CN104865301B - A kind of coaxial type combined type oxygen microelectrode and preparation method thereof - Google Patents
A kind of coaxial type combined type oxygen microelectrode and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of coaxial type combined type oxygen microelectrode and preparation method thereof.The oxygen microelectrode includes an outer sleeve, the work cathode column at position at its center and positioned at reference electrode between the two, and the centre of the work cathode column is equipped with platinum filament, electrolyte solution is marked between outer sleeve and work cathode column；The outer wall of work cathode column or the inwall of outer sleeve are coated with one layer of silver layer, and are welded with conductive wire at the upper end face of described silver layer, constitute protection negative electrode.The electrode fabrication process is simple, draws success rate height, as a result shows：The connection of protection negative electrode makes the aftercurrent of coaxial type combined type oxygen microelectrode reduce about 80%, to the response linear dependence R of dissolved oxygen2More than 0.99, to the resolution capability about 0.03mg O of dissolved oxygen2/L。
Description
Technical field
The present invention relates to a kind of microelectrode and preparation method thereof, more particularly to a kind of coaxial type combined type oxygen microelectrode and its
Preparation method.
Background technology
Oxygen microelectrode is technology most ripe electrode so far, and two kinds of combined type and separate type are divided into from structure.Point
It is simple in construction from formula oxygen microelectrode, platinum filament or low-melting alloy generally are wrapped up with capillary glass tube, tip is gold-plated.Due to general
Capillary glass tube is different from the linear expansion coefficient of platinum filament, therefore the process of directly parcel platinum filament is not easy to, between the two usually
There is crack to have influence on electrode performance.The way of most common separate type oxygen microelectrode is that eutectic is irrigated in chunk glass
Point alloy, then serves as the reducing zone of oxygen, compared with platinum, gold utensil has broader oxygen pole in eletrode tip plated with gold or platinum
Change platform [Brito P S D and Sequeira C A C.Cathodic oxygen reduction on noble
metal and carbon electrodes.J Power Sources,1994,52:1-16.], therefore, more suitable for conduct
Electrode material.Alloy is the critical material that separate type oxygen microelectrode makes, by Dowben, Whalen and Linsenmeier etc.
People's progressively in-depth study, alloy material is transitioned into Wood by indium, tin alloy (50%Indium+50%Tin, 110 DEG C of fusing point)
Alloy (50%Bismuth+26.7%Lead+13.3%Tin+10%Cadmium, 73-75 DEG C of fusing point), a kind of last Bi alloys
(44.7%Bi+22.6%Pb+19.1%In+8.3%Sn+5.3%Cd, 47 DEG C of fusing point) material is gradually promoted the use of,
This alloy is using Bi as main component, and fusing point is low, small [the Dowben R M and Rose J E.A metal- of the coefficient of cubical expansion
filled microelectrode.Sci,1953,118:22-24；Whalen W J,Riley J and Nair P.A
microelectrode for measuring intracellular PO2,J Appl Physiol,1967,23:798-
801；Linsenmeier R A and Yancy C M.Improved fabrication of double-barreled
recessed cathode O2microelectrodes.Am Physiol Soc,1987,63(6):2254-2557；
Revsbech N P.An oxygen microsensor with a guard cathode.Limnol Oceanogr,1989,
34(2):474-478.].Bi alloys can reduce the possibility of the frit caused after alloy solidification by volumetric expansion, improve
The success rate of electrode fabrication, and extend electrode life.In addition, the pulling process of separate type oxygen microelectrode is also obtained
Simplify, including capillary glass tube need not be cleaned, it is not necessary to the process such as sophisticated alloy formation recess of corrosion, further highlight easily
In the advantage of making.But the shortcoming of separated electrode is it is also obvious that test signal is easily by external electromagnetic signal and vibrations
Influence, need in test process to be combined with outer reference electrode, other oxidizing substances ginseng also had under the reduction potential of oxygen
With reaction, so as to have influence on the accuracy of test result.
