CN104865301B - A co-axial oxygen microelectrode composite type and preparation method - Google Patents

A co-axial oxygen microelectrode composite type and preparation method Download PDF

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CN104865301B
CN104865301B CN 201510204564 CN201510204564A CN104865301B CN 104865301 B CN104865301 B CN 104865301B CN 201510204564 CN201510204564 CN 201510204564 CN 201510204564 A CN201510204564 A CN 201510204564A CN 104865301 B CN104865301 B CN 104865301B
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tip
cathode
silver
oxygen
working
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CN104865301A (en )
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周小红
施汉昌
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清华大学
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Abstract

本发明公开了一种共轴型复合式氧微电极及其制备方法。 The present invention discloses a composite coaxial type oxygen microelectrode and its preparation method. 该氧微电极包括一个外部套管、位于其中心部位的工作阴极柱和位于两者之间的参比电极,所述工作阴极柱的中心部位装有铂丝,外部套管和工作阴极柱之间注有电解质溶液;工作阴极柱的外壁或外部套管的内壁镀有一层银层,并在所述的银层的上端表面处焊接有导电金属丝,构成保护阴极。 The oxygen microelectrode includes an outer sleeve, between the two reference in its central portion is located in the work string and the cathode electrode, the working center of the column portion of the cathode with a platinum wire, and the outer sleeve of the working cathode stem room marked with an electrolyte solution; between the outer wall of the column or outside the working cathode sleeve with a layer of silver plated layer, and a conductive wire welded on the upper end surface of the silver layer constituting a cathode protection. 该电极制作过程简单,拉制成功率高,结果表明:保护阴极的接通使共轴型复合式氧微电极的残余电流降低约80%,对溶解氧的响应线性相关性R2在0.99以上,对溶解氧的分辨能力约0.03mg O2/L。 The electrode manufacturing process is simple, drawing success rate, the results show that: the residue is turned cathodic protection current coaxial composite type oxygen microelectrode is reduced about 80% in response to linear correlation R2 of the dissolved oxygen above 0.99, resolution of dissolved oxygen from about 0.03mg O2 / L.

Description

一种共轴型复合式氧微电极及其制备方法 A co-axial oxygen microelectrode composite type and preparation method

技术领域 FIELD

[0001] 本发明涉及一种微电极及其制备方法,特别涉及一种共轴型复合式氧微电极及其制备方法。 [0001] The present invention relates to a micro-electrode and its preparation method, particularly to a coaxial type oxygen microelectrode compound and its preparation method.

