CN111285443B - Boron-doped diamond composite electrode and preparation method and application thereof - Google Patents

Boron-doped diamond composite electrode and preparation method and application thereof Download PDF

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CN111285443B
CN111285443B CN201811506416.5A CN201811506416A CN111285443B CN 111285443 B CN111285443 B CN 111285443B CN 201811506416 A CN201811506416 A CN 201811506416A CN 111285443 B CN111285443 B CN 111285443B
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doped diamond
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王海龙
张珂皓
王溢仁
李强
邵刚
张锐
许红亮
卢红霞
范冰冰
刘雯
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Zhengzhou University
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    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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    • C02F1/46109—Electrodes
    • C02F2001/46133—Electrodes characterised by the material
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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Abstract

The invention belongs to the technical field of electrode materials, and particularly relates to a boron-doped diamond composite electrode and a preparation method thereof,Application is carried out. The boron-doped diamond composite electrode comprises boron-doped diamond and Al3BC3Said boron-doped diamond and Al3BC3The mass ratio of (A) to (B) is 8.5-9.5: 0.5 to 1.5. The invention mixes the boron-doped diamond raw material, the aluminum raw material, the boron raw material and the carbon raw material uniformly, and compounds them at high temperature and high pressure to form the boron-doped diamond/Al3BC3And (3) a composite electrode. The boron-doped diamond composite electrode has better electrochemical performance. Compared with the prior art, the preparation process is simple to operate, the preparation time is saved, and the cost is lower. The boron-doped diamond composite electrode has higher degradation rate when being used for treating wastewater.

Description

Boron-doped diamond composite electrode and preparation method and application thereof
Technical Field
The invention belongs to the technical field of electrode materials, and particularly relates to a boron-doped diamond composite electrode and a preparation method and application thereof.
Background
The discharge amount of industrial sewage in China is increasing day by day, the types of organic matters in the sewage are becoming complex day by day, and the traditional sewage treatment method can not treat the sewage thoroughly and efficiently. The electrolytic water treatment technology has attracted much attention as an advanced sewage and drinking water treatment technology. In the electrolytic water treatment technology, the electrode is a core part of the electrochemical reaction. The diamond has low background current, high signal-to-background ratio and signal-to-noise ratio, strong corrosion resistance and difficult surface adsorption, and is a clean electrode material. Based on the characteristics, diamond becomes a new generation of high-efficiency, energy-saving and environment-friendly electrode material. The boron-doped diamond electrode can be applied to degrading various high-concentration, toxic and difficult-to-degrade wastewater due to the high oxidation potential and the wide potential window.
Chinese patent application publication No. CN107267953A discloses a method for preparing a sensor electrode of a carbon hollow sphere and porous boron-doped diamond composite membrane. The preparation method comprises the steps of preparing a boron-doped diamond film by a hot filament CVD method, preparing a porous boron-doped diamond film by a radio frequency magnetron sputtering technology and a direct current arc plasma jet CVD method, and synthesizing the carbon hollow sphere/porous boron-doped diamond composite electrode by a hydrothermal method. The preparation method has complex preparation process and higher cost.
Disclosure of Invention
The invention aims to provide a boron-doped diamond composite electrode which has better electrochemical performance.
The second purpose of the invention is to provide a preparation method of the boron-doped diamond composite electrode, which is simple to operate and low in cost.
The third purpose of the invention is to provide the application of the boron-doped diamond composite electrode in wastewater treatment, and the boron-doped diamond composite electrode has higher degradation rate when used for treating wastewater.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a boron-doped diamond composite electrode comprises boron-doped diamond and Al3BC3Said boron-doped diamond and Al3BC3The mass ratio of (A) to (B) is 8.5-9.5: 0.5 to 1.5.
The boron-doped diamond composite electrode has stable electrochemical potential windows in acidic, alkaline and neutral electrolyte environments. When the boron-doped diamond composite electrode is used for degradation treatment of dye wastewater, the degradation rate of the dye reaches 97.8% in 120min, and the boron-doped diamond composite electrode has good electrochemical performance.
