CN104865301A - Coaxial compound oxygen microelectrode and preparation method thereof - Google Patents
Coaxial compound oxygen microelectrode and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a coaxial compound oxygen microelectrode and a preparation method thereof. The oxygen microelectrode includes an external casing, a working cathode column located at the central part, and a reference electrode located between the external casing and the working cathode column, the central part of the working cathode column is provided with a platinum wire, an electrolyte solution is filled between the external casing and the working cathode column, the outer wall of the working cathode column or the inner wall of the external casing is plated with a layer of silver layer, and the upper end surface of the silver layer is welded with a conductive metal wire to form a protection cathode. The electrode making process is simple, and high in control success rate, the results show that the protection cathode switches on to reduce residual current of the coaxial compound oxygen microelectrode by about 80%, dissolved oxygen response linear dependence R2 is more than 0.99, and the dissolved oxygen resolution is about 0.03 mg O2/L.
Description
Technical field
The present invention relates to a kind of microelectrode and preparation method thereof, particularly a kind of coaxial type combined type oxygen microelectrode and preparation method thereof.
Background technology
Oxygen microelectrode is the electrode that technology is the most ripe up to now, is divided into combined type and separate type two kinds from structure.Separate type oxygen microelectrode structure is simple, usually with glass capillary parcel platinum filament or low-melting alloy, most advanced and sophisticated gold-plated.Because general glass capillary is different from the linear expansion coefficient of platinum filament, therefore directly wrap up the process of platinum filament and be not easy, usually occur crack between the two thus have influence on electrode performance.The way of modal separate type oxygen microelectrode pours into low-melting alloy in chunk glass, then the reducing zone of oxygen is served as in eletrode tip plated with gold or platinum, compared with platinum, gold utensil has wider oxygen polarization platform [Brito P S D and Sequeira C A C.Cathodic oxygen reductionon noble metal and carbon electrodes.J Power Sources, 1994,52:1-16.], therefore, be more suitable for as electrode material.Alloy is the critical material that separate type oxygen microelectrode makes, through Dowben, the research that the people such as Whalen and Linsenmeier are progressively deep, alloy material is by indium, ashbury metal (50%Indium+50%Tin, fusing point 110 DEG C) be transitioned into Wood alloy (50%Bismuth+26.7%Lead+13.3%Tin+10%Cadmium, fusing point 73-75 DEG C), last a kind of Bi alloy (44.7%Bi+22.6%Pb+19.1%In+8.3%Sn+5.3%Cd, fusing point 47 DEG C) material obtains gradually and promotes the use of, this alloy take Bi as principal ingredient, fusing point is low, little [the Dowben R M and Rose J E.A metal-filled microelectrode.Sci of volume expansivity, 1953, 118:22-24, Whalen W J, Riley J and Nair P.A microelectrode for measuring intracellular PO
2, J ApplPhysiol, 1967,23:798-801, Linsenmeier R A and Yancy C M.Improved fabrication ofdouble-barreled recessed cathode O
2microelectrodes.Am Physiol Soc, 1987,63 (6): 2254-2557, Revsbech N P.An oxygen microsensor with a guard cathode.LimnolOceanogr, 1989,34 (2): 474-478.].The possibility of the frit that Bi alloy is caused by volumetric expansion after can reducing alloy solidification, improves the success ratio of electrode fabrication, and extends electrode life.In addition, the pulling process of separate type oxygen microelectrode have also been obtained simplification, comprises and does not need to clean glass capillary, does not need to corrode most advanced and sophisticated alloy and forms the processes such as recess, highlight the advantage being easy to make further.But the shortcoming of separated electrode also clearly, test signal is easily subject to the impact of external electromagnetic signal and vibrations, need in test process and outer contrast electrode coupling, under the reduction potential of oxygen, also have other oxidizing substances participate in reaction, thus have influence on the accuracy of test result.
