Spherical MOF derivative composite material and preparation method thereof
By growing Co(OH)2 nanosheets in situ on a SiO2 support, monodisperse spherical MOF derivative composite materials are formed, solving the problems of uncontrollable morphology and structural collapse, and improving the application performance of the materials.
Patent Information
- Application Number
- CN202511130061.4
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-08-13
- Publication Date
- 2025-11-07
AI Technical Summary
Existing MOF derivative materials suffer from problems in morphology control, such as irregular particles, high risk of structural collapse, and reduced specific surface area due to high-temperature treatment, which affect their pore distribution and performance during electrode filling.
A composite structure of spherical SiO2 support and Co(OH)2 nanosheets was adopted. Co(OH)2 nanosheets were grown in situ on the SiO2 surface using the ZIF-67 template method to form a monodisperse spherical structure. The growth process was mediated by surfactant.
Precise control of the monodisperse spherical structure was achieved, which improved the packing density, mass transfer efficiency and electrochemical performance of the material, while maintaining high specific surface area and structural integrity.
Smart Images
Figure CN120900627A_ABST
Abstract
Description
TECHNICAL FIELD
[0001] The application belongs to the field of chemical material preparation, and particularly relates to a spherical MOF derivative composite material and a preparation method thereof. BACKGROUND
[0002] Metal-organic framework (MOF) compounds have great potential in the fields of catalysis, energy storage, gas adsorption, etc. due to their ultrahigh specific surface area, adjustable pore structure and diversified chemical composition. Through high-temperature pyrolysis, sulfidation or phosphidation, etc. derivative treatment, MOF can be converted into derivative materials (such as porous carbon, metal sulfide / phosphide) with higher stability and functionality, but the morphology control is still a technical difficulty.
[0003] Existing research shows that the spherical structure can improve the packing density, mass transfer efficiency and electrochemical performance of the material, but the high-precision spherical morphology of MOF derivatives still faces the following technical bottlenecks: (1) the product is irregular particles, which leads to uneven pore distribution when the electrode is filled, affecting the performance of the device; (2) the risk of structure collapse is high; (3) high temperature in the derivative process leads to particle adhesion, and the specific surface area is significantly reduced.
[0004] Therefore, it is of great significance to develop a method for controllable preparation of monodisperse spherical MOF derivative composite materials to improve their application performance. SUMMARY
[0005] In order to avoid the shortcomings of the prior art, and considering the economic benefits, the present application aims to solve the three core problems of uncontrolled morphology, poor compatibility of template method and performance loss in the preparation of existing MOF derivative materials, and provides a spherical MOF derivative composite material and a preparation method thereof, realizing high-precision spherical morphology control of MOF derivatives and obtaining monodisperse spherical structure composite materials.
[0006] The technical scheme of the present application is as follows: A spherical MOF derivative composite material, which takes spherical SiO2 as a carrier, grows Co (OH)2 nanosheets on the surface thereof in situ through a ZIF-67 template method, and forms a monodisperse spherical structure.
[0007] The preparation method comprises the following steps: Step 1: preparing nano-SiO2 balls: 100 mL of anhydrous ethanol, 15 mL of deionized water and 15 mL of ammonia water are added to a beaker, and magnetic stirring is performed for 0.5 h to obtain solution A; 50 mL of tetraethyl orthosilicate is added to solution A, and magnetic stirring is performed for 2 h to obtain solution B; solution B is centrifuged, the substrate is dried at 120℃ for 6 h, and then calcined at 600℃ for 4 h to obtain nano-SiO2 balls.
[0008] Step 2: Preparation of solution C: 0.673g of 2-methylimidazole was dissolved in 30mL of methanol under magnetic stirring.
[0009] Step 3: Preparation of solution D: 150mg of nano-SiO2 balls, 1.5mg of CTMAB were ultrasonically dispersed in 15mL of methanol for 30-40min, 1.2g of cobalt nitrate hexahydrate was added and mixed uniformly.
[0010] Step 4: Hydrothermal reaction: solution D was injected into solution C, and after ultrasonic treatment for 5min, it was transferred to a 50mL high-pressure reaction kettle lined with polytetrafluoroethylene, and heated at 110℃ for 4h.
[0011] Step 5: Post-processing: the reaction was centrifuged and washed with methanol 3 times, and dried at 60℃ for 7h to obtain the target composite material.
[0012] The present application has the following beneficial effects: 1. The present application realizes precise control of the monodisperse spherical structure of the composite material through surfactant-mediated in-situ growth, solving the problem of irregular product in the prior art; 2. The composite structure of spherical SiO2 carrier and Co (OH)2 nanosheet adopted by the present application is not easy to collapse, can maintain the integrity of the sphere, and improves the compatibility of the template method; 3. The Co (OH)2 nanosheet of the present application is uniformly loaded on the surface of the spherical SiO2, avoiding particle adhesion, which is conducive to maintaining the high specific surface area and excellent performance of the material. BRIEF DESCRIPTION OF DRAWINGS
[0013] Figure 1 SEM image of the nano-SiO2 ball of the present application; Figure 2 SEM image of the spherical MOF derivative composite material of the present application; Figure 3 Distribution image of O element in the spherical MOF derivative composite material of the present application; Figure 4 Distribution image of Co element in the spherical MOF derivative composite material of the present application; Figure 5 Distribution image of Si element in the spherical MOF derivative composite material of the present application. DETAILED DESCRIPTION
[0014] The technical solutions of the present application will be further analyzed and described below through specific examples.
