CN116356279A - High specific surface area gold nanoparticle modified boron-doped diamond electrode and preparation method and application thereof - Google Patents

High specific surface area gold nanoparticle modified boron-doped diamond electrode and preparation method and application thereof Download PDF

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CN116356279A
CN116356279A CN202310266615.8A CN202310266615A CN116356279A CN 116356279 A CN116356279 A CN 116356279A CN 202310266615 A CN202310266615 A CN 202310266615A CN 116356279 A CN116356279 A CN 116356279A
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doped diamond
bdd
boron
film
surface area
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史丹
黄楠
刘鲁生
翟朝峰
杨兵
宋昊哲
姜辛
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Institute of Metal Research of CAS
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Abstract

The invention discloses a high specific surface area gold nanoparticle modified boron-doped diamond electrode and a preparation method and application thereof, and belongs to the technical field of diamond electrodes. The preparation method comprises the following steps: (1) Preparing a boron-doped diamond film by adopting a hot filament chemical vapor deposition method; (2) Performing reactive oxygen plasma etching on the boron-doped diamond film by adopting a reactive ion etching method to obtain a nano boron-doped diamond film with a nano grass morphology; (3) Depositing a layer of gold film on the surface of the nanometer boron-doped diamond film by adopting an electron beam evaporation technology; (4) And (3) annealing the composite film in an argon protective atmosphere to prepare the high specific surface area gold nanoparticle modified boron-doped diamond electrode. The method solves the problems of low specific surface area and insufficient electrochemical active sites of the traditional boron-doped diamond electrode by two means of reactive ion etching and gold nanoparticle modification, and can remarkably improve the electrochemical sensing performance of the electrode.

Description

High specific surface area gold nanoparticle modified boron-doped diamond electrode and preparation method and application thereof
Technical Field
The invention belongs to the technical field of diamond electrodes, and particularly relates to a high specific surface area gold nanoparticle modified boron-doped diamond electrode, and a preparation method and application thereof.
Background
The boron doped diamond thin film electrode (BDD) has many excellent electrochemical characteristics such as wide electrochemical window, low background current and excellent physicochemical stability due to its unique crystal structure, so that the BDD has excellent application prospect in the electrochemical sensing field.
However, the traditional BDD electrode has a low specific surface area, which causes the electrode surface to lack effective electrochemical active sites, so that the mass transfer efficiency of the electrode surface is limited, and the BDD electrode becomes a short plate in electrochemical sensing application. Gold nanoparticles (AuNPs) have electrochemical properties different from those of bulk materials in the electrochemical process, can effectively improve the electrochemical contact between the electrode surface and a solution, promote charge conduction between electrodes/interfaces, and enhance electrochemical response. Therefore, the AuNPs are loaded on the surface of the electrode, so that the electrochemical active site of the electrode can be significantly increased, which is very beneficial to BDD film electrodes lacking the electrochemical active site. Research shows that the BDD electrode surface loading AuNPs can significantly improve the electrochemical activity.
However, the specific surface area of the matrix carrying AuNPs has a significant effect on the electrochemical properties after modification. A large number of researches show that the application of carbon materials with high specific surface areas such as graphite, carbon nano tubes and graphene as a matrix for supporting AuNPs to electrochemical sensing achieves good effects. However, for the traditional BDD electrode, the specific surface area is not dominant due to the inherent structural characteristics, which restricts the exertion of electrochemical sensing performance of the BDD electrode after the BDD electrode is loaded with AuNPs.
In summary, increasing the specific surface area of the BDD electrode, and realizing controllable preparation of the supported AuNPs at the same time becomes a key point for further improving the electrochemical sensing performance of the AuNPs modified BDD electrode.
