Preparation method of poly (diallyldimethylammonium chloride)-graphene oxide doped cobalt oxide MOF material
By using the preparation method of PDDA-rGO doped cobalt oxide MOF material in the preparation of nanomaterials, the problem of insufficient performance of composite nanomaterials in the prior art is solved, and the preparation of materials with high thermal conductivity and stability is achieved, which has improved its Performance in energy storage, sensing and catalytic applications.
Patent Information
- Application Number
- CN202311071253.3
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2023-08-23
- Publication Date
- 2025-02-25
AI Technical Summary
It is difficult to effectively prepare composite nanomaterials with high thermal conductivity and stability, especially in the energy storage, sensing and catalytic applications of nanomaterials.
The preparation method of polydiallyldimethylammonium chloride (PDDA)-graphene oxide doped with cobalt oxide metal-organic frame material (MOF) is adopted, and graphene oxide, cobalt salt, MOF ligand and PDDA are used. The components were stirred evenly in an alcohol solution, stood, centrifuged, washed, dried, and calcined at high temperature under an inert atmosphere to obtain a PDDA-rGO doped cobalt oxide MOF material.
It realizes the simple and efficient preparation of PDDA-rGO doped cobalt oxide MOF materials with excellent thermal conductivity and stability, improving their performance in energy storage, sensing and catalytic applications.
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Figure CN119505550A_ABST
Abstract
Description
Technical Field
[0001] The present application relates to a method for preparing a polydiallyldimethylammonium chloride-graphene oxide doped cobalt oxide MOF material, belonging to the technical field of nanomaterial preparation. Background Art
[0002] With the continuous development of productivity and the improvement of quality of life, people's demands for production and life are getting higher and higher, which has promoted the demand for nanomaterials. Nanomaterials have important applications in energy storage, sensing, catalysis and other fields. After long-term exploration, scientific researchers have developed more and more efficient methods for preparing nanomaterials. rGO itself has excellent thermal conductivity, electrical conductivity, performance and stability, and is extremely suitable for the preparation of composite nanomaterials. This patent explores this and proposes a simple and efficient preparation method. Summary of the invention
[0003] According to one aspect of the present application, a method for preparing a polydiallyldimethylammonium chloride-graphene oxide doped cobalt oxide MOF material is provided, the preparation method comprising:
[0004] A mixture containing graphene oxide, cobalt salt, MOF ligand, polydiallyldimethylammonium chloride (PDDA) and a solvent is stirred, centrifuged, dried and calcined to obtain the polydiallyldimethylammonium chloride-graphene oxide doped cobalt oxide MOF material.
[0005] Optionally, the usage of the graphene oxide and the polydiallyldimethylammonium chloride is 2-55 mL: 0.001-0.01 g.
[0006] Optionally, the amount of the graphene oxide and the polydiallyldimethylammonium chloride is selected from any value among 2mL: 0.001g, 5mL: 0.001g, 10mL: 0.001g, 20mL: 0.001g, 30mL: 0.001g, 40mL: 0.001g, 55mL: 0.001g, 2mL: 0.01g, 10mL: 0.01g, 20mL: 0.01g, 30mL: 0.01g, 40mL: 0.01g, 55mL: 0.01g or a range between any two of the above.
[0007] Optionally, the usage of the graphene oxide, cobalt salt, MOF ligand and solvent is: 2-55 mL: 0.02-15 g: 1-15 g: 25-120 mL.
[0008] Optionally, the concentration of the graphene oxide is 2 to 20 g / L.
[0009] Optionally, the concentration of the graphene oxide is selected from any value of 2 g / L, 5 g / L, 10 g / L, 15 g / L, 20 g / L, or a range between any two of the above values.
[0010] Optionally, the cobalt salt is selected from at least one of cobalt chloride, cobalt nitrate and cobalt acetate.
[0011] Optionally, the MOF ligand is selected from at least one of 2-methylimidazole and porphyrin.
