CN107267953B - A kind of preparation method of carbon hollow ball and porous boron-doped diamond compound film sensor electrode - Google Patents

A kind of preparation method of carbon hollow ball and porous boron-doped diamond compound film sensor electrode Download PDF

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CN107267953B
CN107267953B CN201710350348.7A CN201710350348A CN107267953B CN 107267953 B CN107267953 B CN 107267953B CN 201710350348 A CN201710350348 A CN 201710350348A CN 107267953 B CN107267953 B CN 107267953B
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doped diamond
boron
hollow ball
porous
porous boron
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CN107267953A (en
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李明吉
王雪峰
李红姬
李翠平
孙大智
杨保和
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Tianjin University of Technology
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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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    • C23C16/271—Diamond only using hot filaments
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    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
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    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/14—Metallic material, boron or silicon
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    • C23C14/185—Metallic material, boron or silicon on other inorganic substrates by cathodic sputtering
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    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
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    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/34—Sputtering
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    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/58—After-treatment
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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
    • 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
    • C23C16/27—Diamond only
    • C23C16/278—Diamond only doping or introduction of a secondary phase in the diamond
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
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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
    • C23C16/56—After-treatment

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Abstract

A kind of preparation method of carbon hollow ball and porous boron-doped diamond compound film sensor electrode.Preparation step is as follows: 1) depositing boron-doped diamond film on tantalum piece using filament CVD, be passed through hydrogen, carbon source and boron source in chamber, open filament supply, biasing adjusts pressure and control temperature, time；2) nickel plating on boron-doped diamond film of rf magnetron sputtering instrument is used, argon gas is passed through to vacuum chamber, opens shielding power supply, adjust pressure and power；3) boron-doped diamond is performed etching using DC arc plasma jet CVD equipment, is passed through hydrogen and argon gas, opened magnetic field control power supply, adjust chamber pressure and pump pressure, control temperature and time, prepare porous boron-doped diamond；4) carbon hollow ball/porous boron-doped diamond compounded electrode is prepared using hydro-thermal method.Porous boron-doped diamond is put into beta-cyclodextrin and F-127 mixing suspension, hydro-thermal process is carried out, is freeze-dried after taking-up, annealing prepares combination electrode in Muffle furnace.

Description

A kind of preparation of carbon hollow ball and porous boron-doped diamond compound film sensor electrode Method
Technical field
The invention belongs to thin film electronic Material Field, a kind of electrochemical sensor electrodes and preparation method thereof, tool are disclosed Body is related to boron-doped diamond, the preparation and its application in electrochemical sensor of carbon hollow ball and compound.
Background technique
Electrochemical sensor because high sensitivity, fast response time, it is at low cost due to start to be widely applied to chemical industry, food and doctor In the every field such as treatment.The critical component of electrochemical sensor is sensor electrode, and moment sensor electrode there are the problem of It is that stability is poor due to the film-substrate cohesion of sensitive membrane and solid electrode is weak, response cannot be detected in height because potential window is narrow Substance at current potential and it can not achieve more substances while detecting, can not advanced optimize detection limit because background current is big and realize Constant detection.
For boron-doped diamond (Boron-doped diamond BDD) film as electrode material, it possesses corrosion resistance, width Potential windows, low background current and the conductivity close to conductor.Carbon hollow ball density is smaller, large specific surface area, stability are relatively good And hollow structure can be filled, have the characteristics that strong adsorptivity and catalytic action.Boron-doped diamond is hollow with carbon Ball is compound to be used as sensor electrode, and there is presently no relevant reports.
Summary of the invention
The purpose of the present invention is moment sensor there are aiming at the problem that, a kind of carbon hollow ball and porous boron-doping Buddha's warrior attendant are provided The preparation method of stone composite membrane sensor electrode, is realized while detection is various including ascorbic acid, dopamine and uric acid Substance, realizing reduces detection limit, improves the purpose of sensitivity.
