WO2021228016A1 - 一种基于金属修饰多孔掺硼金刚石电极的非酶生物传感器及其制备方法和应用 - Google Patents

一种基于金属修饰多孔掺硼金刚石电极的非酶生物传感器及其制备方法和应用 Download PDF

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WO2021228016A1
WO2021228016A1 PCT/CN2021/092645 CN2021092645W WO2021228016A1 WO 2021228016 A1 WO2021228016 A1 WO 2021228016A1 CN 2021092645 W CN2021092645 W CN 2021092645W WO 2021228016 A1 WO2021228016 A1 WO 2021228016A1
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deposition
doped diamond
metal
nickel
nanoparticles
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PCT/CN2021/092645
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French (fr)
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魏秋平
马莉
周科朝
曾思超
朱睿童
杨万林
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中南大学
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Priority to US17/924,683 priority Critical patent/US20230184710A1/en
Publication of WO2021228016A1 publication Critical patent/WO2021228016A1/zh

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    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
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    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/26—Deposition of carbon only
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    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/34—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates
    • C23C28/343—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates with at least one DLC or an amorphous carbon based layer, the layer being doped or not
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    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25F—PROCESSES FOR THE ELECTROLYTIC REMOVAL OF MATERIALS FROM OBJECTS; APPARATUS THEREFOR
    • C25F5/00—Electrolytic stripping of metallic layers or coatings
    • G—PHYSICS
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    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
    • G01N27/28—Electrolytic cell components
    • G01N27/30—Electrodes, e.g. test electrodes; Half-cells
    • G01N27/327—Biochemical electrodes, e.g. electrical or mechanical details for in vitro measurements
    • G01N27/3275—Sensing specific biomolecules, e.g. nucleic acid strands, based on an electrode surface reaction
    • G01N27/3278—Sensing specific biomolecules, e.g. nucleic acid strands, based on an electrode surface reaction involving nanosized elements, e.g. nanogaps or nanoparticles
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    • G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
    • G01N33/48—Biological material, e.g. blood, urine; Haemocytometers
    • G01N33/483—Physical analysis of biological material
    • G01N33/487—Physical analysis of biological material of liquid biological material
    • G01N33/48707—Physical analysis of biological material of liquid biological material by electrical means
    • G01N33/48714—Physical analysis of biological material of liquid biological material by electrical means for determining substances foreign to the organism, e.g. drugs or heavy metals
    • G—PHYSICS
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    • G01N33/48—Biological material, e.g. blood, urine; Haemocytometers
    • G01N33/483—Physical analysis of biological material
    • G01N33/487—Physical analysis of biological material of liquid biological material
    • G01N33/48785—Electrical and electronic details of measuring devices for physical analysis of liquid biological material not specific to a particular test method, e.g. user interface or power supply
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
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    • B82Y40/00—Manufacture or treatment of nanostructures

Definitions

  • the invention relates to a non-enzyme biosensor based on a metal-modified porous boron-doped diamond electrode, and a preparation method and application thereof, belonging to the technical field of non-enzyme biosensor preparation.
  • Biosensor is a device or device that uses biologically active materials (enzymes, proteins, DNA, antibodies, antigens, biofilms, etc.) to organically combine with physical transducers. It is an advanced detection that is indispensable for the development of biotechnology. Methods and monitoring methods are also rapid and microanalysis methods at the molecular level of substances.
  • the structure (composition) of the biosensor includes two parts: 1. Bioactive materials (also called biosensitive membranes, molecular recognition elements). 2. Physical transducer (also called sensor).
  • this patent relates to the sensor part, whose function is to convert various biological, chemical and physical information into electrical signals. The information generated by the biological reaction process is diversified. The modern achievements of microelectronics and sensor technology provide a wealth of means for detecting this information, so that researchers have enough leeway in the choice of transducers when designing biosensors.
  • enzyme-based sensors are limited by the biochemical properties of enzymes, they are extremely susceptible to factors such as environmental pH, temperature, and humidity. During the preparation, packaging, transportation and storage of enzyme-based sensors, there will inevitably be the risk of exposure to thermal and chemical deformation. This brings quality control and production cost issues to the commercialization of enzyme-based sensors.
  • the degree of immobilization of enzyme-based sensors will greatly affect the performance of the sensor, although there are currently a variety of enzyme immobilization methods, including direct adsorption, sol-gel encapsulation, and cross-linking.
  • simple and reusable enzyme immobilization methods are still the biggest research difficulty at present.
  • the non-enzyme sensor is simple and controllable in the immobilization process, suitable for large-scale sound field, and has higher stability during use.
  • the catalytic activity of non-enzymatic sensors is different for different substances to be tested, and it is necessary to perform specific and precise control of the modified sensitive materials on the non-enzymatic sensors to obtain good selectivity and practical performance.
  • the first object of the present invention is to provide a non-enzymatic biosensor based on a metal modified porous boron-doped diamond electrode.
  • the second object of the present invention is to provide a method for preparing a non-enzymatic biosensor based on a metal modified porous boron-doped diamond electrode.
  • the third object of the present invention is to provide a non-enzymatic biosensor based on metal modified porous boron-doped diamond electrode.
  • the present invention is a non-enzymatic biosensor based on a metal-modified porous boron-doped diamond electrode.
  • the working electrode of the non-enzyme biosensor is a metal-modified porous boron-doped diamond electrode.
  • the metal-modified porous boron-doped diamond electrode includes a silicon wafer substrate.
  • the electrode working layer; the electrode working layer is arranged on the surface of the silicon wafer substrate, the electrode working layer is a porous boron-doped diamond layer modified with metal nanoparticles on the surface, and the pore surface of the porous boron-doped diamond layer contains sp 2 phases.
  • the chemical reaction rate can increase the detection sensitivity and linear range of the sensor.
  • it can increase the adhesion to the metal nanoparticles, and further improve the stability of the electrode.
  • the present invention is a non-enzyme biosensor based on a metal modified porous boron-doped diamond electrode.
  • the thickness of the porous boron-doped diamond layer is 5-20 ⁇ m
  • the crystal grain size is 5-20 ⁇ m
  • the (111) crystal plane is the exposed surface. Since the boron-doped diamond (111) crystal face is macroscopically pyramid-shaped, controlling the (111) crystal face as an exposed surface can have a larger specific surface area and higher intrinsic catalytic activity.
  • the present invention is a non-enzymatic biosensor based on a metal modified porous boron-doped diamond electrode, and the particle size of the metal nano particles is 20-30 nm.
  • the particle size of the metal nanoparticles is controlled to 20-30 nm, the electrode has the highest catalytic activity.
  • the present invention is a non-enzymatic biosensor based on a metal modified porous boron-doped diamond electrode.
