CN105152225A - Preparation method of nanometer transition metal oxide and metal elementary substance material - Google Patents

Abstract

A method for preparing nano-sized transition metal oxides and metal elemental materials, including Cr ₂ O ₃ , TiO ₂ , MnO, Fe ₃ O ₄ , CoO, NiO, ZnO, Cu, Au and Ag nanoparticles, the steps are as follows: 1) Mix the metal salt and the long-chain amino organic compound solution, carry out condensation and reflux reaction under nitrogen or argon atmosphere, and obtain the reaction liquid after cooling to room temperature; 2) Add the low boiling point solvent A into the above reaction liquid and stir evenly, then let stand After settling, the granular product obtained by centrifugation was dispersed with n-hexane and stored in a ventilated and dry place. The invention has the advantages of small particle size, narrow particle size distribution, good dispersion and easy control, high catalytic activity, good electrochemical performance and cycle performance; the preparation method has simple process, low cost and easy operation , low energy consumption and environmental protection, suitable for large-scale production.

Description

A kind of preparation method of nano-sized transition metal oxide and metal elemental material

technical field

The invention relates to a method for preparing metal oxide nanoparticles, in particular to a method for preparing nanometerized transition metal oxides and metal elemental materials.

Background technique

Metal oxides are an important class of multifunctional materials, and their applications in the energy field have attracted much attention. Among them, the nano-sized and cheap transition metal oxides with small particle size and high dispersion have been widely studied and applied because of their high activity and simple structure. However, the current synthetic methods, such as hydrothermal method and sol-gel method, limit the practical application because of the large particle size of the prepared product and the high reaction temperature. Therefore, it is of great significance to develop an easy-to-operate, low-cost, and environmentally friendly method to synthesize nanoscale transition metal oxide materials.

Contents of the invention

The object of the present invention is to address the above existing problems and provide a method for preparing nano-sized transition metal oxides and metal elemental materials with simple process, low reaction temperature, low cost and low energy consumption.

Technical scheme of the present invention:

A method for preparing nano-sized transition metal oxides and simple metal materials, the nano-sized transition metal oxides and simple metal materials include Cr ₂ O ₃ , TiO ₂ , MnO, Fe ₃ O ₄ , CoO, NiO, ZnO, Cu, Au and Ag nanoparticles, the steps are as follows:

1) After mixing the metal salt and the long-chain amino organic solution and vigorously stirring, condense and reflux under nitrogen or argon atmosphere, the reflux temperature is 100-200°C, the reflux time is 1-12 hours, and the reaction solution is obtained after cooling to room temperature ;

2) Add the low-boiling point solvent A into the above reaction solution, stir evenly, and then let it settle down, and disperse the granular product obtained by centrifugation with n-hexane and store it in a ventilated and dry place.

The metal salt is chloride, nitrate, carbonate or sulfate of a transition metal, wherein the transition metal is titanium, chromium, manganese, iron, cobalt, nickel, copper, zinc, silver or gold; long-chain amino organic solution It is oleic acid solution, dodecylamine solution, hexadecylamine solution or octadecylamine solution; the molar ratio of metal salt to long-chain amino organic solution is 1:40.

The solvent A is ethanol, acetone or methylene chloride, and the volume ratio of the low boiling point solvent A to the reaction solution is 3:1.

Advantage and beneficial effect of the present invention are:

The preparation method has the advantages of simple process, low cost, easy operation and low energy consumption; the prepared product has small particle size, narrow particle size distribution, good dispersion and easy control, and the nano-sized transition metal oxide exhibits higher catalytic activity. Activity, better electrochemical performance and cycle performance; the preparation process will not cause environmental pollution, green and environmentally friendly, and suitable for large-scale production.

Description of drawings

Figure 1 is the XRD pattern of Fe ₃ O ₄ nanoparticles.

Figure 2 is a TEM image of Fe ₃ O ₄ nanoparticles.

Figure 3 is the XRD pattern of CoO nanoparticles.

Figure 4 is a TEM image of CoO nanoparticles.

Figure 5 is the XRD pattern of NiO nanoparticles.

Fig. 6 is a TEM image of NiO nanoparticles.

FIG. 7 is an XRD pattern of ZnO nanoparticles.

Fig. 8 is a TEM image of ZnO nanoparticles.

Detailed ways

The present invention will be further described below in conjunction with the examples.

Example 1:

A preparation method of transition metal oxide Fe ₃ O ₄ nanoparticles, the steps are as follows:

1) Add 0.2g Fe(NO ₃ ) ₃ ·9H ₂ O and 10mL oleic acid solution into a three-necked flask and stir vigorously, then condense and reflux under an argon atmosphere. The reflux temperature is 200°C, and the reflux time is 4 hours. Cool to Obtain reaction solution after room temperature;

2) Add 30mL of ethanol to the above reaction solution, stir evenly, and then let it settle down, disperse the granular product obtained by centrifugation with n-hexane, and store it in a ventilated and dry place.

