METHOD FOR CONTINUOUSLY PREPARING NOBLE METAL AND ALLOY NANOPARTICLES THEREOF

Abstract

The present invention discloses a method for continuously preparing noble metal and alloy nanoparticles thereof, and belongs to the technical field of preparation of inorganic nanomaterials. A three-way quartz tube microreactor is designed; noble metal solutions used as raw materials are continuously inputted into the microreactor by injection pumps; and a plasma technology is coupled to form discharge in the microreactor to directly prepare noble metal and alloy nanoparticles thereof. The device and the method of the present invention have low energy consumption, wide operation range, safety, high efficiency, green and environmental protection. The synthesized nanoparticles have high purity, small size, narrow particle size distribution and adjustable components.

Claims

1. A method for continuously preparing noble metal and alloy nanoparticles thereof, completed by a device, coupling microreactor and plasma technology, using noble metal solution as precursor, continuously delivering the precursor solution into a three-way quartz tube microreactor (7) through injection pumps (1) and rapidly reducing a reaction solution into nanoparticles under the action of plasma, wherein the device comprises an argon cylinder (8), a mass flow control meter (3), the injection pumps (1), a three-way valve (2), the three-way quartz tube microreactor (7), a plasma power supply (5), a ballast (6) and a stainless steel electrode (4); one end of the three-way quartz tube microreactor (7) is respectively connected with two injection pumps (1) through a microchannel and the three-way valve (2); the two injection pumps (1) are respectively connected with a container A and a container B for delivering a precursor solution; the other end of the three-way quartz tube microreactor (7) is connected with a container C for product output; the upper end of a quartz tube of the three-way quartz tube microreactor (7) is provided with the stainless steel electrode (4) as a cathode; a metal coil is wound outside as a grounding anode; the three-way quartz tube microreactor (7), the plasma power supply (5) and the ballast (6) form a closed circuit; the stainless steel electrode (4) is also connected with the mass flow control meter (3) and the argon cylinder (8) in sequence; the stainless steel electrode (4) has a tube length of 50-100 mm, internal pipe diameter of 1-2.6 mm and external pipe diameter of 1.5-3.2 mm; preparation steps for continuously preparing noble metal and alloy nanoparticles thereof are as follows: (1) preparing noble metal precursor solution with concentration of 0.01-5 mM as the reaction solution by taking deionized water as solvent, and adding 1%-5% of PVA into the reaction solution to ensure stable nanoparticles in colloidal solution, wherein ratio of the volume of reaction solution to the volume of 1%-5% of PVA is 10:1 to 1:1; (2) connecting reaction devices: using the three-way quartz tube microreactor (7) as a coupling interface of the microchannel and the plasma, and introducing argon into the three-way quartz tube microreactor (7) through the mass flow control meter (3) to eliminate impurity gas; (3) applying DC negative bias to the fixed stainless steel electrode (4) in the atmosphere of argon to ensure the plasma power of 10-20 W to break through the argon to generate the plasma; (4) controlling the flow velocity of the precursor solution as 0.1-1 mL/min after the plasma is ignited, delivering the precursor solution to a plasma region, and rapidly reducing noble metal ions into nanoparticles under the action of the plasma; (5) allowing the generated nanoparticles to flow out from the right end of the three-way quartz tube microreactor (7) under the push of the solution, and collecting the nanoparticles into the container C; (6) obtaining noble metal and alloy nanoparticles thereof with high purity through the processes of centrifugation and drying, wherein the particle sizes of the noble metal and alloy nanoparticles thereof are 3-8 mm.

2. The method for continuously preparing noble metal and alloy nanoparticles thereof according to claim 1, wherein a spacing between the cathode and the anode is kept at 2-3 mm.

3. The method for continuously preparing noble metal and alloy nanoparticles thereof according to claim 1, wherein the three-way quartz tube microreactor (7) has a total tube length of 70-150 mm, internal pipe diameter of 1.5-3.6 mm and external pipe diameter of 2-5 mm.

4. The method for continuously preparing noble metal and alloy nanoparticles thereof according to claim 1, wherein the three-way valve (2) has an internal diameter of 1.5-3.2 mm.