Combined type oxygen microelectrode can make up disadvantage mentioned above well, and it is a kind of Clark type sensors of miniaturization.Work
Make negative electrode and reference electrode is placed in parallel in an outer glass tube.Interior reference electrolyte solution covering work in outer tube is cloudy
Pole, serves good shielding action.One layer of oxygen permeability barrier film of outer glass tube tip covering, can be obstructed other in sample
Oxidizing substance is in work cathode surface reduction.Because the oxygen in internal-filling liquid can also be reduced in cathode surface so that combined type oxygen
The aftercurrent of microelectrode is higher, can reach 200pA or so, and with the change of aftercurrent, electrode output signal it is steady
It is qualitative very weak.1989, Revsbech proposed a kind of improved Clark types oxygen microelectrode, and protection negative electrode is added in the electrodes,
Effect is oxygen [the Revsbech N P.An oxygen microsensor with a guard in reference liquid in consumption
cathode.Limnol Oceanogr,1989,34(2):474-478.].Protection negative electrode is the filamentary silver after root-rot erosion, tip
About 5 μm or so, protection cathode point needs to be accurately positioned position between the two with work cathode point, to reach reduction residual electricity
The effect of stream.But the protection negative electrode added in this form also brings series of malpractice.Including：In order to be stayed to protection negative electrode
Go out the space of placement, the tip diameter of outer glass tube has to increase, therefore, obtain the microelectrode tip diameter within 10 μm and become
Obtain extremely difficult, the application of microelectrode is limited significantly；Accurate adjustment work negative electrode with protection cathode point distance completely according to
Rely in microscope and artificial operation, regulation process is complicated difficult, draws success rate low.
The content of the invention
It is an object of the invention to provide a kind of coaxial type combined type oxygen microelectrode and preparation method thereof.
Coaxial type combined type oxygen microelectrode provided by the present invention, including work cathode column, reference electrode and outer sleeve,
Work cathode column and reference electrode are set in parallel in outer sleeve, are marked between the outer sleeve and the work cathode column
Electrolyte solution, the outer wall of the work cathode column or the inwall of the outer sleeve are coated with one layer of silver layer, and in the silver layer
Surface soldered has conductive wire.
In above-mentioned coaxial type combined type oxygen microelectrode, the thickness of the silver layer is 0.1-1 μm.
The conductive wire is any in filamentary silver, copper wire and platinum filament, is preferably in the end of the silver layer surface
It is welded with conductive wire.The end of the silver layer surface refers to one end at the non-tip of the work cathode column.
The work cathode column sintering after head and the tail are nested in glass tube B non-tip is inserted into by glass tube A tip and
Into.
The tip of the glass tube B is equipped with platinum filament, and the free-end of the platinum filament is contacted with filamentary silver or copper wire, the platinum filament
The other end is wrapped up by described glass tube B tip and has part platinum filament exposed outside.
At the outer sleeve upper end open between the work cathode column, it is equal at the work cathode column upper end open
By epoxy resin sealing.
One end of the outer sleeve is marked with oxygen flow silica gel for pointed and sophisticated end.
The reference electrode is Ag/AgCl reference electrodes.
The electrolyte solution is NaHCO3、Na2CO3With KCl mixed liquor, wherein, in the electrolyte solution
NaHCO3、Na2CO3Molar concentration with KCl is respectively 0.01-1mol/L, 0.01-1mol/L and 0.01-3mol/L.
The tip diameter of glass tube B after the parcel platinum filament is 7~12 μm, and length is 1.5-3.0cm.
The sophisticated length that the platinum filament stretches into the glass tube B is 1.5~2cm.
The not wrapped and exposed platinum filament length of the non extensive of the platinum filament is 10-30 μm.
The sophisticated diameter of the outer sleeve is less than 50 μm.
Inner face 20-50 μ of the exposed end away from the oxygen permeability barrier film of platinum filament at the tip of the work cathode column
m。
The thickness of the oxygen flow silica gel is 10~20 μm.
The epoxy resin concretely AB glue.
The platinum filament that is wrapped up of tip by glass tube B, in addition to the step of corrode in advance to it, it is described not to be corroded
Platinum filament a diameter of 0.05-0.2mm, concretely 0.1mm, a diameter of 5~10 μm of platinum filament after the corrosion.
