CN111215636A - Preparation method of Ag nano particles - Google Patents
Preparation method of Ag nano particles Download PDFInfo
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- CN111215636A CN111215636A CN202010049907.2A CN202010049907A CN111215636A CN 111215636 A CN111215636 A CN 111215636A CN 202010049907 A CN202010049907 A CN 202010049907A CN 111215636 A CN111215636 A CN 111215636A
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- 239000002105 nanoparticle Substances 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
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- 239000007788 liquid Substances 0.000 claims abstract description 56
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 40
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 36
- 239000010439 graphite Substances 0.000 claims abstract description 36
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 33
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(I) nitrate Inorganic materials [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims abstract description 30
- 230000002572 peristaltic effect Effects 0.000 claims abstract description 22
- 239000002245 particle Substances 0.000 claims abstract description 9
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- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 claims description 23
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- 238000004519 manufacturing process Methods 0.000 claims description 6
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- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 1
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- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/14—Making metallic powder or suspensions thereof using physical processes using electric discharge
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
Abstract
The invention provides a preparation method of Ag nano particles, which uses a high-voltage direct-current power supply to provide electric energy, uses a platinum needle as an anode and AgNO3The solution flows through the buffer bottle under the driving of the peristaltic pump and overflows from the top end of the capillary tube penetrating into the graphite carbon rod, and the overflowing solution is used as a discharge cathode. When a sufficiently high voltage is applied between the two electrodes, the overflowing liquid generates glow to form plasma, and active particles generated by the liquid cathode glow discharge plasma and Ag in the solution are utilized+Reacting, and allowing the generated Ag nano particle turbid liquid to flow into a collector along the wall of the graphite carbon rod. And finally, carrying out ultrasonic dispersion on the turbid solution, carrying out centrifugal separation, washing with distilled water, drying to constant weight, and grinding to obtain the Ag nano particles. The Ag nano particles synthesized by the preparation method have the advantages of uniform structure, good dispersibility, low agglomeration degree and wide application prospect in the aspects of catalysis, sensors, electrode materials and the like.
Description
Technical Field
The invention belongs to the technical field of nano material preparation, relates to a preparation method of Ag nano particles, and particularly relates to a method for preparing Ag nano particles by using a liquid cathode glow discharge plasma technology3Direct preparation of solutionA method for preparing Ag nano particles.
Background
Due to excellent catalytic, optical and electrical properties, silver (Ag) nano materials are widely applied to the aspects of surface enhanced Raman spectroscopy, light emitting and displaying devices, high-efficiency catalysts, biosensors, high-performance electrode materials and the like. The shape, distribution and size of the silver nanoparticles can affect the performance of the silver nanoparticles, so that the preparation of various silver nanoparticles with different shapes plays a key role in the application of the silver nanoparticles, and the preparation is a hot spot of the research of nano materials in recent years.
The preparation method of the silver nano-particles mainly comprises the following steps: reduction, ultrasound-assisted, sol-gel, microwave, precipitation, alcoholysis, and the like. The reduction method for preparing silver nanoparticles is a relatively simple and effective method, and includes a chemical reduction method and an electrochemical reduction method, wherein the chemical reduction method generally adopts a simple silver salt with higher purity, a reducing agent such as sodium borohydride, formaldehyde, dimethylacetamide, citrate and the like is used for reducing and preparing the silver nanoparticles, and a stabilizing agent (PVP, CTAB, a silane coupling agent and the like) is generally added in the process of preparing the silver nanoparticles to prevent the nanoparticles from agglomerating, so that the size of the generated particles is controlled to be in a nanometer level. However, the chemical reduction method has complex process, generates waste liquid and waste gas, pollutes the environment, increases the cost, and prepares the silver nano particles with irregular shapes and wide particle size distribution. The electrochemical method is to prepare the nano material under the mild condition through the powerful electrolysis, and the method has the advantages of simple equipment, simple operation, mild condition and the like, and has the defects that a protective agent is required to be added, and the silver nano particles are difficult to form. For example, the silver nanospheres and dendritic silver nanoparticles with different sizes are synthesized by electrochemical method (advanced chemical bulletin, 2000, 21(12): 1837) and 1839) through adding EDTA protective agent under the action of ultrasonic wave. The method has the advantages of short time consumption, simple steps, no pollution and the like.
