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CN-122010093-A - Porous curved surface hollow dodecahedron carbon nano box material and preparation method and application thereof

CN122010093ACN 122010093 ACN122010093 ACN 122010093ACN-122010093-A

Abstract

The invention discloses a porous curved surface hollow dodecahedron carbon nano box material, a preparation method and application thereof, and a preparation method and application thereof The quantum dots can be used for adjusting the force balance of the ZIF-67 framework structure in heat treatment, so that the polyhedron shape of the material can be reserved, the material with abundant micropore structures and large specific surface area can be obtained, and the material is beneficial to exposing abundant catalytic active sites, so that high-efficiency electrocatalysis is realized. The catalyst prepared by the invention has excellent difunctional oxygen catalysis performance. Wherein OER is 10 mA +. The overpotential is only 130 mV, and the half-wave potential of ORR can reach 0.86V. The proposal provides a new strategy for designing the high-efficiency bifunctional electrocatalyst, which is helpful for further promoting the development of the air electrode catalyst in the metal-air battery.

Inventors

  • ZHAO DENGKE
  • CUI XUEYAN
  • Sheng Zemin
  • WANG ZHITAO

Assignees

  • 河南师范大学

Dates

Publication Date
20260512
Application Date
20260113

Claims (8)

  1. 1. The preparation method of the porous curved surface hollow dodecahedral carbon nano box material is characterized by comprising the following steps of: S1 synthesis block ; S2 preparation A quantum dot; s3, preparing the porous curved surface hollow dodecahedron carbon nano box CNQD/CoNBs, wherein the porous curved surface hollow dodecahedron carbon nano box is introduced in the ZIF-67 synthesis process Quantum dot is self-assembled by adopting a surfactant auxiliary method to form a precursor with a dodecahedral structure, and then the precursor is prepared in the following steps of Pyrolyzing in atmosphere, and forming the porous curved surface hollow dodecahedron carbon nano-box CNQD/CoNBs after pyrolysis.
  2. 2. The method for preparing the porous curved surface hollow dodecahedral carbon nano-box material according to claim 1, wherein the S2 is prepared by the steps of firstly mixing concentrated sulfuric acid and concentrated nitric acid Etching into multiple holes Then, the mixture is subjected to hydrothermal treatment in ammonia water, and Peeling to obtain ultrathin nanometer sheet with porous structure, and finally, ultrasonic treating in water Peeling the nano sheet to obtain a single layer Quantum dots.
  3. 3. The preparation process of porous curved surface hollow decaoctahedral carbon nanometer box material according to claim 1, wherein S1 is prepared through synthesizing block shape Heating 10 g melamine to 600 deg.C at a rate of 10 deg.C/min and keeping the temperature for 2 hours, and cooling to room temperature at the same rate to obtain yellow block The product is obtained.
  4. 4. The method for preparing the porous curved surface hollow dodecahedron carbon nano-box material according to claim 1, wherein the specific preparation process of S2 comprises the steps of firstly, preparing 1 g of The powder was treated at room temperature for about 2 hours in a mixture of concentrated sulfuric acid and concentrated nitric acid each containing 20 mL, then diluted with 1L deionized water and washed several times to give a white product as a porous one Next, 354 mg the porous material obtained by the above steps Dispersing in 30 mL concentrated ammonia water, transferring to 45 mL reactor liner, heating in sealed autoclave at 150deg.C for 12 hr, and making porous during hydrothermal process Will be stripped as Dispersing the obtained product in 100 mL water, and performing ultrasonic treatment for about 6 hr to obtain a mixture Aqueous solutions of quantum dots.
  5. 5. The method for preparing a porous curved surface hollow dodecahedral carbon nano-box material as claimed in claim 4, wherein the specific preparation process of S3 comprises the steps of adding 4.54 g of 2-methylimidazole into the aqueous solution finally obtained in S2, and adding 292 mg Dissolving in 10mL deionized water containing 5mg cetyl trimethyl ammonium bromide CTAB, rapidly pouring into the 100mL aqueous solution, stirring at room temperature for 20 minutes, washing with ethanol for several times, centrifugally collecting the product, drying in a 60 ℃ oven for 12 hours, further grinding the dried powder to obtain a composite precursor, heating the prepared precursor to 800 ℃ at a heating rate of 10 ℃ per minute under an N 2 atmosphere, pyrolyzing for 2 hours, finally collecting a black solid product, and cooling to room temperature to obtain a final sample, namely the porous curved hollow dodecahedral carbon nano-box CNQD/CoNBs.
  6. 6. A porous curved surface hollow dodecahedron carbon nano-box material, which is characterized by being prepared by the method of any one of claims 1-5.
  7. 7. An air electrode material of a zinc-air battery, which is characterized by being manufactured by adopting the porous curved surface hollow dodecahedron carbon nano box material of claim 6.
  8. 8. The method for preparing an air electrode material of a zinc-air battery according to claim 7, wherein the specific operation steps are as follows: Firstly, weighing CNQD/CoNBs material and binder polyvinylidene fluoride according to a mass ratio of 8:1, taking N-methyl pyrrolidone as a dispersion solvent, placing the dispersion solvent in an agate mortar, grinding 15 min with the aid of an infrared baking lamp to obtain uniform sticky electrode slurry, secondly, manually coating the slurry on the surface of a hydrophobic Carbon Cloth (CC) current collector, then placing the coated carbon cloth on a toughened glass carrier, transferring the toughened glass carrier to a 110 ℃ vacuum drying box, drying for 8 h to obtain an air electrode modified by CNQD/CoNBs, and finally, taking the CNQD/CoNBs modified carbon cloth as the air electrode, and 6M KOH+0.2M The mixed solution is electrolyte, the metal zinc sheet is a negative electrode, the zinc-air battery is assembled and performance measurement is carried out, and the test result shows that the zinc-air battery has excellent discharge capacity and cycle charge-discharge stability.