Disclosure of Invention
Aiming at the problems of insufficient specific surface area and low electrochemical active sites of the traditional BDD electrode, the invention aims to provide the high specific surface area gold nanoparticle modified boron-doped diamond electrode, the preparation method and the application thereof, and the prepared high specific surface area AuNPs particle modified BDD electrode has higher electrochemical sensing performance, excellent sensitivity and good reproducibility and long-term measurement stability.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
a method for preparing a high specific surface area gold nanoparticle (AuNPs) modified boron doped diamond electrode (BDD) electrode, comprising the following steps:
1. preparing a boron-doped diamond film:
and sequentially placing monocrystalline silicon into acetone, alcohol and deionized water, respectively ultrasonically cleaning for 10 minutes, blow-drying with nitrogen, and then placing monocrystalline silicon into the nano diamond suspension for ultrasonic treatment for 30 minutes, so as to perform crystal planting treatment. Taking out, then carrying out ultrasonic treatment in alcohol for 3 minutes, and then drying with nitrogen for standby.
Before the film is prepared, carbonizing the tantalum wire, wherein in the carbonizing process, the flow rate of hydrogen is 350-450 sccm, the flow rate of methane is 15-25 sccm, the gas flow rate ratio of methane to hydrogen is guaranteed to be 4-6%, the temperature of the tantalum wire is controlled to be 2200-2400 ℃, the air pressure is 2.5-3.5 kPa, and the carbonizing time is 1.5-2.5 hours.
After carbonization, cooling, placing the monocrystalline silicon substrate subjected to crystal planting treatment into a cavity of hot filament chemical vapor deposition equipment, taking hydrogen and methane as reaction gases, taking mixed gas containing trimethylborane as boron doping agent (namely boron source gas, wherein the volume ratio of TMB in the boron source gas is 0.5-1.5%), and the volume flow ratio of the hydrogen, the methane and the boron source gas in the step (1) is as follows: (750-850): (7-9): (8-10) to obtain a B/C atomic ratio of (0.01-0.015): 1.
In the hot filament chemical vapor deposition, the deposition power is 3-4 kW, the air pressure is 3-4 kPa, the substrate temperature is 800-850 ℃, the deposition time is 7-8 hours, and the BDD film is obtained on the surface of the substrate.
2. Reactive ion etching
And placing the prepared BDD film in a cavity of reactive ion etching equipment, introducing oxygen, and performing reactive oxygen plasma etching on the BDD film, wherein the power is 250-350W, the oxygen pressure is 15-25 Pa, the oxygen flow is 5-15 sccm, and the treatment time is 30-90 s, so that the nano BDD film (BDD-RIE) with the nano grass morphology is obtained.
3. Coating film
And (3) placing the nano BDD film (BDD-RIE) with the nano grass morphology into electron beam evaporation equipment, plating the gold film on the surface of the BDD film, wherein the evaporation current is 700-900 mA, and the deposition time is 100-300 s, so as to obtain the Au/BDD-RIE composite film.
4. Annealing
And (3) placing the Au/BDD-RIE composite film in a tube furnace, carrying out annealing treatment under Ar protective atmosphere, controlling Ar flow within a range of 50-150 sccm, annealing temperature within a range of 400-800 ℃ and annealing time within a range of 1-3 hours, and changing the Au film into Au nano particles (AuNPs) after treatment to obtain the AuNPs modified BDD-RIE electrode (AuNPs/BDD-RIE) with high specific surface area.
The invention has the beneficial effects that:
compared with the traditional BDD electrode, the method of combining reactive ion etching and AuNPs modification is adopted, and finally, the surface of the electrode is formed into a bell-shaped pit and gold nanoparticle embedded structure, the structure not only enables the specific surface area of the BDD electrode to be obviously improved, and overcomes the shortboards with low specific surface areas of the traditional BDD electrode, but also enables the modification of the AuNPs to obviously improve the electrochemical active sites of the BDD electrode, and effectively solves the problem of insufficient electrochemical active sites of the BDD electrode.
The high specific surface area AuNPs particle modified BDD electrode prepared by the invention has higher electrochemical sensing performance, the AuNPs/BDD-RIE electrode is used for testing the salinity of seawater, when the salinity is 40 per mill, the salinity current response of the AuNPs/BDD-RIE electrode is enhanced by 2.19 times compared with that of the traditional BDD electrode, the sensitivity is excellent, and the high-specific surface area AuNPs particle modified BDD electrode has good reproducibility and long-term measurement stability.
The invention provides a new way for improving the electrochemical sensing performance of the BDD electrode for the preparation method of the BDD electrode modified by the AuNPs particles with high specific surface area.