Technical solution of the present invention
A kind of preparation method of carbon hollow ball and porous boron-doped diamond compound film sensor electrode, steps are as follows:
(1) boron-doped diamond film is deposited on tantalum piece using hot-wire chemical gas-phase deposition (CVD) method, wherein carbon source is first Alkane, boron source are trimethylborate, are substituted into after being dissolved with ethyl alcohol by hydrogen, and the flow of boron source, hydrogen and methane is respectively 6mL/ Min, 300mL/min and 6mL/min, react 35~39Torr of chamber pressure, 800 DEG C~1000 DEG C of base reservoir temperature, growth time 45 ~72h；
(2) sputter one layer of nickel particle on boron-doped diamond film using rf magnetron sputtering instrument, successively start primary pump with Two stage pump makes reaction chamber vacuum degree reach 10-4Pa, is passed through the argon gas that purity is 99.999%, and flow 15mL/min is adjusted and divided It is 1~2Pa that son pump, which keeps chamber pressure,.Radio frequency source is opened, 5~10min is preheated, regulation power is 120~150W, and sputtering time is 30~50s.
(3) DC arc plasma jet CVD equipment is used, it is multiple to the nickel and boron-doped diamond that are prepared in step (2) It closes film and carries out plasma etching, for sample apart from plasma spray 2~4cm of loophole, plasma atmosphere is the hydrogen of 1.5L/min With the argon gas of 1.5L/min, holding chamber presses 2800~3000Pa, is pumped 13000~13500Pa, starts adjustable magnetic field control voltage extremely 6V, arc voltage is 52V, arc current 95.6A after starting.700~800 DEG C of temperature, the time is 2~5min, is mixed thus to obtain porous Boron diamond film；
(4) mixing suspension of linear polymer and cyclic polymer is prepared.Linear polymer can use polyoxyethylene- Polyoxypropylene polyoxyethylene triblock copolymer (F127), cyclic polymer can use alpha-cyclodextrin or beta-cyclodextrin.
(5) porous boron-doped diamond obtained in step (3) is put into the linear polymer prepared in step (4) and ring-type 6~24 hours are stirred in the mix suspending solution of polymer；
(6) by porous boron-doped diamond obtained in step (5) and the mix suspending of linear polymer and cyclic polymer Liquid is transferred in counteracting tank and is sealed, 200 DEG C progress hydro-thermal process 6~12 hours, take out porous diamond after being down to room temperature Film is freeze-dried, and setting temperature is -53~-50 DEG C, pressure 10-15Pa, drying time 30-60min.
(7) carbon hollow ball/porous boron-doped diamond compound film prepared in step (6) is put into 450~550 in Muffle furnace DEG C carbonization 30min~60min to get carbon hollow ball and porous boron-doped diamond compound film.
(8) using carbon hollow ball/porous boron-doped diamond compound film as working electrode, platinized platinum is used as to electrode, is saturated sweet Mercury electrode constructs three-electrode system as reference electrode, in electrode insertion determinand related solution, connects electrochemical operation It stands, is -0.4 one 0.6V using differential pulse voltammetry setting potential range, current potential increment is 0.001 1 0.05V, amplitude setting For 0.01 1 0.05V, 0.005 1 0.025s are arranged in pulse width, 0.01 1 0.5s are arranged in the pulse period, to test electrode Electrochemical sensing performance.
The advantages of the present invention:
(1) preparation method of porous boron-doped diamond electrode is provided.
(2) the strong carbon hollow ball of binding force/porous diamond compound film electrode preparation method is provided.
(3) three kinds of substances such as Ascorbic Acid in Blood Serum, dopamine, uric acid can be quickly detected simultaneously.
(4) the detection range of linearity of sensor is wide, high sensitivity, and detection limit is low.
(5) reproducibility, repeatability, stability of sensor are good, and the service life is long.
