CN111579606A - High-stability metal-modified boron-doped diamond electrode and preparation method and application thereof - Google Patents

High-stability metal-modified boron-doped diamond electrode and preparation method and application thereof Download PDF

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CN111579606A
CN111579606A CN202010390538.3A CN202010390538A CN111579606A CN 111579606 A CN111579606 A CN 111579606A CN 202010390538 A CN202010390538 A CN 202010390538A CN 111579606 A CN111579606 A CN 111579606A
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doped diamond
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魏秋平
马莉
周科朝
朱睿童
杨万林
陈尹豪
李志伸
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Central South University
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Abstract

The invention discloses a high-stability metal-modified boron-doped diamond electrode and a preparation method and application thereof. The metal modified boron-doped diamond electrode realizes the firm wrapping of the bottom of the metal particles and the electrode, thereby achieving the effect of fixing the metal particles and fully combining the excellent stability of the boron-doped diamond material and the good electrocatalytic activity of the metal. The metal modified boron-doped diamond electrode can be widely applied to the fields of electrochemical biosensors, detection of heavy metals, detection of organic wastewater and the like.

Description

High-stability metal-modified boron-doped diamond electrode and preparation method and application thereof
Technical Field
The invention relates to a high-stability metal-modified boron-doped diamond electrode and a preparation method and application thereof, belonging to the field of electrode preparation.
Background
The boron-doped diamond film electrode (BDD) has high mechanical strength, chemical inertness and excellent electrochemical performance, such as a wide potential window, a high oxygen evolution overpotential and a low background current in an aqueous solution, can efficiently generate hydroxyl radicals under the same current density, thereby enabling organic matters to be rapidly removed, has the poisoning and pollution resistance on the surface, and can stably work in a strong corrosive medium for a long time. Even under high electrochemical load, the passing current density is 2-10A cm2There were also no obvious signs of erosion for thousands of hours of electrochemical reaction. The diamond film has high and high-quality performances in the aspects of hardness and strength, can resist the strong wave impact of the ultrasonic cavitation effect on the surface of the electrode, and has longer service life in a high-strength environment. With the continuous development of the coating technology of the chemical vapor deposition CVD artificial synthesis polycrystalline diamond film and the research of the boron-doped P-type semiconductor, the resistivity of the CVD diamond film is reduced to 0.01-100 omega cm, and the electrode material is good in conductivity. Research shows that the electrode has wide application prospect in the aspects of reducing organic pollutants by electrooxidation and the aspects of analyzing and detecting high-sensitivity organic matters.
The boron-doped diamond electrode also has the defects of low electrocatalytic activity, poor selectivity and sensitivity and the like, and the sensitivity of the BDD electrode is often improved through metal modification. However, BDD has surface chemical inertness, so metal-modified BDD electrodes often have the phenomenon of metal falling off, and the detection stability and sensitivity of the electrodes are seriously damaged. Thereby limiting its application.
Disclosure of Invention
In view of the deficiencies of the prior art, it is a first object of the present invention to provide a metal modified boron doped diamond electrode with high stability.
The second purpose of the invention is to provide a preparation method of the high-stability metal-modified boron-doped diamond electrode.
The third purpose of the invention is to provide the application of the high-stability metal-modified boron-doped diamond electrode.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention relates to a high-stability metal-modified boron-doped diamond electrode which comprises a substrate and an electrode working layer arranged on the surface of the substrate, wherein the electrode working layer comprises a first layer of boron-doped diamond film, a second layer of boron-doped diamond film grown on the surface of the first layer of boron-doped diamond film, and metal nano-particles grown on the surface of the first layer of boron-doped diamond film and embedded in the second layer of boron-doped diamond film.
Preferably, the particle size of the metal nano particles is larger than the thickness of the second layer of boron-doped diamond film.
In the invention, the particle size of the metal nano-particles is larger than the thickness of the second layer of boron-doped diamond film; thereby enabling the metal nano particles to be exposed out of the surface of the second layer of boron-doped diamond film, and being more beneficial to improving the sensitivity of the electrode.