[0015] The preparation method of the spherical MOF derivative composite material of the present application comprises the following steps: (1) 100 mL of anhydrous ethanol, 15 mL of ionized water, 15 mL of ammonia water were added into a 250 mL beaker, and magnetic stirring was carried out for 0.5 h to obtain solution A; (2) 50 mL of tetraethyl orthosilicate was added into solution A, and magnetic stirring was carried out for 2 h to obtain solution B; (3) Solution B was centrifuged, the substrate was dried in an oven at 120℃ for 6 h, and then was calcined in a high-temperature furnace at 600℃ for 4 h to obtain nano-SiO2 balls, as shown in Figure 1 (4) 0.673 g of 2-methylimidazole was dissolved in 30 mL of methanol under magnetic stirring to obtain solution C; (5) 150 mg of nano-SiO2 balls, 1.5 mg of CTMAB were added into 15 mL of methanol, and ultrasonic treatment was carried out for 30-40 min, then 1.2 g of cobalt nitrate hexahydrate was added, and stirring was carried out until dissolution to obtain solution D; (6) Solution D was slowly injected into solution C, ultrasonic treatment was carried out for 5 min, and the mixed solution was transferred into a 50 mL high-pressure reaction kettle lined with polytetrafluoroethylene, and heating was carried out at 110℃ for 4 h; (7) After the reaction was completed, the reaction was centrifuged, washed with methanol for 3 times, and the obtained substance was dried at 60℃ for 7 h to obtain a spherical MOF derivative composite material, as shown in Figure 2
[0016] As shown in Figure 2 , the spherical MOF derivative composite material comprises a spherical SiO2 carrier and Co(OH)2 nanosheets loaded on the surface of the spherical SiO2 carrier; the Co(OH)2 nanosheets are in-situ grown on the surface of the spherical SiO2 by a ZIF-67 template method, and the composite material is a monodisperse spherical structure.
[0017] As can be seen from the figure, it can be seen from Figure 1 that the scanning electron microscope (SEM) image of the nano-SiO2 balls shows that it is a regular spherical structure; as can be seen from Figure 2 , the SEM image of the spherical MOF derivative composite material prepared by the application shows that it is a monodisperse spherical structure; as can be seen from Figures 3-5 , the spherical MOF derivative composite material prepared by the application shows that the O, Co and Si elements in the composite material are uniformly distributed, which proves that the Co(OH)2 nanosheets are uniformly loaded on the surface of the spherical SiO2.
[0018] The above shows and describes the basic principles, main features and advantages of the present application. Those skilled in the art should understand that the present application is not limited to the above-mentioned embodiments, and the above-mentioned embodiments and descriptions in the specification are only to illustrate the principles of the present application. Without departing from the spirit and scope of the present application, various changes and improvements can be made to the present application, and these changes and improvements all fall within the scope of the claimed present application. The scope of protection of the present application is defined by the appended claims and their equivalents.
Claims
1. A spherical MOF derivative composite material, characterized in that, The composite material comprises a spherical SiO2 carrier and Co(OH)2 nanosheets loaded on the surface of the spherical SiO2 carrier; the Co(OH)2 nanosheets are in-situ grown on the surface of the spherical SiO2 by a ZIF-67 template method, and the composite material is a monodisperse spherical structure.
2. The spherical MOF derivative composite material of claim 1, wherein, The surfactant used in the ZIF-67 template method is cetyltrimethylammonium bromide (CTMAB).
3. A method for preparing a spherical MOF derivative composite material, characterized in that The method comprises the following steps: Step 1: preparing nano-SiO2 balls: mixing anhydrous ethanol, deionized water and ammonia water and stirring for 0.5 h, then adding tetraethyl orthosilicate and continuing to stir for 2 h, and then drying and calcining after centrifugation to obtain nano-SiO2 balls; Step 2: preparing solution C: dissolving 2-methylimidazole in methanol; Step 3: preparing solution D: ultrasonically dispersing nano-SiO2 balls and a surfactant in methanol, and then adding cobalt nitrate hexahydrate and mixing uniformly; Step 4: hydrothermal reaction: transferring solution D to a high-pressure reaction kettle after ultrasonic treatment, and then heating at 100-120℃ for 3-5 h; Step 5: post-treatment: centrifuging, washing and drying to obtain a spherical MOF derivative composite material.
4. The method for preparing the spherical MOF derivative composite material according to claim 3, characterized in that, In step 1, the volume ratio of the anhydrous ethanol, deionized water and ammonia water is 100:15:15; the amount of the tetraethyl orthosilicate added is 50 mL; the drying temperature is 120℃, and the time is 6 h; and the calcination temperature is 600℃, and the time is 4 h.
5. The method for preparing the spherical MOF derivative composite material according to claim 3, characterized in that, In step 2, the mass of the 2-methylimidazole is 0.673 g, and the volume of the methanol is 30 mL.
6. The method of preparing a spherical MOF derivative composite material according to claim 3, characterized in that, In step 3, the mass of the nano-SiO2 balls is 150 mg, the surfactant is CTMAB and the mass is 1.5 mg, the volume of the methanol is 15 mL; the mass of the cobalt nitrate hexahydrate is 1.2 g; and the ultrasonic treatment time is 30 min-40 min.
7. The method of preparing a spherical MOF derivative composite material according to claim 3, characterized in that, In step 4, the ultrasonic treatment time is 5 min; the inner lining of the high-pressure reaction kettle is polytetrafluoroethylene, and the volume is 50 mL; the heating temperature is 110℃, and the time is 4 h.
8. The method for preparing the spherical MOF derivative composite material according to claim 3, characterized in that, In step 5, the washing uses methanol, and the number of times is 3; the drying temperature is 60℃, and the time is 7 h.