Drawings
FIG. 1 is a gold nanoparticle modified boron doped diamond (AuNPs/BDD-RIE) electrode prepared in example 1; wherein: (a) scanning electron microscopy images; (b) Raman spectrum, abscissa Raman shift (cm) -1 ) Representing wavenumber, and ordinate Intensity (a.u.) representing Intensity; (c) X-ray diffraction pattern, abscissa 2Theta (depth) represents diffraction angle, and ordinate Intensity (a.u.) represents Intensity; (d) Salinity Current response curve, abscissa Salinity (mill) represents Salinity, ordinate Current Density (mA cm) -2 ) Representing the current density.
FIG. 2 is a gold nanoparticle modified boron doped diamond (AuNPs/BDD-RIE) electrode prepared in example 2; wherein: (a) scanning electron microscopy images; (b) Raman spectrum, abscissa Raman shift (cm) -1 ) Representing wavenumber, and ordinate Intensity (a.u.) representing Intensity; (c) X-ray diffraction pattern, abscissa 2Theta (depth) represents diffraction angle, and ordinate Intensity (a.u.) represents Intensity; (d) Salinity Current response curve, abscissa Salinity (mill) represents Salinity, ordinate Current Density (mA cm) -2 ) Representing the current density.
FIG. 3 is a real viewThe gold nanoparticles prepared in example 3 modified boron doped diamond (AuNPs/BDD-RIE) electrodes; wherein: (a) scanning electron microscopy images; (b) Raman spectrum, abscissa Raman shift (cm) -1 ) Representing wavenumber, and ordinate Intensity (a.u.) representing Intensity; (c) X-ray diffraction pattern, abscissa 2Theta (depth) represents diffraction angle, and ordinate Intensity (a.u.) represents Intensity; (d) Salinity Current response curve, abscissa Salinity (mill) represents Salinity, ordinate Current Density (mA cm) -2 ) Representing the current density.
FIG. 4 is a view of a gold nanoparticle-modified boron doped diamond (AuNPs/BDD-RIE) electrode prepared in comparative example 1; wherein: (a) scanning electron microscopy images, (b) raman spectra, (c) X-ray diffraction images.
Detailed Description
In the specific implementation process, a monocrystalline silicon substrate is placed in hot wire chemical vapor deposition equipment, methane, hydrogen and boron source gas are introduced, a boron doped diamond film is prepared through hot wire chemical vapor deposition, then reactive oxygen plasma etching is carried out on the boron doped diamond film, the surface of the film is enabled to form a nano grass shape, then a layer of gold film is plated on the surface of the film with the nano grass shape through electron beam evaporation, and finally annealing is carried out under an argon protective atmosphere, so that the high specific surface area gold nanoparticle modified boron doped diamond electrode is prepared.
The present invention will be further illustrated with reference to the following examples, but the present invention is not limited to the following examples.
Example 1
Step 1: and sequentially placing monocrystalline silicon into acetone, alcohol and deionized water, respectively carrying out ultrasonic treatment for 10 minutes, blow-drying by using nitrogen, placing monocrystalline silicon into nano-diamond suspension (the nano-diamond content is 0.025 g/L) for ultrasonic treatment for 30 minutes, carrying out crystal planting treatment, taking out, then carrying out ultrasonic treatment for 3 minutes in alcohol, and blow-drying for later use.
Step 2: the tantalum wire is carbonized, the flow rate of hydrogen is 400sccm, the flow rate of methane is 20sccm, so that the gas volume flow rate ratio of methane and hydrogen is ensured to be 5%, the temperature of the tantalum wire is controlled to be 2200-2400 ℃, the air pressure is 3kPa, and the carbonization time is 2 hours.
Step 3: placing the monocrystalline silicon substrate subjected to the crystal planting treatment in a cavity of hot filament chemical vapor deposition equipment, controlling gas flow rates of hydrogen, methane and boron source gas (the boron source gas is mixed gas of trimethylborane and hydrogen according to the volume ratio of 1:99) to be 800sccm, 8sccm and 9sccm, controlling deposition power to be 3.3kW, air pressure to be 3.5kPa, and deposition time to be 7.5 hours, and controlling the substrate temperature to be about 820 ℃.