Detailed description of the invention
Fig. 1 is boron-doped diamond electron scanning micrograph prepared by the present invention；
Fig. 2 is the electron scanning micrograph of porous boron-doped diamond prepared by the present invention；
Fig. 3 is carbon hollow ball prepared by the present invention/porous boron-doped diamond compound film electrode scanning electron microscope photograph Piece；
Fig. 4 be use it is prepared by the present invention by carbon hollow ball/porous boron-doped diamond compound film electrode as working electrode, it is full It is reference electrode with calomel electrode, platinized platinum is the three-electrode system constructed to electrode, in ascorbic acid, dopamine, uric acid mixing The differential pulse voltammetry curve (b) of the differential pulse voltammetry curve (a), uric acid that obtain in solution, work corresponding with uric acid are bent The relation curve (d) of line (c) and different pH value and peak current.
Specific embodiment
Implementation of the invention is described in detail with reference to the accompanying drawing.The present embodiment with the technical scheme is that Under the premise of implemented, give detailed embodiment and specific operating process, but protection scope of the present invention is not limited to Following embodiments.
Embodiment 1
Step 1 prepares boron-doped diamond using filament CVD, firstly, reaction chamber internal washing is clean, and hang up properly 6 18.5cm tantalum wire.Ultrapure water, acetone are successively used, dehydrated alcohol is cleaned by ultrasonic tantalum piece to metallic luster.With alcohol Buddha's warrior attendant Mountain flour suspension, and cleaned tantalum piece is put into bortz powder suspension, it is ultrasonically treated 2h.The tantalum piece handled well is put into Apart from tantalum wire 1cm on copper platform, chamber is closed.Mechanical pump is opened, reaction chamber pressure starts to be passed through methane and hydrogen to 5Pa or less, flow Amount is respectively 6mL/min and 300mL/min, and when air pressure rises to 16Torr, open filament electric current to 138A keeps 30min, and Make stable gas pressure in 37.7Torr, opens grid bias power supply, slowly reduce copper platform, increase bias, the electric current of biasing voltage source is 10A has and continues to drop copper platform after aura and be biased to 200V, and observes base reservoir temperature at 850 DEG C or more.Start to be passed through after 30min Boron source flow is 25mL/min, growth time 48h.
Step 2 sputters one layer of nickel particle using rf magnetron sputtering instrument on boron-doped diamond film.Wherein nickel target purity It is 99.99%, thickness 5mm, diameter 100mm, the distance between axis and specimen holder of target are 100mm.Successively starting primary pump And two stage pump, so that reaction chamber vacuum degree is reached 10-4Pa then passes to the argon gas that purity is 99.999%, flow 15mL/min Adjusting molecular pump and keeping pressure is 1Pa.Radio frequency source is opened, 5min, regulation power 150W are preheated, baffle is opened and carries out pre-sputtering 5min adjusts sample and target face, carries out formal sputtering, time 30s.
The boron-doped diamond of nickel plating is etched into porous knot using DC arc plasma jet CVD equipment by step 3 The boron-doped diamond of nickel plating is placed on the sample stage of DC arc plasma jet CVD equipment by structure, and it is high to adjust sample stage Degree, makes it apart from plasma jet mouth 3cm.It closes anti-room to start to vacuumize, presses and be pumped when display is -100 when chamber and lead to Inbound traffics are the hydrogen and argon gas of 1.500L/min.Holding chamber presses 3000Pa, is pumped 13000Pa, starts adjustable magnetic field control electricity Be depressed into 6V, after starting arc voltage be 52V, arc current 95.6A, 700 DEG C of base reservoir temperature, etch period 2.5min.
