Preparation method and application of bimetal organic framework composite material

A composite material and organic framework technology, applied in biochemical fuel cells, electrical components, battery electrodes, etc., can solve the problems of inability to connect porous carbon, easy to fall off, unfavorable oxygen adsorption and desorption, etc., to achieve excellent electrochemical performance and chemical Good stability and low production cost

Active Publication Date: 2020-01-31
NANJING UNIV OF POSTS & TELECOMM
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Problems solved by technology

After searching, it was found that the patent with the publication number CN108834389A disclosed a bimetallic organic framework derived porous carbon / multi-walled carbon nanotube nanocomposite absorbing material. Although the method adopts a simple high-temperature pyrolysis method to prepare the nanocomposite material in one step, However, the carbon nanotubes in the composite material cannot effectively connect the dispersed porous carbon, and they are easy to fall off during the oxygen reduction reaction in the solution, which cannot guarantee the long-term stable operation of the fuel cell; the patent with the publication number of 109126885 discloses a copper-cobalt Bimetallic organic framework / nanofiber composite material, although the composite material prepared by this method has strong stability, the conductivity of the metal organic framework in the composite material is not very good, which is not conducive to the rapid transmission of electrons, which limits its performance in the electrical field. Application in the field of chemical catalysis; the patent publication No. 109546107A discloses a method for preparing a graphene / two-dimensional Co-Zn dual-core metal framework composite material. Although the method adopts a simple preparation process, the prepared composite material is The two-dimensional flake morphology is not conducive to the adsorption and desorption of oxygen, and does not contain Co-Nx active centers that are conducive to oxygen reduction, which limits its application in MFC cathode catalysts
[0005] In summary, currently synthesized metal-organic framework-derived porous carbon / graphene materials are not ideal for catalyzing the oxygen reduction reaction, which greatly limits their practical application in microbial fuel cells.

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  • Preparation method and application of bimetal organic framework composite material
  • Preparation method and application of bimetal organic framework composite material
  • Preparation method and application of bimetal organic framework composite material

Examples

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Embodiment 1

[0033] The preparation method of the bimetallic organic framework composite material of this embodiment comprises the following steps:

[0034] S1, 0.90gZn(NO 3 ) 2 •6H 2 O was dissolved in 30ml of methanol to obtain solution A; 1.0g of 2-methylimidazole was dissolved in 20ml of methanol to obtain solution B; under stirring, solution B was slowly added to solution A, stirred for 10min, at room temperature After standing still for 24 hours, centrifuge at 9000 rpm for 5 minutes to obtain a precipitate, wash the precipitate three times with methanol, and dry it at 60°C for 12 hours to obtain ZIF-8.

[0035] S2, 0.10g ZIF-8 was dissolved in 30ml methanol to obtain solution C; 0.30g 2-methylimidazole and 0.15g Co(NO 3 ) 2 •6H 2 O was dissolved in 10ml of methanol to obtain solution D; under stirring, solution D was slowly added to solution C, stirred for 10 minutes, left at room temperature for 24 hours, and then centrifuged at 9000 rpm for 5 minutes to obtain a precipitate, ...

Embodiment 2

[0047] The difference between this example and Example 1 is that: Weigh 50 mg of acidified derivative porous carbon, mix with 10 mL PDDA aqueous solution, stir for 2 h, centrifuge (9000 rpm, 5 min), and use twice After washing with water for 3 times, 5 mL of graphene oxide (GO) with a concentration of 1.0 mg / mL was added, stirred for 6 h, washed with water for 3 times by centrifugation, and then freeze-dried in a tube furnace under Ar atmosphere at 900 °C ( 3°C / min) high temperature annealing for 2 h, the target product NC@CoNC / rGO-5 composite nanomaterial was obtained, and the cathode polarization curve of the NC@CoNC / rGO-5 composite nanomaterial when used as MFC cathode catalyst was as follows Figure 4 shown.

Embodiment 3

[0049] The difference between this example and Example 1 is that: Weigh 50 mg of acidified derivative porous carbon, mix with 10 mL PDDA aqueous solution, stir for 2 h, centrifuge (9000 rpm, 5 min), and use twice After washing with water for 3 times, 15 mL of graphene oxide (GO) with a concentration of 1.0 mg / mL was added, stirred for 6 h, centrifuged and washed 3 times with water, freeze-dried and placed in a tube furnace at 900 °C (3 ℃ / min) high-temperature annealing for 2 h to obtain the target product NC@CoNC / rGO-15 composite nanomaterial, and the cathode polarization curve of NC@CoNC / rGO-15 composite nanomaterial when used as MFC cathode catalyst, as shown in Figure 4 shown.

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Abstract

The invention provides a preparation method of a bimetal organic framework composite material. According to the preparation method, the methanol solution of 2-methylimidazole is added into a zinc salt-containing solvent, and the methanol solution and the zinc salt-containing solvent are stirred uniformly, an obtained mixed solution stands still, so that ZIF-8 can be obtained; the methanol solutionof 2-methylimidazole is added into a solvent containing a proper amount of ZIF-8 and cobalt salt, and the methanol solution and the solvent are uniformly stirred, and an obtained mixed solution stands still, so that a bimetal organic framework precursor ZIF-8@ZIF-67 is obtained; the precursor is transferred into a tubular furnace so as to be subjected to high-temperature annealing, and porous carbon of a core-shell structure is obtained through derivation; the porous carbon material is mixed with PDDA, an obtained mixture is stirred, and the mixture is compounded with graphene oxide; and an obtained product is subjected to freeze-drying and high-temperature annealing sequentially, so that a porous carbon / graphene composite material is obtained. The porous carbon material prepared by the method disclosed by the invention is uniformly distributed on a graphene sheet layer; the composite material is good in stability and low in cost; and when the composite material is applied to an MFC cathode catalyst, the composite material shows good electrochemical catalytic performance.

Description

technical field [0001] The invention relates to a preparation method and application of a bimetallic organic framework composite material, in particular to a preparation method and application of a bimetallic organic framework derived porous carbon / graphene composite material, and belongs to the technical field of microbial dye batteries. Background technique [0002] Microbial fuel cell (MFC) is a new energy technology that converts organic matter in wastewater into electrical energy. MFC can process wastewater while generating electricity, and has broad application prospects. However, problems such as low power output, high internal resistance, and high cost of MFC limit its commercial application, in which the electron transfer and oxygen reduction reaction of the cathode become the bottleneck of battery performance improvement. Therefore, the development of low-cost, high-activity, and high-stability cathode non-platinum-based catalysts is the key to the application of ...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): H01M4/88H01M4/90H01M8/16
CPCH01M4/9041H01M4/9083H01M4/88H01M8/16Y02E60/50
Inventor 赵翠娥马延文秦景邱子夜
Owner NANJING UNIV OF POSTS & TELECOMM
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