mg / mL; the second solvent is ethanol; Step 3: Add solution A to solution B at a volume ratio of 1:8, and mechanically stir for 1 hour at a stirring speed of 200 r / min until homogeneous to obtain a mixed solution of A / B. Step 4: Add the A / B mixed solution to the high-pressure reactor and carry out the temperature-controlled reaction at a reaction temperature of 140℃ for 2 days. After the reaction is completed, cool the high-pressure reactor to room temperature, then filter and collect the filter cake. Wash the filter cake once with water and then dry it at a drying temperature of 50℃ for 10 hours to obtain borate clusters. Example 5:
[0023] This embodiment describes a method for synthesizing borate clusters, comprising the following steps: Step 1: Dissolve the metal salt in the first solvent to prepare a metal salt solution, obtaining solution A with a concentration of 150 mg / mL; the metal salt is a mixture of cobalt nitrate and modified metal salt in a mass ratio of 10:1; the modified metal salt is nickel nitrate; the first solvent is N,N-dimethylacetamide; Step 2: Dissolve boric acid in a second solvent to prepare a boric acid solution, obtaining solution B with a concentration of 600 mg / mL; the second solvent is chloroform. Step 3: Add solution A to solution B at a volume ratio of 1:2, and mechanically stir for 3 hours at a stirring speed of 1000 r / min until homogeneous to obtain a mixed solution of A / B. Step 4: Add the A / B mixed solution to the high-pressure reactor and carry out a temperature-controlled reaction at a reaction temperature of 210℃ for 6 days. After the reaction is completed, cool the high-pressure reactor to room temperature, then filter and collect the filter cake. Wash the filter cake with water 4 times, and then dry it at a drying temperature of 80℃ for 15 hours to obtain borate clusters.
[0024] Comparative Example 1: This comparative example illustrates a method for synthesizing a borate cluster, comprising the following steps: Step 1: Dissolve the metal salt in the first solvent to prepare a metal salt solution, obtaining solution A with a concentration of 30 mg / mL; the metal salt is cobalt nitrate; the first solvent is N,N-dimethylacetamide; Step 2: Dissolve boric acid in a second solvent to prepare a boric acid solution, obtaining solution B with a concentration of 400 mg / mL; the second solvent is deionized water; Step 3: Add solution A to solution B at a volume ratio of 1:4, and mechanically stir for 1 hour at a stirring speed of 200 r / min until homogeneous to obtain a mixed solution of A / B. Step 4: Add the A / B mixed solution to the high-pressure reactor and carry out the temperature-controlled reaction at a reaction temperature of 140℃ for 2 days. After the reaction is completed, cool the high-pressure reactor to room temperature, then filter and collect the filter cake. Wash the filter cake once with water and then dry it at a drying temperature of 50℃ for 10 hours to obtain borate clusters.
[0025] Comparative Example 2: This comparative example illustrates a method for synthesizing a borate cluster, comprising the following steps: Step 1: Dissolve the metal salt in the first solvent to prepare a metal salt solution, obtaining solution A with a concentration of 80 mg / mL; the metal salt is cobalt nitrate; the first solvent is N,N-dimethylformamide and N,N-dimethylacetamide mixed in equal volumes; Step 2: Dissolve boric acid in a second solvent to prepare a boric acid solution, obtaining solution B with a concentration of 200 mg / mL; the second solvent is acetonitrile. Step 3: Add solution A to solution B at a volume ratio of 1:2, and mechanically stir for 3 hours at a stirring speed of 1000 r / min until homogeneous to obtain a mixed solution of A / B. Step 4: Add the A / B mixed solution to the high-pressure reactor and carry out a temperature-controlled reaction at a reaction temperature of 210℃ for 6 days. After the reaction is completed, cool the high-pressure reactor to room temperature, then filter and collect the filter cake. Wash the filter cake with water 4 times, and then dry it at a drying temperature of 80℃ for 15 hours to obtain borate clusters.
[0026] Comparative Example 3: This comparative example illustrates a method for synthesizing a borate cluster, comprising the following steps: Step 1: Dissolve the metal salt in the first solvent to prepare a metal salt solution, obtaining solution A with a concentration of 160 mg / mL; the metal salt is cobalt nitrate; the first solvent is N,N-dimethylformamide; Step 2: Dissolve boric acid in a second solvent to prepare a boric acid solution, obtaining solution B with a concentration of 800 mg / mL; the second solvent is chloroform. Step 3: Add solution A to solution B at a volume ratio of 1:1, and mechanically stir for 6 hours at a stirring speed of 1800 r / min until homogeneous to obtain a mixed solution of A / B. Step 4: Add the A / B mixed solution to the high-pressure reactor and carry out the temperature-controlled reaction at a reaction temperature of 280℃ for 10 days. After the reaction is completed, cool the high-pressure reactor to room temperature, then filter and collect the filter cake. Wash the filter cake with water 8 times, and then dry it at a drying temperature of 110℃ for 20 hours to obtain borate clusters.
[0027] Comparative Example 4: This comparative example illustrates a method for synthesizing a borate cluster, comprising the following steps: Step 1: Dissolve the metal salt in the first solvent to prepare a metal salt solution, obtaining solution A with a concentration of 100 mg / mL; the metal salt is cobalt nitrate; the first solvent is N,N-dimethylformamide and N,N-dimethylacetamide mixed in equal volume ratio; Step 2: Dissolve boric acid in a second solvent to prepare a boric acid solution, obtaining solution B with a concentration of 400 mg / mL; the second solvent is ethanol; Step 3: Add solution A to solution B at a volume ratio of 1:8, and mechanically stir for 1 hour at a stirring speed of 200 r / min until homogeneous to obtain a mixed solution of A / B. Step 4: Add the A / B mixed solution to the high-pressure reactor and carry out the temperature-controlled reaction at a reaction temperature of 140℃ for 2 days. After the reaction is completed, cool the high-pressure reactor to room temperature, then filter and collect the filter cake. Wash the filter cake once with water and then dry it at a drying temperature of 50℃ for 10 hours to obtain borate clusters.