Combined type oxygen microelectrode can make up above shortcoming well, and it is a kind of Clark type sensor of microminiaturization.Working, negative electrode is parallel with contrast electrode to be placed in an outer glass tube.Interior reference electrolyte solution covering work negative electrode in outer tube, serves good shielding action.Outer glass tube tip covers one deck oxygen permeability barrier film, and other oxidizing substance that can intercept in sample reduces at work cathode surface.Because the oxygen in internal-filling liquid also can reduce at cathode surface, make the aftercurrent of combined type oxygen microelectrode higher, can about 200pA be reached, and along with the change of aftercurrent, the stability of electrode output signal is very weak.1989; Revsbech proposes a kind of Clark type oxygen microelectrode of improvement; add protection negative electrode in the electrodes; effect is oxygen [the Revsbech N P.An oxygenmicrosensor with a guard cathode.Limnol Oceanogr in consuming in reference liquid; 1989,34 (2): 474-478.].Protection negative electrode is the filamentary silver after a root-rot erosion, about about 5 μm, tip, and protection cathode point and work cathode point need the position of accurately locating between the two, to reach the effect reducing residual current.But the protection negative electrode added in this form also brings series of malpractice.Comprise: in order to reserve the space of placement to protection negative electrode, the tip diameter of outer glass tube must increase, and therefore, the microelectrode tip diameter within obtaining 10 μm becomes very difficult, and the range of application of microelectrode is greatly limited; Fine adjustment work negative electrode and protection cathode point distance place one's entire reliance upon microscope and manual operation, and the complicated difficulty of regulation process, is drawn into power low.
Summary of the invention
The object of the present invention is 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, comprise work cathode column, contrast electrode and outer sleeve, work cathode column and contrast electrode are set in parallel in outer sleeve, electrolyte solution is marked with between described outer sleeve and described work cathode column, the outer wall of described work cathode column or the inwall of described outer sleeve are coated with one deck silver layer, and are welded with conductive wire at described silver layer surface.
In above-mentioned coaxial type combined type oxygen microelectrode, the thickness of described silver layer is 0.1-1 μm.
Described conductive wire is selected from any one in filamentary silver, copper wire and platinum filament, is preferably welded with conductive wire at the end of described silver layer surface.The end of described silver layer surface depends on the one end at nearly described work cathode column non-tip place.
Described work cathode column is inserted into the nested rear sintering of head and the tail in the non-tip of glass tube B by the tip of glass tube A and forms.
Platinum filament is equipped with at the tip of described glass tube B, and the free-end of described platinum filament contacts with filamentary silver or copper wire, the other end of described platinum filament wrap up by the tip of described glass tube B and have part platinum filament outside exposed.
Between described outer sleeve upper end open place and described work cathode column, described work cathode column upper end open place is by epoxy resin sealing.
One end of described outer sleeve is that pointed and most advanced and sophisticated end is marked with oxygen flow silica gel.
Described contrast electrode is Ag/AgCl contrast electrode.
Described electrolyte solution is NaHCO
3, Na
2cO
3with the mixed liquor of KCl, wherein, NaHCO in described electrolyte solution
3, Na
2cO
30.01-1mol/L, 0.01-1mol/L and 0.01-3mol/L is respectively with the volumetric molar concentration of KCl.
The tip diameter of the glass tube B after the described platinum filament of described parcel is 7 ~ 12 μm, and length is 1.5-3.0cm.
The length that described platinum filament stretches into the tip of described glass tube B is 1.5 ~ 2cm.
Not not being wrapped of non extensive of described platinum filament and exposed platinum filament length is 10-30 μm.
The diameter at the tip of described outer sleeve is less than 50 μm.
The exposed end of the platinum filament at the tip place of described work cathode column is apart from the inner face 20-50 μm of described oxygen permeability barrier film.
The thickness of described oxygen flow silica gel is 10 ~ 20 μm.
Described epoxy resin specifically can be AB glue.
Described the platinum filament that wraps up by the tip of glass tube B, also comprise in advance to the step of its corrosion, the diameter of the described platinum filament be not corroded is 0.05-0.2mm, specifically can be 0.1mm, and the diameter of the platinum filament after described corrosion is 5 ~ 10 μm.
The preparation method of coaxial type combined type oxygen microelectrode provided by the present invention, comprises the steps:
1) make work negative electrode: platinum filament is inserted 1-2cm in chloroazotic acid by (a), corrosion 80-90min, make the corrosion of platinum filament insertion end be 5 ~ 10 μm to diameter;
B () gets glass tube A and glass tube B is all drawn into tip glass tube, and be inserted in the tip of glass tube B by the platinum filament end corroded, and inserting it into length is 1.5 ~ 2cm, then insert in the non-tip of green glass pipe B by glass tube A tip, sintering;
C the tip of the glass tube B obtained in step (b) is fixed on heater coil centre position by (), increase heating wire both end voltage, make the tip melts of glass tube B wrap platinum filament, obtain work negative electrode.