The preparation method of coaxial type combined type oxygen microelectrode provided by the present invention, comprises the following steps：
1) work negative electrode is made：(a) platinum filament is inserted into 1-2cm in chloroazotic acid, corrodes 80-90min, corrode platinum filament insertion end
To a diameter of 5~10 μm；
(b) take glass tube A and glass tube B to be drawn into tip glass tube, and the platinum filament end corroded is inserted into glass
In pipe B tip, length is inserted it into for 1.5~2cm, then glass tube A tips is inserted in the non-tips of green glass pipe B, sintering；
(c) the glass tube B obtained in step (b) tip is fixed on heating coil centre position, increases heating wire two
Terminal voltage, makes glass tube B tip melts wrap platinum filament, obtains work negative electrode.
2) work cathode surface silver coating：Silver ammino solution and reproducibility compound are mixed to get upper silver-colored mixed liquor, and will
The work negative electrode is suspended in silver-colored mixed liquor, in work cathode surface plating last layer silver layer, and in the upper end face of silver layer
Locate welding conductive metal silk.
3) coaxial type combined type oxygen microelectrode is assembled：Pasteur pipe one end is drawn into tip below 50 μm of diameter (i.e.
Capillary), the working electrode of silver coating is loaded into the center portion thereof position, meanwhile, reference electrode is loaded wherein, is sealed with epoxy resin
Mouthful, and by Pasteur tip end siphon silica gel, form oxygen permeability barrier film, finally, electrolyte solution is injected in Pasteur pipe,
Obtain coaxial type combined type oxygen microelectrode.
In above-mentioned preparation method, step 1) in (a), a diameter of 0.05-0.2mm of the platinum filament, concretely 0.1mm.
The chloroazotic acid is by volume ratio 4:1:3 H2O、HNO3With HCl compositions.
Step 1) in (b), the tip outer diameter of the glass tube A is 1.5-2.0cm, concretely 2cm.
The tip outer diameter of the glass tube B is 0.3-0.7mm, concretely 0.5mm.
The sintering is that glass tube to be sintered is placed on alcolhol burner or other flames, is rotated repeatedly, until reaching institute
Need standard.
The heating coil is O-shaped nickel-iron wire.
In above-mentioned preparation method, step 1) in (c), in addition to the tip of work negative electrode is heated, make glass melting
And receding, the step of exposing platinum filament.
The tip diameter of glass tube B after the parcel platinum filament is 7~12 μm, concretely 10 μm, and length is
1.5-3.0cm, concretely 2.5cm.
In above-mentioned preparation method, step 2) in, the volume ratio of the silver ammino solution and reproducibility compound is 2:1.
The reproducibility compound is that, containing aldehyde compound, the aldehyde compound that contains is in formaldehyde, acetaldehyde and glucose
At least one.
The time of the suspension is 15~20min.
In above-mentioned preparation method, step 3) in, inner face 20- of the exposed end away from the oxygen permeability barrier film of the platinum filament
50 μm, concretely 30 μm.
The thickness of the oxygen permeability barrier film is 10~20 μm.
The upper silver-colored mixed liquor should be filled up once, can not be added halfway.
The electrolyte solution is NaHCO3、Na2CO3With KCl mixed liquor, wherein, in the electrolyte solution
NaHCO3、Na2CO3Molar concentration with KCl is respectively 0.05-0.15mol/L, 0.10-0.20mol/L and 0.45-0.55mol/
L, can be respectively specifically 0.1mol/L, 0.15mol/L and 0.5mol/L.
The reference electrode is Ag/AgCl reference electrodes.
The epoxy resin concretely AB glue.
Coaxial type combined type oxygen microelectrode prepared by the present invention, overcomes the shortcoming of conventional composite formula dissolved oxygen micro electrode,
Its structure is optimized, according to silver mirror reaction principle, in working electrode outer surface of column or outer sleeve inwall silver coating, so
Electric lead is connected in coating end afterwards, as protection negative electrode, electrode fabrication process is simplified, electrode is drawn success rate and obtains
Significantly improve.
Compared with prior art, the present invention has the advantages that：
(1) in working electrode outer surface of column or outer sleeve inwall silver coating, electric lead then is connected in coating end,
As protection negative electrode, electrode fabrication process is simplified, electrode is drawn success rate and is significantly improved.
