CN104209514A

CN104209514A - Method for preparing Ni@C or Co@C core-shell nanoparticles

Info

Publication number: CN104209514A
Application number: CN201410450731.6A
Authority: CN
Inventors: 王一菁; 焦丽芳; 袁华堂; 安翠华; 王俊婷; 黄娅楠; 陈程成
Original assignee: Nankai University
Current assignee: Nankai University
Priority date: 2014-09-05
Filing date: 2014-09-05
Publication date: 2014-12-17

Abstract

The invention relates to a method for preparing Ni@C or Co@C core-shell nanoparticles. The method comprises the steps: (1) adding nickel chloride or cobalt chloride into an isopropanol aqueous solution, adding nitrilotriacetic acid, and stirring for 1 hour at room temperature, so as to obtain a mixed solution; (2) transferring the mixed solution to a reactor, placing the reactor into an air-blasting drying oven, carrying out heat preservation for 6 hours at the temperature of 180 DEG C, cooling, then, separating a product, cleaning and drying in vacuum, so as to obtain a precursor; (3) putting the precursor into a tubular furnace, heating to the temperature of 500-600 DEG C at the heating rate of 2 DEG C/min, and carrying out heat preservation for 2 hours, thereby obtaining a black product, namely the Ni@C or Co@C core-shell nanoparticles. The method has the advantages that the method is simple in process, low in energy consumption, low in cost and free from environmental pollution, and the in-situ synthesis of the Ni@C or Co@C core-shell nanoparticles is realized; the prepared core-shell nanoparticles have porous structures and are larger in specific surface area and narrower in pore size distribution, thereby being a promising catalyst or energy storage material.

Description

The preparation method of a kind of Ni@C or Co@C core shell nanoparticles

Technical field

The present invention relates to the preparation method of metal@carbon core shell nanoparticles, particularly the preparation method of a kind of Ni@C or Co@C core shell nanoparticles.

Background technology

Transition metal simple substance is the important multifunctional material of a class, and the application in catalysis, magnetic is extensively concerned.But transition metal simple substance is very easily oxidized under air, thus limits it and apply widely.Solution conventional is at present that carbon is coated, to prevent the oxidation of transition metal simple substance, also has positive effect to its performance simultaneously.But the sol-gel process preparation adopted at present, limits because of its needs longer reaction time and higher reaction temperature and commercially produces.Therefore, exploitation is a kind of simple to operate, with low cost, and the method for eco-friendly fabricated in situ M@C (M=Ni, Co) core shell nanoparticles has great importance.

Summary of the invention

The object of the invention is for above-mentioned existing problems, the preparation method of a kind of Ni@C or Co@C core shell nanoparticles is provided, this preparation method's technique is simple, do not need the synthesis step that long reaction time and high reaction temperature etc. are complicated, simplify flow process, reduce energy consumption, achieve the fabricated in situ of Ni@C or Co@C core shell nanoparticles.

Technical scheme of the present invention:

A preparation method for Ni@C or Co@C core shell nanoparticles, step is as follows:

1) by NiCl ₂6H ₂o or CoCl ₂6H ₂o adds in isopropanol water solution, under constantly stirring, adds nitrilotriacetic acid and at room temperature stirs 1 hour, obtaining mixed liquor;

2) transfer in reactor by above-mentioned mixed liquor, reactor is placed in air dry oven and is incubated 6 hours at 180 DEG C, be then down to room temperature, separated product also uses water and ethanol purge three times successively, after vacuum drying, obtains presoma Ni-NTA or Co-NTA;

3) above-mentioned presoma Ni-NTA or Co-NTA is placed in tube furnace, is heated to 500-600 DEG C with 2 DEG C/min heating rate and is incubated 2 hours, obtain product Ni@C or the Co@C core shell nanoparticles of black.

In described isopropanol water solution, the volume ratio of isopropyl alcohol and water is 1:1; NiCl in mixed liquor ₂6H ₂o or CoCl ₂6H ₂the amount ratio of O and isopropanol water solution, nitrilotriacetic acid is 1.5 g:40 mL:0.6 g.

Advantage of the present invention and beneficial effect are:

Preparation method's abundant raw material source of described core shell nanoparticles, technique are simple, do not need the step that HTHP etc. is complicated, simplify preparation flow, reduce energy consumption, cost is low, achieve the fabricated in situ of Ni@C or Co@C core shell nanoparticles; Obtained core shell nanoparticles is a kind of loose structure, and its specific area is comparatively large, and pore-size distribution is narrower, is up-and-coming catalyst or energy storage material; Can not environmental pollution be caused in preparation process, environmental protection, be applicable to large-scale industrial production.