Step 4: and placing the prepared BDD film in a cavity of reactive ion etching equipment, introducing oxygen, and performing reactive oxygen plasma etching on the BDD film, wherein the power is 300W, the oxygen pressure is 20Pa, the oxygen flow is 10sccm, and the treatment time is 1min, so that the nano boron-doped diamond film (BDD-RIE) with the nano grass morphology is obtained.
Step 5: putting a nano boron-doped diamond film (BDD-RIE) with a nano grass morphology into electron beam evaporation equipment, depositing a layer of Au film on the surface of the nano boron-doped diamond film, wherein the evaporation current is 800mA, the deposition time is 200s, and preparing the Au film with the thickness of
Figure BDA0004133193660000051
Au/BDD-RIE composite film of (c).
Step 6: and (3) placing the Au/BDD-RIE composite film in a tube furnace, annealing the Au/BDD-RIE composite film in an Ar atmosphere, controlling the Ar flow to be 100sccm, setting the annealing temperature to be 800 ℃, and setting the annealing time to be 2 hours, wherein the Au film becomes AuNPs after the treatment, and obtaining the AuNPs modified boron-doped diamond film electrode (AuNPs/BDD-RIE) with high specific surface area.
As shown in FIG. 1, the SEM image, raman spectrum, X-ray diffraction pattern and salinity current response curve analysis of AuNPs/BDD-RIE electrode prepared under the conditions of this example were used to characterize the results. SEM images show that typical polycrystalline diamond crystal boundaries still exist, crystal planes show an inlaid structure of Stalactitum-shaped pits and gold nanoparticles, the pit diameter is about 20nm, and the AuNPs diameter is about 20nm, so that the prepared electrode has a high specific surface area due to the microstructure; raman spectra showed that the electrode maintained typical characteristics of a heavily doped BDD electrode, although non-diamond carbon peaks were present, according to I Diamond /I G Analysis, the purity of the diamond phase is higher; from XRD diffraction patternsCharacteristic peaks of diamond are observed, which shows that the preparation conditions have no influence on the phase structure of the BDD film, and the film has higher crystallization quality.
The AuNPs/BDD-RIE electrode prepared based on the technological conditions of the embodiment tests a salinity current curve in a standard seawater solution with the salinity range of 5-40 per mill, and the result shows that compared with the traditional BDD electrode, the salinity current response of the AuNPs/BDD-RIE electrode is remarkably improved, and when the salinity is 40 per mill, the salinity current response of the AuNPs/BDD-RIE electrode is enhanced by 2.19 times compared with that of the traditional BDD electrode.
Example 2
Step 1: and sequentially placing monocrystalline silicon into acetone, alcohol and deionized water, respectively carrying out ultrasonic treatment for 10 minutes, blow-drying by using nitrogen, placing monocrystalline silicon into nano-diamond suspension (the nano-diamond content is 0.025 g/L) for ultrasonic treatment for 30 minutes, carrying out crystal planting treatment, taking out, then carrying out ultrasonic treatment for 3 minutes in alcohol, and blow-drying for later use.
Step 2: the tantalum wire is carbonized, the flow rate of hydrogen is 400sccm, the flow rate of methane is 20sccm, so that the gas volume flow rate ratio of methane and hydrogen is ensured to be 5%, the temperature of the tantalum wire is controlled to be 2200-2400 ℃, the air pressure is 3kPa, and the carbonization time is 2 hours.
Step 3: placing the monocrystalline silicon substrate subjected to the crystal planting treatment in a cavity of hot filament chemical vapor deposition equipment, controlling gas flow rates of hydrogen, methane and boron source gas (the boron source gas is mixed gas of trimethylborane and hydrogen according to the volume ratio of 1:99) to be 800sccm, 8sccm and 9sccm, controlling deposition power to be 3.3kW, air pressure to be 3.5kPa, and deposition time to be 7.5 hours, and controlling the substrate temperature to be about 820 ℃.