Along with the improvement of the environmental protection consciousness of people, the green chemical preparation method of the silver nano particles, which is simple and convenient in research method, controllable in appearance, low in energy consumption and low in pollution, draws more and more attention. In recent years, the technology of the present invention has been developedMeanwhile, there has been a method for preparing silver nanoparticles by a liquid separation membrane plasma method, such as maderly, which uses a silver sheet as an anode, stainless steel as a cathode, and an electrolyte of Na2SO4The solution was used to prepare silver nanoparticles using a liquid diaphragm discharge plasma of a sacrificial anode under continuous stirring (a method for preparing silver nanoparticles using a liquid diaphragm discharge plasma, application No. 201710829462.8).
At present, liquid cathode glow discharge plasma is mostly combined with spectra to be used for detecting the content of metal elements in a solution in more reports (Yu J, et al Spectrochimaacta Part B, 2018, 145: 64-70; C.Yang, et al Talanta, 2016, 155: 314-.
Disclosure of Invention
The invention aims to solve the problems of complex preparation process, high production cost, environmental pollution and the like of the Ag nano particles in the prior art, and provides a simple, quick and green method for synthesizing the Ag nano particles, namely, the Ag nano particles are directly prepared from a silver nitrate solution with pH =1 by using a liquid cathode glow discharge plasma method.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows: a process for preparing Ag nanoparticles includes such steps as generating liquid-cathode glow discharge plasma, high-voltage DC power supply, sealing the platinum needle in quartz tube as anode, and AgNO (pH = 1)3The solution flows through the buffer bottle under the drive of the peristaltic pump, overflows from the top end of the capillary tube inserted with the graphite carbon rod, the overflowing solution is used as a discharge cathode, when enough high voltage is applied between the two electrodes, the liquid overflowing between the platinum needle anode and the capillary tube generates glow discharge plasma, and active particles generated by the liquid cathode glow discharge plasma and Ag in the solution are utilized+Reacting to prepare the silver nano particles.
The preparation method specifically comprises the following steps: taking a liquid cathode glow discharge plasma generating device shown in figure 1, wherein the generating device comprises a solution pool 3, a liquid collector 9 and a three-dimensional moving platform 15, and the bottom of the liquid collector 9 is communicated with a product pool 7 through a liquid conveying pipe; an end cover 10 is installed on a liquid collector 9, an exhaust pipe 11 and a graphite pipe 12 are arranged on the end cover 10, the graphite pipe 12 is vertically arranged, discontinuous gaps are formed between the graphite pipe 12 and the end cover, a capillary 8 is arranged in the graphite pipe 12, the top end of the capillary 8 extends out of the top end of the graphite pipe 12, the distance between the top surface of the capillary 8 and the top surface of the graphite pipe 12 is 2-4 mm, the lower end of the capillary 8 is communicated with a peristaltic pump 4 through a peristaltic pump rubber pipe 5, a buffer bottle 6 with the volume of 3-7 mL is arranged on the peristaltic pump rubber pipe 5, and the peristaltic pump 4 is communicated with a solution pool 3 through the; the graphite tube 12 is communicated with the negative electrode of the direct current voltage-stabilizing and current-stabilizing power supply 1; the three-dimensional moving platform 15 is vertically provided with a quartz tube 16, a platinum needle electrode 14 is sealed and stored in the quartz tube 16, two ends of the platinum needle electrode 14 extend out of the quartz tube 16, one end of the platinum needle electrode faces the capillary tube 8, and the other end of the platinum needle electrode is communicated with the positive electrode of the direct-current voltage-stabilizing and current-stabilizing power supply 1. The diameter of the platinum needle electrode 14 is 0.3 to 0.7mm, the length of the platinum needle electrode 14 exposed out of the quartz tube 16 toward one end of the capillary tube 8 is 1mm, and the inner diameter of the capillary tube 8 is 0.5 to 1.2 mm.