  • the metal nanoparticles are selected from at least one of gold, platinum, nickel, and copper nanoparticles.
  • the present invention is a non-enzymatic biosensor based on a metal modified porous boron-doped diamond electrode.
  • the inventor found that when the metal nanoparticles are selected from gold and nickel, when gold:nickel 2:8, the resulting electrode has the highest catalytic activity.
  • the present invention is a non-enzymatic biosensor based on a metal-modified porous boron-doped diamond electrode.
  • the present invention is a non-enzymatic biosensor based on a metal-modified porous boron-doped diamond electrode.
  • the inventor found that when the metal nanoparticles are selected from nickel and copper, when nickel:copper 6:4, the resulting electrode has the highest catalytic activity.
  • the invention provides a method for preparing a non-enzyme biosensor based on a metal modified porous boron-doped diamond electrode, which comprises the following steps.
  • Step 1 Seed crystals are planted on the surface of the silicon wafer substrate first, and a boron-doped diamond film is deposited on the surface of the substrate by hot-wire chemical vapor deposition.
  • Step 2 Using magnetron sputtering to deposit a metal nickel layer on the surface of the boron-doped diamond film.
  • Step 3 Thermally etch the sample covered with the metallic nickel layer prepared in Step 2 to form nickel particles embedded in the boron-doped diamond film.
  • Step 4 The sample inlaid with nickel particles prepared in step 3 is subjected to anodic polarization treatment using an electrochemical workstation to remove metallic nickel on the surface of the sample to form a porous structure.
  • Step 5 Use an electrochemical workstation to deposit metal nanoparticles on the porous structure sample obtained in step 4 by electrodeposition to obtain a metal modified porous boron-doped diamond electrode.
  • Step 6 The metal modified porous boron-doped diamond electrode obtained in step 5 is used as a working electrode to assemble a non-enzyme biosensor.
  • the present invention is a method for preparing a non-enzyme biosensor based on a metal modified porous boron-doped diamond electrode.
  • the silicon wafer is a p-type heavily doped silicon wafer.
  • the present invention is a method for preparing a non-enzymatic biosensor based on a metal-modified porous boron-doped diamond electrode.
  • step 1 the process of planting a seed crystal is: immersing a substrate in a suspension containing nano-diamond and ultrasonic vibration for ⁇ 30 min, Finally, it is washed and dried.
  • the P-type heavily doped silicon wafer is first placed in an acetone solution for ultrasonic cleaning for 10 minutes to remove surface stains, and dried for later use.
  • the present invention is a method for preparing a non-enzymatic biosensor based on a metal-modified porous boron-doped diamond electrode.
  • the present invention is a method for preparing a non-enzymatic biosensor based on a metal-modified porous boron-doped diamond electrode.
  • the magnetron sputtering process is as follows: a nickel target with a purity of ⁇ 99.99% is used, and the distance between the substrate and the target is 10-12 cm, with an argon atmosphere, the deposition pressure is 0.5 ⁇ 0.05 Pa, the sputtering power is 50-150 W, the deposition time is 60 s, and the deposition thickness of the nickel layer is 5-50 nm.
  • the present invention is a method for preparing a non-enzymatic biosensor based on a metal-modified porous boron-doped diamond electrode.
  • step 3 the process of thermocatalytic etching is as follows: hydrogen is introduced for etching, and the mass flow rate of hydrogen is 40-100 SCCM.
  • the etching temperature is 600-1000°C
  • the etching pressure is controlled at 10-20KPa
  • the etching time is 100-300min.
  • the hydrogen in the tubular atmosphere annealing furnace reacts with the carbon atoms precipitated on the surface of the nickel particles at high temperatures to form hydrocarbon groups and leave the surface of the nickel particles to ensure the kinetic conditions for the nickel particles to etch the boron-doped diamond, and finally the nickel particles continue to deepen Inside the boron-doped diamond, a mosaic structure is formed, and sp 2 phase is generated at the interface between the nickel particles and the boron-doped diamond.
  • the present invention is a method for preparing a non-enzymatic biosensor based on a metal-modified porous boron-doped diamond electrode.
  • the anodic polarization process is as follows: firstly, the sample inlaid with nickel particles prepared in step 3 is insulated and sealed, Then put it under the three-electrode system and connect it with the electrochemical workstation, the anode polarization voltage is +2.0 ⁇ 0.1V, the polarization time is 150-180 s, and the electrolyte is 1.0 M sodium sulfate solution.
  • the nickel particles on the surface of the boron-doped diamond are removed by anodic polarization.
  • the boron-doped diamond exhibits a porous structure, and its specific surface area as a carrier is greatly increased.
  • the sp 2 phase generated at the interface can be retained and the interface charge transfer can be improved.
  • the present invention is a method for preparing a non-enzymatic biosensor based on a metal-modified porous boron-doped diamond electrode.
  • the electrodeposited metal nano-particles have a process: the deposition potential is -2.0V ⁇ -1.2V; and each cycle is deposited The time is 30 s-50 s, and the concentration of the deposition solution is 1 mM-10 mM.
  • the type and content of metals can be accurately controlled by changing the deposition time of different metals and the number of potential transition cycles, and the properties of different test objects can be targeted to achieve the performance control of the metal particles co-modified electrode.
  • the number of deposition cycles is 5; the gold nanoparticles are deposited first, the deposition potential is -1.0V, the deposition time of one cycle is 30 s, and the deposition solution is 1 mM Then, the deposition potential is -2.0V, the deposition time of one cycle is 50 s, and the deposition solution is 10 mM nickel nitrate solution.
  • the size of the gold-nickel composite nanoparticles is controlled to be 20-30 nm, and the gold-nickel content ratio is 2:8, and the best catalytic performance is obtained at this time.
  • the number of deposition cycles is 4; the gold nanoparticles are deposited first, and the deposition potential is -1.0 V, the deposition time of one cycle is 50 s, the deposition solution is 1 mM chloroauric acid solution, then platinum nanoparticles are deposited, the deposition potential of one cycle is -1.2V, the deposition time of one cycle is 50 s, and the deposition solution is 1 mM chlorine Platinum acid solution.
  • the size of the gold-platinum composite nanoparticles is controlled to be 25-30 nm, and the gold-platinum content ratio is about 2:8, and the best catalytic performance is obtained at this time.
  • the number of deposition cycles is 5, the nickel nanoparticles are deposited first, the deposition potential is -2.0V, the deposition time of one cycle is 50 s, and the deposition solution is 10 mM Nickel nitrate solution; during the deposition of copper nanoparticles, the deposition potential is -1.5 V, the deposition time of one cycle is 30 s, and the deposition solution is a 10 mM copper nitrate solution.