A preparation method of a boron-doped diamond composite electrode comprises the following steps:
(1) uniformly mixing a boron-doped diamond raw material with an aluminum raw material, a boron raw material and a carbon raw material, and performing ball milling to obtain a mixed precursor;
(2) and (4) pressurizing, sintering and molding the mixed precursor to obtain the composite material.
The preparation method of the boron-doped diamond composite electrode uses an Al-B-C system as a sintering aid, and utilizes the characteristic of low melting point of aluminum and the principle of liquid phase sintering in the reaction process to realize rapid densification in the early stage of sintering. The Al-B-C system is a sintering aid and generates Al through in-situ reaction in the sintering process3BC3A ternary compound. Al (Al)3BC3As an n-type semiconductor material, the boron-doped diamond has good conductivity, has the characteristics of corrosion resistance and high hardness, and cannot cause negative effects on the physical properties and the electrochemical properties of the boron-doped diamond. And the aluminum element and the boron element are all constituent elements of the boron-doped diamond electrode, and the Al-B-C system is used as a sintering aid, so that excessive impurity introduction cannot be caused.
Compared with the prior art, the boron-doped diamond composite electrode is simple to operate, saves the preparation time and has lower cost.
The mass ratio of the boron-doped diamond raw material, the aluminum raw material, the boron raw material and the carbon raw material in the step (1) is 85-95: 3-9: 0.5-1: 1.5 to 4.5. The aluminum raw material, the boron raw material and the carbon raw material in the proportion can form a sintering aid Al-B-C system with the mass fraction of 5-15% in the composite electrode, so that the compact structure of the composite electrode can be ensured, and the electrochemical performance of the electrode is not influenced.
In order to remove impurities such as grease on the surface of the boron-doped diamond raw material, the boron-doped diamond raw material in the step (1) is cleaned before being mixed, and the cleaning is carried out for 30min by boiling in a sodium hydroxide solution.
In order to uniformly mix the raw materials, the ball milling time is 12-24 h.
And (3) the temperature of the pressure sintering molding in the step (2) is 1450-1500 ℃. The composite electrode can be sintered by selecting the sintering temperature in the range, and if the sintering temperature is higher, the boron-doped diamond can be graphitized and transformed, so that the electrode fails.
And (3) the time for pressure sintering and forming in the step (2) is 150-300 s. If the sintering time is less than 150 seconds, the densification of the electrode cannot be guaranteed, and if the sintering time is too long, the boron-doped diamond is graphitized, so that the performance of the electrode is affected.
And (3) the pressure of the pressure sintering molding in the step (2) is 5-5.5 GPa. The density of the composite electrode can reach more than 90% by the pressure in the range, and if higher pressure is selected, not only more energy is consumed, but also the residual stress in the sintered composite electrode is more difficult to remove.
An application of the boron-doped diamond composite electrode in wastewater treatment. The boron-doped diamond composite electrode can be used for degrading high-concentration and difficult-to-degrade wastewater, and the degradation rate of the dye reaches 97.8% in 120min when the dye wastewater is degraded.
Drawings
FIG. 1 is an XRD pattern of a composite electrode of examples 1 to 3 of the boron-doped diamond composite electrode of the present invention;
FIG. 2 is an SEM image of a composite electrode of example 2 of a boron-doped diamond composite electrode of the present invention after treatment with hydrofluoric acid;
FIG. 3 is a plot of cyclic voltammetry for the composite electrode of example 1 of the boron-doped diamond composite electrode of the present invention;
FIG. 4 is a plot of cyclic voltammetry for the composite electrode of example 2 of the boron-doped diamond composite electrode of the present invention;
fig. 5 is a plot of cyclic voltammetry for the composite electrode of example 3 of the boron-doped diamond composite electrode of the present invention.
Detailed Description
The boron-doped diamond raw material used by the boron-doped diamond composite electrode is purchased from Zhengzhou abrasive grinding research institute limited company.
In the preparation process of the boron-doped diamond composite electrode, the ball milling media are absolute ethyl alcohol and zirconia balls, and the mass ratio of the total mass of the boron-doped diamond raw material, the aluminum raw material, the boron raw material and the carbon raw material to the mass of the zirconia balls and the absolute ethyl alcohol is 1: 1.5: 2.
the mould used in the preparation process of the boron-doped diamond composite electrode is formed by compounding and assembling tantalum metal and graphite flakes, and boron nitride slurry is sprayed on the surface of the mould in order to prevent the mixed precursor from reacting with the surface of the mould.
