CN114195186B - Preparation method of niobium pentoxide nanoparticles - Google Patents
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Abstract
The invention discloses a preparation method of niobium pentoxide nano particles, which utilizes cathode glow discharge electrolysis plasma to prepare Nb 2 O 5 The nanometer particle uses the mixed solution of sodium sulfate solution, hydrofluoric acid and stabilizer as electrolyte, niobium sheet as anode, needle platinum wire as cathode, and high voltage is applied between the cathode and anode to make the needle platinum wire tip glow and form stable plasma. After discharging for a period of time, the ultrasonic dispersion is kept stand, high-speed centrifugation is carried out, and the centrifugal product is washed by ethanol and distilled water for several times in turn, vacuum drying is carried out to constant weight, and grinding is carried out, thus obtaining Nb 2 O 5 And (3) nanoparticles. The preparation method has the advantages of simple process, mild condition, no need of additional gas, high product purity and uniform particles; the method has the advantages of few chemical reagent types, low dosage and low cost, and is used for preparing Nb 2 O 5 New technology of nano particles.
Description
Technical Field
The invention belongs to the technical field of nano material preparation, and relates to niobium pentoxide (Nb) 2 O 5 ) The preparation process of nanometer particle, especially one kind of cathode glow discharge electrolytic plasma technology for preparing Nb directly from anode Nb sheet 2 O 5 Nanoparticle methods.
Background
Niobium pentoxide (Nb) 2 O 5 ) Is a transition metal oxide, has the characteristics of wide energy band gap, high light absorption, good chemical stability and the like, and is widely applied to the fields of super capacitors, batteries, catalysts, biomedicine and the like. At present, nb is prepared 2 O 5 The nanoparticle can be prepared by microwave combustion method, anodic oxidation method, hydrothermal synthesis method, etc. The microwave combustion method is to prepare Nb by using ammonium niobium oxalate as a precursor, ammonium nitrate as an oxidant and urea as fuel and adopting a microwave combustion technology 2 O 5 Nanoparticles (F.alpha.bioN, et al chemical Physics Letters,2019,729: 37-41). The advantage of this method is that the heating is faster, however, the requirements on the equipment are higher. The anodic oxidation method is to prepare Nb by taking niobium foil as an anode and platinum net as a cathode 2 O 5 Films (JeongBY, et al applied Surface Science, 2014, 307:28-32). The method has low cost and simple operation, but only can generate a layer of nano film on the surface of the anode, and cannot generate nano particles in the solution. The hydrothermal synthesis method adopts different structure directing agents oxalic acid and hydrogen peroxide, and successfully prepares the niobium pentoxide nano structure (PradoNT, et al applied Catalysis B: environmental, 2017, 205: 481-488) through hydrothermal treatment, and has the advantages of capability of creating high-temperature and high-pressure environment-induced chemical reaction, long reaction period and stronger dependence on equipment. In addition, the method is characterized in that the precursor is prepared in solution, and then the precursor is dried and roasted to obtain Nb 2 O 5 The nano material has the defects of complex process, complicated steps, easy secondary pollution and the like.
The plasma is formed by mixing electrons, free radicals, ions and neutral particles, and the non-thermal plasma has low gas temperature and high electron energy, and can induce a plurality of chemical reactions which are difficult to occur (HorikoshiS, et al, RSC Advances, 2017, 7:47196-47218). Recently, the cathode glow discharge electrolytic plasma method was applied to the synthesis of CuO nanoparticles (Quanfang Lu, et al materials Letters 2020, 264: 127316). However, the cathode glow discharge electrolytic plasma method is used for preparing Nb 2 O 5 The research of the nano particles is not reported in the literature at home and abroad.