  • the size of the nickel-copper composite nanoparticles obtained under this process is 20-30 nm, and the nickel-copper content ratio is 6:4. At this time, the best catalytic performance is obtained.
  • the porous boron-doped diamond substrate has a large specific surface area, which can increase the load of metal nanoparticles.
  • the porous structure can ensure that the metal nanoparticles are anchored on the surface of the boron-doped diamond, and ultimately improve the sensitivity and stability of the electrode.
  • the present invention is a method for preparing a non-enzyme biosensor based on a metal-modified porous boron-doped diamond electrode.
  • the metal-modified porous boron-doped diamond obtained after step (5) is used as a working electrode, a platinum electrode is used as a counter electrode, and an Ag/AgCl electrode is used as The contrast electrode constitutes a non-enzymatic sensor.
  • the present invention is an application of a non-enzymatic biosensor based on a metal modified porous boron-doped diamond electrode.
  • the non-enzymatic biosensor is used to detect dopamine or glucose.
  • the non-enzymatic biosensor is used to detect glucose.
  • the present invention provides a non-enzymatic biosensor based on a metal-modified porous boron-doped diamond electrode.
  • the working electrode of the non-enzyme biosensor is a metal-modified porous boron-doped diamond electrode, and the electrode working layer is surface-modified with metal nanoparticles
  • the porous boron-doped diamond layer contains sp 2 phase on the surface of the pores of the porous boron-doped diamond layer.
  • the increase in the detection sensitivity and linear range of the sensor, on the other hand, can increase the adhesion to the metal nanoparticles, and further improve the stability of the electrode.
  • the preparation method provided by the present invention can realize the controllable removal of nickel particles by adopting anodic polarization treatment to form a porous structure while retaining the sp 2 phase generated at the interface.
  • the type and content of metals can be accurately controlled by changing the deposition time of different metals and the number of potential transition cycles, and the properties of different test objects can be targeted to achieve the performance control of the metal particle co-modified electrode. So as to obtain the best detection performance.
  • FIG. 1 is an unetched scanning (SEM) image of the diamond film in Example 1.
  • SEM unetched scanning
  • FIG. 2 is a scanning (SEM) image of the porous morphology of the diamond film etched in Example 1.
  • SEM scanning
  • Figure 3 is the CV detection curve of the obtained metal modified porous boron-doped diamond electrode modified with different proportions of gold and platinum in Comparative Example 2, where curve 1 is 1:9, curve 2 is 3:7, curve 4 is 1:1, curve 3 is 3:2.
  • FIG. 4 is a SEM image of the Ni nanoparticles modified with unetched diamond in Comparative Example 3.
  • FIG. 4 is a SEM image of the Ni nanoparticles modified with unetched diamond in Comparative Example 3.
  • Step 1 Preparation of boron-doped diamond film. First place the silicon wafer substrate in an acetone solution, ultrasonically clean for 5-20 minutes to remove surface oil stains; then ultrasonically clean in deionized water for 10-20 minutes, blow dry in a drying oven, and put it into a chemical vapor deposition chamber for mixing.
  • the number of turns of the hot wire during the growth process is 10-20 turns
  • the temperature of the hot wire is controlled at 2000-2500 °C
  • the surface temperature of the substrate is 700-900 °C
  • the gas ratio is methane/borane/hydrogen equal to 1/49/0.3
  • the cavity pressure is about 2.5-5 kPa
  • the grown diamond film has a grain size of 5-10 microns in diameter, and a film thickness in the range of 5-20 microns.
  • Step 2 Sputtering the nickel layer.
  • the method is to use physical magnetron sputtering equipment, use a high-purity nickel target with a purity of 99.99% under a pressure of 0.5-2 Pa, and sputter a layer of nickel film uniformly on the diamond film in step 1, with a sputtering power of 50- 150 watts, the thickness of the nickel layer is 5-50 nm.
  • Step 3 High temperature heat treatment and etching in a hydrogen environment.
  • the method is to put the sheet prepared in step 2 into a cold-wall heat treatment furnace, and pass hydrogen gas of 40-100 SCCM, and the etching temperature is controlled at 600-1000 °C, the etching pressure is controlled at 10-20 kPa, and the etching time is 100-300 minutes.
  • Step 4 Removal of nickel particles.
  • the method is to encapsulate the sample obtained in step 3 and place it in an electrochemical workstation for anodic polarization.
  • the anodic polarization voltage is +2.0 V
  • the polarization time is 180 s
  • the electrolyte is 1.0 M sodium sulfate solution.
  • Step 5 Co-modification of gold and nickel nanoparticles.
  • a square wave transition potential was used to deposit metal nanoparticles, and the number of deposition cycles was 5.
  • the deposition potential is -1.0 V
  • a deposition cycle time is 30 s
  • the deposition solution is 1 mM chloroauric acid solution
  • the deposition potential is -2.0 V
  • the deposition time of one cycle is 50 s
  • the deposition solution is 10 mM nickel nitrate solution.
  • the size of the gold-nickel composite nanoparticles obtained under this process is 20-30 nm, and the gold-nickel content ratio is about 2:8. At this time, the best catalytic performance is obtained.
  • Step 6 Preparation of the sensor.
  • the method is that after the electrode obtained in step 5 is packaged, the reference electrode and the counter electrode are used together with the packaged electrode to form a three-electrode detection sensor.
  • the three-electrode detection sensor obtained in Example 1 was used to detect the glucose concentration.
  • the sensitivity is 1586 ⁇ Acm -2 mM -1 , the linear range is 0.001-30 mM, and the detection limit is 0.0005 mM.
  • the 30-day cycle stability test only 7% of the response current was lost.
  • Step 1 Preparation of boron-doped diamond film.
  • the number of turns of the hot wire during the growth process is 15 turns, the temperature of the hot wire is controlled at 2250 °C, the surface temperature of the substrate is 800 °C, the gas ratio is methane/borane/hydrogen equal to 1/49/0.3, and the cavity pressure is about 3.0 thousand.
  • the size of the grown diamond film is 6-8 microns in diameter, and the film thickness is in the range of 10-15 microns.
  • Step 2 Sputtering the nickel layer.
  • the method is to use physical magnetron sputtering equipment, using a high-purity nickel target with a purity of 99.99% under a pressure of 1 Pa, sputter a layer of nickel film uniformly on the diamond film in step 1, with a sputtering power of 100 watts, and nickel Layer thickness in 20-40 nm.
  • Step 3 High temperature heat treatment and etching in a hydrogen environment.
  • the method is to put the sheet prepared in step 2 into a cold-wall heat treatment furnace, pass 60 SCCM of hydrogen, the etching temperature is controlled at 800°C, the etching pressure is controlled at 15 kPa, and the etching time is 200 minutes.
  • Step 4 Removal of nickel particles.