背景技术 Background technique

[0002] 氧微电极是迄今为止技术最成熟的电极,从结构上分为复合式和分离式两种。 [0002] The oxygen microelectrode is by far the most mature technology electrode into the composite structure and separate two. 分离式氧微电极结构简单,通常用玻璃毛细管包裹铂丝或低熔点合金,尖端镀金。 Simple separation type oxygen microelectrode structure, usually a platinum wire wrapped with glass capillary or low melting point alloy, gold-plated tip. 由于一般的玻璃毛细管与铂丝的线膨胀系数不同,因此直接包裹铂丝的过程并不容易,两者之间常常出现裂缝从而影响到电极性能。 Due to the different linear expansion coefficient of the glass capillary general platinum wire, a platinum wire wrapped directly and therefore not easy to process, often cracks therebetween affecting the electrode performance. 最常见的分离式氧微电极的做法是在玻璃毛坯中灌注低熔点合金,然后在电极尖端镀上金或铂充当氧的还原区,与铂金属相比较,金具有更宽的氧极化平台[Brito PSD and Sequeira CA C. Cathodic oxygen reduction on noble metal and carbon electrodes. J Power Sources, 1994,52:1-16·],因此,更适合于作为电极材料。 The most common practice separate oxygen microelectrode perfusion low-melting alloy in the glass blank, and then plated with gold or platinum electrode tip region to act as the reduction of oxygen, as compared with platinum metal, metal oxide having a wider platform polarization [ brito PSD and Sequeira CA C. Cathodic oxygen reduction on noble metal and carbon electrodes J Power Sources, 1994,52:. 1-16 ·], and therefore, is more suitable as an electrode material. 合金是分离式氧微电极制作的关键材料,经过Dowben,Whalen和Linsenmeier等人逐步深入的研究,合金材料由铟、锡合金(50%Indium+50%Tin,熔点Il(TC)过渡到Wood 合金(50%8丨811111也+26.7%1^3(1+13.3%1111+10%〇3(1111丨11111,熔点73-75°(:),最后一种羾合金(44 · 7 %Bi+22 · 6 %Pb+19 · 1 % In+8 · 3 % Sn+5 · 3 % Cd,熔点47 °C)材料逐渐得到了推广使用, 这种合金以Bi为主要成分,恪点低,体积膨胀系数小[Dowben RM and Rose J EA metal-filled microelectrode .Sci,1953,118:22-24;ffhalen ff J1Riley J and Nair PA microelectrode for measuring intracellular P02, J Appl Physiol,1967,23:798-801;Linsenmeier RA and Yancy C M.Improved fabrication of double-barreled recessed cathode 02microelectrodes . 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.KBi合金能够降低合金固化后由体积膨胀造成的玻璃裂缝的可 Alloy is the key material separate microelectrode produced oxygen, study after Dowben, Whalen and Linsenmeier et al gradual deepening, alloys transition from indium, tin alloy (50% Indium + 50% Tin, m.p. Il (TC) to Wood alloy (also 50% 8 811 111 + 26.7% Shu ^ 3 1 (1 + 13.3% + 10% 〇3 1111 (1111 Shu 11111, mp 73-75 ° (:), the last Hong alloy (44 · 7% Bi + 22 · 6% Pb + 19 · 1% in + 8 · 3% Sn + 5 · 3% Cd, m.p. 47 ° C) to promote the use of the material gradually, such an alloy containing Bi as a main component, the low point Ke, volume expansion coefficient [Dowben RM and Rose J EA metal-filled microelectrode .Sci, 1953,118: 22-24; ffhalen ff J1Riley J and Nair PA microelectrode for measuring intracellular P02, J Appl Physiol, 1967,23: 798-801; Linsenmeier RA and Yancy C M.Improved fabrication of double-barreled recessed cathode 02microelectrodes 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.KBi glass alloys can be reduced after solidification of the alloy cracks caused by volume expansion 性,提高了电极制作的成功率,并延长了电极使用寿命。此外,分离式氧微电极的拉制过程也得到了简化,包括不需要清洗玻璃毛细管,不需要腐蚀尖端合金形成凹处等过程,进一步突出了易于制作的优点。但是分离式电极的缺点也很明显,测试信号容易受到外界电磁信号及震动的影响,测试过程中需要与外参比电极联用,在氧的还原电位下还会有其他氧化性物质参与反应,从而影响到测试结果的准确性。 Resistance, improve the success rate of electrode fabrication, and extends the life of the electrodes. Further, the drawing process separate oxygen microelectrode has been simplified, including no cleaning glass capillary tip does not require etching processes such as an alloy of recesses further highlight the advantage of being easily fabricated, but the disadvantages of separate electrodes is also apparent, the test signal is easily affected by external electromagnetic signals and vibration testing process needs external reference electrode in combination with further in the reduction potential of oxygen there will be other oxidizing substances involved in the reaction, thus affecting the accuracy of the test results.