The boron-doped diamond used in the preparation process of the boron-doped diamond composite electrode is boron-doped diamond powder, the particle size of the boron-doped diamond powder is 1-3.9 mu m, and the content of the boron-doped diamond in the boron-doped diamond powder is more than or equal to 99.9%.
The aluminum raw material used in the preparation process of the boron-doped diamond composite electrode is aluminum powder, the particle size of the aluminum powder is 10 mu m, and the aluminum content in the aluminum powder is more than or equal to 99 percent.
The boron raw material used in the preparation process of the boron-doped diamond composite electrode is boron powder, the particle size of the boron powder is 1-5 mu m, and the boron content in the boron powder is more than or equal to 99%.
The carbon raw material used in the preparation process of the boron-doped diamond composite electrode is activated carbon powder, the particle size of the activated carbon powder is 38 mu m, and the carbon content in the activated carbon powder is more than or equal to 99.5 percent.
The invention is further described with reference to the following specific embodiments and the accompanying drawings.
Example 1 of boron-doped diamond composite electrode
The boron-doped diamond composite electrode of the embodiment is prepared from boron-doped diamond and Al3BC3Is compounded with boron-doped diamond and Al3BC3The mass ratio of (A) to (B) is 9.5: 0.5. specifically, the boron-doped diamond is granular, and Al3BC3Filling the gaps of the boron-doped diamond particles.
Example 2 of boron-doped diamond composite electrode
The boron-doped diamond composite electrode of the embodiment is prepared from boron-doped diamond and Al3BC3Is compounded with boron-doped diamond and Al3BC3The mass ratio of (A) to (B) is 9: 1.
example 3 of boron-doped diamond composite electrode
The true bookThe boron-doped diamond composite electrode of the embodiment is prepared from boron-doped diamond and Al3BC3Is compounded with boron-doped diamond and Al3BC3The mass ratio of (A) to (B) is 8.5: 1.5.
example 4 of boron-doped diamond composite electrode
The boron-doped diamond composite electrode of the embodiment is prepared from boron-doped diamond and Al3BC3Is compounded with boron-doped diamond and Al3BC3The mass ratio of (A) to (B) is 9.5: 0.5.
example 5 of boron-doped diamond composite electrode
The boron-doped diamond composite electrode of the embodiment is prepared from boron-doped diamond and Al3BC3Is compounded with boron-doped diamond and Al3BC3The mass ratio of (A) to (B) is 9: 1.
example 6 of boron-doped diamond composite electrode
The boron-doped diamond composite electrode of the embodiment is prepared from boron-doped diamond and Al3BC3Is compounded with boron-doped diamond and Al3BC3The mass ratio of (A) to (B) is 8.5: 1.5.
example 1 of a method for making a boron-doped diamond composite electrode
This example is a method of making the boron-doped diamond composite electrode of example 1, comprising the steps of:
(1) crushing boron-doped diamond particles prepared by a high-temperature and high-pressure method, sorting boron-doped diamond powder with the particle size of 1-3.9 microns, putting the boron-doped diamond powder into a 10g/L sodium hydroxide solution, boiling for 30min, washing the boron-doped diamond powder with deionized water to be neutral, filtering, and putting the boron-doped diamond powder into a vacuum drying oven to be dried for 12h at the temperature of 60 ℃;
(2) mixing dry boron-doped diamond powder with aluminum powder, boron powder and activated carbon powder according to a mass ratio of 95: 3: 0.5: 1.5 to obtain mixed powder, adding zirconia balls and absolute ethyl alcohol as grinding media, wherein the mass ratio of the mixed powder to the zirconia balls to the absolute ethyl alcohol is 1: 1.5: 2. then placing the mixture in a roller ball mill for ball milling for 12h, then using ultrasonic waves to ultrasonically disperse the obtained slurry for 30min, and finally drying the slurry through a rotary evaporator to obtain a mixed precursor;
(3) and (3) filling the mixed precursor into a die (the inner diameter is 10mm) formed by compositely assembling tantalum metal and graphite sheets, and then putting the die into a synthesis cavity of a hinge type cubic hydraulic press for pressure sintering and forming, wherein the pressure sintering temperature is 1450 ℃, the pressure of the pressure sintering is 5GPa, and the pressure sintering time is 300 s.