  • the method is to encapsulate the sample obtained in step 3 and place it in an electrochemical workstation for anodic polarization.
  • the anodic polarization voltage is +2.0 V
  • the polarization time is 180 s
  • the electrolyte is 1.0 M sodium sulfate solution.
  • Step 5 Co-modification of gold and platinum nanoparticles.
  • a square wave transition potential was used to deposit metal nanoparticles, and the number of deposition cycles was 4.
  • the deposition potential was -1.0 V
  • the deposition time was 50 s
  • the deposition solution was 1 mM chloroauric acid solution
  • the deposition potential was -1.2 V
  • the deposition time of one cycle is 50 s
  • the deposition solution is 1 mM chloroplatinic acid solution.
  • the gold-platinum composite nanoparticles obtained under this process have a size of 25-30 nm, and the gold-platinum content ratio is about 1:1. At this time, the best catalytic performance is obtained.
  • Step 6 Preparation of the sensor.
  • the method is that after the electrode obtained in step 5 is packaged, the reference electrode and the counter electrode are used together with the packaged electrode to form a three-electrode detection sensor for detecting the concentration of dopamine.
  • the sensitivity is 208 ⁇ Acm -2 mM -1 and the detection limit is 0.07 ⁇ M.
  • Step 1 Preparation of boron-doped diamond film.
  • the number of turns of the hot wire during the growth process is 15 turns, the temperature of the hot wire is controlled at 2250 °C, the surface temperature of the substrate is 800 °C, the gas ratio is methane/borane/hydrogen equal to 1/49/0.3, and the cavity pressure is about 3.0 thousand.
  • the size of the grown diamond film is 6-8 microns in diameter, and the film thickness is in the range of 10-15 microns.
  • Step 2 Sputtering the nickel layer.
  • the method is to use physical magnetron sputtering equipment, using a high-purity nickel target with a purity of 99.99% under a pressure of 1 Pa, sputter a layer of nickel film uniformly on the diamond film in step 1, with a sputtering power of 100 watts, and nickel Layer thickness in 20-40 nm.
  • Step 3 High temperature heat treatment and etching in a hydrogen environment.
  • the method is to put the sheet prepared in step 2 into a cold-wall heat treatment furnace, pass 60 SCCM of hydrogen, the etching temperature is controlled at 800°C, the etching pressure is controlled at 15 kPa, and the etching time is 200 minutes.
  • Step 4 Removal of nickel particles.
  • the method is to encapsulate the sample obtained in step 3 and place it in an electrochemical workstation for anodic polarization.
  • the anodic polarization voltage is +2.0 V
  • the polarization time is 180 s
  • the electrolyte is 1.0 M sodium sulfate solution.
  • Step 5 Co-modification of nickel and copper nanoparticles.
  • a square wave transition potential was used to deposit metal nanoparticles, and the number of deposition cycles was 5.
  • the deposition potential was -2.0 V
  • the deposition time was 50 s
  • the deposition solution was 10mM nickel nitrate solution
  • the deposition potential was -1.5 V
  • the deposition time of one cycle is 30 s
  • the deposition solution is 10 mM copper nitrate solution.
  • the size of the nickel-copper composite nanoparticles obtained under this process is 20-30 nm, and the nickel-copper content ratio is about 6:4. At this time, the best catalytic performance is obtained.
  • Step 6 Preparation of the sensor.
  • the method is that after the electrode obtained in step 5 is packaged, the reference electrode and the counter electrode are used together with the packaged electrode to form a three-electrode detection sensor.
  • the three-electrode detection sensor obtained in Example 3 was used to detect the glucose concentration.
  • the sensitivity is 1730 ⁇ Acm -2 mM -1
  • the linear range is 0.02-8.5 mM
  • the detection limit is 0.005 mM.
  • Example 2 The other conditions are the same as in Example 1, except that nitric acid is used to remove the nickel particles. As a result, the SP2 phase on the interface is removed, and then the result of Comparative Example 1 for detecting the glucose concentration is given.
  • the sensitivity of the electrode is only 566 ⁇ Acm -2 mM -1 , the linear range is 0.01- 3.87 mM, and the detection limit is 0.008 mM. In the 30-day stability test, the response current loss is more than 80%.
  • Example 2 The other conditions are the same as in Example 2.
  • the deposition time of one cycle is designed to be 5, 25, 50, 75s, and four electrical levels are obtained.
  • the Pt:Au content of each electrode is 1:9; 3:7; 1:1; 3:2.
  • 1:1 is the electrode of Example 2.
  • Example 3 The other conditions are the same as in Example 3, except that the metal nickel is not etched into a porous structure, and the results show (as shown in Figure 4), the metal nickel can be successfully etched, but during the application process, peeling occurs. Cause the electrode to be unstable.