Figure 1 is the XRD pattern of the prepared Fe ₃ O ₄ nanoparticles, which shows that all the diffraction peaks of the product can be attributed to the cubic phase Fe ₃ O ₄ .

Fig. 2 is a TEM image of the prepared Fe ₃ O ₄ nanoparticles, which shows that the appearance of the Fe ₃ O ₄ nanoparticles is quantum dots, and the particle size is 3-7nm.

Example 2:

A preparation method of transition metal oxide CoO nanoparticles, the steps are as follows:

1) Add 0.2g CoCO ₃ and 10mL oleic acid solution into the three-necked flask and stir vigorously, then condense and reflux under an argon atmosphere. The reflux temperature is 180°C, the reflux time is 8 hours, and the reaction solution is obtained after cooling to room temperature;

2) Add 30 mL of acetone into the above reaction solution, stir evenly, and then let it settle down. The granular product obtained by centrifugation is dispersed with n-hexane, and stored in a ventilated and dry place.

Figure 3 is the XRD pattern of the prepared CoO nanoparticles, which shows that all the diffraction peaks of the product can be attributed to the cubic phase of CoO.

FIG. 4 is a TEM image of the prepared CoO nanoparticles, which shows that the shape of the CoO nanoparticles is nanocubic, and the particle size is 20-25nm.

Example 3:

A preparation method of transition metal oxide NiO nanoparticles, the steps are as follows:

1) Add 0.5gNiSO ₄ ·6H ₂ O and 8mL dodecylamine solution into a three-necked flask and stir vigorously, then condense and reflux under an argon atmosphere, the reflux temperature is 100°C, the reflux time is 12 hours, and after cooling to room temperature, The reaction solution;

2) Add 30 mL of acetone into the above reaction solution, stir evenly, and then let it settle down. The granular product obtained by centrifugation is dispersed with n-hexane, and stored in a ventilated and dry place.

Figure 5 is the XRD pattern of the prepared NiO nanoparticles, which shows that all the diffraction peaks of the product can be attributed to the cubic NiO.

Fig. 6 is a TEM image of the prepared NiO nanoparticles, which shows that the appearance of the NiO nanoparticles is nanoflowers, and the particle size is 30-40nm.

Example 4:

A preparation method of transition metal oxide ZnO nanoparticles, the steps are as follows:

1) Add 0.3g of ZnCl ₂ ·6H ₂ O and 10mL of octadecylamine solution into a three-necked flask and stir vigorously, then condense and reflux under a nitrogen atmosphere, the reflux temperature is 200°C, the reflux time is 8 hours, and after cooling to room temperature, The reaction solution;

2) Add 20mL of dichloromethane into the above reaction solution and stir evenly, then let it settle down, disperse the granular product obtained by centrifugation with cyclohexane, and store it in a ventilated and dry place.

Figure 7 is the XRD pattern of the prepared ZnO nanoparticles, which shows that all the diffraction peaks of the product can be attributed to the hexagonal ZnO.

FIG. 8 is a TEM image of the prepared ZnO nanoparticles, which shows that the morphology of the ZnO nanoparticles is nanosheets, and the particle size is 30-40nm.

Claims (3)

1. the transition metal oxide of nanometer and a preparation method for metal simple-substance material, is characterized in that: transition metal oxide and the metal simple-substance material of described nanometer comprise Cr ₂o ₃, TiO ₂, MnO, Fe ₃o ₄, CoO, NiO, ZnO, Cu, Au and Ag nano particle, step is as follows:

1) by metal-salt and long chain amino organic solution mixing and vigorous stirring after, under nitrogen or argon gas atmosphere, carry out condensing reflux, reflux temperature is 100-200 DEG C, and return time 1-12 hour obtains reaction solution after being cooled to room temperature;

2) low boiling point solvent A is added stir in above-mentioned reaction solution after standing sedimentation, the centrifugal granular product normal hexane obtained is disperseed and is kept at air seasoning place.

2. the transition metal oxide of nanometer and the preparation method of metal simple-substance material according to claim 1, it is characterized in that: described metal-salt is the muriate of transition metal, nitrate, carbonate or vitriol, wherein transition metal is titanium, chromium, manganese, iron, cobalt, nickel, copper, zinc, silver or golden; Long chain amino organic solution is oleic acid solutions, amino dodecane solution, cetylamine solution or octadecenyl amine solution; The mol ratio of metal-salt and long chain amino organic solution is 1:40.

3. the transition metal oxide of nanometer and the preparation method of metal simple-substance material according to claim 1, it is characterized in that: described solvent orange 2 A is ethanol, acetone or methylene dichloride, the volume ratio of low boiling point solvent A and reaction solution is 3:1.