CN104772472B - Method for preparing nano-metal material and nano-metal material prepared therefrom - Google Patents

Abstract

A method for preparing a nano metal material and the prepared nano metal material, the method for preparing the nano metal material comprises the following steps: placing one or more metal azides in a closed environment; applying a driving energy to excite the metal azide to perform detonation reaction; then, carrying out rapid cooling treatment to obtain the nano metal material; the metal azide is silver azide, copper azide, zinc azide, lead azide, gold azide, zirconium azide or cerium azide; the nano metal material is nano metal or nano metal alloy; when a metal azide is used, the nanometal material is a nanometal; and when a plurality of metal azide compounds are used, the nano metal material is a nano metal alloy. The nano metal material is prepared by the method for preparing the nano metal material. The invention has simple preparation method, low cost and quick production, and simultaneously conforms to the energy-saving and environment-friendly concept.

Description

Method for preparing nano-metal material and nano-metal material prepared therefrom

technical field

The invention relates to a method for manufacturing a nanometer metal material and the nanometer metal material, in particular to a method for preparing a nanometer metal material by using a metal azide compound and the prepared nanometer metal material.

Background technique

Nano-metals or nano-metal alloys have applications in many fields, for example, as catalysts or conductive materials for industrial use, or as drug carriers or biomarker display agents for medical engineering. Therefore, nano-metals or nano-metals Metal alloys are extensively researched and developed. Generally, methods such as chemical vapor phase method, co-precipitation method or ball milling method can be used to prepare nano-metal or nano-metal alloy.

In the chemical vapor phase method, a metal-containing compound is decomposed by heating or reacted by heating to form nano-metal or nano-metal alloy. However, the metal-containing compound used in the chemical vapor phase method needs to be volatile or easy to vaporize, or it needs to use high energy to turn the metal-containing compound into a gas phase. Therefore, the chemical vapor phase method used The metal-containing compound is easily limited, and various nano-metals or nano-metal alloys cannot be widely prepared, and the use of high energy does not conform to the current environmental protection concept of energy saving.

In view of the above, there is still a need to develop a low-cost and simple method for preparing nano-metals to meet the needs of the industry.

Contents of the invention

The first object of the present invention is to provide a method for preparing nano-metal materials with low cost and simple manufacturing process.

The method for preparing nano-metal materials of the present invention includes the following steps: placing one or more metal azide compounds (metalazide) in a closed environment; applying a driving energy (driving energy) to excite the metal azide compounds to perform The detonation reaction (detonation) treatment; then, the nano-metal material can be obtained by rapid cooling treatment; the metal azide compound is silver azide, copper azide, zinc azide, lead azide , gold azide, zirconium azide or cerium azide; the nano metal material is nano metal or nano metal alloy; when using a metal azide compound, the nano metal material is nano metal; and when using more When a metal azide compound is used, the nano-metal material is a nano-metal alloy.

The detonation reaction in the present invention refers to a chemical reaction process in which the metal azide compound undergoes decomposition or atomic reorganization accompanied by a large amount of energy release.

The metal azide compound is a material with high energy density, and when a driving energy is applied to it, it can provide the conditions of high temperature and high pressure in the closed environment. The metal azide compound can be prepared in a conventional manner, for example, it can be formed by performing a metal replacement reaction with an alkali metal azide compound and a silver source, a copper source, a zinc source, a lead source, a gold source, a zirconium source or a cerium source. Preferably, the alkali metal azide compound is sodium azide. The silver source is for example but not limited to AgNO ₃ or AgCl etc.; the copper source is for example but not limited to Cu(NO ₃ ) ₂ or CuCl ₂ etc.; the zinc source is for example but not limited to Zn(NO ₃ ) ₂ or ZnCl ₂ etc.; the Lead source such as but not limited to Pb(NO ₃ ) ₂ or PbCl ₂ ; the gold source such as but not limited to Au(NO ₃ ) ₂ or AuCl ₂ etc.; the zirconium source such as but not limited to Zr(NO ₃ ) ₂ , Zr( NO ₃ ) ₄ or ZrCl ₄ etc.; the cerium source is for example but not limited to Ce(NO ₃ ) ₃ or Ce(NO ₃ ) ₄ etc.