[0003] 复合式氧微电极能够很好地弥补以上缺点,它是一种微型化的Clark型传感器。 [0003] Composite oxygen microelectrode can well compensate for the above shortcomings, it is a miniaturized Clark type sensor. 工作阴极和参比电极平行放置在一根玻璃外管中。 The working cathode and a reference electrode disposed in parallel with a glass outer tube. 外管中的内参比电解质溶液覆盖工作阴极,起到了良好的屏蔽作用。 Outer tube internal reference electrolyte solution cover the working cathode, played a good shielding effect. 玻璃外管尖端覆盖一层氧透过性隔膜,可以阻隔样品中的其它氧化性物质在工作阴极表面还原。 Outer glass tube tip covered with an oxygen permeable membrane, the sample can be blocked in other oxidative species reduction in the working surface of the cathode. 由于内充液中的氧也会在阴极表面还原,使得复合式氧微电极的残余电流较高,可达到200pA左右,而且随着残余电流的变化,电极输出信号的稳定性很弱。 Since the filling of oxygen will be reduced at the cathode surface, so that the residual current type oxygen microelectrode complex higher, up to about 200pA, and with the change of the residual current, the output signal is weak stability of the electrode. 1989年,Revsbech提出了一种改进的Clark型氧微电极,在电极中加入保护阴极, 作用是消耗内参比液中的氧[Revsbech N P.An oxygen microsensor with a guard cathode.Limnol Oceanogr,1989,34 (2) :474-478.]。 1989, Revsbech proposed an improved Clark type oxygen microelectrode was added in protecting the cathode electrode, is the effect of consumption of the internal reference liquid oxygen [Revsbech N P.An oxygen microsensor with a guard cathode.Limnol Oceanogr, 1989, 34 (2): 474-478]. 保护阴极是一根腐蚀后的银丝,尖端约5μπι左右,保护阴极尖端与工作阴极尖端需要精确定位两者间的位置,以达到降低残留电流的作用。 Protect the cathode is a silver corrosion after the tip about about 5μπι, protecting the cathode tip and the working position of the cathode tip requires precise positioning between the two, in order to reduce the effect of the residual current. 但是以这种形式加入的保护阴极也带来了一系列弊端。 But added to this form of cathodic protection also brought a series of drawbacks. 包括:为了给保护阴极留出放置的空间,玻璃外管的尖端直径必须要增大,因此,获得IOym以内的微电极尖端直径变得非常困难,微电极的应用范围大大受限;精确调节工作阴极与保护阴极尖端距离完全依赖于显微镜和人工操作,调控过程复杂困难,拉制成功率低。 Comprising: in order to protect the cathode leave space for the tip diameter of the outer glass tube must be increased, and thus, to obtain a tip diameter of the micro electrode within IOym becomes very difficult, the application range is greatly limited microelectrodes; precise adjustment work protect the cathode from the cathode and is totally dependent on the microscope tip and manual operation, the regulation process complex and difficult, drawn low success rate.

发明内容 SUMMARY

[0004] 本发明的目的在于提供一种共轴型复合式氧微电极及其制备方法。 [0004] The object of the present invention is to provide a coaxial type oxygen microelectrode compound and its preparation method.

[0005] 本发明所提供的共轴型复合式氧微电极,包括工作阴极柱、参比电极和外部套管, 工作阴极柱和参比电极平行设置于外部套管内,所述外部套管和所述工作阴极柱之间注有电解质溶液,所述工作阴极柱的外壁或所述外部套管的内壁镀有一层银层,并在所述银层表面焊接有导电金属丝。 [0005] coaxial type oxygen microelectrode composite of the present invention is provided, comprising a working cathode stem, reference electrode and the outer sleeve, the working and reference column cathode electrodes arranged in parallel within the outer sleeve and the outer sleeve Note the working cathode with an electrolyte solution between the column inner wall of the working cathode stem outer wall or the outer sleeve with a layer of silver plated layer, and a conductive wire welded on the surface of the silver layer.

[0006] 上述共轴型复合式氧微电极中,所述银层的厚度为0.1-1μπι。 [0006] The coaxial composite type oxygen microelectrode, the thickness of the silver layer is 0.1-1μπι.

[0007] 所述导电金属丝选自银丝、铜丝和铂丝中任一种,优选为在所述银层表面的末端焊接有导电金属丝。 The [0007] conductive metallic wire is selected from silver, copper and platinum wire of any one, preferably at an end surface of the silver layer with a conductive metal welding wire. 所述银层表面的末端指靠近所述工作阴极柱非尖端处的一端。 The end surface of the silver layer is a non-working end of the finger near the cathode stem tip.

[0008] 所述工作阴极柱由玻璃管A的尖端插入到玻璃管B的非尖端内首尾嵌套后烧结而成。 [0008] The working cathode stem inserted into the non-sintered tip end to end within a glass tube nested B A tip of the glass tube.

