Method for preparing small-size HKUST material at room temperature
Small-sized HKUST MOF nanoparticles were successfully prepared by using potassium chloride and dilute nitric acid support agent at room temperature, adding phenylatic acid solution dropwise, centrifuging and cleaning after reaction, which solved the complex preparation method in the prior art and The problem of large size achieves the effect of simple, green and large-scale production.
Patent Information
- Application Number
- CN202411525142.X
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-10-30
- Publication Date
- 2025-02-11
AI Technical Summary
The prior art is difficult to effectively prepare small-sized HKUST MOF nanomaterials, and the preparation method is complex, requiring high-temperature and high-pressure environments and expensive medicines.
Using room temperature conditions, potassium chloride and dilute nitric acid as support agents, add phthalic acid solution dropwise to common methanol solution by magnetic stirring, and react for 5-24 hours, followed by centrifugation and cleaning to obtain small-sized HKUST MOF nanoparticles. .
The preparation of small-sized HKUST MOF nanoparticles under mild reaction conditions is achieved, reducing the production cost and time, suitable for large-scale production without the need for surfactants or templates.
Smart Images
Figure CN119409982A_ABST
Abstract
Description
Technical Field
[0001] The invention belongs to the field of nanomaterials, and more specifically, relates to a method for preparing small-sized HKUST nanoparticles at room temperature. Background Art
[0002] Nanomaterials are a type of metastable substance with unique properties such as large specific surface area, small particle size, high surface atomic ratio, electron motion state and surface effect. They have great application potential in catalysis, batteries, sensors, etc., especially small-sized nanomaterials.
[0003] HKUST, also known as MOF-199, is a typical carboxylic acid metal organic framework (MOF) material, which is formed by the coordination of Cu clusters and carboxyl groups. The pore window is about 0.9nm×0.9nm and is widely used in gas sensing, catalysis, batteries and other fields. At present, researchers have reported different methods for preparing HKUST MOF materials, such as the extended crystal method, the soft and hard template method, the hydrothermal method, etc. These methods have made certain progress, but the operation steps are complicated, the required ligands are expensive, the required environment is high temperature and high pressure, and the soft and hard templates need to be processed later, which is not suitable for further scale-up production. At the same time, the size of the HKUSTMOF material prepared using the previously reported method is relatively large. Therefore, it is urgent to develop a synthesis method that is simple in process, green, and can prepare small-sized HKUST MOF materials on a large scale.
[0004] Using potassium chloride and dilute nitric acid as supporting agents, HKUST materials were prepared at room temperature without templates or surfactants. The results showed that both methods can effectively prepare nanoparticles. Compared with potassium chloride solution, the amount of material prepared in dilute nitric acid is larger, which is more suitable for large-scale production in industrialization. Summary of the invention
[0005] The object of the present invention is to provide a method for producing small-sized HKUST nanomaterials under mild reaction conditions and scalable. The object of the present invention is achieved through the following technical solutions:
[0006] A method for preparing small-sized HKUST MOF nanoparticles at room temperature comprises the following steps:
[0007] S1: Weigh 125 mg of copper sulfate using an analytical balance and dissolve it in 10 mL of 0.01 M potassium chloride solution in methanol under magnetic stirring;
[0008] S2: Weigh 10 mg of trimesic acid using an analytical balance and dissolve it in 10 mL of 0.01 M potassium chloride solution in methanol under magnetic stirring;
[0009] S3: Next, the solution prepared in S2 is added dropwise to the solution prepared in S1, and the reaction is continued for 5-24 hours;
[0010] S4: The product after the reaction in S3 is centrifuged at different speeds to obtain the product, which is then washed in a mixture of ethanol and water and dried to obtain the product.
[0011] A method for preparing small-sized HKUST MOF nanoparticles at room temperature comprises the following steps:
[0012] S1: Weigh 125 mg of copper sulfate using an analytical balance and dissolve it in 10 mL of methanol solution containing 14 mL of 0.01 M concentrated nitric acid under magnetic stirring;
[0013] S2: Weigh 10 mg of trimesic acid using an analytical balance and dissolve it in 10 mL of 0.01 M potassium chloride solution in methanol under magnetic stirring;
[0014] S3: Next, the solution prepared in S2 is added dropwise to the solution prepared in S1, and the reaction is continued for 5-24 hours;
[0015] S4: The product after the reaction in S3 is centrifuged at different speeds to obtain the product, which is then washed in a mixture of ethanol and water and dried to obtain the product.
[0016] Compared with the prior art, this application has the following effects:
[0017] 1. The method for preparing HKUST MOF provided in this application does not require a complicated preparation method, toxic substances, pre-treatment of reactants, expensive drugs and instruments, a long time, a special atmosphere and high temperature environment, surfactants and templates. The instrument used is also a common magnetic stirrer, and the reaction environment does not require a clean room.
[0018] 2. The size of nano HKUST MOF materials prepared using this technology can be reduced to dozens of nanometers. At the same time, this method can be used to prepare HKUST MOF materials of dozens of nanometers in common potassium chloride salt and common nitric acid, which also broadens the types of common acids for regulating the size of MOF. BRIEF DESCRIPTION OF THE DRAWINGS
[0019] Figure 1 This is a scanning image of the nano HKUST MOF material prepared by the present invention after reacting in a KCl solution for 5 hours.
[0020] Figure 2 This is a scanning image of the nano HKUST MOF material prepared in the present invention after reacting in a KCl solution for 10 hours.