Example 2 of the method of making boron-doped diamond composite electrode
The embodiment is a preparation method of the boron-doped diamond composite electrode in embodiment 2, and the preparation method comprises the following steps:
(1) crushing boron-doped diamond particles prepared by a high-temperature and high-pressure method, sorting boron-doped diamond powder with the particle size of 1-3.9 microns, putting the boron-doped diamond powder into a 10g/L sodium hydroxide solution, boiling for 30min, washing the boron-doped diamond powder with deionized water to be neutral, filtering, and putting the boron-doped diamond powder into a vacuum drying oven to be dried for 12h at the temperature of 60 ℃;
(2) mixing the dried boron-doped diamond powder with aluminum powder, boron powder and activated carbon powder according to the mass ratio of 90: 6: 1: 3 to obtain mixed powder, and then adding zirconia balls and absolute ethyl alcohol as grinding media, wherein the mass ratio of the mixed powder to the zirconia balls to the absolute ethyl alcohol is 1: 1.5: 2. then placing the mixture in a roller ball mill for ball milling for 12h, then using ultrasonic waves to ultrasonically disperse the obtained slurry for 30min, and finally drying the slurry through a rotary evaporator to obtain a mixed precursor;
(3) and (3) filling the mixed precursor into a die (the inner diameter is 10mm) formed by compositely assembling tantalum metal and graphite sheets, and then putting the die into a synthesis cavity of a hinge type cubic hydraulic press for pressure sintering and forming, wherein the pressure sintering temperature is 1450 ℃, the pressure of the pressure sintering is 5GPa, and the pressure sintering time is 300 s.
Example 3 of the method of making boron-doped diamond composite electrode
The embodiment is a preparation method of the boron-doped diamond composite electrode in the embodiment 3, which comprises the following steps:
(1) crushing boron-doped diamond particles prepared by a high-temperature and high-pressure method, sorting boron-doped diamond powder with the particle size of 1-3.9 microns, putting the boron-doped diamond powder into a 10g/L sodium hydroxide solution, boiling for 30min, washing the boron-doped diamond powder with deionized water to be neutral, filtering, and putting the boron-doped diamond powder into a vacuum drying oven to be dried for 12h at the temperature of 60 ℃;
(2) mixing the dried boron-doped diamond powder with aluminum powder, boron powder and activated carbon powder according to the mass ratio of 85: 9: 1.5: 4.5 to obtain mixed powder, and then adding zirconia balls and absolute ethyl alcohol as grinding media, wherein the mass ratio of the mixed powder to the zirconia balls to the absolute ethyl alcohol is 1: 1.5: 2. then placing the mixture in a roller ball mill for ball milling for 12h, then using ultrasonic waves to ultrasonically disperse the obtained slurry for 30min, and finally drying the slurry through a rotary evaporator to obtain a mixed precursor;
(3) and (3) filling the mixed precursor into a die (the inner diameter is 10mm) formed by compositely assembling tantalum metal and graphite sheets, and then putting the die into a synthesis cavity of a hinge type cubic hydraulic press for pressure sintering and forming, wherein the pressure sintering temperature is 1450 ℃, the pressure of the pressure sintering is 5GPa, and the pressure sintering time is 300 s.