[0009] 所述玻璃管B的尖端装有铂丝,所述铂丝的游离端与银丝或铜丝接触,所述铂丝的另一端被所述的玻璃管B的尖端所包裹、且有部分铂丝裸露在外。 The free end of the [0009] B of the glass tube with the tip of a platinum wire, the platinum wire in contact with copper or silver, the platinum wire and the other end of the glass tube being encased tip B, and platinum wire exposed part.

[0010] 所述外部套管上端开口处和所述工作阴极柱之间、所述工作阴极柱上端开口处均由环氧树脂封闭。 [0010] The upper end of the outer sleeve between the opening and the working cathode column, the column side cathode working opening is closed by an epoxy resin.

[0011] 所述外部套管的一端为尖状且尖端末尾注有透氧硅胶。 [0011] The end of the outer sleeve is tapered and the tip end of the silica gel impregnated with oxygen.

[0012] 所述参比电极为Ag/AgCl参比电极。 [0012] The reference electrode was Ag / AgCl reference electrode.

[0013] 所述电解质溶液为NaHC03、Na2⑶3和KC1的混合液,其中,所述电解质溶液中NaHC〇3、Na2C〇3 和KCl 的摩尔浓度分别为0 · 01-lmol/L、0 · ΟΙ-lmol/L和0 · 01-3mol/L。 [0013] The electrolyte solution is NaHC03, Na2⑶3 KC1, and a mixture, wherein the electrolyte solution NaHC〇3, Na2C〇3 molar concentration and KCl were 0 · 01-lmol / L, 0 · ΟΙ- lmol / L and 0 · 01-3mol / L.

[0014] 所述包裹所述铂丝后的玻璃管B的尖端直径为7〜12μπι,长度为1.5-3.0cm。 [0014] The wrapping of the tip diameter of the glass tube after the platinum wire B is 7~12μπι, a length of 1.5-3.0cm.

[0015] 所述铂丝伸入所述玻璃管B的尖端的长度为1.5〜2cm。 The [0015] platinum wire extending into the tip of the glass tube length B is 1.5~2cm.

[0016] 所述铂丝的非游离端的未被包裹而裸露在外的铂丝长度为10_30μπι。 [0016] The platinum wire unencapsulated non-free end of the platinum wire exposed length 10_30μπι.

[0017] 所述外部套管的尖端的直径小于50μπι。 The tip diameter of the outer sleeve of the [0017] less than 50μπι.

[0018] 所述工作阴极柱的尖端处的铂丝的裸露端距所述氧透过性隔膜的内端面20_50μ m〇 [0018] The exposed end of the platinum wire at the tip of the work string from said oxygen cathode 20_50μ m〇 pervious inner end surface of the separator

[0019] 所述透氧娃胶的厚度为10〜20μηι。 [0019] The thickness of the oxygen baby gum is 10~20μηι.

[0020] 所述环氧树脂具体可为AB胶。 [0020] The epoxy resin may be specifically AB glue.

[0021] 所述被玻璃管B的尖端所包裹的铂丝,还包括预先对其腐蚀的步骤,所述未被腐蚀的钼丝的直径为0.05-0.2mm,具体可为0.1mm,所述腐蚀后的钼丝的直径为5〜ΙΟμπι。 [0021] The glass tube B is wrapped by a platinum wire tip, further comprising the step of etching its advance, the diameter of the molybdenum wire unetched as 0.05-0.2 mm, particularly may be 0.1mm, the diameter molybdenum wire after etching is 5~ΙΟμπι.