Step 4: and placing the prepared BDD film in a cavity of reactive ion etching equipment, introducing oxygen, and performing reactive oxygen plasma etching on the BDD film, wherein the power is 300W, the oxygen pressure is 20Pa, the oxygen flow is 10sccm, and the treatment time is 1min, so that the nano boron-doped diamond film (BDD-RIE) with the nano grass morphology is obtained.
Step 5: putting a nano boron-doped diamond film (BDD-RIE) with a nano grass morphology into electron beam evaporation equipment, depositing a layer of Au film on the surface of the nano boron-doped diamond film, wherein the evaporation current is 800mA, and the deposition time is long200s, and the thickness of the prepared Au film is
Figure BDA0004133193660000061
Au/BDD-RIE composite film of (c).
Step 6: and (3) placing the Au/BDD-RIE composite film in a tube furnace, annealing the Au/BDD-RIE composite film in an Ar atmosphere, controlling the Ar flow to be 100sccm, setting the annealing temperature to be 600 ℃, and setting the annealing time to be 1h, wherein the Au film becomes AuNPs after the treatment, and obtaining the AuNPs modified boron-doped diamond film electrode (AuNPs/BDD-RIE) with high specific surface area.
As shown in FIG. 2, the SEM image, raman spectrum, X-ray diffraction pattern and salinity current response curve analysis of AuNPs/BDD-RIE electrode prepared under the conditions of this example were used to characterize the results. SEM images show that typical polycrystalline diamond grains are clearly visible, crystal faces show an inlaid structure of Stalactitum-shaped pits and gold nanoparticles, the pit diameter is about a few nanometers, and the AuNPs diameter is also about a few nanometers, so that the prepared electrode has a high specific surface area by virtue of the microstructure; raman spectra showed that the electrode maintained typical characteristics of a heavily doped BDD electrode, although non-diamond carbon peaks were present, according to I Diamond /I G The purity of the diamond phase is still higher after analysis; the characteristic peak of diamond can be observed from XRD diffraction pattern, which shows that the preparation condition has no influence on the phase structure of BDD film, and the diamond phase has high purity although the non-diamond phase exists in the electrode, so that the application of AuNPs/BDD-RIE electrode in the electrochemical sensing field is not influenced.
The AuNPs/BDD-RIE electrode prepared based on the technological conditions of the embodiment tests a salinity current curve in a standard seawater solution with the salinity range of 5-40 per mill, and the result shows that compared with the traditional BDD electrode, the salinity current response of the AuNPs/BDD-RIE electrode is remarkably improved, and when the salinity is 40 per mill, the salinity current response of the AuNPs/BDD-RIE electrode is enhanced by 1.61 times compared with that of the traditional BDD electrode.
Example 3
Step 1: and respectively carrying out ultrasonic treatment on monocrystalline silicon in acetone, alcohol and deionized water for 10 minutes, drying by using nitrogen, carrying out ultrasonic treatment on the monocrystalline silicon in nano-diamond suspension (the nano-diamond content is 0.025 g/L) for 30 minutes, carrying out crystal planting treatment, taking out the monocrystalline silicon, carrying out ultrasonic treatment in the alcohol for 3 minutes, and drying for later use.
Step 2: the tantalum wire is carbonized, the flow rate of hydrogen is 400sccm, the flow rate of methane is 20sccm, so that the gas volume flow rate ratio of methane and hydrogen is ensured to be 5%, the temperature of the tantalum wire is controlled to be 2200-2400 ℃, the air pressure is 3kPa, and the carbonization time is 2 hours.
Step 3: placing the monocrystalline silicon substrate subjected to the crystal planting treatment in a cavity of hot filament chemical vapor deposition equipment, controlling gas flow rates of hydrogen, methane and boron source gas (the boron source gas is mixed gas of trimethylborane and hydrogen according to the volume ratio of 1:99) to be 800sccm, 8sccm and 9sccm, depositing power to be 3.3kW, air pressure to be 3.5kPa, depositing time to be 7.5 hours, and controlling the substrate temperature to be about 820 ℃.