Example 4 method for preparing boron-doped diamond composite electrode
The embodiment is a preparation method of the boron-doped diamond composite electrode in embodiment 4, and the preparation method comprises the following steps:
(1) crushing boron-doped diamond particles prepared by a high-temperature and high-pressure method, sorting boron-doped diamond powder with the particle size of 1-3.9 microns, putting the boron-doped diamond powder into a 10g/L sodium hydroxide solution, boiling for 30min, washing the boron-doped diamond powder with deionized water to be neutral, filtering, and putting the boron-doped diamond powder into a vacuum drying oven to be dried for 12h at the temperature of 60 ℃;
(2) mixing dry boron-doped diamond powder with aluminum powder, boron powder and activated carbon powder according to a mass ratio of 95: 3: 0.5: 1.5 to obtain mixed powder, adding zirconia balls and absolute ethyl alcohol as grinding media, wherein the mass ratio of the mixed powder to the zirconia balls to the absolute ethyl alcohol is 1: 1.5: 2. then placing the mixture in a roller ball mill for ball milling for 20h, then using ultrasonic waves to ultrasonically disperse the obtained slurry for 30min, and finally drying the slurry through a rotary evaporator to obtain a mixed precursor;
(3) and (3) putting the mixed precursor into a die (the inner diameter is 10mm) which is formed by compositely assembling tantalum metal and graphite sheets, and then putting the die into a synthesis cavity of a hinge type cubic hydraulic press for pressure sintering and forming, wherein the pressure sintering temperature is 1500 ℃, the pressure of the pressure sintering is 5.2GPa, and the pressure sintering time is 300s, thus obtaining the tantalum-graphite composite material.
Example 5 method for preparing boron-doped diamond composite electrode
This example is a method of making the boron-doped diamond composite electrode of example 5, comprising the steps of:
(1) crushing boron-doped diamond particles prepared by a high-temperature and high-pressure method, sorting boron-doped diamond powder with the particle size of 1-3.9 microns, putting the boron-doped diamond powder into a 10g/L sodium hydroxide solution, boiling for 30min, washing the boron-doped diamond powder with deionized water to be neutral, filtering, and putting the boron-doped diamond powder into a vacuum drying oven to be dried for 12h at the temperature of 60 ℃;
(2) mixing the dried boron-doped diamond powder with aluminum powder, boron powder and activated carbon powder according to the mass ratio of 90: 6: 1: 3 to obtain mixed powder, and then adding zirconia balls and absolute ethyl alcohol as grinding media, wherein the mass ratio of the mixed powder to the zirconia balls to the absolute ethyl alcohol is 1: 1.5: 2. then placing the mixture in a roller ball mill for ball milling for 24h, then using ultrasonic waves to ultrasonically disperse the obtained slurry for 30min, and finally drying the slurry through a rotary evaporator to obtain a mixed precursor;
(3) and (3) putting the mixed precursor into a die (the inner diameter is 10mm) formed by compositely assembling tantalum metal and graphite sheets, and then putting the die into a synthesis cavity of a hinge type cubic hydraulic press for pressure sintering and forming, wherein the pressure sintering temperature is 1500 ℃, the pressure of the pressure sintering is 5GPa, and the pressure sintering time is 200s, thus obtaining the tantalum/graphite composite material.
Example 6 method for preparing boron-doped diamond composite electrode
The present example is a method of preparing the boron-doped diamond composite electrode of example 6, including the steps of:
(1) crushing boron-doped diamond particles prepared by a high-temperature and high-pressure method, sorting boron-doped diamond powder with the particle size of 1-3.9 microns, putting the boron-doped diamond powder into a 10g/L sodium hydroxide solution, boiling for 30min, washing the boron-doped diamond powder with deionized water to be neutral, filtering, and putting the boron-doped diamond powder into a vacuum drying oven to be dried for 12h at the temperature of 60 ℃;
(2) mixing the dried boron-doped diamond powder with aluminum powder, boron powder and activated carbon powder according to the mass ratio of 85: 9: 1.5: 4.5 to obtain mixed powder, and then adding zirconia balls and absolute ethyl alcohol as grinding media, wherein the mass ratio of the mixed powder to the zirconia balls to the absolute ethyl alcohol is 1: 1.5: 2. then placing the mixture in a roller ball mill for ball milling for 24h, then using ultrasonic waves to ultrasonically disperse the obtained slurry for 30min, and finally drying the slurry through a rotary evaporator to obtain a mixed precursor;
(3) and (3) putting the mixed precursor into a die (the inner diameter is 10mm) which is formed by compositely assembling tantalum metal and graphite sheets, and then putting the die into a synthesis cavity of a hinge type cubic hydraulic press for pressure sintering and forming, wherein the pressure sintering temperature is 1500 ℃, the pressure of the pressure sintering is 5.5GPa, and the pressure sintering time is 150s, thus obtaining the tantalum-graphite composite material.