During preparation, the three-dimensional moving platform 15 is adjusted to enable the distance between the lower end of the platinum needle electrode 14 and the top end of the capillary tube 8 to be 1-3 mm; injecting a silver nitrate solution with the pH value of 1 and the molar volume concentration of 0.05-0.15 mol/L into the solution pool 3, starting the peristaltic pump 4, enabling the silver nitrate solution in the solution pool 3 to enter the capillary tube 8 at a constant speed at a flow rate of 1-6 mL/min, overflowing from the top end of the capillary tube 8, and contacting with the lower end of the platinum needle electrode 14; starting a direct-current voltage-stabilizing and current-stabilizing power supply 1, and controlling the voltage between a cathode and an anode to be 480-600V and the current to be 28-58 mA; the direct current voltage and current stabilizing power supply 1, the platinum needle electrode 14 and the graphite tube 12 form a closed loop; in the electrifying process, the solution overflowing from the top end of the capillary tube 8 flows downwards along the outer wall of the graphite tube 12 after discharging, flows into the liquid collector 9 through a discontinuous gap between the graphite tube 12 and the end cover 10, then enters the product pool 7, and is continuously electrified for 3-5 hours to obtain black turbid liquid, the turbid liquid is subjected to ultrasonic dispersion for 10-15 min, centrifugal separation is carried out at the rotating speed of 6000-10000 r/min, and distilled water is washed for several times to remove Ag+And drying the mixture in vacuum at 40-60 ℃ to constant weight, and grinding the mixture to obtain the Ag nano particles.
The solution overflowing from the capillary tube 8 fluctuates due to the pulsation of the peristaltic pump 4, so that the generated discharge plasma fluctuates, the pulsation of the solution caused by the peristaltic pump 4 can be eliminated by the buffer bottle 6, and the stable air pressure in the buffer bottle 6 can assist the peristaltic pump 4 to supply liquid to the capillary tube 8 at a constant speed, so that the purpose of improving the discharge stability is achieved. The excess liquid from the capillary 8 acts as a wire to make a connection to the graphite tube 12.
Liquid cathode glow discharge is a new method of generating non-equilibrium low temperature plasma. In the preparation process, the graphite tube is connected with the negative electrode of a power supply, the capillary tube is embedded in the graphite tube, the Pt needle point is connected with the positive electrode of the power supply, the overflow liquid of the capillary tube is contacted with the tip end of the Pt needle, and when a certain voltage is applied between the two electrodes in an atmospheric pressure air environment, stable glow is emitted to generate ultraviolet light, shock waves, high-energy radiation and high-activity particles such as HO ∙, H ∙, O ∙ and HO2∙ and H2O2。
Principle of preparation of nanoparticles
1. Current-voltage curve
The current under different voltages is measured by a DH1722A-6 direct current voltage-stabilizing and current-stabilizing power supply (voltage is 0-1000V, and current is 0-500 mA) of Beijing Dahua radio company. FIG. 2 is a graph showing the pH value for AgNO with a molar volume concentration of 0.05mol/L3When the electrolyte is electrolyzed, the current-voltage curve chart of the liquid cathode glow discharge plasma is drawn by adjusting different voltages. As can be seen from fig. 2, the whole discharge process is divided into 4 segments: in the section AB (0-200V), the current and the voltage basically form a linear relation, and common electrolysis occurs; a BC (200-400V) section, wherein the current fluctuation is reduced along with the voltage increase; in the CD (400-470V) section, the current is stable, and discontinuous sparks are generated; and the DE (after more than 480V) section is gradually enhanced in glow with the increase of voltage. Due to the over-high voltage, the energy consumption is large, and the strong glow causes excessive damage to the capillary and the platinum needle electrode. Therefore, the preparation method of the invention selects the voltage of 480-600V. The voltage range for preparing the Ag nano particles is 480-600V, stable glow is generated in the range, and stable plasma is formed, so that the current-voltage curve shows that the preparation method of the invention is applied to the preparation of the Ag nano particlesThe discharge process of (a) is not a general electrolysis process but a glow discharge process. The inset in fig. 2 is a glow photo with voltages of 480V, 550V and 600V, respectively, the glow increases with the increase of the voltage, the larger the volume of the generated plasma, further illustrating the reaction of the Ag nanoparticles prepared by the method of the present invention in the plasma state.