Preferably, the step of imparting a driving energy in the method for preparing a nano-metal material is to impart a driving energy to at least two metal azides.

Preferably, the driving energy is a heat source. The temperature range of the heat source is not particularly limited, as long as the metal azide compound can be excited to undergo a detonation reaction. In order to effectively excite the metal azide compound for detonation reaction, the way of imparting driving energy should be as fast as possible and reach the detonation point of the metal azide compound instantaneously. According to the characteristics of different metal azide compounds, the speed of imparting driving energy is also different, preferably, the speed is 30° C./min to 100° C./min.

Preferably, during the detonation reaction, the instantaneous maximum pressure of the airtight environment ranges from 1 GPa to 10 GPa. Preferably, during the detonation reaction, the instantaneous maximum temperature range of the airtight environment is 3,000K to 4,000K.

After the detonation reaction, the rapid cooling treatment can be performed in a general way, such as introducing nitrogen or liquid nitrogen to lower the temperature. Preferably, the flow rate of the nitrogen or liquid nitrogen ranges from 300mL/min to 500mL/min. Preferably, the cooling rate of the cooling treatment ranges from 5°C/s to 10°C/s.

The equipment used in the method for preparing the nano-metal material can be any equipment as long as it has a temperature control device, a cooling fluid introduction device, airtightness, high temperature resistance and high pressure resistance. The equipment can be the equipment used in the past in the technical field, so the details will not be repeated.

The second objective of the present invention is to provide a nano metal material.

The nano-metal material of the present invention is prepared by a method for preparing a nano-metal material as described above.

Preferably, the average particle size range of the nano metal material is less than 10nm.

The beneficial effects of the present invention are: by applying a driving energy to the metal azide compound, the metal azide compound itself undergoes drastic chemical changes, decomposes or reorganizes, and performs rapid cooling treatment to obtain nano-metal or nanometal alloys. The preparation method of the invention is simple, the cost is low, and the nanometer metal material can be produced rapidly, and simultaneously conforms to the concept of energy saving and environmental protection.

Description of drawings

Fig. 1 is an appearance morphological analysis figure, illustrates the particle size of the nano-silver metal material of the present invention;

Fig. 2 is an appearance morphological analysis figure, illustrates the particle size of nanometer cerium-zirconium alloy material of the present invention;

Fig. 3 is a composition analysis figure, illustrates the composition of the nano-silver metal material of the present invention;

Fig. 4 is a compositional analysis figure, illustrates the composition of nano-cerium-zirconium alloy material of the present invention;

Fig. 5 is a lattice structure figure, illustrates the lattice structure of nano-silver metal material of the present invention; And,

Fig. 6 is a lattice structure diagram illustrating the lattice structure of the nano-cerium-zirconium alloy material of the present invention.

detailed description

The present invention will be further described with reference to the following examples, but it should be understood that the examples are for illustrative purposes only and should not be construed as limitations on the practice of the present invention.

<Example>

<Example 1>

Dissolve 10 g of sodium azide containing carbonate in 200 ml of distilled water, add 5 wt% Ba(NO ₃ ) ₂ , then, after filtering, collect the filtrate, and then heat the filtrate to 50°C.

After the temperature of the solution is 50°C, gradually add 240 milliliters of 5wt% silver nitrate solution, and stir so that the average particle size of the precipitate is in the range of 125 μm to 250 μm. Then, filter and wash the filter cake with distilled water until the filtrate Barium ions and silver ions are present. Then, after drying the filter cake in air, silver azide can be obtained.