2) work cathode surface silver coating: silver ammino solution and reductibility compound are mixed to get upper silver-colored mixed liquor, and described work negative electrode is suspended in upper silver-colored mixed liquor, one deck silver layer is plated at work cathode surface, and at the upper end face place welding conductive metal silk of silver layer.
3) coaxial type combined type oxygen microelectrode is assembled: the tip (i.e. kapillary) Pasteur pipe one end being drawn into diameter less than 50 μm, the working electrode of silver coating is loaded its centre, simultaneously, load contrast electrode wherein, with epoxy resin sealing, and by Pasteur tip end siphon silica gel, form oxygen permeability barrier film, finally, in Pasteur pipe, inject electrolyte solution, namely obtain coaxial type combined type oxygen microelectrode.
In above-mentioned preparation method, step 1) in (a), the diameter of described platinum filament is 0.05-0.2mm, specifically can be 0.1mm.
Described chloroazotic acid is by the H of volume ratio 4:1:3
2o, HNO
3form with HCl.
Step 1) in (b), the tip outer diameter of described glass tube A is 1.5-2.0cm, specifically can be 2cm.
The tip outer diameter of described glass tube B is 0.3-0.7mm, specifically can be 0.5mm.
Described sintering is placed on spirit lamp or other flame by glass tube to be sintered, repeatedly rotates, until reach required standard.
Described heater coil is O type nickel-iron wire.
In above-mentioned preparation method, step 1) in (c), also comprise and the tip of work negative electrode is heated, make glass melting and receding, expose the step of platinum filament.
The tip diameter of the glass tube B after the described platinum filament of described parcel is 7 ~ 12 μm, and specifically can be 10 μm, length is 1.5-3.0cm, specifically can be 2.5cm.
In above-mentioned preparation method, step 2) in, the volume ratio of described silver ammino solution and reductibility compound is 2:1.
Described reductibility compound is for containing aldehyde compound, and described is at least one in formaldehyde, acetaldehyde and glucose containing aldehyde compound.
The time of described suspension is 15 ~ 20min.
In above-mentioned preparation method, step 3) in, the exposed end of described platinum filament, apart from the inner face 20-50 μm of described oxygen permeability barrier film, specifically can be 30 μm.
The thickness of described oxygen permeability barrier film is 10 ~ 20 μm.
Described silver-colored mixed liquor should once fill up, and can not add halfway.
Described electrolyte solution is NaHCO
3, Na
2cO
3with the mixed liquor of KCl, wherein, NaHCO in described electrolyte solution
3, Na
2cO
3be respectively 0.05-0.15mol/L, 0.10-0.20mol/L and 0.45-0.55mol/L with the volumetric molar concentration of KCl, specifically can be respectively 0.1mol/L, 0.15mol/L and 0.5mol/L.
Described contrast electrode is Ag/AgCl contrast electrode.
Described epoxy resin specifically can be AB glue.
Coaxial type combined type oxygen microelectrode prepared by the present invention; overcome the shortcoming of conventional composite formula dissolved oxygen micro electrode; its structure is optimized; according to silver mirror reaction principle; at working electrode outer surface of column or outer sleeve inwall silver coating, then connect electrical lead at coating end, as protection negative electrode; simplify electrode fabrication process, make electrode be drawn into power and be significantly improved.
Compared with prior art, the present invention has following beneficial effect:
(1) at working electrode outer surface of column or outer sleeve inwall silver coating, then connect electrical lead at coating end, as protection negative electrode, simplify electrode fabrication process, make electrode be drawn into power and be significantly improved.
(2) it has very high spatial resolution; the quantitative detection of dissolved oxygen DO in microenvironment can be realized; corresponding test performance result shows: the aftercurrent of coaxial type combined type oxygen microelectrode of the present invention before and after connection protection negative electrode reduces about 80%, to the response linear dependence R of dissolved oxygen DO
2more than 0.99,0.03mg O is about to the resolution characteristic of dissolved oxygen concentration
2/ L.