Description

Porous curved surface hollow dodecahedron carbon nano box material and preparation method and application thereof Technical Field The invention belongs to the fields of electrochemical oxygen reduction reaction, oxygen evolution reaction and zinc-air battery, and in particular relates to a porous hollow dodecahedron carbon nano-box material and a preparation method and application thereof. Background Energy crisis and environmental pollution place high demands on renewable clean energy storage and conversion technologies, and therefore rechargeable zinc-air batteries continue to be of interest. But its practical application is still limited by the lack of efficient oxygen evolution/reduction reactions (OER/ORR). This limitation results from the high OER/ORR overpotential resulting from the slow kinetics of the four-electron multi-step reaction during redox. Although conventional noble metal electrocatalysts (Ru, ir, pt, etc.) have higher electrochemical activity, they do not guarantee to maintain high catalytic activity for both ORR and OER in the same alkaline electrolyte. For example, pt is a high performance catalyst for ORR, but it does not perform well enough for OER. In contrast to this,AndHave a high OER activity but their catalytic activity in another reaction is relatively weak. Therefore, to overcome the problems of high price and single activity of noble metal catalysts, the development of non-noble metal electrocatalysts with both ORR and OER high activities has considerable challenges. Related art development Metal Organic Frameworks (MOFs) have great potential as catalyst supports or catalysts themselves in catalysis due to their porosity and large specific surface area. The ZIF-67 is a cobalt-based MOF material and can be synthesized by a simple and environment-friendly method. It has an adjustable pore size and a highly stable structure. In addition, it has been found that active sites tend to be dispersed on curved surfaces of carbon nanospheres and carbon nanotubes. For example, by usingThe coating covers the MOF structure, producing Fe-N-C and Co-N-C on a curved porous carbon structure. However, the above-described techniques do not address the problem of collapse of the ZIF material during pyrolysis. At the same time, the method is complex and requires acid treatment for removalCoatings, which may damage the active structure, result in loss of active sites. And single function, failed to catalyze OER and used in zinc air cells. Disclosure of Invention In order to overcome the problems in the prior art, the invention provides a porous curved surface hollow dodecahedron carbon nano-box material, and a preparation method and application thereof. The preparation method of the porous curved surface hollow dodecahedral carbon nano-box material comprises the following steps: S1 synthesis block ; S2 preparationA quantum dot; s3, preparing the porous curved surface hollow dodecahedron carbon nano box CNQD/CoNBs, wherein the porous curved surface hollow dodecahedron carbon nano box is introduced in the ZIF-67 synthesis process And the quantum dots are self-assembled by adopting a surfactant auxiliary method to form a precursor with a dodecahedron structure, then pyrolyzed in N 2 atmosphere, and after pyrolysis, the porous curved surface hollow dodecahedron carbon nano box CNQD/CoNBs is formed. Further, the S2 is prepared by first treating the substrate with concentrated sulfuric acid and concentrated nitric acidEtching into multiple holesThen, the mixture is subjected to hydrothermal treatment in ammonia water, andPeeling to obtain ultrathin nanometer sheet with porous structure, and finally, ultrasonic treating in waterPeeling the nano sheet to obtain a single layerQuantum dots. Further, the specific preparation process of S1 comprises synthesizing the block shapeHeating 10 g melamine to 600 deg.C at a rate of 10 deg.C/min and keeping the temperature for 2 hours, and cooling to room temperature at the same rate to obtain yellow blockA product; further, S2 is prepared by first, adding 1 g to The powder was treated in a mixture of concentrated sulfuric acid and concentrated nitric acid each containing 20 mL at room temperature for about 2 hours. Then diluted with 1L deionized water and washed several times. The white product obtained is porous. Next, 354 mg the porous material obtained by the above stepsDisperse in 30 mL concentrated ammonia and transfer to 45 mL reactor liner and heat in a sealed autoclave at 150 ℃ for 12 hours. Porous in hydrothermal processWill be stripped asPorous nanoplatelets. Dispersing the obtained product in 100 mL water, and performing ultrasonic treatment for about 6 hr to obtain a mixtureAqueous solutions of quantum dots. Further, S3 is specifically prepared by adding 4.54 g of 2-methylimidazole to the aqueous solution finally obtained in S2. Will 292 mgDissolving in 10 mL deionized water containing 5 mg cetyl trimethyl ammonium bromide CTAB, rapidly pouring into the ab