Nitrogen-sulfur-doped porous carbon-modified carbon nanotube-supported Pt-Ni alloy catalyst and preparation method thereof

A technology of alloy catalysts and nanotubes, which is applied in metal/metal oxide/metal hydroxide catalysts, chemical instruments and methods, physical/chemical process catalysts, etc. control, less functional sites, etc., to achieve the effects of improving dispersion and stability, highlighting catalytic reaction performance, and improving catalytic activity

Active Publication Date: 2020-02-21
NANJING INST OF TECH
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Problems solved by technology

[0002] In recent years, nano-catalytic materials have been widely used in petrochemical catalysis, photocatalysis, electrocatalysis and other fields due to their unique surface structure and multiple active sites; , high chemical stability, has been considered as an ideal carrier material, but carbon nanotubes still have many shortcomings, such as the modified carbon nanotubes have fewer functional sites, serious agglomeration, and insufficient specific surface area. Big and so on
Due to its structure controllability, diversity and high specific surface area, metal organic framework materials have potential application prospects in many fields, especially the rapid development of application research in the field of catalysis; platinum and nickel nano metal particles loaded on the carrier The various catalytic materials produced are widely used in the field of catalysis, but there are also some problems in the use of this kind of nano-metal particles, such as the shape of the supported nano-metal particles is difficult to control, the size of the nanoparticles is too large, and it is easy to reunion, etc.
[0003] Chinese patent 201711018078.6 discloses a method for preparing a Ni-based catalyst modified by using multi-walled carbon nanotubes as a support agent Pt. The preparation method first acid-modifies the multi-walled carbon nanotubes with sulfuric acid mixed acid, Using it as a carrier, adding platinum and nickel precursor salts, supercatalyst acoustic stirring, drying, and finally calcination and reduction, the final Pt-Ni / MWCNT catalyst is obtained, but the catalyst has metal nanoparticles that are difficult to control and prone to Inadequacies such as reunion
The preparation method is as follows: dispersing multi-walled carbon nanotubes in a mixed solution of nickel nitrate and urea, heating and reacting, cooling and standing still to obtain a nanocomposite in which nickel hydroxide is coated on the surface of multi-walled carbon nanotubes; The nano-composite obtained by the above reaction is dispersed in ethylene glycol, and then sodium chloroplatinate is added to adjust the pH of the solution to 10-13, heated and refluxed, washed and dried to obtain a composite material, which can be used as an enzyme-free sub Nitrate sensor, but the nanocomposite material has the disadvantages of less carbon nanotube functionalized sites and insufficient specific surface area.

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  • Nitrogen-sulfur-doped porous carbon-modified carbon nanotube-supported Pt-Ni alloy catalyst and preparation method thereof
  • Nitrogen-sulfur-doped porous carbon-modified carbon nanotube-supported Pt-Ni alloy catalyst and preparation method thereof
  • Nitrogen-sulfur-doped porous carbon-modified carbon nanotube-supported Pt-Ni alloy catalyst and preparation method thereof

Examples

Experimental program
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Effect test

Embodiment 1

[0029] Step a): At 25°C, weigh 0.1 g of carboxylated carbon nanotubes and 50 mL of N,N-dimethylformamide, add carboxylated carbon nanotubes into N,N-dimethylformamide, and ultrasonically disperse 15min, then add 0.7g 2,5-dihydroxythiophene, 0.22g triethylenediamine and 1.213g nickel nitrate hexahydrate, continue ultrasonic dispersion for 15min, transfer to the reaction kettle, react at 130°C for 12h, naturally cool to room temperature, Centrifuge, wash twice with N,N-dimethylformamide and ethanol successively, and dry under vacuum at 65°C for 12 hours to prepare carboxylated carbon nanotubes / Ni-MOF.

[0030] Step b): At 25°C, take 0.1 g of the above-prepared carboxylated carbon nanotubes / Ni-MOF, add 100 mL of deionized water, add 2 mL of trisodium citrate aqueous solution with a concentration of 2 wt % and 0.5 mL of a solution with a concentration of 0.5 Wt% aqueous solution of potassium chloroplatinite was ultrasonically dispersed for 30 min, then 4 mL of 0.2 wt% sodium boroh...