(3) one end of platinum filament contacts with filamentary silver or copper wire, not exclusively adopts the advantage of platinum filament as follows: a) platinum filament is expensive, its part filamentary silver or copper wire is substituted, can reduce cost of manufacture; B) thick filamentary silver or copper wire can be adopted, relatively firmly, not frangibility, and be convenient to follow-up Reusability; C) platinum filament only need contact with filamentary silver or copper wire, without the need to welding, even if therefore have partial dislocation above, also do not affect platinum filament below, avoid wrapped fragile platinum filament to fracture.
Accompanying drawing explanation
Fig. 1 is the coaxial type combined type oxygen microelectrode structural representation in embodiment 1, wherein, the tip (13) of 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/AgCl contrast electrode (9), electrolyte solution (10), filamentary silver or copper wire (11), epoxy resin (12), work cathode column.
Fig. 2 is the work negative electrode schematic diagram before the parcel platinum filament in embodiment 1.
Fig. 3 is the device schematic diagram wrapping up platinum filament in embodiment 1.
Fig. 4 is that coaxial type combined type oxygen microelectrode in embodiment 1 is to the examination criteria curve of dissolved oxygen DO.
Fig. 5 is that coaxial type combined type oxygen microelectrode in embodiment 1 is to the real-time response curve of dissolved oxygen DO.
Embodiment
Be described method of the present invention below by specific embodiment, but the present invention is not limited thereto, all any amendments done within the spirit and principles in the present invention, equivalent replacement and improvement etc., all should be included within protection scope of the present invention.
Experimental technique described in following embodiment, if no special instructions, is conventional method; Described reagent and material, if no special instructions, all can obtain from commercial channels.
Embodiment 1, prepare coaxial type combined type oxygen microelectrode and performance test thereof:
One, coaxial type combined type oxygen microelectrode is prepared:
Coaxial type combined type oxygen microelectrode is prepared by the structural representation shown in Fig. 1:
1) work negative electrode is made: the chloroazotic acid (H adopting boiling
2o:HNO
3: HCl=4:1:3, volume ratio) be the platinum filament (purity 99.95% of 0.1mm by diameter; purchased from Chinese Medicine (group) Shanghai chemical agent company) most advanced and sophisticated corrosion is to 5 ~ 10 μm; specifically chloroazotic acid can be placed in 100mL beaker; and heat up in water-bath; again platinum filament is inserted 2cm in chloroazotic acid; after corrosion 90min, can corrode to 5 μm at platinum filament tip.
Get white glass pipe (hard neutral density glass, external diameter is 3.33mm, and internal diameter is 2.69mm, purchased from Beijing Ao Te glass tube research institute) and green glass pipe (8533 types, external diameter 3.33mm; Internal diameter, 2.69mm, purchased from German Schott AG) some, fully clean post-drying, 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.The platinum filament corroded slowly is inserted in the kapillary of green glass pipe, platinum filament built-in length is 1.5 ~ 2cm, white glass pipe A (4) tip is inserted green glass pipe B (5) outer end (as shown in Figure 2), adopts sintering method assembly working negative electrode.
With O type nickel-iron wire for heating element, heater strip is connected to stabilized voltage supply, by the capillary tip of negative electrode work post through heater strip, is fixed on three-dimensional microoperation platform, keep negative electrode work post to be vertically suspended in (as shown in Figure 3) in the air.Adjust three-dimensional microoperation platform, make negative electrode work column capillary tube be positioned at O type heater strip central authorities, platinum filament is most advanced and sophisticated apart from O type heater strip 1 ~ 1.5cm.Slow increase heating wire both end voltage, starts heating.Move up and down the heated part of negative electrode work post, make it be heated evenly.When voltage rises to 4 ~ 5V, green glass starts to soften, and at this moment increases voltage rapidly, melts rapidly after glass is sharply heated, and wraps platinum filament tip, and whole negative electrode work post falls into below beaker.Under stereomicroscope (XTL-20, purchased from Tyke, Beijing instrument) is observed, guarantee that platinum filament tip is wrapped up by green glass pipe completely.