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Abstract

本发明公开了一种基于金属修饰多孔掺硼金刚石电极的非酶生物传感器及其制备方法和应用。所述非酶生物传感器的工作电极为金属修饰多孔掺硼金刚石电极，所述金属修饰多孔掺硼金刚石电极包括硅片衬底、电极工作层；所述电极工作层设置于硅片衬底的表面，所述电极工作层为表面修饰有金属纳米颗粒的多孔掺硼金刚石层，所述多孔掺硼金刚石层的孔隙表面含有sp 2相。本发明结合化学气相沉积、磁控溅射，管式气氛退火炉和电化学工作站，实现了多金属修饰多孔掺硼金刚石复合材料电极的制备，电极具有高灵敏度和稳定性的特点，分辨率高，可以广泛应用于电化学生物传感器的构建以及重金属检测等领域

Description

一种基于金属修饰多孔掺硼金刚石电极的非酶生物传感器及其制备方法和应用 技术领域
本发明涉及一种基于金属修饰多孔掺硼金刚石电极的非酶生物传感器及其制备方法和应用，属于非酶生物传感器制备技术领域。
 背景技术
生物传感器(biosensor)是用生物活性材料(酶、蛋白质、DNA、抗体、抗原、生物膜等)与物理换能器有机结合的器械或装置，是发展生物技术必不可少的一种先进的检测方法与监控方法，也是物质分子水平的快速、微量分析方法。生物传感器的结构(组成)根据定义，包括两部分： 1、生物活性材料(也叫生物敏感膜、分子识别元件)。 2、物理换能器(也叫传感器)。其中本专利涉及是传感器部分，其作用是将各种生物的、化学的和物理的信息转变成电信号。生物反应过程产生的信息是多元化的，微电子和传感技术的现代成果为检测这些信息提供了丰富的手段，使得研究者在设计生物传感器时对换能器的选择有足够的回旋余地。
由于酶基传感器受限于酶生化特性，极易受到环境pH、温度和湿度等因素影响。在酶基传感器制备、包装、运输和储存环节，不可避免的会存在暴露在热变形和化学变形下的风险。从而给酶基传感器商业化带来质量控制和生产成本问题。此外，酶基传感器的固定化程度会极大影响传感器的使用性能，虽然目前已有多种酶固定化方法，包括直接吸附、溶胶凝胶包封、交联等。但对于酶基传感器固定化技术的大规模生产和商业化，简单、可重复使用的酶固定化方法仍然是目前最大的研究难点。非酶传感器相对于酶传感器，其固定化过程中简单可控，适合大规模化声场，在使用过程中具有较高的稳定性。但非酶传感器针对于不同的待检物质的催化活性不同，需要认为地对非酶传感器上修饰的敏感材料进行特定的精确化调控，以获得良好的选择性和实用性能。
 技术问题
针对现有技术的不足，本发明第一个目的在于提供一种基于金属修饰多孔掺硼金刚石电极的非酶生物传感器。
本发明的第二个目的在于提供一种基于金属修饰多孔掺硼金刚石电极的非酶生物传感器的制备方法。
本发明的第三个目的在于提供一种基于金属修饰多孔掺硼金刚石电极的非酶生物传感器的应用。
 技术解决方案
本发明一种基于金属修饰多孔掺硼金刚石电极的非酶生物传感器，所述非酶生物传感器的工作电极为金属修饰多孔掺硼金刚石电极，所述金属修饰多孔掺硼金刚石电极包括硅片衬底、电极工作层；所述电极工作层设置于硅片衬底的表面，所述电极工作层为表面修饰有金属纳米颗粒的多孔掺硼金刚石层，所述多孔掺硼金刚石层的孔隙表面含有sp 2相。
发明人发现，通过使多孔掺硼金刚石层的孔隙表面保留所产生的sp 2相，一方面可以有利于界面电阻的降低，改善界面电荷转移， 而更快的电荷转移速率意味着更高的电化学反应速率，因此可以使传感器检测灵敏度和线性范围的增加，另一方面可以增加与金属纳米颗粒的附着力，进一步提升电极的稳定性。
本发明一种基于金属修饰多孔掺硼金刚石电极的非酶生物传感器，所述多孔掺硼金刚石层厚度为5-20μm，晶粒大小为5-20 μm，（111）晶面为暴露面。由于掺硼金刚石（111）晶面宏观呈现为金字塔状，控制（111）晶面为暴露面可以具有更大的比表面积和更高的本征催化活性。
本发明一种基于金属修饰多孔掺硼金刚石电极的非酶生物传感器，所述金属纳米颗粒的粒径为20 -30 nm。当将金属纳米颗粒的粒径控制为20-30 nm时，所得电极催化活性最高。
本发明一种基于金属修饰多孔掺硼金刚石电极的非酶生物传感器，所述金属纳米颗粒选自金、铂、镍、铜纳米颗粒中的至少一种。
作为优选，本发明一种基于金属修饰多孔掺硼金刚石电极的非酶生物传感器，所述金属纳米颗粒选自金和镍；按原子比计，金：镍=2:8。发明人发现，当金属纳米颗粒选自金和镍时，金：镍=2:8时，所得电极催化活性最高。
作为优选，本发明一种基于金属修饰多孔掺硼金刚石电极的非酶生物传感器，所述金属纳米颗粒选自金和铂；按原子比计，金：铂=1:1。发明人发现，当金属纳米颗粒选自金和铂时，金：铂=1:1时，所得电极催化活性最高。
作为优选，本发明一种基于金属修饰多孔掺硼金刚石电极的非酶生物传感器，所述金属纳米颗粒选自镍和铜；按原子比计，镍：铜=6:4。发明人发现，当金属纳米颗粒选自镍和铜时，镍：铜=6:4时，所得电极催化活性最高。
本发明一种基于金属修饰多孔掺硼金刚石电极的非酶生物传感器的制备方法，包括如下步骤。
步骤1、先于硅片衬底表面种植籽晶，然而采用热丝化学气相沉积法在衬底表面沉积获得掺硼金刚石薄膜。
步骤2、采用磁控溅射法在掺硼金刚石薄膜表面沉积金属镍层。
步骤3、将步骤2制备的覆盖有金属镍层的样品进行热催化刻蚀形成镍颗粒镶嵌于掺硼金刚石薄膜。
步骤4、将步骤3制备的镶嵌镍颗粒的样品采用电化学工作站进行阳极极化处理，去除样品表面金属镍形成多孔结构。
步骤5、采用电化学工作站在步骤4得到的多孔结构样品上通过电沉积方式沉积金属纳米颗粒即得金属修饰多孔掺硼金刚石电极。
步骤6、将步骤5所得金属修饰多孔掺硼金刚石电极作为工作电极组装成非酶生物传感器。
本发明一种基于金属修饰多孔掺硼金刚石电极的非酶生物传感器的制备方法，步骤1中，所述硅片为p型重掺杂硅片。
本发明一种基于金属修饰多孔掺硼金刚石电极的非酶生物传感器的制备方法，步骤1中，种植籽晶的过程为：将衬底浸入含纳米金刚石的悬浊液中超声震荡≥30 min，最后用清洗、烘干。