The invention relates to a high-stability metal-modified boron-doped diamond electrode, wherein metal nanoparticles are selected from at least one of gold, silver, copper and tin nanoparticles.
The invention relates to a preparation method of a high-stability metal-modified boron-doped diamond electrode, which comprises the following steps:
step 1, planting seed crystals on the surface of a substrate, and depositing on the surface of the substrate by adopting a hot filament chemical vapor deposition method to obtain a first layer of boron-doped diamond film;
step 2, sputtering a metal layer of insoluble carbon on the first layer of boron-doped diamond film by using a physical magnetron sputtering method, wherein the metal of the metal layer is selected from at least one of gold, silver, copper and tin;
step 3, carrying out heat treatment on the sample covered with the metal layer prepared in the step 2 to spheroidize the metal layer into metal nano particles;
and 4, carrying out homoepitaxial growth on a second layer of boron-doped diamond film on the surface of the sample prepared in the step 3 by adopting a hot wire chemical vapor phase method, thus forming the high-stability metal modified boron-doped diamond electrode.
The invention relates to a preparation method of a high-stability metal modified boron-doped diamond electrode, which comprises the following steps of 1, placing a substrate in an acetone solution, carrying out ultrasonic cleaning for 5-20 minutes, then carrying out ultrasonic cleaning for 10-20 minutes in deionized water, and drying. Through the treatment, the oil stain on the surface of the substrate is removed, and the clean and dry substrate is obtained.
The invention relates to a preparation method of a high-stability metal-modified boron-doped diamond electrode, which comprises the following steps of 1, planting seed crystals: vertically suspending and immersing the substrate in the nano diamond powder suspension for ultrasonic oscillation for more than or equal to 30min, and finally cleaning and drying the substrate by using alcohol.
The invention relates to a preparation method of a high-stability metal-modified boron-doped diamond electrode, wherein in step 1, the deposition process parameters of a first layer of boron-doped diamond film are as follows: the number of the hot wire turns is 10-20, the distance between the hot wire and the substrate is 7-12cm, and the mass flow ratio of the introduced gas is B2H6:H2:CH40.4-0.6: 49: 1, the growth pressure is 2.5-5Kpa, and the growth temperature is 600-1000 ℃; the growth time is 3-12 h.
The invention relates to a preparation method of a high-stability metal-modified boron-doped diamond electrode, which comprises the following process steps in step 2: argon is introduced to adjust the air pressure to be 0.5-1Pa, the sputtering power is 50-150W, and the sputtering time is 10-30 s.
The invention relates to a preparation method of a high-stability metal-modified boron-doped diamond electrode, wherein in step 3, the technological parameters of heat treatment are as follows: the air pressure is maintained at 10-20kpa, the heat treatment temperature is 800-2:Ar＝＝1-1.5。
The invention relates to a preparation method of a high-stability metal modified boron-doped diamond electrode, wherein in step 4, the deposition process parameters of a second layer of boron-doped diamond film are as follows: the number of the hot wire turns is 10-20, the distance between the hot wire and the substrate is 7-12cm, and the mass flow ratio B of the introduced gas2H6:H2:CH40.4-0.6: 49: 1, cavity pressure is about 2.5-5 kilopascal, and growth temperature is 600-1000 ℃; the growth time is 3-12 h.
In the actual operation process, in the deposition process of the second layer of boron-doped diamond film, special attention needs to be paid, the growth time length is controlled according to the size of the metal nano particles, and the metal nano particles are ensured to be exposed out of the surface of the second layer of boron-doped diamond film.
Because of the low solid solubility of the selected metal and carbon, boron-doped diamond is less likely to form carbide layers on the surface of the metal particles. Therefore, the second layer of boron-doped diamond film can only grow on the first layer of boron-doped diamond film in a homoepitaxy manner, so that the bottoms of the metal particles and the first layer of boron-doped diamond film are firmly wrapped, and the effect of fixing the metal particles is achieved.
Preferably, the preparation method of the high-stability metal-modified boron-doped diamond electrode comprises the step of carrying out ultrasonic treatment on the high-stability metal-modified boron-doped diamond electrode obtained in the step 4 for 5-10 min.