[0022] 本发明所提供的共轴型复合式氧微电极的制备方法,包括如下步骤: [0022] The method of preparing composite coaxial type oxygen microelectrode of the present invention is provided, comprising the steps of:

[0023] 1)制作工作阴极:(a)将钼丝插入王水中l-2cm,腐蚀80-90min,使钼丝插入端腐蚀至直径为5〜ΙΟμπι; [0023] 1) Production of Cathode work: (a) a molybdenum wire into the aqua regia l-2cm, corrosion 80-90min, etching molybdenum wire insertion end to a diameter of 5~ΙΟμπι;

[0024] (b)取玻璃管A和玻璃管B均拉制成尖嘴玻璃管,并将已腐蚀的铂丝端插入到玻璃管B的尖端中,使其插入长度为1.5〜2cm,再将玻璃管A尖端插入绿玻璃管B非尖端中,烧结; [0024] (b) take both glass A and glass B beak drawn into a glass tube, and the platinum wire inserted corroded to a tip end of the glass tube B, so that the insertion length of 1.5~2cm, then A glass tube was inserted into the tip of the tip of the non-green glass B, the sintered;

[0025] (c)将步骤(b)中得到的玻璃管B的尖端固定在加热线圈中间位置,增大电热丝两端电压,使玻璃管B的尖端熔化包裹住铂丝,得到工作阴极。 [0025] (c) the tip of the step (b) B is obtained in a glass tube fixed to an intermediate position in the heating coil, the voltage across the heating wire is increased, the tip of the molten glass B wrap platinum wire cathode to obtain work.

[0026] 2)工作阴极表面镀银层:将银氨溶液和还原性化合物混合得到上银混合液,并将所述工作阴极悬浮于上银混合液中,在工作阴极表面镀上一层银层,并在银层的上端表面处焊接导电金属丝。 [0026] 2) the working cathode surface layer of silver: silver mixing ammonia solution and a reducing compound to give a mixture of silver, and the working cathode suspended in a mixture of silver, the working surface of the cathode coated with a layer of silver layer, and a conductive wire welded on the upper end surface of the silver layer.

[0027] 3)组装共轴型复合式氧微电极:将巴斯德管一端拉制成直径50μπι以下的尖端(即毛细管),将镀银层的工作电极装入其中心部位,同时,在其中装入参比电极,用环氧树脂封口,并将巴斯德管尖端虹吸硅胶,形成氧透过性隔膜,最后,在巴斯德管内注入电解质溶液, 即得到共轴型复合式氧微电极。 [0027] 3) coaxially assembled composite type oxygen microelectrode: one end of the pipe is drawn into the tip Pasteur (i.e. capillary tube), the working electrode is charged with a silver plating layer below the center thereof 50μπι diameter, while, in wherein the reference electrode is charged with an epoxy resin sealing, and the siphon tube tip Pasteur silica, form an oxygen-permeable membrane, and finally, injecting an electrolyte solution in the Pasteur tube, i.e. to obtain coaxial type composite oxide micro electrode.

[0028] 上述制备方法中,步骤I) (a)中,所述钼丝的直径为0.05-0.2mm,具体可为0.1mm。 [0028] In the above preparation method, step I) (a), the molybdenum wire having a diameter of 0.05-0.2 mm, particularly may be 0.1mm.

[0029] 所述王水由体积比4:1:3的H20、HN〇3和HCl组成。 [0029] The aqua regia by the volume ratio 4: 1: 3 H20, and HCl HN〇3 composition.

[0030] 步骤I) (b)中,所述玻璃管A的尖端外径为1.5-2.0cm,具体可为2cm。 In [0030] Step I) (b), the tip of the outer diameter of the glass tube A is 1.5-2.0cm, particularly may be 2cm.

[0031] 所述玻璃管B的尖端外径为0.3-0.7mm,具体可为0.5mm。 [0031] The outer diameter of the tip of the glass tube B is 0.3-0.7mm, particularly may be 0.5mm.

[0032] 所述烧结是将待烧结的玻璃管置于酒精灯或其它火焰上,反复旋转,直至达到所需标准。 [0032] The glass to be sintered is placed on a sintered alcohol lamp or other flame, repeated rotation, until the desired standard.

[0033] 所述加热线圈为0型镍铁丝。 [0033] The heating coil is a nickel wire 0.

[0034] 上述制备方法中,步骤I) (c)中,还包括对工作阴极的尖端进行加热,使玻璃熔化并向后缩,露出铂丝的步骤。 [0034] The preparation process, step I) (c), further comprising a cathode tip to the work by heating, and the molten glass after condensing, step a platinum wire is exposed.