5. The method for continuously preparing noble metal and alloy nanoparticles thereof according to claim 1, wherein the microchannel for delivering the precursor solution is a polytetrafluoroethylene tube and has a tube length of 30-50 cm, internal pipe diameter of 1-3 mm and external pipe diameter of 1-3 mm.

6. The method for continuously preparing noble metal and alloy nanoparticles thereof according to claim 1, wherein the noble metal precursor is one or a combination of more than two of silver nitrate, chloroauric acid, chloroplatinic acid, palladium chloride and palladium nitrate.

7. The method for continuously preparing noble metal and alloy nanoparticles thereof according to claim 1, wherein the treatment processes of centrifugation and drying are: centrifugal speed is 8000-10000 r/min, drying time is 4-8 h and drying temperature is 50-80° C.

8. The method for continuously preparing noble metal and alloy nanoparticles thereof according to claim 1, wherein the concentration and the flow velocity of the precursor solution are regulated, and the size and the distribution of the noble metal and the alloy nanoparticles thereof are controlled.

Description

DESCRIPTION OF DRAWINGS

[0029] FIG. 1 is a structural schematic diagram of a device for continuously preparing noble metal and alloy nanoparticles thereof;

[0030] FIG. 2 shows the ultraviolet absorption spectrum of a gold colloid prepared in embodiment 1 of the present invention;

[0031] FIG. 3 shows the TEM morphology of gold nanoparticles prepared in embodiment 1 of the present invention;

[0032] FIG. 4 shows the EDX map of gold nanoparticles prepared in embodiment 1 of the present invention;

[0033] FIG. 5 shows the ultraviolet absorption spectrum of a silver colloid prepared in embodiment 2 of the present invention;

[0034] FIG. 6 shows the TEM morphology of silver nanoparticles prepared in embodiment 2 of the present invention;

[0035] FIG. 7 shows the EDX map of silver nanoparticles prepared in embodiment 2 of the present invention;

[0036] FIG. 8 shows the ultraviolet absorption spectrum of gold and silver alloy nanoparticles prepared in embodiment 3 of the present invention;

[0037] FIG. 9 shows the EDX map of gold and silver alloy nanoparticles prepared in embodiment 3 of the present invention;

[0038] FIG. 10 shows the ultraviolet absorption spectrum of a gold and silver colloid mixture prepared in embodiment 6 of the present invention;

[0039] FIG. 11 shows the TEM morphology of gold and silver alloy nanoparticles prepared in embodiment 3 of the present invention; and

[0040] FIG. 12 shows the EDX map of gold and silver alloy nanoparticles prepared in embodiments 3, 4 and 5 of the present invention.

[0041] In the figures: 1 injection pump; 2 three-way valve; 3 mass flow control meter; 4 stainless steel electrode; 5 plasma power supply; 6 ballast; 7 three-way quartz tube microreactor; 8 argon cylinder.

DETAILED DESCRIPTION

[0042] A device comprises an argon cylinder, a mass flow control meter, injection pumps, a three-way valve, a three-way quartz tube microreactor, a plasma power supply, a ballast and a stainless steel electrode (as shown in FIG. 1).

[0043] The present invention is further described below in combination with implementation. However, the present invention is not limited to the following embodiments.

Embodiment 1

[0044] As shown in FIG. 1, a device for continuously preparing noble metal and alloy nanoparticles thereof comprises two injection pumps 1, a three-way valve 2, a mass flow control meter 3, a stainless steel electrode 4, a plasma power supply 5, a ballast 6, a three-way quartz tube microreactor 7 and an argon cylinder 8. The left end of the three-way quartz tube microreactor 7 is connected with a polytetrafluoroethylene pipeline of a microchannel, the upper end is connected with the stainless steel electrode and the right end is used for a product to flow out to collect the product into a container C.