In the actual operation process, the high-stability metal modified boron-doped diamond electrode can be packaged after being subjected to ultrasonic treatment for 5-10min, or the high-stability metal modified boron-doped diamond electrode can be packaged and then subjected to ultrasonic treatment for 5-10min, and then the high-stability metal modified boron-doped diamond electrode is applied.
After the high-stability metal modified boron-doped diamond electrode is subjected to ultrasonic treatment, the carbon layer covering the modified metal particles can be removed, and the electrode sensitivity is improved.
The invention relates to application of a high-stability metal-modified boron-doped diamond electrode, which is applied to a three-electrode detection sensor as a working electrode.
Advantageous effects
The invention provides a high-stability metal-modified boron-doped diamond electrode, wherein an electrode working layer comprises a first layer of boron-doped diamond film, a second layer of boron-doped diamond film grown on the surface of the first working layer, and metal nano-particles grown on the surface of the first working layer and embedded in the second layer of boron-doped diamond film. The special structure can realize the firm wrapping of the bottom of the metal particles and the electrode, thereby achieving the effect of fixing the metal particles and fully combining the excellent stability of the boron-doped diamond material and the good electrocatalytic activity of the metal.
Drawings
FIG. 1 is a schematic representation of a high stability metal modified boron doped diamond electrode; 1 is a silicon wafer, 2 is a first layer of boron-doped diamond film, 3 is a second layer of boron-doped diamond film, and 4 is modified metal nano-particles.
Detailed Description
Example 1
Step 1, placing a silicon wafer substrate in an acetone solution, ultrasonically cleaning for 15 minutes, then ultrasonically cleaning for 2 minutes in deionized water, and drying. Through the treatment, the oil stain on the surface of the substrate is removed, and the clean and dry substrate is obtained. Then suspending and immersing the clean and dry substrate in a nano diamond powder suspension for ultrasonic oscillation for 30min, finally cleaning and drying by alcohol to obtain a silicon wafer substrate with nano diamond particles adsorbed on the surface, then placing the silicon wafer substrate with the nano diamond particles adsorbed on the surface in a chemical vapor deposition method for hot wire chemical vapor deposition to obtain a first layer of boron-doped diamond film, wherein the number of turns of the hot wire is 12, the distance between the hot wire and the substrate is 10cm, and the mass flow ratio of introduced gas is B2H6:H2:CH40.4: 49: 1, the growth pressure is 3Kpa, and the growth temperature is 800 degrees; the growth time was 6 h.
Step 2, sputtering a layer of gold on the first layer of boron-doped diamond film by using a physical magnetron sputtering method; the process of the physical magnetron sputtering comprises the following steps: argon is introduced to adjust the air pressure to be 0.5Pa, the sputtering current to be 200mA, the sputtering power to be 50W and the sputtering time to be 10 s.
Step 3, the stepCarrying out heat treatment on the sample covered with the metal layer prepared in the step 2 to spheroidize the metal layer into nano particles; the technological parameters of the heat treatment are as follows: the pressure is maintained at 10kpa, the heat treatment temperature is 800 ℃, the heat treatment time is 2H, and H passes2The mass flow of (3) is 50sccm, and the mass flow of Ar introduced is 50 sccm.
Step 4, putting the sample covered with the gold nanoparticles in the step 3 into a chemical vapor deposition chamber for growing a second layer of boron-doped diamond film, wherein the number of turns of a hot wire is 12, the distance between the hot wire and a substrate is 10cm, and the mass flow ratio of introduced gas is B2H6:H2:CH40.4: 49: 1, the growth pressure is 3Kpa, and the growth temperature is 800 degrees; the growth time was 6 h. And packaging the prepared high-stability metal modified boron-doped diamond electrode.
And 5, putting the electrode packaged in the step 4 into an ultrasonic tank for ultrasonic cleaning for 5min, so that the carbon layer covered on the modified metal particles is separated, and the electrode sensitivity is improved. And then, a platinum sheet is used as a counter electrode, an Ag/AgCl electrode is used as a reference electrode, and the three-electrode detection sensor is assembled.