2. Emission spectroscopy
The emission spectrum of liquid cathode glow discharge was measured by an eight-channel high-resolution CCD fiber spectrometer (AvaSpec-ULS 2048, AvaSpec Co., Netherlands), and AgNO nanoparticles having a pH of 1 and a molar volume concentration of 0.05mol/L, prepared at 600V (example 3) were shown in FIG. 33Emission spectrum of the solution. The spectral line with the wavelength of 306.0-309.0 nm is HO (A)2Ʃ+→X2Π) ((1,0) and (0.0)) transition bands, 486.1nm and 656.3nm H β (4d2D→2p2P0) And H α (3d2D→2p2P0) Line, excited O (3 p) at 716.1nm, 763.5nm and 845.6nm5P→3s5S0) And (3 p)3P→3s3S0) Atomic transition spectral line. This is due to the large amount of HO, H, O generated by the vaporized water molecules excited by the energetic electrons. Atomic lines of Na at 589nm and 589.9nm indicate that the electrolyte contains a trace amount of Na+. The resulting lines at 327.9nm and 338.3nm correspond to the atomic emission lines of Ag. The results show that HO, H and O are generated in the solution in the process of preparing the nano Ag by liquid cathode glow discharge. Combining the current-voltage curve and emission spectrum analysis, the mechanism for preparing Ag nano particles by liquid cathode glow discharge plasma is provided as follows: under the action of applied voltage, the liquid cathode glow discharge plasma technology makes H at plasma-solution interface2The O is bombarded by high-energy electrons (e) and decomposed to generate HO, O, H, eaq −And the reaction is as follows:
H2O+e*→H· + OH· + O· + H2O· + H2+ O2+ H2O2+eaq −+H3O+（1）
ag in solution+When present, may be reacted with H or eaq −Reduction reaction occurs:
Ag++eaq −= Ag （2）
Ag++H·=Ag+H+（3）
by controlling the discharge voltage, H.and e in the solution can be controlledaq −The generation speed and concentration of the Ag nanoparticles are promoted to move the formulas (2) and (3) to the right, and the morphology of the Ag nanoparticles is controlled.
The preparation method of the invention has the following beneficial effects:
1. a plasma-liquid interface is constructed, and stable glow discharge plasma is formed between the two electrodes to prepare the silver nano particles, thereby providing a unique condition for the preparation process.
2. The method has the advantages of mild conditions (room temperature, no inert gas protection, low power consumption), simple equipment, convenient operation, controllable process (changing parameters such as electrolyte concentration, discharge voltage, discharge time and the like, and being capable of obtaining Ag nano particles with different particle sizes), environmental protection and the like.
3. The used chemical reagents have few types, low dosage and no secondary pollution, and are an environment-friendly green preparation technology.
4. The product has less impurities, high purity, good dispersibility and convenient separation.
Drawings
FIG. 1 is a schematic view of a liquid cathode glow discharge plasma generating apparatus used in the production method of the present invention.
Fig. 2 is a current-voltage curve of a liquid cathode glow discharge plasma of the present invention.
FIG. 3 shows an emission spectrum at 600V.
FIG. 4 shows XRD patterns (a480V, 28mA, b550V, 32mA, c600V, 58mA) of Ag nanoparticles prepared at different voltages.
FIG. 5 shows SEM images (a480V, 28mA, b550V, 32mA, c600V, 58mA) of Ag nanorods prepared at different voltages.
FIG. 6 is an EDS spectrum of Ag nanoparticles prepared under 550V voltage.
FIG. 7 is a UV spectrum of Ag nanoparticles prepared under 550V voltage.
In fig. 1: 1. the device comprises a direct-current voltage-stabilizing and current-stabilizing power supply, 2a first peristaltic pump rubber tube, 3 a solution pool, 4a peristaltic pump, 5 a second peristaltic pump rubber tube, 6 a buffer bottle, 7 a product pool, 8 a capillary tube, 9 a liquid collector, 10 an end cover, 11 an exhaust pipe, 12 a graphite pipe, 13 overflowing liquid, 14 a platinum needle electrode, 15 a three-dimensional moving platform and 16 a quartz tube.