Accompanying drawing explanation

Fig. 1 is XRD figure and the SEM figure of Ni@C core shell nanoparticles prepared by embodiment 1, in figure: a is XRD figure, b is SEM figure.

Fig. 2 is XRD figure and the SEM figure of Co@C core shell nanoparticles prepared by embodiment 2, in figure: a is XRD figure, b is SEM figure.

Fig. 3 is the Ni@C of embodiment 1 and 2 preparation and the TEM figure of Co@C core shell nanoparticles, and in figure: a is Ni@C core shell nanoparticles, b is Co@C core shell nanoparticles.

Detailed description of the invention

Below in conjunction with embodiment, the present invention is described further.

embodiment 1:

A preparation method for Ni@C core shell nanoparticles, step is as follows:

1) by 1.5 g NiCl ₂6H ₂o adds in the isopropanol water solution be made up of 20 mL water and 20 mL isopropyl alcohols, under constantly stirring, adds 0.6 g nitrilotriacetic acid (NTA) and at room temperature stirs 1 hour, obtaining mixed liquor;

2) transfer in reactor by above-mentioned mixed liquor, reactor is placed in air dry oven and is incubated 6 hours at 180 DEG C, be then down to room temperature, separated product also uses water and ethanol purge three times successively, after vacuum drying, obtains presoma Ni-NTA;

3) above-mentioned presoma Ni-NTA is placed in tube furnace, is heated to 500 DEG C with 2 DEG C/min heating rate and is incubated 2 hours, obtain the product Ni@C core shell nanoparticles of black.

Fig. 1 is XRD figure and the SEM figure of Ni@C core shell nanoparticles prepared by embodiment 1, in figure: a is XRD figure, b is SEM figure.Fig. 3 a is the TEM figure of Ni@C core shell nanoparticles prepared by embodiment 1.Show in above figure: Ni@C core shell nanoparticles is a kind of loose structure, its specific area is comparatively large, and pore-size distribution is narrower.

embodiment 2:

A preparation method for Co@C core shell nanoparticles, step is as follows:

1) by 1.5 g CoCl ₂6H ₂o adds in the isopropanol water solution be made up of 20 mL water and 20 mL isopropyl alcohols, under constantly stirring, adds 0.6 g nitrilotriacetic acid (NTA) and at room temperature stirs 1 hour, obtaining mixed liquor;

2) transfer in reactor by above-mentioned mixed liquor, reactor is placed in air dry oven and is incubated 6 hours at 180 DEG C, be then down to room temperature, separated product also uses water and ethanol purge three times successively, after vacuum drying, obtains presoma Co-NTA;

3) above-mentioned forerunner Co-NTA is placed in tube furnace, is heated to 500 DEG C with 2 DEG C/min heating rate and is incubated 2 hours, obtain the product C o@C core shell nanoparticles of black.

Fig. 2 is XRD figure and the SEM figure of Co@C core shell nanoparticles prepared by embodiment 2, in figure: a is XRD figure, b is SEM figure.Fig. 3 b is the TEM figure of Co@C core shell nanoparticles prepared by embodiment 2.Show in above figure: Ni@C core shell nanoparticles is a kind of loose structure, its specific area is comparatively large, and pore-size distribution is narrower.

embodiment 3:

A preparation method for Ni@C core shell nanoparticles, step is as follows:

3) above-mentioned presoma Ni-NTA is placed in tube furnace, is heated to 600 DEG C with 2 DEG C/min heating rate and is incubated 2 hours, obtain the product Ni@C core shell nanoparticles of black.

XRD figure, SEM figure and the TEM figure of the Ni@C core shell nanoparticles of preparation and embodiment 1 are roughly the same.

embodiment 4:

A preparation method for Co@C core shell nanoparticles, step is as follows:

3) above-mentioned forerunner Co-NTA is placed in tube furnace, is heated to 600 DEG C with 2 DEG C/min heating rate and is incubated 2 hours, obtain the product C o@C core shell nanoparticles of black.

XRD figure, SEM figure and the TEM figure of the Co@C core shell nanoparticles of preparation and embodiment 2 are roughly the same.

Claims

1. a preparation method for Ni C or Co C core shell nanoparticles, is characterized in that step is as follows:

2. the preparation method of Ni@C or Co@C core shell nanoparticles according to claim 1, is characterized in that: in described isopropanol water solution, the volume ratio of isopropyl alcohol and water is 1:1; NiCl in mixed liquor ₂6H ₂o or CoCl ₂6H ₂the amount ratio of O and isopropanol water solution, nitrilotriacetic acid is 1.5 g:40 mL:0.6 g.