[0012] Optionally, the solvent is selected from at least one of methanol, ethanol, n-propanol and isopropanol.
[0013] Optionally, the calcination is performed under an inactive atmosphere, and the inactive atmosphere is selected from at least one of nitrogen, hydrogen and argon.
[0014] Optionally, the flow rate of the inert atmosphere is 5 to 50 mL / min.
[0015] Optionally, the flow rate of the inert atmosphere is selected from any value of 5 mL / min, 10 mL / min, 15 mL / min, 20 mL / min, 30 mL / min, 40 mL / min, 50 mL / min or a range between any two of the above values.
[0016] Optionally, the calcination temperature is 250-550° C., and the calcination time is 0.5-15 h.
[0017] Optionally, the calcination temperature is selected from any value of 250°C, 300°C, 350°C, 400°C, 500°C, 550°C or a range between any two of the above values.
[0018] Optionally, the calcination time is selected from any value of 0.5h, 1h, 5h, 8h, 10h, 12h, 15h or a range between any two of the above.
[0019] Optionally, the stirring temperature is 15 to 40° C., and the stirring time is 2 to 72 hours.
[0020] Optionally, the centrifugal speed is 5000-12000 rpm, and the centrifugal time is 5-20 min.
[0021] Optionally, the drying temperature is 55-95°C.
[0022] According to another aspect of the present application, a PDDA-rGO doped cobalt oxide MOF material prepared by the above-mentioned preparation method is provided.
[0023] This application is implemented using the following technical solutions:
[0024] A method for preparing rGO-doped cobalt oxide MOF comprises the following steps: dispersing a certain amount of graphene oxide dispersion and a certain amount of cobalt salt into an alcohol solution, adding a certain amount of MOF ligand and PDDA, stirring evenly, standing for a certain period of time, centrifuging, washing, and drying; and calcining the powder obtained above at a high temperature for a certain period of time under the protection of an inert gas.
[0025] Optionally, the alcohol solution is one or more of methanol, ethanol, n-propanol, and isopropanol, and the added amount is 25 to 120 mL.
[0026] Optionally, the stirring time is 2 to 72 hours, the standing time is 10 to 72 hours, the centrifugal speed is 5000 to 12000 rpm, the washing liquid is water and methanol, and the drying temperature is 55 to 95°C.
[0027] The beneficial effects of this application include:
[0028] 1) The rGO-doped cobalt oxide MOF process provided in this application is simple.
[0029] 2) The PDDA-rGO doped cobalt oxide MOF material provided in this application can obtain rGO (graphene oxide) doped cobalt oxide MOF by in-situ growing cobalt oxide MOF on rGO sheet structure, and adding a certain amount of polydiallyldimethylammonium chloride (PDDA) during the synthesis process. Since rGO itself has excellent thermal and electrical conductivity and stability, with the assistance of PDDA conductive polymer, the performance is even better. This application provides a simple and fast method for preparing composite materials, which has important practical and research value in this technical field. BRIEF DESCRIPTION OF THE DRAWINGS
[0030] Figure 1 This is a characterization diagram of the XRD spectrum of the rGO-doped cobalt oxide MOF prepared in Example 1 of the present application. DETAILED DESCRIPTION
[0031] The present application is described in detail below with reference to embodiments, but the present application is not limited to these embodiments.
[0032] Unless otherwise specified, the raw materials in the examples of this application were purchased through commercial channels.
[0033] In the examples of the present application, an X-ray diffractometer was used to perform XRD characterization on the PDDA-rGO doped cobalt oxide MOF material.
[0034] Example 1
[0035] Measure 10mL of 2g / L graphene oxide dispersion and weigh 1.7g of cobalt nitrate hexahydrate, disperse them in 65mL of methanol, add 1.7g of 2-methylimidazole and 0.001g of PDDA, stir at room temperature for 1.5h, and let stand for 36h. Centrifuge at 6000rpm for 8min, wash three times with methanol, and dry at 65℃ to obtain graphene-doped MOF powder. The above powder was calcined at 300℃ for 2.5h in a nitrogen gas flow of 10mL / min to obtain PDDA-rGO doped cobalt oxide MOF material.