[0045] An appropriate amount of chloroauric acid is weighed and added into deionized water, uniformly stirred and prepared into a reaction solution with a concentration of 0.1 mM. 10 mL of reaction solution and 2.5 ml of 1% PVA are placed in a container A, and the microchannel and the plasma are coupled through the three-way quartz tube microreactor 7. After a reaction device is connected, argon gas of 30 sccm is introduced into a system to eliminate impurity gas. DC negative bias is applied to a fixed stainless steel tube cathode in the atmosphere of argon to break through the argon to generate the plasma, to ensure plasma power of 10 W. The flow velocity of the precursor solution is controlled as 0.5 mL/min through the injection pumps after the plasma is ignited; the chloroauric acid solution is delivered to a plasma region, and gold ions are rapidly reduced into gold nanoparticles under the action of the plasma; the colloid of nanogold is centrifuged at 8000 r/min and dried at 50° C. for 5 h to obtain nanogold powder.

Embodiment 2

[0046] The treatment technology and operating conditions are the same as those in embodiment 1, but the difference is that: the precursor is 0.1 mM of silver nitrate solution.

[0047] It can be seen from FIG. 2 and FIG. 5 that the gold nanoparticles and the silver nanoparticles respectively have characteristic absorption peaks at 548 nm and 400 nm due to special surface plasma resonance, which indicates that the gold nanoparticles and the silver nanoparticles are successfully prepared by the method. It can be seen from the TEM images of FIG. 3 and FIG. 6 that the prepared gold nanoparticles and silver nanoparticles have narrow particle size distribution and good uniformity. It can be seen from X-ray energy dispersion spectra of FIG. 4 and FIG. 7 that except for small amounts of carbon and oxygen (from a carbon film on a copper grid and air), the contents of gold and silver are 96% and 95% respectively, which indicates that the synthesized gold and silver nanoparticles have no impurity and high purity.

Embodiment 3

[0048] The treatment technology and operating conditions are the same as those in embodiment 1, but the differences are that: 10 mL of 3 mM silver nitrate and 2.5 ml of 1% PVA are placed in the container A, and 10 mL of 1 mM chloroauric acid solution and 2.5 ml of 1% PVA are placed in the container B.

[0049] It can be seen from FIG. 8 that when the mixture of silver nitrate and chloroauric acid is used as the precursor, the ultraviolet absorption peaks of the prepared colloid appear in the form of single peaks at 432 nm between the absorption peaks of gold and silver, which proves the formation of gold and silver alloy nanoparticles. It can also be visually seen from the energy spectrum map of gold and silver alloy in FIG. 9 that the prepared gold and silver alloy nanoparticles have good dispersibility.

Embodiment 4

[0050] The treatment technology and operating conditions are the same as those in embodiment 1, but the differences are that: 10 mL of 2 mM silver nitrate and 2.5 ml of 1% PVA are placed in the container A, and 10 mL of 2 mM chloroauric acid solution and 2.5 ml of 1% PVA are placed in the container B.

Embodiment 5

[0051] The treatment technology and operating conditions are the same as those in embodiment 1, but the differences are that: 10 mL of 1 mM silver nitrate and 2.5 ml of 1% PVA are placed in the container A, and 10 mL of 3 mM chloroauric acid solution and 2.5 ml of 1% PVA are placed in the container B.

Embodiment 6

[0052] 1.5 mL of gold colloid prepared in embodiment 1 is mixed with 1.5 mL of silver colloid prepared in embodiment 2.

[0053] It can be seen from FIG. 10 that when separate gold and silver colloids are mixed, two ultraviolet absorption peaks appear, which further proves that the gold and silver alloy nanoparticles are obtained by the method. It can be seen from the TEM image of FIG. 11 that the prepared gold and silver alloy nanoparticles also have the characteristics of narrow particle size distribution and good uniformity. In addition, it can be seen from the X-ray energy dispersion spectra of FIG. 12 that the contents of gold and silver in the obtained gold and silver nanoparticles are changed with the change of the ratio of the chloroauric acid to the silver nitrate in the precursor, and meanwhile, no other impurity peaks are observed in the energy spectra, which indicates that controllable preparation of the gold and silver alloy nanoparticles can be realized by the method and the synthesized gold and silver alloy has no impurity and high purity.

[0054] The above embodiments are only used for clearly describing the technological process of the present invention, but the present invention is not limited to the above embodiments. For those ordinary skilled in the art, various modifications, changes and improvements can be derived without departing from the principle of the present invention, and shall also fall within the protection scope of the present invention.