Disclosure of Invention
The invention aims at Nb in the prior art 2 O 5 The method has the advantages of complex preparation process, harsh conditions, high production cost and the like, and provides a method for simply, conveniently and rapidly synthesizing Nb from niobium sheets by utilizing a cathode glow discharge electrolysis plasma method 2 O 5 Nanoparticle methods.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows: a preparation method of niobium pentoxide nano particles adopts cathode glow discharge electrolysis plasma to prepare Nb 2 O 5 The nano particle comprises the following steps:
1) The cathode glow discharge electrolytic plasma device shown in fig. 1 comprises a direct current power supply 1, a magnetic stirrer 7 and a reaction container 10, wherein the reaction container 10 is sleeved with a cooling water tank 9 for controlling the temperature, a water inlet 11 and a water outlet 4 are arranged on the side wall of the cooling water tank 9, and the water inlet 11 and the water outlet 4 are positioned in the 180-degree direction and are communicated through a cooling water channel; an openable and closable container cover 14 is arranged at the open end of the reaction container 10, two wires are arranged on the container cover 14 side by side, the upper end of one wire is connected with one end of a resistor 2, the other end of the resistor 2 is connected with the positive electrode of a direct current power supply 1, the lower end of the wire penetrates through the container cover 14 to extend into the reaction container 10 and is connected with an L-shaped electrode niobium sheet 5, and the wire is connected with the longer side wall of the electrode niobium sheet 5; the upper end of the other lead is connected with the negative electrode of the direct current power supply 1, the lower end of the other lead is connected with the upper end of a platinum needle electrode 13 positioned in the reaction container 10, a platinum needle tip 12 at the lower end of the platinum needle electrode 13 is positioned between two side walls of the L-shaped electrode niobium sheet 5 and is not contacted with the electrode niobium sheet 5, and at least one air outlet 3 is further arranged on the container cover 14;
the platinum needle electrode 13 is arranged coaxially with the electrode niobium sheet 5. The distance between the platinum needle tip 12 and the bottom plate and the two side walls of the electrode niobium sheet 5 is equal and is 0.5-1.0 cm.
Taking a niobium sheet with the length of 3-4 cm, the width of 0.5-1 cm and the thickness of 0.1-0.3 mm, polishing by using abrasive paper, soaking in acetone for 15-20 min, respectively ultrasonically washing in ethanol and deionized water for 5-10 min, and removing grease on the surface; then, the electrode niobium sheet 5 was formed by bending into an L shape. The L-shaped electrode niobium sheet 5 can increase the glow radiation area of the electrode niobium sheet 5, so that the glow generated by the platinum needle tip 12 just irradiates on the electrode niobium sheet 5.
And (3) sealing a platinum wire with the diameter of 0.5-1.0 mm in the quartz tube, wherein the length of the tip of the platinum wire exposed out of the quartz tube is 0.5-1.0 mm, so as to obtain the platinum needle electrode 13, and the part of the tip of the platinum wire exposed out of the quartz tube is the platinum needle tip 12.
The resistance value of the resistor 2 is 1-5 k omega.
Preparing sodium sulfate solution with mass volume concentration of 3-6 g/L;
2) Placing a cooling water tank 9 on a magnetic stirrer 7, placing a stirring magnet 8 in a reaction container 10, respectively connecting a water inlet 11 and a water outlet 4 with a cooling water supply system, opening a container cover 14, injecting a sodium sulfate solution into the reaction container 10, adding 1-6 mL hydrofluoric acid and 0.01-0.07 g stabilizer into the sodium sulfate solution according to the proportion of 150mL hydrofluoric acid and 0.01-0.07 g stabilizer to form an electrolyte 6, covering the container cover 14, and completely immersing the shorter side wall of an electrode niobium sheet 5 in the electrolyte 6;
the mass fraction of hydrofluoric acid is more than or equal to 40 percent.
The stabilizer is Cetyl Trimethyl Ammonium Bromide (CTAB).
3) Starting a magnetic stirrer 7, a direct current power supply 1 and a cooling water supply system, stirring the electrolyte 6 at a rotating speed of 80-150 r/min, starting the direct current power supply 1, applying 450-540V discharge voltage between the platinum needle tip 12 and the electrode niobium sheet 5 by the direct current power supply 1, generating bright glow at the tip of the platinum needle tip 12 to form stable discharge plasma, keeping the temperature of the electrolyte 6 at 10-40 ℃ in the reaction process, gradually consuming the electrode niobium sheet 5 in the discharge process, and generating milky Nb in the electrolyte 2 O 5 Reacting the nano particles for 1-3 hours to obtain milky turbid liquid;
4) Dispersing the turbid liquid by ultrasonic for 10-20 min, standing for 12-24 h, centrifugally separating the lower solution at the rotating speed of 10000-15000 r/min, washing with distilled water to remove electrolyte, washing with absolute ethyl alcohol for several times, drying in a vacuum oven at 40-60 ℃ to constant weight, and grinding to obtain the niobium pentoxide nanoparticles.
