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A nitrogen-phosphorus co-doped metal-organic framework package platinum-cobalt-based alloy and its preparation method and application

A metal-organic framework and cobalt-based alloy technology, which is applied in nanotechnology, structural parts, electrical components, etc. for materials and surface science, can solve the problems of reduced catalytic activity and reduced defect sites, and achieve increased activity and improved porosity. The effect of high rate and large specific surface area

Active Publication Date: 2021-09-24
DALIAN INST OF CHEM PHYSICS CHINESE ACAD OF SCI
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Although the ordered structure enhances the stability of the catalyst, there are still some disadvantages: first, the defect sites are reduced after the alloy is ordered, and second, this type of catalytic material will be sintered into large nanoparticles under harsh conditions. Both of these can lead to reduced catalytic activity

Method used

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  • A nitrogen-phosphorus co-doped metal-organic framework package platinum-cobalt-based alloy and its preparation method and application
  • A nitrogen-phosphorus co-doped metal-organic framework package platinum-cobalt-based alloy and its preparation method and application

Examples

Experimental program
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Effect test

Embodiment 1

[0035] The method of preparing a metal organic framework encapsulating a platinum-cobalt-based alloy co-doping of nitrogen and phosphorus, comprising the steps of:

[0036] (1) In a typical synthesis of the ZIF-67, the 1.7mmol cobalt nitrate was dissolved in methanol and 25.0mL, 15.2mmol 2- methylimidazole was added a clear solution was dissolved in 40.0mL of methanol under stirring. The mixture was stirred for 30min at room temperature to give non-uniform purple mixture, which was then sealed and kept at room temperature for 12h. Collected by centrifugation (5000 rpm for) crystal violet, washed three times in methanol, and then dried in vacuo overnight at 80 ℃, to give ZIF-67.

[0037] Step (2) to (5) were carried out with magnetic stirring and under nitrogen.

[0038] (2) alkylene take 0.1mmol potassium hexachloroplatinate, 0.026 mmol 0.016mmol cobalt nitrate and nickel nitrate were dissolved in 20mL of isopropanol was added 1mol / L KOH pH of the solution was 12 to 13. Nitrogen...

Embodiment 2

[0046] The method of preparing a metal organic framework encapsulating a platinum-cobalt-based alloy co-doping of nitrogen and phosphorus, comprising the steps of:

[0047] (1) In a typical synthesis of the ZIF-67, the 1.7mmol cobalt nitrate was dissolved in methanol and 25.0mL, 15.2mmol 2- methylimidazole was added a clear solution was dissolved in 40.0mL of methanol under stirring. The mixture was stirred for 30min at room temperature to give non-uniform purple mixture, which was then sealed and kept at room temperature for 12h. Collected by centrifugation (5000 rpm for) crystal violet, washed three times in methanol, and then dried in vacuo overnight at 80 ℃, to give ZIF-67.

[0048] Step (2) to (5) were carried out with magnetic stirring and under a protective gas environment.

[0049] (2) taking 0.1mmol chloroplatinic acid, 0.016 mmol of cobalt acetate, 0.026 mmol nickel acetate dissolved in 35mL of isopropanol was added 1mol / L NaOH pH of the solution was 12 to 13. An argon...

Embodiment 3

[0057] The method of preparing a metal organic framework encapsulating a platinum-cobalt-based alloy co-doping of nitrogen and phosphorus, comprising the steps of:

[0058] (1) In a typical synthesis of the ZIF-67, the 1.7mmol cobalt nitrate was dissolved in methanol and 25.0mL, 15.2mmol 2- methylimidazole was added a clear solution was dissolved in 40.0mL of methanol under stirring. The mixture was stirred for 30min at room temperature to give non-uniform purple mixture, which was then sealed and kept at room temperature for 12h. Collected by centrifugation (5000 rpm for) crystal violet, washed three times in methanol, and then dried in vacuo overnight at 80 ℃, to give ZIF-67.

[0059] Step (2) to (5) were carried out with magnetic stirring and under nitrogen.

[0060] (2) potassium hexachloroplatinate take 0.1mmol, 0.026mmol 0.016mmol cobalt nitrate and nickel nitrate were dissolved in 20mL of isopropanol was added 1mol / L KOH pH of the solution was 12 to 13. Nitrogen at room t...

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Abstract

The invention discloses a nitrogen-phosphorus co-doped metal-organic framework-encapsulated platinum-cobalt-based alloy, a preparation method and application thereof, and belongs to the technical field of fuel cell nano-catalyst synthesis. Dissolve the platinum precursor, cobalt precursor and doped metal precursor in isopropanol, and adjust the pH of the solution to > 11; stir at room temperature under a protective gas environment to obtain a metal salt mixed solution; impregnate ZIF‑67 into the metal In the salt mixed solution, seal the ultrasonic wave and let it stand still, then disperse it in the polyol solvent, stir and reflux under the atmosphere of protective gas and heat the reaction; drop NaBH dissolved in isopropanol 4 Solution, react for a period of time; after stopping the reaction, cool to room temperature, centrifuge to separate the solid product, wash, and dry; grind and mix adenine phosphate and the dried solid product, then heat-treat, and cool to room temperature to obtain the product. The method has the advantages of simplicity, safety, etc., and is especially suitable for the preparation of cathode catalysts for fuel cells and metal-air batteries.

Description

Technical field [0001] The present invention relates to a method for preparing nano-particles embedded in a metal-organic framework alloy composite material, and more particularly to platinum-cobalt-based alloy packaging and preparation method and use of metal organic framework of co-doping of nitrogen and phosphorus, is the fuel cell catalyst synthesis nano Field . Background technique [0002] Oxygen reduction catalyst proton exchange membrane fuel cells is largely divided into two categories: a platinum alloy catalyst is platinum (Pt) based catalyst, there are special structure of platinum on carbon, platinum alloys, and core-shell, hollow like; Another non-platinum-based catalyst, comprising a transition metal (Mn, Fe, Co, Ni, Cu) complexes of nitrogen-carbon catalyst, a transition metal chalcogen (S, Se, Te) compound, non-metallic hetero atoms (B, N, S, P, BN, NP, NS, F, Cl, Br, I) doped carbon catalyst. Catalytic properties of the non Pt-based catalyst only in an alkaline e...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): H01M4/86H01M4/92B82Y30/00B82Y40/00
CPCH01M4/8647H01M4/926B82Y40/00B82Y30/00Y02E60/50
Inventor 邵志刚索妮秦晓平
Owner DALIAN INST OF CHEM PHYSICS CHINESE ACAD OF SCI
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