[0035] 所述包裹所述铂丝后的玻璃管B的尖端直径为7〜12μπι,具体可为ΙΟμπι,长度为1.5-3.0cm,具体可为2.5cm。 [0035] The wrapping of the tip diameter of the glass tube after the platinum wire B is 7~12μπι, it may be particularly ΙΟμπι, length 1.5-3.0cm, may be particularly 2.5cm.

[0036] 上述制备方法中,步骤2)中,所述银氨溶液和还原性化合物的体积比为2:1。 [0036] In the above preparation method, step 2), the volume of the ammonia solution of silver compound and a reducing ratio of 2: 1.

[0037] 所述还原性化合物为含醛基化合物,所述含醛基化合物为甲醛、乙醛和葡萄糖中的至少一种。 The [0037] compound containing a reducing aldehyde compound, the aldehyde group-containing compound is at least one of formaldehyde, acetaldehyde, and dextrose.

[0038] 所述悬浮的时间为15〜20min。 [0038] The suspension time 15~20min.

[0039] 上述制备方法中,步骤3)中,所述铂丝的裸露端距所述氧透过性隔膜的内端面20-50μηι,具体可为30μηι。 [0039] In the above-described production method, in step 3), the exposed end of the platinum wire from the oxygen-permeable inner end surface of the separator 20-50μηι, may be particularly 30μηι.

[0040] 所述氧透过性隔膜的厚度为10〜20μπι。 [0040] The oxygen permeability of the separator thickness is 10~20μπι.

[0041] 所述上银混合液应当一次加足,不可中途补加。 [0041] The silver add a little mixture should not be supplemented halfway.

[0042] 所述电解质溶液为NaHC03、Na 2⑶3和K C1的混合液,其中,所述电解质溶液中NaHC〇3、Na2C〇3 和KCl 的摩尔浓度分别为0.05-0.15mol/L、0.10-0.20mol/L和0.45-0.55mol/ L,具体可分别为0. lmol/L、0.15mol/L和0.5mol/L。 [0042] The electrolyte solution is NaHC03, Na 2⑶3 K C1 and a mixture, wherein the electrolyte solution NaHC〇3, Na2C〇3 molar concentration and KCl were 0.05-0.15mol / L, 0.10-0.20 mol / L and 0.45-0.55mol / L, respectively, may be particularly 0. lmol / L, 0.15mol / L and 0.5mol / L.

[0043] 所述参比电极为Ag/AgCl参比电极。 [0043] The reference electrode was Ag / AgCl reference electrode.

[0044] 所述环氧树脂具体可为AB胶。 [0044] The epoxy resin may be specifically AB glue.

[0045] 本发明制备的共轴型复合式氧微电极,克服了传统复合式溶解氧微电极的缺点, 对其结构进行优化,根据银镜反应原理,在工作电极柱外表面或者外部套管内壁镀银层,然后在镀层末端连接电导线,作为保护阴极,简化了电极制作过程,使电极拉制成功率得到了显者提尚。 [0045] The coaxial type oxygen microelectrode composite prepared according to the invention, overcomes the drawbacks of conventional compound dissolved oxygen microelectrode optimize its structure, according to principles of the silver mirror reaction, within the outer sleeve or in the outer cylindrical surface of the working electrode wall silver plating layer, the plating is then connected to the end of the electrical lead, as protecting the cathode, the electrode manufacturing process is simplified, the power drawn into the electrode obtained by the mention still significant.

[0046] 与现有技术相比,本发明具有如下有益效果: [0046] Compared with the prior art, the present invention has the following advantages:

[0047] (1)在工作电极柱外表面或者外部套管内壁镀银层,然后在镀层末端连接电导线, 作为保护阴极,简化了电极制作过程,使电极拉制成功率得到了显著提高。 [0047] (1) on the outer cylindrical surface of the working electrode or the inner wall of the outer sleeve silver plating layer, and electrically connected to the end of wire coating, as protecting the cathode, the electrode manufacturing process is simplified, and the electrode drawn into the power has been significantly improved.