The above-mentioned 1.5 grams of silver azide is placed in a closed environment of equipment with high temperature resistance, high pressure resistance and temperature control device, and the closed environment is filled with nitrogen, then, the temperature control device is used to provide a heat source, and with The temperature is raised from room temperature to 300°C at a speed of 30°C/min. At this time, the silver azide is heated for a moment to undergo a detonation reaction, and the instantaneous maximum pressure of the closed environment is 5GPa. Then, the flow rate of 300mL/min is introduced into Liquid nitrogen, the temperature is lowered to room temperature, and the cooling rate is 5°C/s, and the nano-silver metal material can be obtained.

<Example 2>

Dissolve 10 g of sodium azide containing carbonate in 200 ml of distilled water, add 5 wt% Ba(NO ₃ ) ₂ , then, after filtering, collect the filtrate, and then heat the filtrate to 40°C.

After the temperature of the solution is 40°C, gradually add 160 ml of 5wt% lead nitrate solution, and stir to make the average particle size of the precipitate range from 125 μm to 250 μm, then filter, and use distilled water to wash the filter cake until the filtrate There are barium ions and lead ions. Then, after drying the filter cake in air, lead azide can be obtained.

The lead azide of above-mentioned 1.5 grams is placed in the airtight environment of the equipment that has high temperature resistance, high pressure and temperature control device, and this airtight environment is filled with nitrogen, then, utilizes temperature control device to provide a heat source, and with The temperature is raised from room temperature to 280°C at a speed of 50°C/min. At this time, the lead azide is heated instantaneously to undergo a detonation reaction, and the instantaneous maximum pressure of the closed environment is 5GPa. Then, it is introduced at a flow rate of 300mL/min. Liquid nitrogen, the temperature is lowered to room temperature, and the cooling rate is 5°C/s, and the nano-lead metal material can be obtained.

<Example 3>

Dissolve 10 g of sodium azide containing carbonate in 200 ml of distilled water, add 5 wt% Ba(NO ₃ ) ₂ , then, after filtering, collect the filtrate, and then heat the filtrate to 50°C.

After the temperature of the solution is 50°C, gradually add 120 milliliters of 5wt% silver nitrate solution and 80 milliliters of 5wt% lead nitrate solution, and stir so that the average particle size of the precipitate is in the range of 125 μm to 250 μm, then filter, and Use distilled water to wash the filter cake until there are no barium ions, silver ions and lead ions in the filtrate. Then, after drying the filter cake in the air, a mixture containing lead azide and silver azide can be obtained.

The above-mentioned 1.5 gram mixture is placed in a closed environment with high-temperature-resistant, high-pressure-resistant and temperature-controlled equipment, and the closed environment is filled with nitrogen. Then, a heat source is provided by the temperature-controlled device, and the temperature is controlled at 50 ° C / The speed of min increases the temperature from room temperature to 210°C. At this time, the mixture is heated for a detonation reaction instantaneously, and the instantaneous maximum pressure of the closed environment is 5GPa. Then, liquid nitrogen is introduced at a flow rate of 300mL/min to lower the temperature. to room temperature, and the cooling rate is 5°C/s, and the nano-silver-lead alloy material can be obtained.

<Example 4>

Dissolve 10 g of sodium azide containing carbonate in 200 ml of distilled water, add 5 wt% Ba(NO ₃ ) ₂ , then, after filtering, collect the filtrate, and then heat the filtrate to 70°C.

After the temperature of the solution is 70°C, gradually add 100 milliliters of 5wt% zirconium nitrate solution and 100 milliliters of 5wt% cerium nitrate solution, and stir so that the average particle size of the precipitate is in the range of 125 μm to 250 μm, then filter, and Use distilled water to wash the filter cake until there are no barium ions, zirconium ions and cerium ions in the filtrate. Then, after drying the filter cake in the air, a mixture containing zirconium azide and cerium azide can be obtained.

Place the above-mentioned 1.5 g mixture in a closed environment of equipment with high temperature resistance, high pressure resistance and temperature control device, and introduce nitrogen gas, then, use the temperature control device to provide a heat source, and at a speed of 100 °C/min. The temperature rises from room temperature to 325°C to 400°C. At this time, the silver azide is instantly heated to undergo a detonation reaction, and the instantaneous maximum pressure of the closed environment is 5GPa. Then, liquid nitrogen gas is introduced at a flow rate of 300mL/min, and the The temperature drops to room temperature, and the cooling rate is 5°C/s, and the nano-cerium-zirconium alloy material can be obtained.