2) cover silver layer at work cathode surface: utilize the compound (as aldehyde, monose, potassium tartrate sodium salt etc.) of tool reductibility to be reduced by silver-amino coordination ion, make argent wherein become the mode of silver foil to form silver mirror at the glass surface of cleaning with close-packed arrays.Evenly can separate out on minute surface and firm attachment to make argent, except with soda acid process, washing, making outside mirror surface cleaning, also will carry out " sensitization " process to minute surface, its reason is: the sodium silicate of minute surface is when soda acid process, and a part becomes silicic acid.When silver-plated, silver and silicic acid exchange velocity are comparatively slow, and basic ion in plating solution and silicic acid exchange velocity are very soon, and the difference of this activity just have impact on the even of coating.Therefore, use ethanol and acetone immersion treatment working electrode, at clean ventilation, place dries; The SnCl of 5% is adopted after drying
2solution (sensitizing solution) processes minute surface, after then using distilled water flushing cleaning, just can start silver-plated on minute surface,
Concrete steps are as follows: in a clean test tube, add 1ml 3%AgNO
3aqueous solution, dropwise instills 2% ammoniacal liquor subsequently, drips while vibrate, solution is produced to precipitation disappears just from there being precipitation, and solution becomes water white transparency, then (3-6 drips to drip suitable NaOH solution, maintain alkalescence), obtain colourless silver ammino solution.
Glucose solution is prepared: take 4g glucose and be dissolved in and mix for subsequent use in 96g distilled water, and add 1 ~ 2g tartrate in solution.
Silver ammino solution and glucose solution are mixed into upper silver-colored mixed liquor by the volume ratio of 2:1, rapidly working electrode are placed in mixed liquor and suspend, leave standstill 15 ~ 20min.Afterwards electrode is carefully taken out, with ultrapure water surface, dry in aeration-drying place.Evenly, the thickness of silver layer is about 0.5 μm to dried silver layer light.Soldering is used to fix filamentary silver, for transmitting electric signal at silver layer outside surface after working electrode completes.
In the process of silver coating, should note: upper silver-colored mixed liquor should once fill up, and can not add halfway, otherwise, minute surface is formed the flaws such as plaque-like, strip or whirlpool vestige, affect electric signal, even cause waste; Leaving standstill in process can not disturbance, otherwise depositing silver layers can adhere to insecure, and color is black dull; After plating terminates, by work cathode point slowly near the heater strip of energising.Adjustment voltage, makes the glass at parcel platinum filament tip melt and receding, exposes platinum filament, powered-down.
3) assemble coaxial type combined type oxygen microelectrode: kapillary Pasteur tip end being pulled into diameter less than 50 μm, as microelectrode column jacket, examine under a microscope pruning, make most advanced and sophisticated smooth; Working electrode after silver-plated is stretched into electrode column jacket, the tip of working electrode is apart from most advanced and sophisticated about 30 μm of column jacket, insert AgCl/AgCl silk as contrast electrode simultaneously, the relative position of three is fixed with AB glue, leave standstill solidification AB glue after 24 hours, at the most advanced and sophisticated siphon silica gel of microelectrode (Silastic Medical Adhensive Type A, Dow Corning Co., the U.S.) form oxygen permeability barrier film (i.e. layer of silica gel), its thickness is 10 ~ 20 μm.After silica gel solidification, inject with the syringe with 0.2 μm of filtering needle and boil (the 0.1mol/L NaHCO of reference solution in deoxygenation in advance
3+ 0.15mol/L Na
2cO
3the mixed liquor of+0.5mol/L KCl); Finally, with AB glue, preformed hole is sealed.By the microelectrode cover top cement plug made, insert test tube kept dry stand-by, its structural representation as shown in Figure 1:
Prepared coaxial type combined type oxygen microelectrode comprises following structure:
Work cathode column, contrast electrode and outer sleeve, work cathode column and Ag/AgCl contrast electrode are set in parallel in outer sleeve, are marked with electrolyte solution (0.1mol/L NaHCO between described outer sleeve and described work cathode column
3+ 0.15mol/L Na
2cO
3the mixed liquor of+0.5mol/L KCl), the outer wall of described work cathode column is coated with one deck 0.5 μm of silver layer, and is welded with filamentary silver at the end of silver layer surface.
Wherein, described work cathode column be inserted into green glass pipe B by the tip of white glass pipe A non-tip in the nested rear sintering of head and the tail form.
Platinum filament is equipped with at the tip of described glass tube B, the free-end of described platinum filament contacts with filamentary silver or copper wire, the other end of described platinum filament wrap up by the tip of described glass tube B and have the platinum filament of 20 μm outside exposed, and the tip diameter of glass tube B after the described platinum filament of described parcel is 10 μm, length is 2cm.