[0048] (2)其具有很高的空间分辨率,能够实现微环境中溶解氧的定量检测,相应的测试性能结果表明:本发明的共轴型复合式氧微电极在接通保护阴极前后的残余电流降低80% 左右,对溶解氧的响应线性相关性R2在0.99以上,对溶解氧浓度的分辨能力约0.03mg 02/L。 [0048] (2) with a high spatial resolution can be achieved in the quantitative detection of dissolved oxygen in the microenvironment of the respective test performance results show: coaxial type oxygen microelectrode composite of the present invention before and after the cathodic protection ON the residual current is reduced about 80% in response to linear correlation R2 of the dissolved oxygen above 0.99, the resolving power of the dissolved oxygen concentration of from about 0.03mg 02 / L.

[0049] (3)铂丝的一端与银丝或铜丝接触,不完全采用铂丝的优点如下:a)铂丝昂贵,将其部分用银丝或铜丝替代,可降低制作成本;b)可采用粗银丝或铜丝,相对牢固,不易折断, 且便于后续反复使用;c)铂丝只需与银丝或铜丝接触即可,无需焊接,故即使上面有部分位移,亦不影响下面铂丝,避免被包裹的脆弱铂丝折断。 [0049] (3) in contact with one end of a platinum wire or silver copper wire, a platinum wire is not completely following advantages: a) Scion expensive platinum, silver or the part thereof with copper Alternatively, the manufacturing cost can be reduced; B ) the crude silver or copper may be employed, relatively strong, not easily broken, and ease of subsequent re-use; c) into contact with the platinum wire only silver or copper can be, without welding, so that even if some displacement above, nor the following effects of platinum wire, to avoid being wrapped fragile platinum wire snapped.

附图说明 BRIEF DESCRIPTION

[0050] 图1为实施例1中的共轴型复合式氧微电极结构示意图,其中,外部套管(1)、透氧硅胶⑵、工作阴极柱(3)、玻璃管A (4)、玻璃管B (5)、铂丝(6)、银层(7)、导电金属丝(8)、Ag/ AgCl参比电极(9)、电解质溶液(10)、银丝或铜丝(11)、环氧树脂(12)、工作阴极柱的尖端(13) 〇 Schematic coaxial type oxygen microelectrode composite structure [0050] Example 1 is an embodiment, wherein the outer sleeve (1), oxygen silica ⑵, working cathode stem (3), a glass tube A (4), glass B (5), platinum wires (6), a silver layer (7), a conductive wire (8), Ag / AgCl reference electrode (9), an electrolyte solution (10), silver or copper (11) , the epoxy resin (12), a tip (13) working cathode square column

[0051] 图2为实施例1中的包裹铂丝前的工作阴极示意图。 [0051] FIG. 2 is a schematic view of the working cathode in Example 1 prior to platinum wire wrapped embodiment.

[0052] 图3为实施例1中包裹铂丝的装置示意图。 [0052] FIG. 3 is a schematic view of embodiment apparatus of the embodiment 1 of platinum wire wrapping.

[0053] 图4为实施例1中的共轴型复合式氧微电极对溶解氧的检测标准曲线。 [0053] FIG. 4 is a composite coaxial type oxygen microelectrode in Example 1 for detecting a standard curve of dissolved oxygen.

[0054] 图5为实施例1中的共轴型复合式氧微电极对溶解氧的实时响应曲线。 Real-time response curve of compound of formula coaxial type oxygen microelectrode [0054] Example 5 is an embodiment of dissolved oxygen.

具体实施方式 detailed description

[0055] 下面通过具体实施例对本发明的方法进行说明,但本发明并不局限于此,凡在本发明的精神和原则之内所做的任何修改、等同替换和改进等,均应包含在本发明的保护范围之内。 [0055] The following specific examples by the method of the present invention will be described, but the present invention is not limited thereto, where any modifications within the spirit and principle of the present invention, equivalent substitutions and improvements should be included in the within the scope of the present invention.