(2) it has very high spatial resolution, can realize the quantitative detection of dissolved oxygen in microenvironment, corresponding test
Results of property shows：Aftercurrent reduction by 80% of the coaxial type combined type oxygen microelectrode of the present invention before and after protection negative electrode is connected
Left and right, to the response linear dependence R of dissolved oxygen2More than 0.99, to the resolution capability about 0.03mg O of dissolved oxygen concentration2/L。
(3) one end of platinum filament is contacted with filamentary silver or copper wire, not exclusively as follows using the advantage of platinum filament：A) platinum filament is expensive, will
Its part filamentary silver or copper wire are substituted, it is possible to decrease cost of manufacture；B) thick filamentary silver or copper wire can be used, relatively firmly, is not easily broken,
And it is easy to follow-up Reusability；C) platinum filament need to only be contacted with filamentary silver or copper wire, without welding, even if therefore having part position above
Move, following platinum filament is not also influenceed, it is to avoid wrapped fragile platinum filament fractures.
Brief description of the drawings
Fig. 1 is the coaxial type combined type oxygen microelectrode structural representation in embodiment 1, wherein, outer sleeve (1), oxygen flow
Silica gel (2), work cathode column (3), glass tube A (4), glass tube B (5), platinum filament (6), silver layer (7), conductive wire (8), Ag/
The tip of AgCl reference electrodes (9), electrolyte solution (10), filamentary silver or copper wire (11), epoxy resin (12), the cathode column that works
(13)。
Fig. 2 is the work negative electrode schematic diagram wrapped up before platinum filament in embodiment 1.
Fig. 3 is the schematic device of parcel platinum filament in embodiment 1.
Fig. 4 is examination criteria curve of the coaxial type combined type oxygen microelectrode in embodiment 1 to dissolved oxygen.
Fig. 5 is real-time response curve of the coaxial type combined type oxygen microelectrode in embodiment 1 to dissolved oxygen.
Embodiment
The method of the present invention is illustrated below by specific embodiment, but the invention is not limited in this, it is all at this
Any modifications, equivalent substitutions and improvements done within the spirit and principle of invention etc., should be included in the protection model of the present invention
Within enclosing.
Experimental method described in following embodiments, is conventional method unless otherwise specified；The reagent and material, such as
Without specified otherwise, commercially obtain.
Embodiment 1, prepare coaxial type combined type oxygen microelectrode and its performance test：
First, coaxial type combined type oxygen microelectrode is prepared：
Structural representation as shown in Figure 1 prepares coaxial type combined type oxygen microelectrode：
1) work negative electrode is made：Using the chloroazotic acid (H of boiling2O:HNO3:HCl=4:1:3rd, volume ratio) by a diameter of 0.1mm
Platinum filament (purity 99.95%, purchased from Chinese Medicine (group) Shanghai chemical agent company) tip corrosion to 5~10 μm, specifically
Chloroazotic acid can be placed in 100mL beakers, and be inserted in heating in water-bath, then by platinum filament after 2cm in chloroazotic acid, corrosion 90min, can
The corrosion of platinum filament tip is to 5 μm.
Taking white glass pipe, (hard neutral density glass, external diameter is 3.33mm, and internal diameter is 2.69mm, purchased from Beijing special glass tube difficult to understand
Research institute) and green glass pipe (8533 types, external diameter 3.33mm；Internal diameter, 2.69mm, purchased from German Schott AG) some, fully
Dried after cleaning, with pulling tip glass tube processed.White glass pipe tip external diameter is pulled to 2cm, and green glass pipe tip external diameter is pulled to
0.5mm.In the capillary that the platinum filament corroded is slowly inserted to green glass pipe, platinum filament built-in length is 1.5~2cm, by white glass
Glass pipe A (4) tip inserts green glass pipe B (5) outer end (as shown in Figure 2), using sintering method assembly working negative electrode.