[0036] Example 2
[0037] Measure 5mL of 5g / L graphene oxide dispersion and weigh 2g of cobalt nitrate hexahydrate, disperse them in 75mL of methanol, add 2.6g of 2-methylimidazole and 0.002g of PDDA, stir at room temperature for 3h, and let stand for 48h. Centrifuge at 7000rpm for 6min, wash three times with methanol, and dry at 70℃ to obtain graphene-doped MOF powder. The above powder is calcined at 500℃ for 3h in an argon gas flow of 15mL / min to obtain PDDA-rGO doped cobalt oxide MOF material.
[0038] Example 3
[0039] Measure 2mL of 10g / L graphene oxide dispersion and weigh 1.9g of cobalt nitrate hexahydrate, disperse them in 69mL of methanol, add 2.2g of 2-methylimidazole and 0.005g of PDDA, stir at room temperature for 2h, and let stand for 40h. Centrifuge at 9000rpm for 6min, wash three times with methanol, and dry at 80℃ to obtain graphene-doped MOF powder. The above powder was calcined at 400℃ for 3.5h in a nitrogen gas flow of 8mL / min to obtain PDDA-rGO doped cobalt oxide MOF material.
[0040] The above are only a few embodiments of the present application and do not constitute any form of limitation to the present application. Although the present application is disclosed as above with preferred embodiments, it is not intended to limit the present application. Any technician familiar with the profession, without departing from the scope of the technical solution of the present application, using the technical content disclosed above to make slight changes or modifications are equivalent to equivalent implementation cases and fall within the scope of the technical solution.
Claims
1. A method for preparing polydiallyldimethylammonium chloride-graphene oxide doped cobalt oxide MOF material, characterized in that: The preparation method comprises: A mixture containing graphene oxide, cobalt salt, MOF ligand, polydiallyldimethylammonium chloride and solvent is stirred, centrifuged, dried and calcined to obtain the polydiallyldimethylammonium chloride-graphene oxide doped cobalt oxide MOF material.
2. The preparation method according to claim 1, characterized in that: The amount of the graphene oxide and the polydiallyldimethylammonium chloride is 2-55 mL: 0.001-0.01 g; Preferably, the usage of the graphene oxide, cobalt salt, MOF ligand and solvent is: 2-55 mL: 0.02-15 g: 1-15 g: 25-120 mL.
3. The preparation method according to claim 1, characterized in that: The concentration of the graphene oxide is 2-20 g / L.
4. The preparation method according to claim 1, characterized in that: The cobalt salt is selected from at least one of cobalt chloride, cobalt nitrate and cobalt acetate; Preferably, the MOF ligand is selected from at least one of 2-methylimidazole and porphyrin; Preferably, the solvent is selected from at least one of methanol, ethanol, n-propanol and isopropanol.
5. The preparation method according to claim 1, characterized in that: The calcination is performed under an inert atmosphere, and the inert atmosphere is selected from at least one of nitrogen, hydrogen, and argon.
6. The preparation method according to claim 5, characterized in that: The flow rate of the inert atmosphere is 5 to 50 mL / min.
7. The preparation method according to claim 1, characterized in that: The calcination temperature is 250-550° C., and the calcination time is 0.5-15 hours.
8. The preparation method according to claim 1, characterized in that: The stirring temperature is 15-40° C., and the stirring time is 2-72 hours.
9. The preparation method according to claim 1, characterized in that: The centrifugal speed is 5000-12000 rpm, and the centrifugal time is 5-20 min; Preferably, the drying temperature is 55-95°C.
10. The polydiallyldimethylammonium chloride-graphene oxide doped cobalt oxide MOF material prepared by the preparation method according to any one of claims 1 to 9.