Test example 1
XRD tests were performed on the composite electrodes of examples 1-3 of the boron-doped diamond composite electrode, and the test results are shown in FIG. 1. As can be seen from FIG. 1, diamond, Al, was observed in all three samples as can be seen from FIG. 14C3，Al3BC3And graphite peaks. With increasing sintering aid content, Al3BC3The intensity of the peak increases. Al was detected by XRD4C3And Al3BC3Indicating that a reaction occurred between the sintering aids. Al (Al)3BC3Formed during the Al-B-C reaction densification. Al formed by reaction of aluminum with carbon or diamond in the early stages of in situ reaction4C3Not completely converted to Al at the later stage of the sintering process3BC3. Graphite may be formed by a phase change of diamond during sintering.
Test example 2
The composite electrode of example 2 of the boron-doped diamond composite electrode was etched with hydrofluoric acid at a mass fraction of 40% for 4min, and then subjected to SEM test, with the test results shown in fig. 2. As can be seen from fig. 2, the size of the diamond particles is about 3-5 μm, which is similar to the size of the original boron-doped diamond (BDD) particles. In the process of sinteringAl formed in the process4C3Or Al3BC3The BDD crystal grain boundary is distributed at the BDD crystal grain boundary and is relatively uniform in distribution.
Test example 3
The composite electrodes of the boron-doped diamond composite electrodes of the embodiments 1 to 6 were subjected to an electrical property test by a hall measurement system, and the specific test conditions were as follows: the thickness of a selected sample is 1mm, the current range is 1 nA-20 mA, the measurement delay time is 0.1s, and the magnetic field intensity is 0.55T. The test results are shown in table 1.
TABLE 1
Sample (I) Hall mobility (cm)2/v·s) Resistivity (omega cm) Concentration of holes (cm)-3)
Example 1 2.18 6.73×10-2 4.26×1019
Example 2 2.85 4.81×10-2 4.55×1019
Example 3 2.33 5.73×10-2 4.68×1019
Example 4 2.53 4.12×10-2 5.07×1019
Example 5 3.13 3.78×10-2 6.10×1019
Example 6 2.78 4.65×10-2 5.27×1019
Test example 4
The specific test conditions for measuring the electrochemical performance of the composite electrodes of examples 1 to 6 of the boron-doped diamond composite electrode in acidic, alkaline and neutral electrolyte environments respectively by using an electrochemical workstation were that a three-electrode system was used for testing at a scan rate of 50mV/s within a potential range of-2.5V to 3V by Cyclic Voltammetry (CV). Platinum electrodes and Ag/AgCl/saturated KCl were used as auxiliary and reference electrodes, respectively. The BDD composite electrodes of examples 1-6 of the invention, 10mm x 1mm, were used as working electrodes. In the electrochemical potential window test process, the electrolyte is 0.1mol/L NaOH (alkaline) and 0.1mol/L Na2SO4(neutral), 0.1mol/L H2SO4(acidic). The test results are shown in table 2.
TABLE 2
Figure BDA0001899559710000081
Test example 5
For the composite electrodes of the boron-doped diamond composite electrodes of examples 1 to 3, electrochemical work stations were adopted to respectively measure the concentration of boron in the composite electrode at 5mmol/LK3Fe(CN)6And the electrochemical performance of the solution is measured in 1mol/L KCl mixed solution, and the test results are shown in figures 3 to 5. For a scan rate of 10 to 100mV/s, the difference between the oxidation potential and the reduction potential of the composite electrodes of examples 1 to 3 is 97.16 to 134.91mV, 51.67 to 169.01mV, and 83.3 to 108.46mV, respectively, and the ratio of oxidation peak current to reduction peak current is close to 1: 1, indicating that the reversibility is good.
Test example 6
The composite electrode of example 2 (area 1 cm) of the boron-doped diamond composite electrode was taken2) The copper wire is used as a lead, the epoxy resin is packaged to be used as an anode, the stainless steel plate with the same area is used as a cathode, the simulated dye wastewater is used as electrolyte (50ml, the components of the simulated dye wastewater are 40mg/L methylene blue and 2g/L sodium chloride) and used for simulating a dye wastewater degradation experiment, a certain voltage is applied between electrodes through a direct current stabilized voltage power supply to enable the electrodes to be in a constant current mode, the current density is 25mA/cm2. Sampling is carried out once every 30 minutes, the absorbance of the sample is analyzed by an ultraviolet-visible spectrophotometer, the degradation rate is calculated, and the degradation rate of the dye reaches 97.8 percent at 120 min.