Using O-shaped nickel-iron wire as heating element heater, heater strip is connected to voltage-stabilized power supply, the capillary tip for post that negative electrode is worked
Through heater strip, it is fixed on three-dimensional microoperation platform, keeps negative electrode work post to be suspended in vertically in the air (as shown in Figure 3).Adjustment three
Wei Weicaozuotai, makes negative electrode work column capillary tube positioned at O-shaped heater strip center, platinum filament tip is away from O-shaped 1~1.5cm of heater strip.It is slow
Slow increase heating wire both end voltage, begins to warm up.The heated part of negative electrode work post is moved up and down, it is heated evenly.Work as electricity
When pressure rises to 4~5V, green glass starts softening, at this moment rapid increase voltage, glass rapid fusing after being drastically heated, and wraps
Platinum filament tip, whole negative electrode work post is fallen into the beaker of lower section.Seen in stereomicroscope (XTL-20, purchased from Beijing Tyke instrument)
Examine down, it is ensured that wrapped up completely by green glass pipe at platinum filament tip.
2) in work cathode surface covering silver layer：Utilize compound (such as aldehyde, monose, the potassium tartrate sodium salt for having reproducibility
Deng) reduce silver-amino coordination ion, argent therein is formed in the way of close-packed arrays are into silver foil in clean glass surface
Silver mirror.In order that argent can uniformly be separated out and firm attachment on minute surface, except being handled, being washed with soda acid, make minute surface clear
It is clean outer, " sensitization " processing is also carried out to minute surface, its reason is：When the sodium metasilicate of minute surface is handled through soda acid, a part turns into
Silicic acid.When silver-plated, silver is slower with silicic acid exchange velocity, and the basic ion and silicic acid exchange velocity in plating solution are quickly, this work
The difference of property just have impact on the uniform of coating.Therefore, working electrode is handled using ethanol and acetone soak, is dried in the air at clean ventilation
It is dry；Dry the SnCl afterwards using 5%2Solution (sensitizing solution) handles minute surface, then with distilled water flushing it is clean after, just can be in mirror
Start on face it is silver-plated,
Comprise the following steps that：In a clean test tube, 1ml 3%AgNO are added3The aqueous solution, is then instilled dropwise
2% ammoniacal liquor, vibrates in drop, makes solution from there is precipitation to produce untill precipitation disappears just, solution becomes water white transparency, then drips
Plus appropriate NaOH solution (3-6 drops maintain alkalescence), obtain colourless silver ammino solution.
Glucose solution is prepared：Weigh 4g glucose and be dissolved in 96g distilled water and mix standby, and add into solution 1
~2g tartaric acid.
Silver ammino solution and glucose solution are pressed 2:1 volume ratio is mixed into silver-colored mixed liquor, rapidly puts working electrode
Suspended in mixed liquor, stand 15~20min.Electrode is carefully taken out afterwards, ultrapure water surface is used, at aeration-drying
Dry.Dried silver layer light is uniform, and the thickness of silver layer is about 0.5 μm.Working electrode complete after in silver layer appearance
Filamentary silver is fixed in face using soldering, for transmitting electric signal.
During silver coating, it should be noted that：Upper silver-colored mixed liquor should be filled up once, can not be added halfway, otherwise, on minute surface
The flaws such as plaque-like, strip or whirlpool vestige are formed, electric signal is influenceed, or even cause to waste；It can not be disturbed during standing, otherwise
Depositing silver layers can adhere to insecure, and color is black dull；After plating terminates, the cathode point that will work is slow close to the heater strip being powered.
Voltage is adjusted, the glass at parcel platinum filament tip is melted and receding, exposes platinum filament, close power supply.