Step 4 dissolves the beta-cyclodextrin of 1.2g with 40mL ultrapure water and is stirred, with 40mL ultrapure water ultrasonic dissolution The suspension of 0.4g F-127 finishes to F-127 dissolution and is poured slowly into half in the beta-cyclodextrin solution into stirring, 30min Remaining F-127 solution is all poured into afterwards, porous boron-doped diamond is put into 12 hours of stirring in aaerosol solution.It will impregnate Porous boron-doped diamond and F127/ cyclodextrin suspension be transferred in counteracting tank and be sealed, make its 200 DEG C react 6 hours, It is down to after room temperature and takes out porous boron-doped diamond film and be freeze-dried, freeze-drying temperature control is in -50 DEG C, pressure 12Pa is then placed in Muffle furnace and is arranged 500 DEG C of temperature, starts timing and carry out carbonization 30min to mix to get carbon hollow ball/porous Boron diamond compound film.
Step 5 prepares the 0.1mol/L phosphate buffer solution that liquid pH value in bottom is 6~9, and ascorbic acid, dopamine, uric acid are dense Degree is respectively 600 μm of ol/L, 1 μm of ol/L, 8 μm of ol/L.It is detected using differential pulse voltammetry, current potential setting range -0.4~ 0.6V, current potential increment 0.004V, amplitude 0.05V, pulse width 0.05s, pulse period 0.5s.Curve obtained abscissa is peak electricity Position is qualitative index, and ordinate is that electric current is quantitative target.Pass through the big of the peak current that obtains under the more different pH value of Fig. 4 (d) It is small, it can determine the optimal ph 7 for being suitble to this example electrode.
Step 6, the mixed liquor that ascorbic acid, dopamine, uric acid are prepared with the phosphate buffer that pH value is 7, concentration difference For 600 μm of ol/L, 1 μm of ol/L, 8 μm of ol/L.It is tested using the differential pulse voltammetry that identical parameters in step 5 are arranged, Since response of the electrode to every kind of determinand is different, it may appear that the peak of three kinds of different potentials.From simultaneously detection curve Fig. 4 a it is found that Ascorbic acid, dopamine, uric acid spike potential be followed successively by -0.088V, 0.136V, 0.28V.It is set using identical parameters in step 5 The differential pulse voltammetry set carries out the uric acid solution of test various concentration and titer obtains relation curve such as Fig. 4 b, the line of fitting Property regression equation be IUA(A)=1.22333E-7+0.13303 [UA] (mol/L) (Fig. 4 c), sensitivity 10-7A, detection limit can Reach 0.2 μM.Similarly, one group of standard solution for preparing other analysis species, can get equation of linear regression, sensitivity and detection Limit.
Embodiment 2
Step 1 prepares boron-doped diamond using filament CVD, firstly, reaction chamber internal washing is clean, and hang up properly 6 18.5cm tantalum wire.Ultrapure water, acetone are successively used, dehydrated alcohol is cleaned by ultrasonic tantalum piece to metallic luster.With alcohol Buddha's warrior attendant Mountain flour suspension, and cleaned tantalum piece is put into bortz powder suspension, it is ultrasonically treated 2h.The tantalum piece handled well is put into Apart from tantalum wire 1cm on copper platform, chamber is closed.Mechanical pump is opened, reaction chamber pressure starts to be passed through methane and hydrogen to 5Pa or less, flow Amount is respectively 6mL/min and 300mL/min, and when air pressure rises to 16Torr, open filament electric current to 138A keeps 30min, and Making stable gas pressure in 37Torr, open grid bias power supply, slowly reduce copper platform, increases bias, the electric current of biasing voltage source is 10A, Have and continue to drop copper platform after aura and be biased to 200V, and observes base reservoir temperature at 900 DEG C.Start to be passed through boron source flow after 30min For 25mL/min, growth time 45h.