[0021] Figure 3 This is a scanning image of the nano HKUST MOF material prepared in the present invention after reacting in a KCl solution for 24 hours.
[0022] Figure 4 HNO prepared by the present invention 3 Scanning image of nano HKUST MOF material reacting in solution for 24 hours DETAILED DESCRIPTION
[0023] The reagents, methods and equipment used in the present invention are all conventional reagents, methods and equipment in the art. Unless otherwise specified, the reagents and materials used in the following examples are all commercially available.
[0024] Example 1
[0025] A method for preparing small-sized HKUST MOF nanoparticles at room temperature comprises the following steps:
[0026] S1: Weigh 125 mg of copper sulfate using an analytical balance and dissolve it in 10 mL of 0.01 M potassium chloride solution in methanol under magnetic stirring;
[0027] S2: Weigh 10 mg of trimesic acid using an analytical balance and dissolve it in 10 mL of 0.01 M potassium chloride solution in methanol under magnetic stirring;
[0028] S3: Next, the solution prepared in S2 was added dropwise to the solution prepared in S1 and the reaction was continued for 5 h;
[0029] S4: The product after the reaction in S3 is centrifuged at different speeds to obtain the product, which is then washed in a mixture of ethanol and water and dried to obtain the product.
[0030] like Figure 1 As shown, the material morphology is nanoparticles, and the size of the particles is 50 nanometers.
[0031] Example 2
[0032] A method for preparing small-sized HKUST MOF nanoparticles at room temperature comprises the following steps:
[0033] S1: Weigh 125 mg of copper sulfate using an analytical balance and dissolve it in 10 mL of 0.01 M potassium chloride solution in methanol under magnetic stirring;
[0034] S2: Weigh 10 mg of trimesic acid using an analytical balance and dissolve it in 10 mL of 0.01 M potassium chloride solution in methanol under magnetic stirring;
[0035] S3: Next, the solution prepared in S2 was added dropwise to the solution prepared in S1 and the reaction was continued for 10 h;
[0036] S4: The product after the reaction in S3 is centrifuged at different speeds to obtain the product, which is then washed in a mixture of ethanol and water and dried to obtain the product.
[0037] like Figure 2 As shown, the material morphology is nanoparticles, and the size of the particles is 50 nanometers.
[0038] Example 3
[0039] A method for preparing small-sized HKUST MOF nanoparticles at room temperature comprises the following steps:
[0040] S1: Weigh 125 mg of copper sulfate using an analytical balance and dissolve it in 10 mL of 0.01 M potassium chloride solution in methanol under magnetic stirring;
[0041] S2: Weigh 10 mg of trimesic acid using an analytical balance and dissolve it in 10 mL of 0.01 M potassium chloride solution in methanol under magnetic stirring;
[0042] S3: Next, the solution prepared in S2 was added dropwise to the solution prepared in S1 and reacted for 24 hours;
[0043] S4: The product after the reaction in S3 is centrifuged at different speeds to obtain the product, which is then washed in a mixture of ethanol and water and dried to obtain the product.
[0044] like Figure 3 As shown, the material morphology is nanoparticles, and the size of the particles is 50 nanometers.
[0045] Example 4
[0046] A method for preparing small-sized HKUST MOF nanoparticles at room temperature comprises the following steps:
[0047] S1: Weigh 125 mg of copper sulfate using an analytical balance and dissolve it in 10 mL of methanol solution containing 14 mL of 0.01 M concentrated nitric acid under magnetic stirring;
[0048] S2: Weigh 10 mg of trimesic acid using an analytical balance and dissolve it in 10 mL of 0.01 M potassium chloride solution in methanol under magnetic stirring;
[0049] S3: Next, the solution prepared in S2 was added dropwise to the solution prepared in S1 and reacted for 24 hours;
[0050] S4: The product after the reaction in S3 is centrifuged at different speeds to obtain the product, which is then washed in a mixture of ethanol and water and dried to obtain the product.
[0051] like Figure 4 As shown, the material morphology is nanoparticles, and the size of the particles is 50 nanometers.
Claims
1. A method for preparing small-sized HKUST MOF nanoparticles at room temperature, characterized in that: The steps include: S1: Weigh 125 mg of copper sulfate using an analytical balance and dissolve it in 10 mL of 0.01 M potassium chloride solution in methanol under magnetic stirring; S2: Weigh 10 mg of trimesic acid using an analytical balance and dissolve it in 10 mL of 0.01 M potassium chloride solution in methanol under magnetic stirring; S3: Next, add S2 dropwise into S1 and react for 5-24h; S4: The product after the reaction in S3 is centrifuged at different speeds to obtain the product, which is then washed in a mixture of ethanol and water and dried to obtain the product.
2. A method for preparing small-sized HKUST MOF nanoparticles at room temperature, characterized in that: The steps include: S1: Weigh 125 mg of copper sulfate using an analytical balance and dissolve it in 10 mL of methanol solution containing 14 mL of 0.01 M concentrated nitric acid under magnetic stirring; S2: Weigh 10 mg of trimesic acid using an analytical balance and dissolve it in 10 mL of 0.01 M potassium chloride solution in methanol under magnetic stirring; S3: Next, the solution prepared in S2 is added dropwise to the solution prepared in S1, and the reaction is continued for 5-24 hours; S4: The product after the reaction in S3 is centrifuged at different speeds to obtain the product, which is then washed in a mixture of ethanol and water and dried to obtain the product.