Between described outer sleeve upper end open place and described work cathode column, described work cathode column upper end open place closes by AB rubber seal.
The exposed end of the platinum filament at the tip place of described work cathode column is apart from the inner face 30 μm of described oxygen permeability barrier film.
Two, performance test:
It to the examination criteria curve of dissolved oxygen DO as shown in Figure 4, can be learnt from Fig. 4: the present embodiment, is 0.03mg O to the resolution of dissolved oxygen DO
2/ L, after connecting protection negative electrode, aftercurrent reduces by 83%, and the coaxial oxygen microelectrode response data to different partial corresponding with Fig. 4 is as shown in table 1.
It to the real-time response curve of dissolved oxygen DO as shown in Figure 5, can be learnt from Fig. 5: the present embodiment, and the response time reaching 90% maximal value is 4s.
The coaxial oxygen microelectrode of table 1. is to the response data of different partial
Claims (10)
1. a coaxial type combined type oxygen microelectrode, comprise work cathode column (3), contrast electrode (9) and outer sleeve (1), work cathode column (3) and contrast electrode (9) are set in parallel in outer sleeve, electrolyte solution (10) is marked with between described outer sleeve (1) and described work cathode column (3), it is characterized in that: the outer wall of described work cathode column (3) or the inwall of described outer sleeve (1) are coated with one deck silver layer (7), and have conductive wire (8) in described silver layer (7) surface-welding.
2. coaxial type combined type oxygen microelectrode according to claim 1, is characterized in that: the thickness of described silver layer (7) is 0.1-1 μm;
Described conductive wire (8) is selected from any one in filamentary silver, copper wire and platinum filament.
3. coaxial type combined type oxygen microelectrode according to claim 1 and 2, is characterized in that: be welded with conductive wire (8) at the end on described silver layer (7) surface.
4. the coaxial type combined type oxygen microelectrode according to any one of claim 1-3, is characterized in that: in described work cathode column (3) is inserted into glass tube B (5) non-tip by the tip of glass tube A (4), the nested rear sintering of head and the tail forms;
Platinum filament (6) is equipped with at the tip of described glass tube B (5), the free-end of described platinum filament (6) contacts with filamentary silver or copper wire (11), and the other end of described platinum filament (6) is wrapped up by the most advanced and sophisticated of described glass tube B (5) and have part platinum filament outside exposed.
5. the coaxial type combined type oxygen microelectrode according to any one of claim 1-4, is characterized in that: between described outer sleeve (1) upper end open place and described work cathode column (3), described work cathode column (3) upper end open place by epoxy resin (12) close;
One end of described outer sleeve (1) is that pointed and most advanced and sophisticated end is marked with oxygen flow silica gel (2);
Described contrast electrode (9) is Ag/AgCl contrast electrode;
Described electrolyte solution (10) is NaHCO
3, Na
2cO
3with the mixed liquor of KCl, wherein, NaHCO in described electrolyte solution
3, Na
2cO
30.01-1mol/L, 0.01-1mol/L and 0.01-3mol/L is respectively with the volumetric molar concentration of KCl.
6. the coaxial type combined type oxygen microelectrode according to any one of claim 1-5, is characterized in that: the tip diameter of the glass tube B (5) after the described platinum filament of described parcel (6) is 7 ~ 12 μm, and length is 1.5-3.0cm;
The length that described platinum filament (6) stretches into the tip of described glass tube B (5) is 1.5 ~ 2cm;
Not not being wrapped of non extensive of described platinum filament (6) and exposed platinum filament length is 10-30 μm;
The diameter at the tip of described outer sleeve (1) is less than 50 μm;
The exposed end of the platinum filament at tip (13) place of described work cathode column (3) is apart from the inner face 20-50 μm of described oxygen permeability barrier film;
The thickness of described oxygen flow silica gel (2) is 10 ~ 20 μm.