Detailed Description
The present invention will be further described with reference to the following specific examples.
Example 1
The liquid cathode glow discharge plasma generating apparatus shown in fig. 1 was used. Adjusting the three-dimensional moving platform 15 to enable the distance between the lower end of the platinum needle electrode 14 and the top end of the capillary tube 8 to be 1 mm; injecting a silver nitrate solution with the pH =1 and the molar volume concentration of 0.05mol/L into the solution pool 3, starting the peristaltic pump 4, enabling the silver nitrate solution in the solution pool 3 to enter the capillary 8 at a constant speed at a flow rate of 1mL/min, overflowing from the top end of the capillary 8, and contacting with the lower end of the platinum needle electrode 14; turning on the direct-current voltage-stabilizing and current-stabilizing power supply 1, and controlling the voltage between the cathode and the anode to be 480V and the current to be 28 mA; the direct current voltage and current stabilizing power supply 1, the platinum needle electrode 14 and the graphite tube 12 form a closed loop; in the electrifying process, the solution overflowing from the top end of the capillary tube 8 flows downwards along the outer wall of the graphite tube 12 after being electrolyzed, flows into the liquid collector 9 through discontinuous gaps between the graphite tube 12 and the end cover 10, then enters the product pool 7, and is continuously electrified for 5 hours to obtain black turbid liquid, the turbid liquid is subjected to ultrasonic dispersion for 10 minutes, centrifugal separation is carried out at the rotating speed of 10000r/min, and distilled water is washed for several times to remove dissolved Ag+Vacuum drying at 40 deg.C to constant weight, and grinding to obtain the final product.
Example 2
The liquid cathode glow discharge plasma generating device shown in fig. 1 was used. Adjusting the three-dimensional moving platform 15 to enable the distance between the lower end of the platinum needle electrode 14 and the top end of the capillary tube 8 to be 2 mm; pH =1, MoleInjecting a silver nitrate solution with the volume concentration of 0.10mol/L into the solution pool 3, starting the peristaltic pump 4 to enable the silver nitrate solution in the solution pool 3 to enter the capillary 8 at a constant speed at the flow rate of 3.5mL/min, overflow from the top end of the capillary 8 and contact with the lower end of the platinum needle electrode 14; turning on the direct-current voltage-stabilizing and current-stabilizing power supply 1, and controlling the voltage between the cathode and the anode to be 550V and the current to be 32 mA; the direct current voltage and current stabilizing power supply 1, the platinum needle electrode 14 and the graphite tube 12 form a closed loop; in the electrifying process, the solution overflowing from the top end of the capillary tube 8 flows downwards along the outer wall of the graphite tube 12 after being electrolyzed, flows into the liquid collector 9 through discontinuous gaps between the graphite tube 12 and the end cover 10, then enters the product pool 7, and is continuously electrified for 4 hours to obtain black turbid liquid, the turbid liquid is subjected to ultrasonic dispersion for 12 minutes, centrifugal separation is carried out at the rotating speed of 10000r/min, and distilled water is washed for a plurality of times to remove dissolved Ag+Vacuum drying at 60 deg.C to constant weight, and grinding to obtain the final product.
Example 3
A liquid cathode glow discharge plasma apparatus as shown in fig. 1 was used. Adjusting the three-dimensional moving platform 15 to enable the distance between the lower end of the platinum needle electrode 14 and the top end of the capillary tube 8 to be 3 mm; injecting a silver nitrate solution with the pH =1 and the molar volume concentration of 0.15mol/L into the solution pool 3, starting the peristaltic pump 4, enabling the silver nitrate solution in the solution pool 3 to enter the capillary 8 at a constant speed at a flow rate of 6mL/min, overflowing from the top end of the capillary 8, and contacting with the lower end of the platinum needle electrode 14; starting the direct-current voltage-stabilizing and current-stabilizing power supply 1, and controlling the voltage between the cathode and the anode to be 600V and the current to be 58 mA; the direct current voltage and current stabilizing power supply 1, the platinum needle electrode 14 and the graphite tube 12 form a closed loop; in the electrifying process, the solution overflowing from the top end of the capillary tube 8 flows downwards along the outer wall of the graphite tube 12 after being electrolyzed, flows into the liquid collector 9 through a discontinuous gap between the graphite tube 12 and the end cover 10, then enters the product pool 7, and is continuously electrified for 3 hours to obtain black turbid liquid, the turbid liquid is subjected to ultrasonic dispersion for 15 minutes, centrifugal separation is carried out at the rotating speed of 6000r/min, and distilled water is washed for a plurality of times to remove dissolved Ag+Vacuum drying at 50 deg.C to constant weight, and grinding to obtain the final product.