在实际操作过程中，先将P型重掺杂硅片置于丙酮溶液中超声清洗10分钟以除去表面污渍，烘干备用。
本发明一种基于金属修饰多孔掺硼金刚石电极的非酶生物传感器的制备方法，步骤1中，热丝化学气相沉积法的工艺为：热丝匝数为10-20匝；热丝温度2000-2500℃，通入气体的质量流量比为氢气：甲烷：硼烷=49：1：0.3-0.6，优选为0.3，生长压力为2.5-5Kpa，生长温度为700-900℃；生长时间为6-12h。
本发明一种基于金属修饰多孔掺硼金刚石电极的非酶生物传感器的制备方法，步骤2中，所述磁控溅射的工艺为：采用纯度≥99.99%的镍靶，基底与靶材间距为10-12 cm，采取氩气气氛，沉积气压为0.5±0.05  Pa，溅射功率为50-150 W，沉积时间为60 s，获得镍层沉积厚度为5-50nm。
本发明一种基于金属修饰多孔掺硼金刚石电极的非酶生物传感器的制备方法，步骤3中，热催化刻蚀的工艺为：通入氢气进行刻蚀，氢气的质量流量为40-100SCCM，刻蚀温度为600-1000℃，刻蚀气压控制在10-20KPa，刻蚀时间为100-300min。
在上述热催化条件下，镍团聚成纳米颗粒，掺硼金刚石中的碳原子通过镍晶格中的缺陷，界面和表面发生短路扩散，从而不断在镍颗粒表面和界面析出。管式气氛退火炉中的氢气在高温下与镍颗粒表面析出的碳原子反应形成碳氢基团并离开镍颗粒表面，保证镍颗粒对掺硼金刚石刻蚀的动力学条件，最终镍颗粒不断深入掺硼金刚石内部，形成镶嵌结构，同时在镍颗粒与掺硼金刚石界面处产生sp 2相。
本发明一种基于金属修饰多孔掺硼金刚石电极的非酶生物传感器的制备方法，步骤4中，所述阳极极化的过程为：先将步骤3制备的镶嵌镍颗粒的样品，进行绝缘密封，再将其置于三电极体系下与电化学工作站连接，阳极极化电压+ 2.0±0.1V，极化时间为150-180 s，电解质为1.0 M的硫酸钠溶液。
通过阳极极化除去掺硼金刚石表面的镍颗粒，掺硼金刚石展现出多孔结构，其作为载体的比表面积极大增加，同时可以保留界面产生的sp 2相，改善界面电荷转移。
本发明一种基于金属修饰多孔掺硼金刚石电极的非酶生物传感器的制备方法，步骤5中，所述电沉积金属纳米颗粒有工艺为：沉积电位为-2.0V~-1.2V；每周期沉积时间为30 s-50 s，沉积溶液的浓度为1 mM-10 mM。
在本发明中，可以通过改变不同金属的沉积时间和电位跃迁周期数来精确控制金属的种类与含量，可以对于不同待检物的性质，针对性实现金属颗粒共修饰电极的性能调控。
作为优选，所述金属纳米颗粒选自金和镍纳米颗粒时，沉积周期数均为5；先沉积金纳米颗粒，沉积电位为-1.0V，一周期沉积时间为30 s，沉积溶液为1 mM的氯金酸溶液，然后沉积镍纳米颗粒，沉积电位为-2.0V，一周期沉积时间为50 s，沉积溶液为10 mM硝酸镍溶液。
通过上述工艺，控制金镍复合纳米颗粒尺寸为20 -30 nm，金镍含量比为2:8，此时获得最佳的催化性能。
作为优选，所述金属纳米颗粒选自金与铂纳米颗粒时，沉积周期数均为4；先沉积金纳米颗粒，沉积电位为-1.0 V，一周期沉积时间为50 s，沉积溶液为1 mM的氯金酸溶液，然后沉积铂纳米颗粒，一周期沉积电位为-1.2V，一周期沉积时间为50 s，沉积溶液为1 mM氯铂酸溶液。
通过上述工艺，控制金铂复合纳米颗粒尺寸为25-30nm，金铂含量比约为2:8，此时获得最佳的催化性能。
作为优选，所述金属纳米颗粒选自镍与铜纳米颗粒时，沉积周期数均为5，先沉积镍纳米颗粒，沉积电位为-2.0V，一周期沉积时间为50 s，沉积溶液为10mM 的硝酸镍溶液；在铜纳米颗粒沉积过程中，沉积电位为- 1.5 V，一周期沉积时间为30 s，沉积溶液为10 mM的硝酸铜溶液。
在此工艺下获得的镍铜复合纳米颗粒尺寸为20 -30 nm，镍铜含量比为6:4，此时获得最佳的催化性能。
多孔掺硼金刚石基底具有极大比表面积，可以提高金属纳米颗粒负载量，同时多孔结构能够保证金属纳米颗粒在掺硼金刚石表面被锚定，最终提升电极的灵敏度和稳定性。
本发明一种基于金属修饰多孔掺硼金刚石电极的非酶生物传感器的制备方法，将步骤（5）后获得的金属修饰多孔掺硼金刚石作为工作电极，铂电极作为对电极，Ag/AgCl电极作为对比电极构成非酶传感器。
本发明一种基于金属修饰多孔掺硼金刚石电极的非酶生物传感器的应用，将所述非酶生物传感器用于检测多巴胺或葡萄糖。优选的，将所述非酶生物传感器用于检测葡萄糖。
 有益效果
本发明提供了一种基于金属修饰多孔掺硼金刚石电极的非酶生物传感器，所述非酶生物传感器的工作电极为金属修饰多孔掺硼金刚石电极，所述电极工作层为表面修饰有金属纳米颗粒的多孔掺硼金刚石层，所述多孔掺硼金刚石层的孔隙表面含有sp 2相。发明人发现，通过使多孔掺硼金刚石层的孔隙表面保留所产生的sp 2相，一方面可以改善界面电荷转移，而更快的电荷转移速率意味着更高的电化学反应速率，因此可以使传感器检测灵敏度和线性范围的增加，另一方面可以增加与金属纳米颗粒的附着力，进一步提升电极的稳定性。
本发明提供的制备方法，通过采用阳极极化处理，可以可控的实现镍颗粒的去除，形成多孔结构，同时保留界面产生的sp 2相。另外在本发明中，可以通过改变不同金属的沉积时间和电位跃迁周期数来精确控制金属的种类与含量，可以对于不同待检物的性质，针对性实现金属颗粒共修饰电极的性能调控。从而获得最佳的检测性能。
附图说明
图1为实施例1中金刚石膜未刻蚀的扫描(SEM)图。
图2为实施例1中金刚石膜刻蚀完的多孔形貌扫描(SEM)图。
图3为对比例2中不同比例金铂修饰后的所得金属修饰多孔掺硼金刚石电极的CV检测曲线，其中曲线1为1:9，曲线2为3:7，曲线4为1:1，曲线3为3:2。
图4为对比例3中为未刻蚀金刚石修饰完Ni纳米颗粒的形貌扫描(SEM)图。
 本发明的实施方式
通过以下实施例进一步阐明本发明的实质性特点和显著进步,但本发明绝非仅局限于实施例。
实施例 1。