[0028] Comparative Example 5: This comparative example illustrates a method for synthesizing a borate cluster, comprising the following steps: Step 1: Dissolve the metal salt in the first solvent to prepare a metal salt solution, obtaining solution A with a concentration of 150 mg / mL; the metal salt is cobalt nitrate; the first solvent is N,N-dimethylacetamide; Step 2: Dissolve boric acid in a second solvent to prepare a boric acid solution, obtaining solution B with a concentration of 600 mg / mL; the second solvent is chloroform. Step 3: Add solution A to solution B at a volume ratio of 1:2, and mechanically stir for 3 hours at a stirring speed of 1000 r / min until homogeneous to obtain a mixed solution of A / B. Step 4: Add the A / B mixed solution to the high-pressure reactor and carry out a temperature-controlled reaction at a reaction temperature of 210℃ for 6 days. After the reaction is completed, cool the high-pressure reactor to room temperature, then filter and collect the filter cake. Wash the filter cake with water 4 times, and then dry it at a drying temperature of 80℃ for 15 hours to obtain borate clusters.
[0029] The conductivity of the borate clusters from Examples 1-5 and Comparative Examples 1-5 was measured using the four-probe method, and SO4 adsorption experiments were performed. 2- Adsorption rate of MnO4 - Adsorption rate The specific process of the adsorption experiment is as follows: Sodium sulfate and potassium permanganate were weighed and dissolved in deionized water to prepare an anion solution with an initial concentration of 100 mg / L. Then, 0.1 g of borate clusters were added to 100 mL of the anion solution. The solution was then placed in a constant temperature water bath shaker (25 °C, 150 r / min) and shaken for 24 h. The concentration of the anion solution after adsorption was tested, and the anion adsorption rate was obtained accordingly.
[0030] The test results are shown in the table below:
[0031] Referring to the data in the table above, and based on the comparison between Examples 1-5 and Comparative Examples 1-5, it can be seen that the borate clusters of this application have good electrical conductivity and ion adsorption rate, indicating that they have high conductivity and can be used as high conductivity materials, and also have high adsorption properties and can be used as high adsorption materials.
[0032] In the description of this specification, references to terms such as "an embodiment," "example," "specific example," etc., indicate that a specific feature, structure, material, or characteristic described in connection with that embodiment or example is included in at least one embodiment or example of the invention. In this specification, illustrative expressions of the above terms do not necessarily refer to the same embodiment or example. Furthermore, the specific features, structures, materials, or characteristics described may be combined in any suitable manner in one or more embodiments or examples.
[0033] The above description is merely an example and illustration of the present invention. Those skilled in the art can make various modifications or additions to the specific embodiments described or use similar methods to replace them, as long as they do not deviate from the invention or exceed the scope defined in this application, they should all fall within the protection scope of the present invention.
Claims
1. A method for synthesizing borate clusters, characterized in that, Includes the following steps: Step 1: Dissolve the metal salt in the first solvent to prepare a metal salt solution, thus obtaining solution A; Step 2: Dissolve boric acid in a second solvent to prepare a boric acid solution, thus obtaining solution B; Step 3: Add solution A to solution B and stir mechanically until homogeneous to obtain a mixed solution of A / B; Step 4: Add the A / B mixed solution to the high-pressure reactor, control the temperature for reaction, and after the reaction is completed, cool the high-pressure reactor to room temperature. Then filter, collect the filter cake, wash the filter cake with water, and then dry it to obtain borate clusters.
2. The method for synthesizing borate clusters according to claim 1, characterized in that, The metal salt in step one is a mixture of cobalt nitrate and modified metal salt in a mass ratio of 10:0.5-1.5; the modified metal salt is one of ferric nitrate, nickel nitrate and copper nitrate; the first solvent includes, but is not limited to, methanol, ethanol, acetonitrile, tetrahydrofuran, dichloromethane, chloroform, N,N-dimethylformamide, N,N-dimethylacetamide and triethylamine.
3. The method for synthesizing borate clusters according to claim 1, characterized in that, The concentration of solution A in step one is 1-200 mg / mL.
4. The method for synthesizing borate clusters according to claim 1, characterized in that, The second solvent in step two includes, but is not limited to, deionized water, acetonitrile, chloroform, and ethanol.
5. The method for synthesizing borate clusters according to claim 1, characterized in that, The concentration of solution B in step two is 1-800 mg / mL.
6. The method for synthesizing borate clusters according to claim 1, characterized in that, In step three, the volume ratio of solution A to solution B is 1:1-20.
7. The method for synthesizing borate clusters according to claim 6, characterized in that, The volume ratio of solution A to solution B is 1:1-8.
8. The method for synthesizing borate clusters according to claim 1, characterized in that, The mechanical stirring conditions in step three are a stirring time of 0.5-10 hours and a stirring speed of 60-2000 r / min.
9. The method for synthesizing borate clusters according to claim 8, characterized in that, The conditions for mechanical stirring are a stirring time of 1-6 hours and a stirring speed of 200-1800 r / min.
10. The method for synthesizing borate clusters according to claim 1, characterized in that, The temperature control reaction conditions in step four are: reaction temperature of 140-280℃ and reaction time of 2-10 days; the number of times the water is washed is 1-8 times; and the drying conditions are: drying temperature of 50-110℃ and drying time of 10-20 hours.