Step 4: and placing the prepared BDD film in a cavity of reactive ion etching equipment, introducing oxygen, and performing reactive oxygen plasma etching on the BDD film, wherein the power is 300W, the oxygen pressure is 20Pa, the oxygen flow is 10sccm, and the treatment time is 1min, so that the nano boron-doped diamond film (BDD-RIE) with the nano grass morphology is obtained.
Step 5: putting a nano boron-doped diamond film (BDD-RIE) with a nano grass morphology into electron beam evaporation equipment, depositing a layer of Au film on the surface of the nano boron-doped diamond film, wherein the evaporation current is 800mA, the deposition time is 100s, and preparing the Au film with the thickness of
Figure BDA0004133193660000071
Au/BDD-RIE composite film of (c).
Step 6: and (3) placing the Au/BDD-RIE composite film in a tube furnace, annealing the Au/BDD-RIE composite film in an Ar atmosphere, controlling the Ar flow to be 100sccm, setting the annealing temperature to be 800 ℃, and setting the annealing time to be 2 hours, wherein the Au film becomes AuNPs after the treatment, and obtaining the AuNPs modified boron-doped diamond film electrode (AuNPs/BDD-RIE) with high specific surface area.
As shown in FIG. 3, the analysis characterization results of SEM image, raman spectrum, X-ray diffraction pattern and salinity current response curve of AuNPs/BDD-RIE electrode prepared under the conditions of this example. SEM image display, classicalThe crystal face of the polycrystalline diamond presents a mosaic structure of Stalactitum-shaped pits and gold nanoparticles, the pit size is about 10nm, the AuNPs diameter is about 10nm, and the microstructure ensures that the prepared electrode has high specific surface area; raman spectra showed that the electrode maintained typical characteristics of a heavily doped BDD electrode, although non-diamond carbon peaks were present, according to I Diamond /I G Analysis, the purity of the diamond phase is higher; characteristic peaks of diamond can be observed from the XRD diffraction pattern, which shows that the preparation condition has no influence on the phase structure of the BDD film, the diamond phase maintains higher purity, and the film has higher crystallization quality.
The AuNPs/BDD-RIE electrode prepared based on the technological conditions of the embodiment tests a salinity current curve in a standard seawater solution with the salinity range of 5-40 per mill, and the result shows that compared with the traditional BDD electrode, the salinity current response of the AuNPs/BDD-RIE electrode is remarkably improved, and when the salinity is 40 per mill, the salinity current response of the AuNPs/BDD-RIE electrode is enhanced by 1.61 times compared with that of the traditional BDD electrode.
Comparative example 1
This comparative example was compared to example 2, and the annealing temperature was increased to 1000 ℃, all other procedures being identical. At this point the diamond grains disappeared, due to the excessive temperature, resulting in oxidation of the BDD film.
As shown in FIG. 4, the analysis of SEM images, raman spectra, X-ray diffraction patterns and salinity current response curves of AuNPs/BDD-RIE electrodes prepared using this condition characterizes the results. SEM images show that the polycrystalline diamond grains are no longer present, and the AuNPs diameter grows to about 50 nm; raman spectrum shows that the Si peak is extremely strong; the characteristic peaks of diamond were very weak observed from the XRD diffractogram, and the characterization result of SEM, raman, XRD revealed that most of the BDD film had been oxidized under the preparation conditions, which were not suitable for preparing AuNPs/BDD-RIE electrodes.
The results of the embodiment show that the AuNPs/BDD-RIE electrode prepared by the invention has the advantages of high specific surface area, abundant electrochemical active sites and extremely high electrochemical sensing performance.
The above embodiments are only preferred embodiments of the present invention, and any simple modification, equivalent variation and improvement made to the above embodiments according to the technical substance of the present invention still belongs to the protection scope of the technical solution of the present invention.