The structure and morphology of the product prepared in the examples are characterized by X-ray powder diffraction (XRD), Scanning Electron Microscopy (SEM), X-ray Energy Dispersion Spectroscopy (EDS) and ultraviolet spectroscopy (UV-vis) below.
1. XRD test
The products obtained in examples 1 to 3 were tested by means of an X-ray powder diffractometer, model Rigaku D/max-2400. FIG. 4 shows XRD patterns of products obtained at different discharge voltages (where a is example 1, b is example 2, and c is example 3), and it can be seen from FIG. 4 that 2 is 2θThe diffraction peak number of 5 is in the range of 5-90 degrees, the diffraction peaks are respectively positioned at 38.1 degrees, 44.2 degrees, 64.4 degrees, 77.3 degrees and 81.5 degrees, and the peak positions of all diffraction peaks are well matched with the peak positions of a standard spectrogram JCPDS (No. 04-0783) card, and the 5 diffraction peaks respectively correspond to the diffraction of the (111), (200), (220), (311) and (222) crystal faces of the face-centered cubic system Ag. The prepared product is shown to be the metal Ag with a cubic structure. It can also be seen from fig. 4 that all diffraction peaks have very distinct broadening, since the broadening of X-ray diffraction peaks is one of the characteristics of nanoparticles, indicating that the prepared product has a small particle size. As can be seen from fig. 4, no other diffraction peaks are generated in the diffraction spectra of the Ag prepared under different voltages, indicating that the Ag nanoparticles with higher purity are prepared. According to the Debye-Scherrer formulaD=kλ/(βcosθ) (whereink=0.89，λ=0.1542nm，βHalf width), the grain sizes of Ag nanoparticles were calculated to be 60.23nm (fig. 4a),33.67nm (fig. 4b) and 47.62 nm ((fig. 4c) at the main peak (111).
2. Scanning electron microscope test
The Ag nanoparticles prepared in examples 1-3 were scanned using a Quanta2000 Scanning Electron Microscope (SEM) from czech FEI to observe the size and morphology of the sample. Before observation, the sample is dried in vacuum at 60 ℃ and sprayed with gold. SEM of samples under different discharge voltages is shown in figure 5 (wherein, a is example 1, b is example 2, and c is example 3), and it can be seen that the prepared Ag nano-particles mainly have rod shapes, small nano-particle agglomeration, nano-scale and uniform distribution.
3. X-ray Energy Dispersive Spectroscopy (EDS) testing
The composition of the Ag nanoparticles prepared in example 2 was tested by german Quanta type X-ray spectroscopy (EDS), and the test results are shown in fig. 6. EDS analysis showed that the sample had only a characteristic peak of Ag with an atomic fraction of 84.07%, and in EDS analysis 15.93% of the element was Au, which was caused by the gold spraying. The black powder product prepared by the preparation method of the invention is pure Ag.
4. UV-vis Spectroscopy testing
And performing ultraviolet analysis on the Ag nano particles in a 200-800 nm range by using an UV757 ultraviolet-visible spectrophotometer (Shanghai constant). FIG. 7 is a UV spectrum of the sample prepared in example 2. A strong absorption peak appears around 480nm, and in addition, 2 shoulder peaks appear at 268nm and 300nm, which is consistent with an ultraviolet spectrogram of the Ag nano particles, and the prepared particles are the Ag nano particles.