Electrochemical potential window up to 2.6V for glucose detection: has good linear response in the concentration range of 5uM to 32mM and the detection sensitivity as high as 1229.5 muA. mM-1·cm-2The limit of detection is as low as 2 μ M (S/N ═ 3). And (4) placing the electrode after detection into an ultrasonic pool, cleaning for 10 minutes, and then using the electrode for second glucose detection, wherein the detection signal is similar to that of the first detection.
Example 2
Step 1, placing a silicon wafer substrate in an acetone solution, ultrasonically cleaning for 15 minutes, then ultrasonically cleaning for 2 minutes in deionized water, and drying. Through the treatment, the oil stain on the surface of the substrate is removed, and the clean and dry substrate is obtained. Then suspending and immersing the clean and dry substrate in a nano diamond powder suspension for ultrasonic oscillation for 30min, finally cleaning and drying by alcohol to obtain a silicon wafer substrate with nano diamond particles adsorbed on the surface, then placing the silicon wafer substrate with the nano diamond particles adsorbed on the surface in a chemical vapor deposition method for hot wire chemical vapor deposition to obtain a first layer of boron-doped diamond film, and heating the wireThe number of turns is 12, the distance between the hot wire and the substrate is 10cm, and the mass flow ratio of the introduced gas is B2H6:H2:CH40.5: 49: 1, the growth pressure is 4Kpa, and the growth temperature is 800 ℃; the growth time is 8 h.
Step 2, sputtering a layer of copper physical magnetron sputtering on the first layer of boron-doped diamond film by using a physical magnetron sputtering method, wherein the process comprises the following steps: argon is introduced to adjust the air pressure to be 0.7Pa, the sputtering current to be 250mA, the sputtering power to be 100W and the sputtering time to be 20 s.
Step 3, carrying out heat treatment on the sample covered with the metal layer prepared in the step 2 to enable the copper metal layer to be spheroidized into nano particles; the technological parameters of the heat treatment are as follows: the pressure is maintained at 15kpa, the heat treatment temperature is 900 ℃, the heat treatment time is 3H, and H passes2The mass flow of (3) is 50sccm, and the mass flow of Ar introduced is 50 sccm.
Step 4, putting the sample covered with the copper nanoparticles in the step 3 into a chemical vapor deposition chamber for growing a second layer of boron-doped diamond film, wherein the number of turns of a hot wire is 12, the distance between the hot wire and a substrate is 10cm, and the mass flow ratio of introduced gas is B2H6:H2:CH40.5: 49: 1, the growth pressure is 3Kpa, and the growth temperature is 800 ℃; the growth time is 8 h. And packaging the prepared high-stability metal modified boron-doped diamond electrode.
And 5, putting the electrode packaged in the step 4 into an ultrasonic tank for ultrasonic cleaning for 5min, so that the carbon layer covered on the modified metal particles is separated, and the electrode sensitivity is improved. And then, a platinum sheet is used as a counter electrode, an Ag/AgCl electrode is used as a reference electrode, and the three-electrode detection sensor is assembled.
Then, a platinum sheet is taken as a counter electrode, an Ag/AgCl electrode is taken as a reference electrode, and the three-electrode detection sensor is assembled
Electrochemical potential window up to 2.5V for glucose detection: has good linear response in the concentration range of 5uM to 32mM and the detection sensitivity as high as 1452.5 muA. mM-1·cm-2The detection limit is as low as 3 mu M (S/N is 3), the electrode after detection is placed into an ultrasonic pool to be cleaned for 10 minutes and then is used for the second glucose detection, and the detection is carried outThe detection signal is similar to the first detection.