<<Testing items>>

1. Component analysis: put the nano-silver metal material of Example 1 and the nano-cerium-zirconium alloy material of Example 4 into a high-resolution scanning transmission electron microscope (brand: JEOL; model: TEM-3010), observe Internal structure shape and particle size distribution, combined with electron diffraction pattern (DiffractionPattern) to analyze the microstructure and crystal structure in the sample, in addition, the X-ray energy spectrum analyzer (EnergyDispersiveSpectrometer, referred to as EDS) is used to analyze its chemical elements Ingredients and content.

2. Determination of lattice structure: the nano-silver metal material of Example 1 and the nano-cerium-zirconium alloy material of Example 4 were placed in an X-ray diffractometer (brand: RIGAKU; model: MiniFlex) for measurement, and the analysis conditions were: The scanning angle range is -3° to 150° (2θ), and the scanning rate is 0.01° to 100°/min (2θ).

Table 1

From the data in Fig. 1, Fig. 3 and Fig. 5 obtained in Example 1, it can be seen that the method of the present invention can indeed prepare silver metal materials with a nanometer level below 10 nm. From the data in Fig. 2, Fig. 4 and Fig. 6 of Example 4, it can be seen that the preparation method of the present invention can indeed prepare nano-cerium-zirconium alloy materials with a thickness of less than 10 nm. To sum up, by applying a driving energy to the metal azide compound, the metal azide compound itself undergoes drastic chemical changes, undergoes decomposition or recombination, and undergoes rapid cooling treatment to obtain nano-metal or nano- metal alloy. The method of the invention is simple, low in cost and can quickly produce nanometer metal materials. At the same time, it conforms to the concept of energy saving and environmental protection. It does not need to use expensive equipment such as ordinary plasma or laser, and can indeed achieve the purpose of cost-effectiveness and innovative invention.

Claims (9)

1. a kind of method for preparing nano metal material, it is characterised in that comprising below step：By one or more metal nitrine Compound is placed in a closed environment；A driving energy is bestowed, to excite the metal azide to carry out the process of detonation reaction, When detonation is reacted, the moment maximum pressure scope of the closed environment is 1GPa to 10GPa；Then, carry out at cooling rapidly Reason, you can obtain the nano metal material；The metal azide is silver azide, copper azide, lead azide, Azide Gold, Azide zirconium or Azide cerium；The nano metal material is nano metal or nano metal alloy；When using a kind of metal nitrine During compound, the nano metal material is nano metal；And when using various metals azido compound, the nano metal material is to receive Rice metal alloy.

2. the method for preparing nano metal material according to claim 1, it is characterised in that：This bestows a driving energy step, It is that a driving energy is bestowed at least two kinds metal azides.

3. the method for preparing nano metal material according to claim 1, it is characterised in that：The driving energy is a thermal source.

4. the method for preparing nano metal material according to claim 1, it is characterised in that：When detonation is reacted, this is closed The moment maximum temperature range of environment is 3,000K to 4,000K.

5. the method for preparing nano metal material according to claim 1, it is characterised in that：The cooling rate that the cooling is processed Scope is 5 DEG C/s to 10 DEG C/s.

6. the method for preparing nano metal material according to claim 1, it is characterised in that：The metal azide be by One alkali metal azide carries out metal displacement reaction and is formed with Yin Yuan, Tong Yuan, lead source, Jin Yuan, zirconium source or cerium source.

7. the method for preparing nano metal material according to claim 6, it is characterised in that：The alkali metal azide is Sodium azide.

8. a kind of nano metal material, is the method institute for preparing nano metal material by any one of just like claim 1 to 7 It is obtained.

9. nano metal material according to claim 8, it is characterised in that：The average particle size range of the nano metal material is Below 10nm.