Step 2 sputters one layer of nickel particle using rf magnetron sputtering instrument on boron-doped diamond film.Wherein nickel target purity It is 99.99%, thickness 5mm, diameter 100mm, the distance between axis and specimen holder of target are 100mm.Successively starting primary pump And two stage pump, so that reaction chamber vacuum degree is reached 10-4Pa then passes to the argon gas that purity is 99.999%, flow 15mL/min Adjusting molecular pump and keeping pressure is 1.5Pa.Radio frequency source is opened, 5min, regulation power 100W are preheated, baffle is opened and carries out pre-sputtering 5min adjusts sample and target face, carries out formal sputtering, time 40s.
The boron-doped diamond of nickel plating is etched into porous knot using DC arc plasma jet CVD equipment by step 3 The boron-doped diamond of nickel plating is placed on the sample stage of DC arc plasma jet CVD equipment by structure, and it is high to adjust sample stage Degree, makes it apart from plasma jet mouth 3cm.It closes anti-room to start to vacuumize, presses and be pumped when display is -100 when chamber and lead to Inbound traffics are the hydrogen and argon gas of 1.500L/min.Holding chamber presses 2800Pa, is pumped 13200Pa, starts adjustable magnetic field control electricity Be depressed into 6V, after starting arc voltage be 52V, arc current 95.6A, 800 DEG C of base reservoir temperature, etch period 2min.
Step 4 dissolves the beta-cyclodextrin of 1.2g with 40mL ultrapure water and is stirred, with 40mL ultrapure water ultrasonic dissolution The suspension of 0.4g F-127 finishes to F-127 dissolution and is poured slowly into half in the beta-cyclodextrin solution into stirring, 30min Remaining F-127 solution is all poured into afterwards, porous boron-doped diamond is put into 6 hours of stirring in aaerosol solution.It will impregnate Porous boron-doped diamond and F127/ cyclodextrin suspension be transferred in counteracting tank and be sealed, make its 200 DEG C react 6 hours, It is down to after room temperature and takes out porous boron-doped diamond film and be freeze-dried, freeze-drying temperature control is in -50 DEG C, pressure 10Pa is then placed in Muffle furnace and is arranged 450 DEG C of temperature, starts timing and carry out carbonization 40min to mix to get carbon hollow ball/porous Boron diamond compound film.
Step 5 prepares the 0.1mol/L phosphate buffer solution that liquid pH value in bottom is 6~9, and ascorbic acid, dopamine, uric acid are dense Degree is respectively 600 μm of ol/L, 1 μm of ol/L, 8 μm of ol/L.It is detected using differential pulse voltammetry, current potential setting range -0.3~ 0.5V, current potential increment 0.002V, amplitude 0.03V, pulse width 0.04s, pulse period 0.5s.Curve obtained abscissa is peak electricity Position is qualitative index, and ordinate is that electric current is quantitative target.It, can be with by comparing the size of the peak current obtained under different pH value It determines and the optimal ph of this example electrode is suitble to be 7.
Step 6, the mixed liquor that ascorbic acid, dopamine, uric acid are prepared with the phosphate buffer that pH value is 7, concentration difference For 600 μm of ol/L, 1 μm of ol/L, 8 μm of ol/L.It is tested using the differential pulse voltammetry that identical parameters in step 5 are arranged, Since response of the electrode to every kind of determinand is different, it may appear that the peak of three kinds of different potentials, while detecting ascorbic acid, DOPA Amine, uric acid spike potential be followed successively by -0.090V, 0.132V, 0.278V.The differential pulse being arranged using identical parameters in step 5 Voltammetry tests the uric acid solution of various concentration, and the equation of linear regression of fitting is IUA(A)=1.34376E-7+0.15403 [UA] (mol/L), sensitivity 10-7A, detection limit can reach 0.3 μM.