Cooling water is continuously fed into and discharged from the cooling water tank 9 in the reaction process, so that the temperature of the electrolyte 6 is ensured to be 10-40 ℃.
1. Preparation of Nb 2 O 5 Principle of nanoparticles
Cathode glow discharge electrolysis plasma technology, namely under the action of external voltage, the surface of the electrode niobium sheet 5 is oxidized into compact Nb 2 O 5 The film, as the film thickness increases, the current decreases and is self-limiting. Nb in the presence of HF on the surface of the electrode niobium sheet 5 2 O 5 The film is etched to form soluble NbF 7 ] 2− A complex. At the cathode plasma-liquid interface, electrons and H are generated due to higher plasma temperature 2 O reacts to form various active substances, e.g aq − 、H•、OH•、•O 2− 、OH − 、H 2 O 2 、H 2 And O 2 . At the same time, soluble [ NbF 7 ] 2− The complex can react with water to form Nb (OH) 5 Nb (OH) at high plasma temperature 5 Further conversion to Nb 2 O 5 . The main reactions are as follows:
anode: nb+5H 2 O-10e - →Nb 2 O 5 + 10H + (1)
Nb 2 O 5 + 14F − + 10H + → 2[NbF 7 ] 2− + 5H 2 O (2)
And (3) cathode: h 2 O + e − ~→ e aq − , H•, OH•, •O 2− , H 2 , H 2 O 2 , OH − (3)
Complex [ NbF 7 ] 2− Reaction with water:
[NbF 7 ] 2− + 5H 2 O→Nb(OH) 5 + 7F − +5H + (4)
Nb(OH) 5 further conversion:
2Nb(OH) 5 →Nb 2 O 5 + 5H 2 O (5)
control of Nb in solution by controlling the amount of HF added 2 O 5 The rate of nanoparticle generation; CTA can be achieved by adding an appropriate amount of stabilizer CTAB + Attached to Nb by electrostatic attraction 2 O 5 Surface of the particles, synthesizing Nb 2 O 5 The gibbs free energy is reduced during the nanoparticle process, thereby reducing the agglomeration of the nanoparticles.
2. Nb (Nb) 2 O 5 Characterization of nanoparticles
The following analysis of the current-voltage curve illustrates that the preparation process is not a common electrolysis, but a cathode glow discharge electrolysis plasma process; detecting active species generated by the plasma by emission spectroscopy; the structure and morphology of the material were characterized by infrared spectroscopy (FT-IR), X-ray powder diffraction (XRD) and Scanning Electron Microscopy (SEM).
1. Current-voltage curve
The DH1722A-6 DC voltage-stabilizing and current-stabilizing power supply (voltage 0-1000V, current 0-0.5A) of Beijing Dahua radio instrument Limited liability company is used for measuring the current change under different voltages. FIG. 2 is a graph of current versus voltage for a cathode glow discharge electrolytic plasma by varying the voltage with the addition of a 2kΩ resistor, an electrolyte of 150mL sodium sulfate solution at a mass volume concentration of 6g/L, 3mL hydrofluoric acid, and 0.05g stabilizer. As can be seen from fig. 2, the entire discharge process is divided into 4 segments: AB section (0-380V) is a conventional common electrolysis area, and as the voltage increases, the current increases, and the ohm law and Faraday electrolysis law are followed. The BC segment (380-430V) has the current instantaneously reduced with the increase of the voltage, and the larger the voltage is, the more steam bubbles are generated, so that the current is smaller. The CD section (430-540V) has basically unchanged current with the increase of voltage, but the glow is gradually enhanced to generate stable plasma, and the generated high-activity substances oxidize and corrode and dissolve the electrode niobium sheet due to the high voltage in the stage. In DE section (> 540V), the glow becomes strong, the energy consumption is high, and the damage to the cathode platinum needle is serious. Preparation of Nb 2 O 5 The voltage of the nano particles is 450-540V, and the current is 40-110 mA at the moment, which shows that the preparation process of the invention is not common electrolysis, but glow discharge plasma.