3) coaxial type combined type oxygen microelectrode is assembled：The capillary that Pasteur tip end is pulled into below 50 μm of diameter, does
For microelectrode column jacket, observation trimming under the microscope makes tip smooth；Working electrode after will be silver-plated stretches into electrode column jacket,
30 μm or so away from column jacket tip of the tip of working electrode, while insertion AgCl/AgCl fixes three as reference electrode with AB glue
The relative position of person, stood solidification AB glue after 24 hours, in sophisticated siphon silica gel (the Silastic Medical of microelectrode
Adhensive Type A, Dow Corning Co., the U.S.) form oxygen permeability barrier film (i.e. layer of silica gel), its thickness for 10~
20μm.After silica gel solidification, the interior reference solution of deoxygenation is boiled in advance with the syringe injection with 0.2 μm of filtering needle
(0.1mol/L NaHCO3+0.15mol/L Na2CO3+ 0.5mol/L KCl mixed liquor)；Finally, it is with AB glue that preformed hole is close
Envelope.The microelectrode made is covered into top cement plug, insertion test tube kept dry is stand-by, and its structural representation is as shown in Figure 1：
Prepared coaxial type combined type oxygen microelectrode includes following structure：
Work cathode column, reference electrode and outer sleeve, and work cathode column and Ag/AgCl reference electrodes are set in parallel in outer
In parts casing pipe, electrolyte solution (0.1mol/L NaHCO are marked between the outer sleeve and the work cathode column3+
0.15mol/L Na2CO3+ 0.5mol/L KCl mixed liquor), the outer wall of the work cathode column is coated with one layer of 0.5 μm of silver layer,
And it is welded with filamentary silver in the end of silver layer surface.
Wherein, the work cathode column is inserted into head and the tail nesting in green glass pipe B non-tip by white glass pipe A tip
Sintering is formed afterwards.
The tip of the glass tube B is equipped with platinum filament, and the free-end of the platinum filament is contacted with filamentary silver or copper wire, the platinum filament
The other end is wrapped up by described glass tube B tip and has 20 μm of platinum filament exposed outside, and after the parcel platinum filament
Glass tube B tip diameter be 10 μm, length is 2cm.
At the outer sleeve upper end open between the work cathode column, it is equal at the work cathode column upper end open
Closed by AB glue.
Inner face 30 μm of the exposed end away from the oxygen permeability barrier film of platinum filament at the tip of the work cathode column.
2nd, performance test：
Its examination criteria curve to dissolved oxygen from Fig. 4 as shown in figure 4, can learn：In the present embodiment, dissolved oxygen is divided
Resolution is 0.03mg O2/ L, connects aftercurrent reduction by 83%, the coaxial oxygen microelectrode pair corresponding with Fig. 4 after protection negative electrode
The response data of different partial is as shown in table 1.
Its real-time response curve to dissolved oxygen from Fig. 5 as shown in figure 5, can learn：In the present embodiment, reach that 90% is maximum
The response time of value is 4s.
Response data of the coaxial oxygen microelectrode of table 1. to different partial
Claims (5)
1. a kind of coaxial type combined type oxygen microelectrode, including work cathode column（3）, reference electrode（9）And outer sleeve（1）, work
Make cathode column（3）And reference electrode（9）It is set in parallel in outer sleeve, the outer sleeve（1）With the work cathode column
（3）Between be marked with electrolyte solution（10）, it is characterised in that：The work cathode column（3）Outer wall or the outer sleeve（1）
Inwall be coated with one layer of silver layer（7）, and in the silver layer（7）Surface soldered has conductive wire（8）；
The silver layer（7）Thickness be 0.1-1 μm；
The conductive wire（8）It is any in filamentary silver, copper wire and platinum filament；
In the silver layer（7）The end on surface is welded with conductive wire（8）；
The work cathode column（3）By glass tube A（4）Tip be inserted into glass tube B（5）Non- tip in head and the tail it is nested after burn
Knot is formed；
The glass tube B（5）Tip be equipped with platinum filament（6）, the platinum filament（6）Free-end and filamentary silver or copper wire（11）Contact,
The platinum filament（6）The other end by described glass tube B（5）Tip wrap up and have part platinum filament exposed outside；
The outer sleeve（1）At upper end open and the work cathode column（3）Between, the work cathode column（3）Open upper end
By epoxy resin at mouthful（12）Closing；
The outer sleeve（1）One end be marked with oxygen flow silica gel for pointed and sophisticated end（2）, form oxygen permeability barrier film；
The reference electrode（9）For Ag/AgCl reference electrodes；
The electrolyte solution（10）For NaHCO3、Na2CO3With KCl mixed liquor, wherein, NaHCO in the electrolyte solution3、
Na2CO3Molar concentration with KCl is respectively 0.01-1 mol/L, 0.01-1 mol/L and 0.01-3 mol/L；
The parcel platinum filament（6）Glass tube B afterwards（5）Tip diameter be 7 ~ 12 μm, length is 1.5-3.0cm；
The platinum filament（6）Stretch into the glass tube B（5）Sophisticated length be 1.5~2cm；
The platinum filament（6）Non extensive not wrapped and exposed platinum filament length be 10-30 μm；
The outer sleeve（1）Sophisticated diameter be less than 50 μm；
The work cathode column（3）Tip（13）Inner face 20- of the exposed end of the platinum filament at place away from the oxygen permeability barrier film
50μm；
The oxygen flow silica gel（2）Thickness be 10 ~ 20 μm.