Embodiment 3
Step 1 prepares boron-doped diamond using filament CVD, firstly, reaction chamber internal washing is clean, and hang up properly 6 18.5cm tantalum wire.Ultrapure water, acetone are successively used, dehydrated alcohol is cleaned by ultrasonic tantalum piece to metallic luster.With alcohol Buddha's warrior attendant Mountain flour suspension, and cleaned tantalum piece is put into bortz powder suspension, it is ultrasonically treated 2h.The tantalum piece handled well is put into Apart from tantalum wire 1cm on copper platform, chamber is closed.Mechanical pump is opened, reaction chamber pressure starts to be passed through methane and hydrogen to 5Pa or less, flow Amount is respectively 6mL/min and 300mL/min, and when air pressure rises to 16Torr, open filament electric current to 138A keeps 30min, and Making stable gas pressure in 39Torr, open grid bias power supply, slowly reduce copper platform, increases bias, the electric current of biasing voltage source is 10A, Have and continue to drop copper platform after aura and be biased to 200V, and observes base reservoir temperature at 950 DEG C or more.Start to be passed through boron source after 30min Flow is 25mL/min, growth time 72h.
Step 2 sputters one layer of nickel particle using rf magnetron sputtering instrument on boron-doped diamond film.Wherein nickel target purity It is 99.99%, thickness 5mm, diameter 100mm, the distance between axis and specimen holder of target are 100mm.Successively starting primary pump And two stage pump, so that reaction chamber vacuum degree is reached 10-4Pa then passes to the argon gas that purity is 99.999%, flow 15mL/min Adjusting molecular pump and keeping pressure is 2Pa.Radio frequency source is opened, 5min, regulation power 100W are preheated, baffle is opened and carries out pre-sputtering 5min adjusts sample and target face, carries out formal sputtering, time 50s.
The boron-doped diamond of nickel plating is etched into porous knot using DC arc plasma jet CVD equipment by step 3 The boron-doped diamond of nickel plating is placed on the sample stage of DC arc plasma jet CVD equipment by structure, and it is high to adjust sample stage Degree, makes it apart from plasma jet mouth 3cm.It closes anti-room to start to vacuumize, presses and be pumped when display is -100 when chamber and lead to Inbound traffics are the hydrogen and argon gas of 1.500L/min.Holding chamber presses 2700Pa, is pumped 12700Pa, starts adjustable magnetic field control electricity Be depressed into 6V, after starting arc voltage be 52V, arc current 95.6A, 700 DEG C of base reservoir temperature, etch period 4min.
Step 4 dissolves the beta-cyclodextrin of 1.2g with 40mL ultrapure water and is stirred, with 40mL ultrapure water ultrasonic dissolution The suspension of 0.4g F-127 finishes to F-127 dissolution and is poured slowly into half in the beta-cyclodextrin solution into stirring, 30min Remaining F-127 solution is all poured into afterwards, porous boron-doped diamond is put into 24 hours of stirring in aaerosol solution.It will impregnate Porous boron-doped diamond and F127/ cyclodextrin suspension be transferred in counteracting tank and be sealed, make its 200 DEG C react 8 hours, It is down to after room temperature and takes out porous boron-doped diamond film and be freeze-dried, freeze-drying temperature control is in -52 DEG C, pressure 15Pa is then placed in Muffle furnace and is arranged 550 DEG C of temperature, starts timing and carry out carbonization 30min to mix to get carbon hollow ball/porous Boron diamond compound film.
Step 5 prepares the 0.1mol/L phosphate buffer solution that liquid pH value in bottom is 6~9, and ascorbic acid, dopamine, uric acid are dense Degree is respectively 600 μm of ol/L, 1 μm of ol/L, 8 μm of ol/L.It is detected using differential pulse voltammetry, current potential setting range -0.4~ 0.5V, current potential increment 0.001V, amplitude 0.02V, pulse width 0.04s, pulse period 0.4s.Curve obtained abscissa is peak electricity Position is qualitative index, and ordinate is that electric current is quantitative target.It, can be with by comparing the size of the peak current obtained under different pH value Determine the optimal ph 7 for being suitble to this example electrode.