2. Emission spectroscopy analysis
The emission spectrum of the cathode glow discharge electrolytic plasma was measured with an eight-channel high-resolution fiber optic spectrometer (AvaSpec-ULS 2048, avaSpec, netherlands) and the results are shown in FIG. 3. Spectral lines at wavelengths 265.3nm, 283.0nm and 309.0nm are HO (A 2 Ʃ + →X 2 N) ((1, 0) and (0.0)) transitionsH being hydrogen atoms in bands 486.1nm and 656.2 nm β (4d 2 D→2p 2 P 0 ) And H α (3d 2 D→2p 2 P 0 ) The spectral lines at 777.4 nm and 844.8 nm are in the excited state O (3 p 5 P→3s 5 S 0 ) And (3 p) 3 P→3s 3 S 0 ) The transition line of the atom is the ion emission line of OII at 412.1, nm. This is due to the fact that the high-energy electrons excite the vaporized water molecules to generate a large amount of HO, H, O 2– .568.4 Atomic lines of Na at nm,589.0nm and 819.0nm prove that the electrolyte contains Na + Ions.
3. Infrared test
FTS-3000 type Fourier transform infrared spectrometer (FT-IR, KBr tablet, scanning range 400-4000 cm) is adopted –1 DIGILAB, usa) characterizes the structure of the product. FIG. 4 shows an applied resistance of 2kΩ, a discharge voltage of 500V, and a current of 70mA; the electrolyte is composed of 150mL of sodium sulfate solution with the mass volume concentration of 6g/L, 3mL of hydrofluoric acid and 0.05g of stabilizer, and an infrared spectrogram of the product is prepared. 3421 cm –1 The wide absorption peak at the position is an O-H stretching vibration peak for absorbing water; 1646 cm –1 An O-H bending vibration peak belonging to adsorbed water; 827cm –1 The absorption peak at the position is Nb-O-Nb bond; 554cm –1 The absorption peak at this point is an Nb-O bond. Analysis shows that the target product has no OH – Thus preliminarily determining that the synthesized product is Nb 2 O 5 。
4. XRD testing
Adopts a D/max-2400X-ray powder diffractometer (XRD, the radiation source is CuK) α 40 kv,150 mA, λ= 0.15406 nm, japan, rigaku corporation). FIG. 5 is an XRD pattern for the product prepared by adding 0.05g of stabilizer (CTAB) and varying amounts of hydrofluoric acid (1 mL, 3mL, 5 mL) to 150mL of sodium sulfate solution of 6g/L by mass volume at 500V discharge voltage with an additional 2kΩ resistor. As can be seen from fig. 5, there are 8 diffraction peaks in the 2θ=5 to 80° range, which are located at 22.6 °, 28.3 °, 32.7 °, 36.5 °, 46.1 °, 50.9 °, 54.9 ° and 56.3 °, respectively. These 8 derivatives were compared with the JCDF (27-1003) standard cardThe peak of the injection corresponds to the orthorhombic structure Nb 2 O 5 Diffraction of eight crystal planes (001), (180), (250), (181), (002), (380), (182) and (381). It can also be seen from the figure that all of these 8 diffraction peaks have a very pronounced broadening, which is an indication that the prepared sample has a smaller particle size, on the order of nanometers, since X-ray diffraction peak broadening is one of the characteristics of nanoparticles. According to Debye-Scherrer formulaD hkl =kλ/(βcosθ) Estimated Nb for 1mL, 3mL, 5mL hydrofluoric acid dosage) 2 O 5 The crystal face sizes of the nano particles are 8.74nm, 7.76nm and 10.28 nm respectively, which indicate Nb 2 O 5 Nanocrystals have very small grain sizes.
5. Scanning electron microscope test
Nb Using JSM-6700F scanning electron microscope 2 O 5 The nano particles are scanned to observe the size and the shape of the sample, and the sample is dried in vacuum at 60 ℃ before observation and then sprayed with gold. FIGS. 6a, 6b and 6c are Nb made with 1mL, 3mL and 5mL hydrofluoric acid, respectively 2 O 5 The morphology of the nanoparticles, it can be seen that the product particles produced are smaller, although the concentration of hydrofluoric acid in the electrolyte is different, and this result is consistent with the XRD test results.