步骤1、掺硼金刚石膜的制备。首先将硅片衬底放置于丙酮溶液中,超声清洗5-20分钟,去除表面油渍；然后在去离子水中超声清洗10-20分钟,烘干炉中吹干后放入化学气相沉积室进行掺硼金刚石的生长,生长过程中的热丝匝数为10-20匝，热丝温度控制在2000-2500 ℃，基片表面温度为700-900 ℃，气体比例为甲烷/硼烷/氢气等于1/49/0.3，腔压约2.5-5千帕，生长的金刚石膜晶粒大小在5-10微米直径，膜厚范围为5-20微米。
步骤2、镍层溅射。方法为使用物理磁控溅射设备，在0.5-2帕的气压下，使用纯度为99.99%的高纯镍靶，在步骤1中的金刚石膜上均匀溅射一层镍膜，溅射功率为50-150瓦，镍层厚度在5-50 nm。
步骤3、氢环境下的高温热处理刻蚀。方法为，将步骤2中制备得的薄片放入冷壁热处理炉中，通入40-100SCCM的氢气，刻蚀温度控制在600-1000 ℃，刻蚀气压控制在10-20千帕，刻蚀时间为100-300分钟。
步骤4、镍颗粒去除。方法为，将步骤3获取的样品进行封装后，置于电化学工作站进行阳极极化，阳极极化电压+2.0 V，极化时间为180 s，电解质为1.0 M 硫酸钠溶液。
步骤5、金与镍纳米颗粒共修饰。采用方波跃迁电位沉积金属纳米颗粒，沉积周期数为5。在金纳米颗粒沉积过程中，沉积电位为- 1.0 V，一沉积周期时间为30 s，沉积溶液为1 mM氯金酸溶液；在镍纳米颗粒沉积过程中，沉积电位为- 2.0 V，一周期沉积时间为50 s，沉积溶液为10 mM硝酸镍溶液。在此工艺下获得的金镍复合纳米颗粒尺寸为20 -30 nm，金镍含量比约为2:8，此时获得最佳的催化性能。
步骤6、传感器制备。方法为，将步骤5获得的电极封装完后，使用参比电极和对电极与封装后的电极一起构成三电极检测传感器。
将实施例1所得三电极检测传感器用于用于检测葡萄糖浓度。灵敏度为1586 μAcm -2mM -1，线性范围0.001- 30 mM，检测限为0.0005 mM。30天的循环稳定性测试中，仅损失7 %的响应电流。
实施例 2。
步骤1、掺硼金刚石膜的制备。首先将硅片衬底放置于丙酮溶液中,超声清洗10分钟,去除表面油渍；然后在去离子水中超声清洗15分钟,烘干炉中吹干后放入化学气相沉积室进行掺硼金刚石的生长,生长过程中的热丝匝数为15匝，热丝温度控制在2250 ℃，基片表面温度为800 ℃，气体比例为甲烷/硼烷/氢气等于1/49/0.3，腔压约3.0千帕，生长的金刚石膜晶粒大小在6-8微米直径，膜厚范围为10-15微米。
步骤2、镍层溅射。方法为使用物理磁控溅射设备，在1帕的气压下，使用纯度为99.99%的高纯镍靶，在步骤1中的金刚石膜上均匀溅射一层镍膜，溅射功率为100瓦，镍层厚度在20-40 nm。
步骤3、氢环境下的高温热处理刻蚀。方法为，将步骤2中制备得的薄片放入冷壁热处理炉中，通入60 SCCM的氢气，刻蚀温度控制在800℃，刻蚀气压控制在15千帕，刻蚀时间为200分钟。
步骤4、镍颗粒去除。方法为，将步骤3获取的样品进行封装后，置于电化学工作站进行阳极极化，阳极极化电压+2.0 V，极化时间为180 s，电解质为1.0 M 硫酸钠溶液。
步骤5、金与铂纳米颗粒共修饰。采用方波跃迁电位沉积金属纳米颗粒，沉积周期数为4。在金纳米颗粒沉积过程中，沉积电位为- 1.0 V，沉积时间为50 s，沉积溶液为1 mM氯金酸溶液；在铂纳米颗粒沉积过程中，沉积电位为- 1.2 V，一周期沉积时间为50 s，沉积溶液为1mM氯铂酸溶液。在此工艺下获得的金铂复合纳米颗粒尺寸为25 -30 nm，金铂含量比约为1:1，此时获得最佳的催化性能。
步骤6、传感器制备。方法为，将步骤5获得的电极封装完后，使用参比电极和对电极与封装后的电极一起构成三电极检测传感器，用于检测多巴胺浓度。灵敏度为208 μAcm -2mM -1，检测限为0.07 μM。
实施例 3。
步骤1、掺硼金刚石膜的制备。首先将硅片衬底放置于丙酮溶液中,超声清洗10分钟,去除表面油渍；然后在去离子水中超声清洗15分钟,烘干炉中吹干后放入化学气相沉积室进行掺硼金刚石的生长,生长过程中的热丝匝数为15匝，热丝温度控制在2250 ℃，基片表面温度为800 ℃，气体比例为甲烷/硼烷/氢气等于1/49/0.3，腔压约3.0千帕，生长的金刚石膜晶粒大小在6-8微米直径，膜厚范围为10-15微米。
步骤2、镍层溅射。方法为使用物理磁控溅射设备，在1帕的气压下，使用纯度为99.99%的高纯镍靶，在步骤1中的金刚石膜上均匀溅射一层镍膜，溅射功率为100瓦，镍层厚度在20-40 nm。
步骤3、氢环境下的高温热处理刻蚀。方法为，将步骤2中制备得的薄片放入冷壁热处理炉中，通入60 SCCM的氢气，刻蚀温度控制在800℃，刻蚀气压控制在15千帕，刻蚀时间为200分钟。
步骤4、镍颗粒去除。方法为，将步骤3获取的样品进行封装后，置于电化学工作站进行阳极极化，阳极极化电压+2.0 V，极化时间为180 s，电解质为1.0 M 硫酸钠溶液。
步骤5、镍与铜纳米颗粒共修饰。采用方波跃迁电位沉积金属纳米颗粒，沉积周期数为5。在镍纳米颗粒沉积过程中，沉积电位为-2.0 V，沉积时间为50 s，沉积溶液为1 0mM 硝酸镍溶液；在铜纳米颗粒沉积过程中，沉积电位为- 1.5 V，一周期沉积时间为30 s，沉积溶液为10 mM硝酸铜溶液。在此工艺下获得的镍铜复合纳米颗粒尺寸为20 -30 nm，镍铜含量比约为6:4，此时获得最佳的催化性能。
步骤6、传感器制备。方法为，将步骤5获得的电极封装完后，使用参比电极和对电极与封装后的电极一起构成三电极检测传感器。
将实施例3所得三电极检测传感器用于检测葡萄糖浓度。灵敏度为1730 μAcm -2mM -1，线性范围0.02- 8.5 mM，检测限为0.005 mM. 30天的循环稳定性测试中，仅损失5 %的响应电流。
对比例1。
其他条件与实施例1相同，仅是采用硝酸去除镍颗粒，结果，界面上的SP2相被清除，然后给出对比例1用于检测葡萄糖浓度的结果。
该电极灵敏度仅为566 μAcm -2mM -1，线性范围0.01- 3.87 mM，检测限为0.008mM.其在30天内稳定性测试中，响应电流损失80 %以上。
对比例2。