Step 6, the mixed liquor that ascorbic acid, dopamine, uric acid are prepared with the phosphate buffer that pH value is 7, concentration difference For 600 μm of ol/L, 1 μm of ol/L, 8 μm of ol/L.It is tested using the differential pulse voltammetry that identical parameters in step 5 are arranged, Since response of the electrode to every kind of determinand is different, it may appear that the peak of three kinds of different potentials, while detecting ascorbic acid, DOPA Amine, uric acid spike potential be followed successively by -0.089V, 0.142V, 0.267V.The differential pulse being arranged using identical parameters in step 5 Voltammetry carries out the uric acid solution of test various concentration, and the equation of linear regression of fitting is IUA(A)=1.42356E-7+ 0.16472 [UA] (mol/L), sensitivity 10-7A, detection limit can reach 0.4 μM.

Claims (5)

1. the preparation method of a kind of carbon hollow ball and porous boron-doped diamond compound film sensor electrode, it is characterised in that using heat Wire chemical vapor deposition (HFCVD) method, rf magnetron sputtering instrument and DC arc plasma jet CVD equipment, steps are as follows:
(1) boron-doped diamond film is deposited on tantalum piece using hot-wire chemical gas-phase deposition (HFCVD) method, wherein carbon source is methane, Boron source is trimethylborate, is substituted by hydrogen, the flow of boron source, hydrogen and methane be respectively 6mL/min, 300mL/min and 6mL/min reacts 35~39Torr of chamber pressure, 48~72h of growth time；
(2) one layer of nickel particle is sputtered on boron-doped diamond film using rf magnetron sputtering instrument, successively start primary pump and second level Pump, makes reaction chamber vacuum degree reach 10-4Pa is passed through argon gas, and adjusting molecular pump and keeping chamber pressure is 1~2dPa；Radio frequency source is opened, 5~10min is preheated, regulation power is 120~150W；
(3) DC arc plasma jet CVD equipment is used, the nickel and boron-doped diamond film that prepare in step (2) are carried out Plasma etching, plasma gas are hydrogen and argon gas, and holding chamber presses 2800~3000Pa, are pumped 13000~13500Pa, Start adjustable magnetic field and control voltage to 6V, arc voltage is 52V, arc current 95.6A after starting；
(4) carbon hollow ball is prepared using hydrothermal synthesis method, prepares the mixing suspension of linear polymer and cyclic polymer, will walks Suddenly porous boron-doped diamond obtained in (3) be put into the mix suspending solution of linear polymer and cyclic polymer stirring 6~ 24h；
(5) mixing suspension of the porous boron-doped diamond and linear polymer of immersion and cyclic polymer is transferred to counteracting tank Carry out hydro-thermal reaction is inside sealed, is reacted 6~12 hours at 200 DEG C, be down to after room temperature after taking out porous diamond films carry out it is cold It is lyophilized dry, is then placed in Muffle furnace and is carbonized to get carbon hollow ball and porous boron-doped diamond compound film.
2. the preparation side of a kind of carbon hollow ball and porous boron-doped diamond compound film sensor electrode according to claim 1 Method, it is characterised in that: step (1) base reservoir temperature 800 DEG C~1000 that boron-doped diamond film is prepared using filament CVD ℃。
3. the preparation side of a kind of carbon hollow ball and porous boron-doped diamond compound film sensor electrode according to claim 1 Method, it is characterised in that: step (2) purity of argon is 99.999%, flow 15mL/min.
4. the preparation side of a kind of carbon hollow ball and porous boron-doped diamond compound film sensor electrode according to claim 1 Method, it is characterised in that: step (3) time using DC arc plasma jet CVD etching boron-doped diamond film is 2 ~5min.
5. the preparation side of a kind of carbon hollow ball and porous boron-doped diamond compound film sensor electrode according to claim 1 Method, it is characterised in that: step (5) porous boron-doped diamond carburizing temperature in Muffle furnace is 450~550 DEG C, when carbonization Between 30~60min.
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