2. the preparation method of the coaxial type combined type oxygen microelectrode described in claim 1, comprises the following steps：
1）Make work negative electrode：（a）Platinum filament is inserted into 1-2cm in chloroazotic acid, corrodes 80-90min, platinum filament insertion end is corroded to straight
Footpath is 5 ~ 10 μm；
（b）Take glass tube A（4）With glass tube B（5）Tip glass tube is drawn into, and the platinum filament end corroded is inserted into glass
Glass pipe B（5）Tip in, insert it into length for 1.5~2cm, then by glass tube A（4）Tip insertion glass tube B（5）Non- point
In end, sintering；
（c）By step（b）In obtained glass tube B（5）Tip be fixed on heating coil centre position, increase heating wire two ends
Voltage, makes glass tube B（5）Tip melts wrap platinum filament, obtain work negative electrode；
2）Work cathode surface silver coating：Silver ammino solution and reproducibility compound are mixed to get upper silver-colored mixed liquor, and will be described
Work negative electrode is suspended in silver-colored mixed liquor, in work cathode surface plating last layer silver layer, and is welded at the upper end face of silver layer
Connect conductive wire；
3）Assemble coaxial type combined type oxygen microelectrode：Pasteur pipe one end is drawn into the tip below 50 μm of diameter, will be silver-plated
The work negative electrode of layer loads the center portion thereof position, meanwhile, reference electrode is loaded wherein, is sealed with epoxy resin, and by Pasteur
Tip end siphon oxygen flow silica gel, forms oxygen permeability barrier film, finally, electrolyte solution is injected in Pasteur pipe, that is, is total to
Spindle-type combined type oxygen microelectrode.
3. preparation method according to claim 2, it is characterised in that：Step 1）（a）In, the platinum filament it is a diameter of
0.05-0.2mm；
The chloroazotic acid is by volume ratio 4:1:3 H2O、HNO3With HCl compositions；
Step 1）（b）In, the glass tube A（4）Tip outer diameter be 1.5-2.0cm；
The glass tube B（5）Tip outer diameter be 0.3-0.7mm；
The heating coil is O-shaped nickel-iron wire；
Step 1）（c）In, in addition to the tip of work negative electrode is heated, make glass melting and receding, expose platinum filament
Step；
The parcel platinum filament（6）Glass tube B afterwards（5）Tip diameter be 7 ~ 12 μm, length is 1.5-3.0cm.
4. the preparation method according to Claims 2 or 3, it is characterised in that：Step 2）In, the silver ammino solution and reproducibility
The volume ratio of compound is 2：1；
The reproducibility compound be containing aldehyde compound, it is described containing aldehyde compound be formaldehyde, acetaldehyde and glucose in extremely
Few one kind；
The time of the suspension is 15 ~ 20min；
The upper silver-colored mixed liquor should be filled up once, it is impossible to be added halfway.
5. the preparation method according to Claims 2 or 3, it is characterised in that：Step 3）In, the exposed end of the platinum filament is away from institute
State 20-50 μm of the inner face of oxygen permeability barrier film；
The thickness of the oxygen permeability barrier film is 10 ~ 20 μm；
The electrolyte solution is NaHCO3、Na2CO3With KCl mixed liquor, wherein, NaHCO in the electrolyte solution3、
Na2CO3Molar concentration with KCl is respectively 0.01-1 mol/L, 0.01-1 mol/L and 0.01-3 mol/L.
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