Claims (5)

1. The boron-doped diamond composite electrode is characterized by comprising boron-doped diamond and Al3BC3Said boron-doped diamond and Al3BC3The mass ratio of (A) to (B) is 8.5-9.5: 0.5 to 1.5;
the preparation method of the boron-doped diamond composite electrode comprises the following steps:
(1) uniformly mixing a boron-doped diamond raw material with an aluminum raw material, a boron raw material and a carbon raw material, and performing ball milling to obtain a mixed precursor;
(2) pressurizing, sintering and molding the mixed precursor to obtain the composite material;
the mass ratio of the boron-doped diamond raw material, the aluminum raw material, the boron raw material and the carbon raw material in the step (1) is 85-95: 3-9: 0.5-1: 1.5 to 4.5; the boron-doped diamond raw material is boron-doped diamond powder, and the content of boron-doped diamond in the boron-doped diamond powder is more than or equal to 99.9 percent; the aluminum raw material is aluminum powder, and the aluminum content in the aluminum powder is more than or equal to 99 percent; the boron raw material is boron powder, and the boron content in the boron powder is more than or equal to 99 percent; the carbon raw material is activated carbon powder, and the carbon content in the activated carbon powder is more than or equal to 99.5 percent;
the temperature of the pressure sintering molding in the step (2) is 1450-1500 ℃; the time for pressure sintering and molding is 150-300 s; the pressure of the pressure sintering molding is 5-5.5 GPa.
2. The preparation method of the boron-doped diamond composite electrode is characterized by comprising the following steps of:
(1) uniformly mixing a boron-doped diamond raw material with an aluminum raw material, a boron raw material and a carbon raw material, and performing ball milling to obtain a mixed precursor;
(2) pressurizing, sintering and molding the mixed precursor to obtain the composite material;
the mass ratio of the boron-doped diamond raw material, the aluminum raw material, the boron raw material and the carbon raw material in the step (1) is 85-95: 3-9: 0.5-1: 1.5 to 4.5; the boron-doped diamond raw material is boron-doped diamond powder, and the content of boron-doped diamond in the boron-doped diamond powder is more than or equal to 99.9 percent; the aluminum raw material is aluminum powder, and the aluminum content in the aluminum powder is more than or equal to 99 percent; the boron raw material is boron powder, and the boron content in the boron powder is more than or equal to 99 percent; the carbon raw material is activated carbon powder, and the carbon content in the activated carbon powder is more than or equal to 99.5 percent;
the temperature of the pressure sintering molding in the step (2) is 1450-1500 ℃; the time for pressure sintering and molding is 150-300 s; the pressure of the pressure sintering molding is 5-5.5 GPa.
3. The method for preparing the boron-doped diamond composite electrode according to claim 2, wherein the boron-doped diamond raw material in the step (1) is cleaned before mixing, and the cleaning is carried out by boiling in a sodium hydroxide solution for 30 min.
4. The method for preparing the boron-doped diamond composite electrode according to claim 2, wherein the ball milling time in the step (1) is 12-24 hours.
5. Use of the boron-doped diamond composite electrode of claim 1 in wastewater treatment.
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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104962793A (en) * 2015-06-23 2015-10-07 中南钻石有限公司 Polycrystalline diamond compact with excellent electric conductivity and method for manufacturing polycrystalline diamond compact
CN107815580A (en) * 2017-11-08 2018-03-20 吉林大学 A kind of polycrystalline cubic boron nitride/diamond composite and preparation method thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104962793A (en) * 2015-06-23 2015-10-07 中南钻石有限公司 Polycrystalline diamond compact with excellent electric conductivity and method for manufacturing polycrystalline diamond compact
CN107815580A (en) * 2017-11-08 2018-03-20 吉林大学 A kind of polycrystalline cubic boron nitride/diamond composite and preparation method thereof

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