Claims (10)

1. A preparation method and application of a high specific surface area gold nanoparticle modified boron-doped diamond electrode are characterized in that: the method comprises the following steps:
(1) Hot Filament Chemical Vapor Deposition (HFCVD): putting the pretreated monocrystalline silicon substrate into hot wire chemical vapor deposition equipment, introducing hydrogen, methane and boron source gas, and preparing a boron-doped diamond film on the surface of the substrate through hot wire chemical vapor deposition;
(2) Reactive Ion Etching (RIE): placing the BDD film obtained in the step (1) into a chamber of a reactive ion etching device, introducing oxygen, and performing reactive ion etching on the BDD film to obtain a nano boron-doped diamond film (BDD-RIE) with a nano grass morphology;
(3) Coating: putting the nano boron-doped diamond film (BDD-RIE) obtained in the step (2) into electron beam evaporation equipment, plating a gold film on the surface of the BDD-RIE, wherein the evaporation current is 700-900 mA, and the deposition time is 100-300 s; preparing an Au/BDD-RIE composite film;
(4) Annealing: and (3) placing the Au/BDD-RIE composite film obtained in the step (3) into a tube furnace, and carrying out annealing treatment under the protection of argon gas, wherein the annealing temperature is 400-800 ℃, and the annealing time is 1-3 hours, so as to obtain the gold nanoparticle (AuNPs) modified boron-doped diamond electrode (AuNPs/BDD-RIE) with high specific surface area.
2. The method for preparing the high specific surface area gold nanoparticle modified boron doped diamond electrode according to claim 1, which is characterized in that: the pretreatment in the step (1) is as follows: and sequentially placing the monocrystalline silicon substrate in acetone, alcohol and deionized water for respectively carrying out ultrasonic cleaning for 10 minutes, placing the monocrystalline silicon substrate in nano-diamond suspension for ultrasonic treatment for 30 minutes after cleaning and drying, carrying out crystal planting treatment, and then carrying out ultrasonic treatment in alcohol for 3 minutes and drying for later use.
3. The method for preparing the high specific surface area gold nanoparticle modified boron doped diamond electrode according to claim 1, which is characterized in that: in the step (1), in the hot wire chemical vapor deposition, the deposition power is 3-4 kW, the air pressure is 3-4 kPa, the substrate temperature is 800-850 ℃, the deposition time is 7-8 hours, and the Boron Doped Diamond (BDD) film is obtained on the surface of the substrate.
4. The method for preparing the high specific surface area gold nanoparticle modified boron doped diamond electrode according to claim 1 or 3, wherein the method comprises the following steps: in the step (1), the boron source gas is mixed gas of Trimethylborane (TMB) and hydrogen, and the volume ratio of TMB in the boron source gas is 0.5-1.5%; the volume flow ratio of the hydrogen, methane and boron source gases introduced in the step (1) is as follows: (750-850): (7-9): (8-10) to obtain a B/C atomic ratio of (0.01-0.015): 1, a boron doped diamond film.
5. The method for preparing the high specific surface area gold nanoparticle modified boron doped diamond electrode according to claim 1, which is characterized in that: in the step (2) of reactive ion etching, the power is 250-350W, the air pressure is 15-25 Pa, the air flow is 5-15 sccm, and the treatment time is 30-90 s.
6. The method for preparing the high specific surface area gold nanoparticle modified boron doped diamond electrode according to claim 1, which is characterized in that: in the step (3), the target material is bulk gold with the purity of 99.999 percent, and the equipment pressure is less than 8.5x10 -5 Pa。
7. The method for preparing the high specific surface area gold nanoparticle modified boron doped diamond electrode according to claim 1, which is characterized in that: in the step (3), the thickness of the gold-plated film layer on the nanometer boron-doped diamond film with the nanometer grass shape is as follows
Figure FDA0004133193650000021
8. The method for preparing the high specific surface area gold nanoparticle modified boron doped diamond electrode according to claim 1, which is characterized in that: in the step (4), the flow rate of argon is controlled to be 50-150 sccm.
9. A high specific surface area gold nanoparticle modified boron doped diamond electrode (AuNPs/BDD-RIE) prepared using the method of any one of claims 1-8.
10. The use of the high specific surface area gold nanoparticle modified boron doped diamond electrode of claim 9, wherein: the high specific surface area gold nanoparticle modified boron doped diamond electrode (AuNPs/BDD-RIE) is applied to the field of electrochemical sensing.
CN202310266615.8A 2023-03-20 2023-03-20 High specific surface area gold nanoparticle modified boron-doped diamond electrode and preparation method and application thereof Pending CN116356279A (en)

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