6. EDS test
Testing electrolyte containing 3mL of hydrofluoric acid with X-ray energy spectrum (EDS) to obtain Nb 2 O 5 The composition of the nanoparticle and the test results are shown in FIG. 7.EDS analysis showed that: the sample only has characteristic peaks of O and Nb, the mass percentages are 35.86 percent and 64.14 percent respectively, the atomic number ratio of O and Nb is 3.2 and is close to 2.5, and the white powder prepared by the preparation method is further described as Nb by combining with figures 4, 5 and 6 2 O 5 And (3) nanoparticles.
Drawings
FIG. 1 is a schematic view of a cathode glow discharge electrolyzer used in the production process of the present invention.
FIG. 2 shows the preparation of Nb by the preparation method of the present invention 2 O 5 Current-voltage plot at the nanoparticle.
FIG. 3 is a graph showing the emission spectrum of the glow discharge electrolytic plasma at 460V voltage according to the present invention.
FIG. 4 shows Nb production by adding 3mL hydrofluoric acid to the electrolyte of the present invention 2 O 5 Infrared spectrogram of the nanoparticle.
FIG. 5 shows Nb production with addition of different hydrofluoric acid contents to the electrolyte of the present invention 2 O 5 XRD pattern of nanoparticles.
FIG. 6 shows Nb production with addition of different hydrofluoric acid contents to the electrolyte of the present invention 2 O 5 SEM topography of nanoparticles.
FIG. 7 shows that Nb is obtained when 3mL of hydrofluoric acid is contained in the electrolyte 2 O 5 X-ray energy spectrum (EDS) plot of nanoparticles.
In fig. 1: 1. the direct-current power supply, the resistor, the air outlet, the water outlet, the 5.L-shaped niobium sheet electrode, the electrolyte, the magnetic stirrer, the stirring magnet, the cooling water tank, the reaction vessel, the water inlet, the platinum needle tip, the platinum needle electrode and the vessel cover are respectively arranged in sequence, wherein the direct-current power supply, the resistor, the air outlet, the water outlet, the 5.L-shaped niobium sheet electrode, the electrolyte, the magnetic stirrer, the stirring magnet, the cooling water tank, the reaction vessel, the water inlet, the platinum needle tip, the platinum needle electrode and the vessel cover are respectively arranged in sequence.
Detailed Description
The present invention will be described in further detail with reference to the following embodiments.
Example 1
Taking an L-shaped metal niobium sheet as an anode, a needle-shaped platinum wire as a cathode and Na with a mass volume concentration of 6g/L 2 SO 4 The electrolyte is composed of solution 150mL, 1mL of hydrofluoric acid with mass fraction more than or equal to 40% and 0.05g of CTAB, a high-voltage direct-current power supply provides electric energy, voltage 450V is applied between a cathode and an anode, the electrolyte is continuously stirred (150 r/min), a cathode generates glow to form stable glow discharge plasma, an anode niobium sheet is continuously consumed, and milky Nb is generated in the solution 2 O 5 A nanoparticle; maintaining the temperature of the electrolyte at 25 ℃ and continuously discharging for 3 hours to obtain milky turbid liquid; dispersing the turbid liquid by ultrasonic for 10min, standing for 24h, centrifuging the lower solution at 10000r/min at high speed, washing with distilled water to remove electrolyte, washing with absolute ethanol for 3 times, vacuum drying in vacuum oven at 60deg.C to constant weight, and grinding with agate mortar to obtain Nb 2 O 5 And (3) nanoparticles.
Example 2
Taking an L-shaped metal niobium sheet as an anode, a needle-shaped platinum wire as a cathode and Na with a mass volume concentration of 3g/L 2 SO 4 150-mL of solution, 3mL of hydrofluoric acid with mass fraction more than or equal to 40% and 0.01g of CTAB (CTAB) to form electrolyte; the high-voltage direct current power supply supplies electric energy, voltage 500V is applied between the cathode and the anode, and the electrolyte is continuously stirred (the speed is 120 r/min), the cathode generates glow to form stable glow discharge plasma, the anode niobium sheet is continuously consumed, and milky Nb is generated in the solution 2 O 5 A nanoparticle; maintaining the temperature of the electrolyte at 10 ℃ and continuously discharging for 2 hours to obtain milky turbid liquid; then dispersing the turbid liquid for 15 min by ultrasonic, standing for 12 h, centrifuging the lower solution at 12000r/min at high speed, performing ultrasonic dispersion, washing with distilled water to remove electrolyte, washing with absolute ethyl alcohol, vacuum drying in a vacuum oven at 40 ℃ to constant weight, and grinding with agate mortar to obtain milky Nb 2 O 5 And (3) nanoparticles.