Embodiment 2

[0039] The nitrogen-sulfur-doped porous carbon-modified carbon nanotube-loaded Pt-Ni alloy catalyst prepared in Example 1 was applied to the electrocatalytic hydrogen evolution reaction under alkaline conditions, specifically, the nitrogen-sulfur-doped carbon nanotube prepared in Example 1 Porous carbon-modified carbon nanotubes loaded with Pt-Ni alloy catalyst-modified glassy carbon electrode as the working electrode, mercury / mercury oxide electrode as the reference electrode, platinum sheet electrode as the counter electrode, and the electrolyte is 1mol / L potassium hydroxide solution.

[0040] Tested by linear voltammetry sweep, by Figure 5 The voltammetric sweep curve shown can be calculated at a current density of 10mA / cm 2 The lower overpotential is only 0.062V (vs RHE), showing that the catalyst prepared in Example 1 produces a synergistic effect among the components, which improves the catalytic performance of the catalyst.

Embodiment 3

[0042] Step a): At 25°C, weigh 0.1 g of carboxylated carbon nanotubes and 20 mL of N,N-dimethylformamide, add carboxylated carbon nanotubes into N,N-dimethylformamide, and ultrasonically disperse 20min, then add 2g 2,5-dihydroxythiophene, 0.22g triethylenediamine and 1.542g nickel chloride, continue to ultrasonically disperse for 20min, transfer to the reaction kettle, react at 130°C for 24h, naturally cool to room temperature, centrifuge, Washed twice with N,N-dimethylformamide and ethanol successively, and dried in vacuum at 90°C for 8 hours to obtain carboxylated carbon nanotubes / Ni-MOF.

[0043] Step b): At 25°C, take 0.1g of the above-prepared carboxylated carbon nanotubes / Ni-MOF, add 100mL of deionized water, add 0.5mL of 4wt% trisodium citrate aqueous solution and 0.2mL of 2wt% aqueous solution of potassium chloroplatinite was ultrasonically dispersed for 30 minutes, then 4 mL of 0.2wt% sodium borohydride aqueous solution was added, ultrasonically dispersed for 30 minut...

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Abstract

The invention discloses a nitrogen-sulfur-doped porous carbon-modified carbon nanotube-supported Pt-Ni alloy catalyst and a preparation method thereof. The preparation method comprises the following steps: step a) preparation of a carboxylated carbon nanotube/Ni-MOF; step b) preparation of a carboxylated carbon nanotube/Ni-MOF/Pt; and c) preparation of the nitrogen-sulfur-doped porous carbon-modified carbon nanotube-supported Pt-Ni alloy catalyst: putting the carboxylated carbon nanotube/Ni-MOF/Pt prepared in the step b) into a tubular furnace, introducing inert gas, carrying out heating to 550-800 DEG C, and performing roasting for 0.5-4 hours to prepare the catalyst. According to the catalyst, through doping of porous carbon, the specific surface area of a carbon nanotube is increased and the carbon nanotube is endowed with additional functional sites; and since Pt-Ni alloy nanoparticles are encapsulated in pore channels of the porous carbon, the sizes of metal particles are effectively controlled, the metal particles are uniformly dispersed, and the catalytic activity and stability of the catalyst are improved.

Description

technical field [0001] The invention relates to the technical field of nano-catalysis materials, in particular to a nitrogen-sulfur-doped porous carbon-modified carbon nanotube-loaded Pt-Ni alloy catalyst and a preparation method thereof. Background technique [0002] In recent years, nano-catalytic materials have been widely used in petrochemical catalysis, photocatalysis, electrocatalysis and other fields due to their unique surface structure and multiple active sites; , high chemical stability, has been considered as an ideal carrier material, but carbon nanotubes still have many shortcomings, such as the modified carbon nanotubes have fewer functional sites, serious agglomeration, and insufficient specific surface area. Big wait. Due to its structure controllability, diversity and high specific surface area, metal organic framework materials have potential application prospects in many fields, especially the rapid development of application research in the field of cata...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): B01J27/24B01J23/89B01J35/02B01J35/10C25B1/04C25B11/06
CPCB01J27/24B01J35/1019B01J35/023B01J23/892B01J35/0033C25B1/04C25B11/04Y02E60/36
Inventor 张泽武戴逸凡李诗佳史皓峻王陶淼赵威任冲
Owner NANJING INST OF TECH
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