Preparation of Fe-Co-N three-element co-doping three-dimensional graphene with catalytic synergistic effect

A synergistic and co-doping technology, applied in physical/chemical process catalysts, electrical components, chemical instruments and methods, etc., can solve the problems of easy removal of metals by acid, poor durability, and low catalytic performance.

Active Publication Date: 2017-05-10
SHANDONG UNIV OF TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

The present invention differs from metal-nitrogen-carbon clusters prepared by pyrolysis of simple nitrogen-containing organic compounds and transition metal complexes or nitrogen-containing polymers, such as urea resin, melamine resin, etc., and transition metal mixtures in that metal-nitrogen-carbon clusters The atomic cluster is not a graphene structure and has no large π effect, so the catalytic performance is not high, and its metal is easily removed by acid, so the durability is not good enough, especially because the metal-nitrogen-carbon cluster is not a porous structure and its mass transfer effect not good

Method used

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Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0014] [Example 1] Preparation of mPBI: Add polyphosphoric acid (PPA) (100 g) into a three-necked flask equipped with electric stirring and nitrogen protection, and stir at 160° C. for 1 h under nitrogen protection to remove excess water and air. DABz (4g, 18.7mmol) and isophthalic acid (3.1g, 18.7mmol) were mixed evenly, and slowly added into a three-necked flask. The nitrogen flow rate was controlled to prevent DABz from being oxidized, and at the same time, the reaction temperature was raised to 200° C., and the reaction was continued for 5-8 hours with insulation and stirring. With the increase of reaction time, the polymerization system gradually became viscous. Stop the reaction when the viscosity is appropriate, slowly transfer the reaction mixture to a large amount of deionized water, spin, wash, dry, pulverize, and wash with deionized water several times to remove polyphosphoric acid and unreacted reactants to obtain mPBI. The molecular weight of mPBI was determined ...

Embodiment 2

[0015] [Example 2] Synthesis of mPBI by solid-phase method: DABz (4g, 18.7 mmol) and isophthalic acid (3.1g, 18.7 mmol) were mixed in a mortar, thoroughly ground and mixed, and transferred to a stirrer with nitrogen protection. in the three-neck flask. Nitrogen was passed for 15 minutes to exhaust the air in the flask. N 2 Protected and stirred, heated in an oil bath at 225°C for 3h. Take it out after cooling, grind finely, N 2 Under protection, heat in an electric furnace, raise the temperature to 270-275°C, and keep it for 3 hours. After cooling to room temperature, the product was taken out and finely ground to obtain mPBI, and the molecular weight of mPBI was measured with an Ubbelohde viscometer.

[0016] The preparation method of ABPBI is similar to that of mPBI, except that 3,4-diaminobenzoic acid (DABA) is used instead of DABz and isophthalic acid. ABPBI can be obtained using only one raw material. Other reaction conditions and operation steps are with embodiment...

Embodiment 3

[0017] [Example 3] MgO with a particle size of 30nm is used as a template, both iron salt and cobalt salt use acetate, and the molar ratio is 1:1; the mass ratio between the two salts and PBI is 1:2 after mixing, and mPBI is used for PBI , taking the mass ratio of mPBI to MgO template as 1:1 as an example: in a 250mL beaker, add 1g of mPBI (viscosity average molecular weight 20,000 to 30,000) and 20mL DMAc, heat and stir to dissolve, then add 0.5 g of a mixture of cobalt acetate and iron acetate (the two salts are mixed at a molar ratio of 1:1) in 20 mL of DMAc solution, kept at 80 ° C to 100 ° C, stirred for 5 to 8 hours, slowly added 1 g of 30 nm particle size Nano MgO particles, stirred for 4~6 hours to make it evenly dispersed. The obtained viscous liquid was heated and concentrated to nearly dryness under stirring, and dried in a vacuum oven at 120°C. The solid was ground in a mortar, transferred to a porcelain boat, and kept in an electric furnace at 900°C under the prot...

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Abstract

The invention relates to a simple preparation method of Fe (ferrous), Co (cobalt) and N (nitrogen) three-element co-doping three-dimensional graphene with catalytic synergistic effect. The preparation method comprises the following steps of enabling soluble fully-aromatic PBI (polybenzimidazole) to react with a ferrous salt and cobalt salt mixing solution; firstly, preparing a complex of PBI, ferrous ions and cobalt ions; adding a nanometer template agent into the reaction mixing liquid; regularly arranging the complex at the surface of the template agent; pyrolyzing, removing a template, and the like, so as to prepare the Fe-Co-N three-element co-doping three-dimensional graphene. The PBI is selected from fully-aromatic macromolecules, such as ABPBI and mPBI, and the viscosity average molecular weigh is 20,000 to 40,000; the molar ratio of ferrous salt and cobalt salt is 1:2 to 2:1; the mass ratio of PBI and ferrous salt and cobalt salt mixture is 1:2 to 2:1; the template agent is selected from nanometer magnesium oxide, ferric oxide and ferric hydroxide nanoparticles; the particle size of the template agent is 5 to 50nm; the mass ratio of PBI and template agent is 3:1 to 1:3; the pyrolysis temperature is 700 to 1000 DEG C; the Fe-Co-N three-element co-doping three-dimensional graphene can be applied to the fields of redox reaction catalysts, fuel batteries, metal air battery redox catalysts, water electrolysis separation catalysts, supercapacitors and the like.

Description

technical field [0001] Belonging to the field of nanomaterial preparation, it is used in redox reaction catalysts in chemical production, fuel cells in the field of clean energy, cathode catalysts for metal-air batteries, electrolytic water catalysts, lithium-ion battery materials, supercapacitor electrode materials and electrochemical sensors, etc. . Background technique [0002] Graphene is a nanomaterial with a regular hexagonal extended two-dimensional grid structure composed of carbon atoms. Due to its excellent performance and multiple potential applications, it has become a research hotspot that has attracted widespread attention today (Kim K S, et al. Nature (Nature), 2009, 457: 706). However, in the macroscopic world, two-dimensional graphene is very easy to overlap each other layer by layer to form a graphite structure, thus losing its excellent performance. Therefore, the preparation and performance research of three-dimensional graphene has become a research ho...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): B01J27/24H01M4/88H01M4/96H01G11/86H01G11/36
CPCB01J27/24H01G11/36H01G11/86H01M4/88H01M4/96Y02E60/13Y02E60/50
Inventor 李忠芳王素文卢雪伟张廷尉
Owner SHANDONG UNIV OF TECH
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