Claims (8)
1. A preparation method of Ag nano particles is characterized by comprising the following steps: adopting a liquid cathode glow discharge plasma generating device, providing electric energy by a high-voltage direct-current power supply, taking a platinum needle sealed in a quartz tube as an anode, and AgNO3The solution flows through a buffer bottle under the drive of a peristaltic pump, overflows from the top end of a capillary tube inserted with a graphite carbon rod, takes the overflowing solution as a discharge cathode, applies high voltage between a cathode and an anode, generates glow discharge plasma in the overflowing liquid between a platinum needle anode and the capillary tube, and utilizes active particles generated by the liquid cathode glow discharge plasma and Ag in the solution+Reacting to prepare the Ag nano particles.
2. The method for preparing Ag nanoparticles according to claim 1, wherein: the liquid cathode glow discharge plasma generating device comprises a solution pool (3), a liquid collector (9) and a three-dimensional moving platform (15), wherein the bottom of the liquid collector (9) is communicated with a product pool (7); an end cover (10) is installed on the liquid collector (9), an exhaust pipe (11) and a graphite pipe (12) are arranged on the end cover (10), the graphite pipe (12) is vertically arranged, discontinuous gaps are formed between the graphite pipe (12) and the end cover, a capillary tube (8) is arranged in the graphite pipe (12), the top end of the capillary tube (8) extends out of the top end of the graphite pipe (12), the lower end of the capillary tube (8) is communicated with a peristaltic pump (4) through a peristaltic pump rubber tube (5), and the peristaltic pump (4) is communicated with the solution tank (3) through a peristaltic pump rubber tube (2); the graphite tube (12) is communicated with the negative electrode of the direct-current voltage-stabilizing current-stabilizing power supply (1); a quartz tube (16) is vertically arranged on the three-dimensional moving platform (15), a platinum needle electrode (14) is sealed in the quartz tube (16), two ends of the platinum needle electrode (14) extend out of the quartz tube (16), one end of the platinum needle electrode faces the capillary tube (8), and the other end of the platinum needle electrode is communicated with the anode of the direct-current voltage-stabilizing and current-stabilizing power supply (1); during preparation, the three-dimensional moving platform (15) is adjusted to enable the distance between the lower end of the platinum needle electrode (14) and the top end of the capillary tube (8) to be 1-3 mm; injecting a silver nitrate solution into the solution pool (3), starting the peristaltic pump (4) to enable the silver nitrate solution in the solution pool (3) to enter the capillary tube (8) at a constant speed, overflowing from the top end of the capillary tube (8), and contacting with the lower end of the platinum needle electrode (14); starting a direct-current voltage-stabilizing and current-stabilizing power supply (1), controlling the voltage to be 480-600V and the current to be 28-58 mA; in the electrifying process, the solution overflowing from the top end of the capillary tube (8) flows downwards along the outer wall of the graphite tube (12) after electrolysis, flows into the liquid collector (9) through discontinuous gaps between the graphite tube (12) and the end cover (10), then enters the product pool (7), and is continuously electrified to obtain turbid liquid, and the turbid liquid is subjected to ultrasonic dispersion, centrifugal separation, distilled water washing, vacuum drying to constant weight and grinding to obtain the Ag nano particles.
3. The method for preparing Ag nanoparticles according to claim 2, wherein: the distance between the top surface of the capillary tube (8) and the top surface of the graphite tube (12) is 2-4 mm.
4. The method for preparing Ag nanoparticles according to claim 2, wherein: the volume of the buffer bottle (6) is 3-7 mL.
5. A method of making Ag nanoparticles of claim 2, wherein: the length of the platinum needle electrode (14) exposed out of the quartz tube (16) toward one end of the capillary tube (8) is 1 mm.
6. A method of preparing Ag nanoparticles according to claim 2 or claim 5, wherein: the diameter of the platinum needle electrode (14) is 0.3-0.7 mm.
7. A method of making Ag nanoparticles of claim 2, wherein: the silver nitrate solution in the solution pool (3) enters the capillary tube (8) at a constant speed at a flow rate of 1-6 mL/min.
8. The method of making the silver nanoparticles of claim 2, wherein: electrolyte AgNO3The pH value of the solution is 1, and the molar volume concentration is 0.05-0.15 mol/L.
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