7. the preparation method of the coaxial type combined type oxygen microelectrode according to any one of claim 1-6, comprises the steps:
1) make work negative electrode: platinum filament is inserted 1-2cm in chloroazotic acid by (a), corrosion 80-90min, make the corrosion of platinum filament insertion end be 5 ~ 10 μm to diameter;
B () gets glass tube A (4) and glass tube B (5) is all drawn into tip glass tube, and the platinum filament end corroded is inserted in the tip of glass tube B (5), inserting it into length is 1.5 ~ 2cm, again glass tube A (4) tip is inserted in glass tube B (5) non-tip, sintering;
C the tip of the glass tube B (5) obtained in step (b) is fixed on heater coil centre position by (), increase heating wire both end voltage, make the tip melts of glass tube B (5) wrap platinum filament, obtain work negative electrode;
2) work cathode surface silver coating: silver ammino solution and reductibility compound are mixed to get upper silver-colored mixed liquor, and described work negative electrode is suspended in upper silver-colored mixed liquor, one deck silver layer is plated at work cathode surface, and at the upper end face place welding conductive metal silk of silver layer;
3) coaxial type combined type oxygen microelectrode is assembled: tip Pasteur pipe one end being drawn into diameter less than 50 μm, the working electrode of silver coating is loaded its centre, simultaneously, load contrast electrode wherein, with epoxy resin sealing, and by most advanced and sophisticated for Pasteur siphon silica gel, form oxygen permeability barrier film, finally, in Pasteur pipe, inject electrolyte solution, namely obtain coaxial type combined type oxygen microelectrode.
8. preparation method according to claim 7, is characterized in that: step 1) in (a), the diameter of described platinum filament is 0.05-0.2mm;
Described chloroazotic acid is by the H of volume ratio 4:1:3
2o, HNO
3form with HCl.
Step 1) in (b), the tip outer diameter of described glass tube A (4) is 1.5-2.0cm;
The tip outer diameter of described glass tube B (5) is 0.3-0.7mm;
Described heater coil is O type nickel-iron wire;
Step 1) in (c), also comprise and the tip of work negative electrode is heated, make glass melting and receding, expose the step of platinum filament;
The tip diameter of the glass tube B (5) after the described platinum filament of described parcel (6) is 7 ~ 12 μm, and length is 1.5-3.0cm.
9. the preparation method according to claim 7 or 8, is characterized in that: step 2) in, the volume ratio of described silver ammino solution and reductibility compound is 2:1;
Described reductibility compound is for containing aldehyde compound, and described is at least one in formaldehyde, acetaldehyde and glucose containing aldehyde compound;
The time of described suspension is 15 ~ 20min;
Described silver-colored mixed liquor should once fill up, and can not add halfway.
10. the preparation method according to any one of claim 7-9, is characterized in that: step 3) in, the exposed end of described platinum filament is apart from the inner face 20-50 μm of described oxygen permeability barrier film;
The thickness of described oxygen permeability barrier film is 10 ~ 20 μm;
Described electrolyte solution is NaHCO
3, Na
2cO
3with the mixed liquor of KCl, wherein, NaHCO in described electrolyte solution
3, Na
2cO
30.01-1mol/L, 0.01-1mol/L and 0.01-3mol/L is respectively with the volumetric molar concentration of KCl.
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| CN106093156A (en) * | 2016-06-01 | 2016-11-09 | 扬州大学 | The preparation method of the saturated silver silver chloride electrode in microchannel |
| CN110695470A (en) * | 2019-09-29 | 2020-01-17 | 浙江工业大学 | Electrolytic machining method and device for embedded double-cathode tube electrode |
| CN114354707A (en) * | 2021-12-16 | 2022-04-15 | 中国石油大学(华东) | Preparation method of flexible platinum-based electrochemical probe |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106093156A (en) * | 2016-06-01 | 2016-11-09 | 扬州大学 | The preparation method of the saturated silver silver chloride electrode in microchannel |
| CN110695470A (en) * | 2019-09-29 | 2020-01-17 | 浙江工业大学 | Electrolytic machining method and device for embedded double-cathode tube electrode |
| CN110695470B (en) * | 2019-09-29 | 2021-02-26 | 浙江工业大学 | Electrolytic machining method and device for embedded double-cathode tube electrode |
| CN114354707A (en) * | 2021-12-16 | 2022-04-15 | 中国石油大学(华东) | Preparation method of flexible platinum-based electrochemical probe |
| CN114354707B (en) * | 2021-12-16 | 2024-04-05 | 中国石油大学(华东) | Preparation method of flexible platinum-based electrochemical probe |
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| CN104865301B (en) | 2017-10-03 |
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