Example 3
Step 1, placing a silicon wafer substrate in an acetone solution, ultrasonically cleaning for 15 minutes, then ultrasonically cleaning for 2 minutes in deionized water, and drying. Through the treatment, the oil stain on the surface of the substrate is removed, and the clean and dry substrate is obtained. Then suspending and immersing the clean and dry substrate in a nano diamond powder suspension for ultrasonic oscillation for 30min, finally cleaning and drying by alcohol to obtain a silicon wafer substrate with nano diamond particles adsorbed on the surface, then placing the silicon wafer substrate with the nano diamond particles adsorbed on the surface in a chemical vapor deposition method for hot wire chemical vapor deposition to obtain a first layer of boron-doped diamond film, wherein the number of turns of the hot wire is 12, the distance between the hot wire and the substrate is 10cm, and the mass flow ratio of introduced gas is B2H6:H2:CH40.6: 49: 1, the growth pressure is 5Kpa, and the growth temperature is 1000 ℃; the growth time was 12 h.
Step 2, sputtering a layer of tin on the first layer of boron-doped diamond film by using a physical magnetron sputtering method; the process of the physical magnetron sputtering comprises the following steps: argon is introduced to adjust the air pressure to be 0.7Pa, the sputtering current to be 250mA, the sputtering power to be 100W and the sputtering time to be 20 s.
Step 3, carrying out heat treatment on the sample covered with the metal layer prepared in the step 2 to enable the tin metal layer to be spheroidized into nano particles; the technological parameters of the heat treatment are as follows: the pressure is maintained at 20kpa, the temperature of the heat treatment is 1000 ℃, the time of the heat treatment is 3H, and H passes2The mass flow of (3) is 50sccm, and the mass flow of Ar introduced is 50 sccm.
Step 4, putting the sample covered with the tin nano-particles in the step 3 into a chemical vapor deposition chamber for growing a second layer of boron-doped diamond film, wherein the number of turns of a hot wire is 12, the distance between the hot wire and a substrate is 10cm, and the mass flow ratio of introduced gas is B2H6:H2:CH40.6: 49: 1, the growth pressure is 5Kpa, and the growth temperature is 1000 ℃; the growth time was 12 h. And packaging the prepared high-stability metal modified boron-doped diamond electrode.
And 5, putting the electrode packaged in the step 4 into an ultrasonic tank for ultrasonic cleaning for 5min, so that the carbon layer covered on the modified metal particles is separated, and the electrode sensitivity is improved. And then, a platinum sheet is used as a counter electrode, an Ag/AgCl electrode is used as a reference electrode, and the three-electrode detection sensor is assembled.
Electrochemical potential window up to 2.7V for glucose detection: has good linear response in the concentration range of 5uM to 32mM and the detection sensitivity as high as 1325.5 muA. mM-1·cm-2And the detection limit is as low as 4 mu M (S/N is 3), the electrode after detection is placed into an ultrasonic pool to be cleaned for 10 minutes, the electrode after detection is placed into the ultrasonic pool to be cleaned for 10 minutes and then is used for second glucose detection, the detection signal is similar to that of the first detection, and the coverage degree of the metal particles on the surface of the electrode is observed to be not changed greatly under a microscope.
Comparative example 1
The other conditions were the same as in example 1, but a second boron-doped diamond film was not deposited.
Electrochemical potential window up to 2.7V for glucose detection: has good linear response in the concentration range of 5uM to 32mM and the detection sensitivity as high as 956.7 muA. mM-1·cm-2The limit of detection is as low as 3 μ M (S/N ═ 3). And (3) placing the electrode after detection into an ultrasonic pool, cleaning for 10 minutes, and then using the electrode for second glucose detection, wherein the detection signal is greatly weakened compared with the first detection signal. The metal particles on the surface of the electrode are greatly separated under the observation of a microscope.
Comparative example 2
The other conditions were the same as in example 1, except that ultrasonic cleaning of the surface carbon layer was not performed after encapsulation.
Electrochemical potential window up to 2.5V for glucose detection: has good linear response in the concentration range of 5uM to 32mM, and the detection sensitivity is reduced to 856.7 muA. multidot.mM-1·cm-2The limit of detection is as low as 4 μ M (S/N ═ 3). And (3) placing the electrode after detection into an ultrasonic pool, cleaning for 10 minutes, and then using the electrode for second glucose detection, wherein the detection signal is similar to that of the first detection, and the coverage degree of metal particles on the surface of the electrode is not greatly changed under the observation of a microscope.