Example 3
Taking an L-shaped metal niobium sheet as an anode, a needle-shaped platinum wire as a cathode and Na with the mass volume concentration of 4g/L 2 SO 4 150-mL of solution, 6mL of hydrofluoric acid with mass fraction more than or equal to 40% and CTAB of 0.07-g; the high-voltage direct current power supply supplies electric energy, a voltage of 540V is applied between the cathode and the anode, the electrolyte is continuously stirred (80 r/min), the cathode generates glow to form stable glow discharge plasma, the anode niobium sheet is continuously consumed, and milky Nb is generated in the solution 2 O 5 A nanoparticle; maintaining the temperature of the electrolyte at 40 ℃, and continuously discharging for 1h to obtain milky turbid liquid; then dispersing the turbid liquid for 20min by ultrasonic, standing for 18h, centrifuging at a high speed of 15000r/min, washing the product with distilled water for several times to remove electrolyte, washing with absolute ethyl alcohol, vacuum drying in a vacuum oven at 50 ℃ to constant weight, and grinding with an agate mortar to obtain milky Nb 2 O 5 And (3) nanoparticles.
Claims (5)
1. A preparation method of niobium pentoxide nanoparticles is characterized in that the niobium pentoxide nanoparticles are prepared by a cathode glow discharge electrolysis plasma technologyNb 2 O 5 The preparation method of the nanoparticle specifically comprises the following steps:
1) The cathode glow discharge electrolysis plasma device comprises a direct current power supply (1), a magnetic stirrer (7) and a reaction container (10), wherein the reaction container (10) is sleeved with a cooling water tank (9); an openable and closable container cover (14) is arranged at the open end of the reaction container (10), two leads are arranged on the container cover (14) side by side, the upper end of one lead is connected with one end of a resistor (2), the other end of the resistor (2) is connected with the positive electrode of a direct current power supply (1), and the lower end of the lead penetrates through the container cover (14) to extend into the reaction container (10) and is connected with an L-shaped electrode niobium sheet (5) in the reaction container (10); the upper end of the other wire is connected with the negative electrode of the direct current power supply (1), the lower end of the other wire is connected with the upper end of a platinum needle electrode (13) positioned in the reaction container (10), the lower end of the platinum needle electrode (13) is positioned between two side walls of the electrode niobium sheet (5), the platinum needle electrode (13) is not contacted with the electrode niobium sheet (5), and at least one air outlet (3) is arranged on the container cover (14);
preparing sodium sulfate solution with the mass volume concentration of 3-6 g/L;
the electrode niobium sheet (5) is prepared by the following process: taking a niobium sheet with the length of 3-4 cm, the width of 0.5-1 cm and the thickness of 0.1-0.3 mm, polishing by sand paper, soaking in acetone for 15-20 min, respectively ultrasonically washing in ethanol and deionized water for 5-10 min, and then bending into an L shape to prepare an electrode niobium sheet (5);
2) Placing a cooling water tank (9) on a magnetic stirrer (7), placing a stirring magnet (8) in a reaction container (10), communicating the cooling water tank (9) with a cooling water supply system, opening a container cover (14), injecting sodium sulfate solution into the reaction container (10), adding 1-6 mL hydrofluoric acid and 0.01-0.07 g stabilizer according to the proportion of 150mL sodium sulfate solution, adding the hydrofluoric acid and the stabilizer to form an electrolyte (6), and covering the container cover (14), wherein the shorter side wall of the electrode niobium sheet (5) is completely immersed in the electrolyte (6;
3) Starting a magnetic stirrer (7) and a cooling water supply system, stirring the electrolyte (6), starting a direct current power supply (1), and applying 450-540 and V discharge voltage between a platinum needle electrode (13) and an electrode niobium sheet (5) by the direct current power supply (1), wherein the tip of a needle point of the platinum needle electrode (13) forms stable plasma, and keeping the temperature of the electrolyte (6) at 10-40 ℃ in the reaction process for 1-3 hours to obtain turbid liquid;
4) Ultrasonic dispersing the turbid liquid, standing, centrifuging at high speed to separate lower solution, washing with distilled water, washing with absolute ethyl alcohol, drying in vacuum oven to constant weight, and grinding to obtain Nb 2 O 5 And (3) nanoparticles.