其他条件与实施例2相同，通过固定Au沉积参数不变，改变Pt的沉积参数，其一个周期的沉积时间设计为5、25、50、75s，获得四个电级，通过元素分析，这四个电极的Pt:Au含量分别为1:9；3:7；1:1；3:2。其中1:1的即为实施例2的电极。
Pt:Au含量分别为1:9；3:7；1:1；3:2的4个电极在0.5 M NaOH与1 mM葡萄糖混合溶液中的CV检测曲线如图3所示，4个电级分别对应其中曲线1、2、4、3;扫描电位区间为0.2 - 0.6 V，扫描速率为50 mV s -1，从图中可以看出，曲线4，即Pt:Au含量为1:1时，所得BDD的催化活性最高。
对比例3。
其他条件与实施例3相同，仅是不进行刻蚀成多孔结构，即修蚀金属镍，结果显示（如图4所示），可以成功修蚀金属镍，但是在应用过程中，出现脱落，导致电极不稳定。

Claims (10)

  1. 一种基于金属修饰多孔掺硼金刚石电极的非酶生物传感器，其特征在于：所述非酶生物传感器的工作电极为金属修饰多孔掺硼金刚石电极，所述金属修饰多孔掺硼金刚石电极包括硅片衬底、电极工作层；所述电极工作层设置于硅片衬底的表面，所述电极工作层为表面修饰有金属纳米颗粒的多孔掺硼金刚石层，所述多孔掺硼金刚石层的孔隙表面含有sp 2相。
  2. 根据权利要求1所述的一种基于金属修饰多孔掺硼金刚石电极的非酶生物传感器，其特征在于：所述多孔掺硼金刚石层厚度为5-20μm，晶粒大小为5-20 μm，（111）晶面为暴露面。
  3. 根据权利要求1所述的一种基于金属修饰多孔掺硼金刚石电极的非酶生物传感器，其特征在于：所述金属纳米颗粒的粒径为20-30nm；所述金属纳米颗粒选自金、铂、镍、铜纳米颗粒中的至少一种。
  4. 根据权利要求3所述的一种基于金属修饰多孔掺硼金刚石电极的非酶生物传感器，其特征在于：所述金属纳米颗粒选自金和镍；按原子比计，金：镍=2:8；所述金属纳米颗粒选自金和铂；按原子比计，金：铂=1:1；所述金属纳米颗粒选自镍和铜；按原子比计，镍：铜=6:4。
  5. 根据权利要求1-4任意一项所述的一种基于金属修饰多孔掺硼金刚石电极的非酶生物传感器制备方法，其特征在于：包括如下步骤：
    步骤1、先于硅片衬底表面种植籽晶，然而采用热丝化学气相沉积法在衬底表面沉积获得掺硼金刚石薄膜；
    步骤2、采用磁控溅射法在掺硼金刚石薄膜表面沉积金属镍层；
    步骤3、将步骤2制备的覆盖有金属镍层的样品进行热催化刻蚀形成镍颗粒镶嵌于掺硼金刚石薄膜；
    步骤4、将步骤3制备的镶嵌镍颗粒的样品采用电化学工作站进行阳极极化处理，去除样品表面金属镍形成多孔结构，
    步骤5、采用电化学工作站在步骤4得到的多孔结构样品上通过电沉积方式沉积金属纳米颗粒即得金属修饰多孔掺硼金刚石电极；
    步骤6、将步骤5所得金属修饰多孔掺硼金刚石电极作为工作电极组装成非酶生物传感器。
  6. 根据权利要求5所述的一种基于金属修饰多孔掺硼金刚石电极的非酶生物传感器的制备方法，其特征在于：
    步骤1中，种植籽晶的过程为：将衬底浸入含纳米金刚石的悬浊液中超声震荡≥30 min，最后清洗、烘干。
    步骤1中，热丝化学气相沉积法的工艺为：热丝匝数为10-20匝；热丝温度为2000-2500℃，通入气体的质量流量比为氢气：甲烷：硼烷=49：1： 0.3 - 0.6；生长压力为2.5-5Kpa，生长温度为700-900℃；生长时间为6-12h。
  7. 根据权利要求5所述的一种基于金属修饰多孔掺硼金刚石电极的非酶生物传感器的制备方法，其特征在于：
    步骤2中，所述磁控溅射的工艺为：采用纯度≥99.99%的镍靶，基底与靶材间距为10-12 cm，采取氩气气氛，沉积气压为0.5±0.05 Pa，溅射功率为50-150 W，沉积时间为60 s，获得镍层沉积厚度为5-50nm；
    步骤3中，热催化刻蚀的工艺为：通入氢气进行刻蚀，氢气的质量流量为40-100 SCCM，刻蚀温度为600-1000 ℃，刻蚀气压控制在10-20KPa，刻蚀时间为100-300min。
  8. 根据权利要求5所述的一种基于金属修饰多孔掺硼金刚石电极的非酶生物传感器的制备方法，其特征在于：
    步骤4中，所述阳极极化的过程为：先将步骤3制备的镶嵌镍颗粒的样品，进行绝缘密封，再将其置于三电极体系下与电化学工作站连接，阳极极化电压+ 2.0±0.1V，极化时间为150- 180 s，电解质为1.0 M的硫酸钠溶液；
    步骤5中，所述电沉积金属纳米颗粒有工艺为：沉积电位为-2.0V~-1.2V；每周期沉积时间为30 s-50s，沉积溶液的浓度为1 mM-10 mM。
  9. 根据权利要求8所述的一种基于金属修饰多孔掺硼金刚石电极的非酶生物传感器的制备方法，其特征在于：
    所述金属纳米颗粒选自金和镍纳米颗粒时，沉积周期数均为5；先沉积金纳米颗粒，沉积电位为-1.0 V，一周期沉积时间为30 s，沉积溶液为1 mM的氯金酸溶液，然后沉积镍纳米颗粒，沉积电位为-2.0 V，一周期沉积时间为50 s，沉积溶液为10 mM硝酸镍溶液；
     
    所述金属纳米颗粒选自金与铂纳米颗粒时，沉积周期数均为4；先沉积金纳米颗粒，沉积电位为-1.0V，一周期沉积时间为50 s，沉积溶液为1mM的氯金酸溶液，然后沉积铂纳米颗粒，一周期沉积电位为-1.2 V，一周期沉积时间为50s，沉积溶液为1 mM氯铂酸溶液。
    所述金属纳米颗粒选自镍与铜纳米颗粒时，沉积周期数均为5，先沉积镍纳米颗粒，沉积电位为-2.0V，一周期沉积时间为50 s，沉积溶液为10mM 硝酸镍溶液；在铜纳米颗粒沉积过程中，沉积电位为-1.5V，一周期沉积时间为30s，沉积溶液为10 mM硝酸铜溶液。
  10. 根据权利要求1-4任意一项所述的一种基于金属修饰多孔掺硼金刚石电极的非酶生物传感器的应用，其特征在于：将所述非酶生物传感器用于检测多巴胺或葡萄糖。
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