Claims (10)

1. A high-stability metal-modified boron-doped diamond electrode is characterized in that: the electrode working layer comprises a first layer of boron-doped diamond film, a second layer of boron-doped diamond film growing on the surface of the first layer of boron-doped diamond film, and metal nano-particles growing on the surface of the first layer of boron-doped diamond film and embedded in the second layer of boron-doped diamond film.
2. The high stability metal modified boron doped diamond electrode of claim 1, wherein: the grain size of the metal nano-particles is larger than the thickness of the second layer of boron-doped diamond film.
3. The high stability metal modified boron doped diamond electrode of claim 1, wherein: the metal nano-particles are at least one selected from gold, silver, copper and tin nano-particles.
4. A method for preparing a high stability metal modified boron doped diamond electrode according to any one of claims 1 to 3, comprising the steps of:
step 1, planting seed crystals on the surface of a substrate, and depositing on the surface of the substrate by adopting a hot filament chemical vapor deposition method to obtain a first layer of boron-doped diamond film;
step 2, sputtering a metal layer of insoluble carbon on the first layer of boron-doped diamond film by using a physical magnetron sputtering method, wherein the metal of the metal layer is selected from at least one of gold, silver, copper and tin;
step 3, carrying out heat treatment on the sample covered with the metal layer prepared in the step 2 to spheroidize the metal layer into metal nano particles;
and 4, carrying out homoepitaxial growth on a second layer of boron-doped diamond film on the surface of the sample prepared in the step 3 by adopting a hot wire chemical vapor phase method, thus forming the high-stability metal modified boron-doped diamond electrode.
5. The method for preparing a high-stability metal-modified boron-doped diamond electrode according to claim 1, wherein the method comprises the following steps:
in the step 1, the process of planting seed crystals comprises the following steps: vertically suspending and immersing the substrate in the nano diamond powder suspension for ultrasonic oscillation for more than or equal to 30min, and finally cleaning and drying the substrate by using alcohol;
in the step 1, the deposition process parameters of the first layer of boron-doped diamond film are as follows: the number of the hot wire turns is 10-20, the distance between the hot wire and the substrate is 7-12cm, and the mass flow ratio of the introduced gas is B2H6:H2:CH40.4-0.6: 49: 1, the growth pressure is 2.5-5Kpa, and the growth temperature is 600-1000 ℃; the growth time is 3-12 h.
6. The method for preparing a high-stability metal-modified boron-doped diamond electrode according to claim 1, wherein the method comprises the following steps:
in the step 2, the process of the physical magnetron sputtering comprises the following steps: argon is introduced to adjust the air pressure to be 0.5-1Pa, the sputtering power is 50-150W, and the sputtering time is 10-30 s.
7. The method for preparing a high-stability metal-modified boron-doped diamond electrode according to claim 1, wherein the method comprises the following steps:
in step 3, the technological parameters of the heat treatment are as follows: the air pressure is maintained at 10-20kpa, the heat treatment temperature is 800-2:Ar＝＝1-1.5。
8. The method for preparing a high-stability metal-modified boron-doped diamond electrode according to claim 1, wherein the method comprises the following steps:
in step 4, the deposition process parameters of the second layer of boron-doped diamond film are as follows: the number of the hot wire turns is 10-20, the distance between the hot wire and the substrate is 7-12cm, and the mass flow ratio B of the introduced gas2H6:H2:CH40.4-0.6: 49: 1, cavity pressure is about 2.5-5 kilopascal, and growth temperature is 600-1000 ℃; the growth time is 3-12 h.
9. The method for preparing a high-stability metal-modified boron-doped diamond electrode according to claim 1, wherein the method comprises the following steps: and (4) carrying out ultrasonic treatment on the high-stability metal modified boron-doped diamond electrode obtained in the step (4) for 5-10 min.
10. Use of a high stability metal modified boron doped diamond electrode according to any one of claims 1 to 3, wherein: and applying the boron-doped diamond electrode as a working electrode to a three-electrode detection sensor.
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