2. The preparation method of the niobium pentoxide nanoparticle according to claim 1, wherein the platinum needle electrode (13) is prepared by the following process: and (3) sealing a platinum wire with the diameter of 0.5-1.0 mm in the quartz tube, wherein the length of the tip of the platinum wire exposed out of the quartz tube is 0.5-1.0 mm, so as to obtain the platinum needle electrode (13).
3. The preparation method of niobium pentoxide nanoparticles according to claim 1, wherein the side wall of the cooling water tank (9) is provided with a water inlet (11) and a water outlet (4), and the water inlet (11) and the water outlet (4) are positioned in the 180-degree direction and are communicated through a cooling water channel; before the reaction, the water inlet (11) and the water outlet (4) are respectively communicated with a cooling water supply system.
4. The method for producing niobium pentoxide nanoparticles as claimed in claim 1, wherein in step 4), the high-speed centrifugation is performed at a rotational speed of 10000 to 15000 r/min.
5. The method for producing niobium pentoxide nanoparticles as claimed in claim 1, wherein in step 4), the vacuum drying temperature is 40 to 60 ℃.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106673058A (en) * | 2017-01-23 | 2017-05-17 | 上海朗研光电科技有限公司 | Preparation method of titanium dioxide nano-particles based on nano gold solution glow discharge |
| CN106744676A (en) * | 2017-01-23 | 2017-05-31 | 上海朗研光电科技有限公司 | The device and its synthetic method of glow discharge synthesizing nano-particle |
| CN107620085A (en) * | 2017-09-13 | 2018-01-23 | 西北师范大学 | A kind of method that hexagonal phase nanometer h molybdenum trioxides are prepared using liquid phase cathode glow discharging plasma |
| CN107739052A (en) * | 2017-11-27 | 2018-02-27 | 江苏大学 | A kind of method of no hydrothermal template controlledly synthesis different-shape niobium pentoxide nano material |
| CN111204819A (en) * | 2020-01-21 | 2020-05-29 | 西北师范大学 | Method for preparing nano Co by using liquid cathode glow discharge plasma technology3O4Method (2) |
| CN111215636A (en) * | 2020-01-17 | 2020-06-02 | 西北师范大学 | Preparation method of Ag nano particles |
| CN111235588A (en) * | 2020-01-17 | 2020-06-05 | 西北师范大学 | Method for preparing nano zinc oxide by liquid cathode glow discharge plasma |
-
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Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106673058A (en) * | 2017-01-23 | 2017-05-17 | 上海朗研光电科技有限公司 | Preparation method of titanium dioxide nano-particles based on nano gold solution glow discharge |
| CN106744676A (en) * | 2017-01-23 | 2017-05-31 | 上海朗研光电科技有限公司 | The device and its synthetic method of glow discharge synthesizing nano-particle |
| CN107620085A (en) * | 2017-09-13 | 2018-01-23 | 西北师范大学 | A kind of method that hexagonal phase nanometer h molybdenum trioxides are prepared using liquid phase cathode glow discharging plasma |
| CN107739052A (en) * | 2017-11-27 | 2018-02-27 | 江苏大学 | A kind of method of no hydrothermal template controlledly synthesis different-shape niobium pentoxide nano material |
| CN111215636A (en) * | 2020-01-17 | 2020-06-02 | 西北师范大学 | Preparation method of Ag nano particles |
| CN111235588A (en) * | 2020-01-17 | 2020-06-05 | 西北师范大学 | Method for preparing nano zinc oxide by liquid cathode glow discharge plasma |
| CN111204819A (en) * | 2020-01-21 | 2020-05-29 | 西北师范大学 | Method for preparing nano Co by using liquid cathode glow discharge plasma technology3O4Method (2) |
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