[0056] 下述实施例中所述实验方法,如无特殊说明,均为常规方法;所述试剂和材料,如无特殊说明,均可从商业途径获得。 [0056] In the following examples the experimental procedure, if no special instructions, all conventional methods; the reagents and materials, as no special instructions, are available from commercial sources.

[0057] 实施例1、制备共轴型复合式氧微电极及其性能测试: [0057] Example 1. Preparation of Compound of Formula coaxial type oxygen microelectrode and performance test:

[0058] 一、制备共轴型复合式氧微电极: [0058] First, the prepared composite coaxial type oxygen microelectrode:

[0059] 按图1所示的结构示意图制备共轴型复合式氧微电极: [0059] in Figure 1 a schematic view of the structure shown in FIG prepared coaxial type oxygen microelectrode compound of formula:

[0060] 1)制作工作阴极:采用沸腾的王水(H20:HN03:HC1 = 4:1:3、体积比)将直径为0. Imm 的铂丝(纯度99.95%,购自中国医药(集团)上海化学药剂公司)尖端腐蚀至5〜ΙΟμπι,具体可将王水置于IOOmL烧杯中,并于水浴锅内升温,再将铂丝插入王水中2cm,腐蚀90min后,可钼丝尖端腐蚀至5μηι。 [0060] 1) Production of Cathode work: The boiling aqua regia (H20: HN03: HC1 = 4: 1: 3, volume ratio) having a diameter of 0. Imm platinum wire (99.95% purity, purchased from China Pharmaceutical (Group ) Shanghai chemical company) to tip corrosion 5~ΙΟμπι, aqua regia may be specifically placed IOOmL beaker pot and warmed in a water bath, and then aqua regia the platinum wire is inserted 2cm, after etching 90min, molybdenum wire tip can be corrosive to 5μηι.

[0061] 取白玻璃管(硬质中性玻璃,外径为3.33mm,内径为2.69mm,购自北京奥特玻璃管研究所)和绿玻璃管(8533型,外径3.33mm;内径,2.69mm,购自德国肖特公司)若干根,充分清洗后烘干,用手拉制尖嘴玻璃管。 [0061] Take a white glass (hard glass neutral, an outer diameter of 3.33 mm, an inner diameter of 2.69mm, available from Beijing Institute Ott glass), and green glass (type 8533, an outer diameter of 3.33 mm; inner diameter, 2.69mm, available from Schott, Germany) a plurality of roots, after sufficient washing and drying, hand drawn glass beak. 白玻璃管管尖外径拉至2cm,绿玻璃管管尖外径拉至0.5mm。 White glass pulled to an outer diameter of the tip 2cm, green glass is pulled to the outer diameter of the tip 0.5mm. 将腐蚀好的铂丝慢慢插入绿玻璃管的毛细管中,铂丝伸入长度为1.5〜2cm,将白玻璃管A (4)管尖插入绿玻璃管B (5)外端(如图2所示),采用烧结方法组装工作阴极。 The good corrosion platinum wire inserted slowly green glass capillary, the protrusion length of platinum wire 1.5~2cm, the white glass A (4) is inserted into the tip of the glass tube Green B (5) the outer end (in FIG. 2 shown), a cathode assembly work by sintering method.

[0062] 以0型镍铁丝为加热元件,将加热丝连接到稳压电源,将阴极工作柱的毛细管尖端穿过加热丝,固定于三维微操作台上,保持阴极工作柱竖直悬在空中(如图3所示)。 [0062] 0 to nickel wire heating element, the heating wire is connected to the power supply, the operation of the cathode tip of the capillary column through a heating wire, three-dimensional microstructure is fixed to the operating table, the vertical column to maintain operation of the cathode in the air (As shown in Figure 3). 调整三维微操作台,使阴极工作柱毛细管位于〇型加热丝中央,铂丝尖端距〇型加热丝1〜1.5cm。 Through three-dimensional micro-console, the cathode is located in the work string capillary central square type heating wire, a platinum wire from the tip of the square-type heating wire 1~1.5cm. 缓慢增大电热丝两端电压,开始加热。 Gradually increasing the voltage across the heating wire, heating was started. 上下移动阴极工作柱的受热部位,使其受热均匀。 Vertically moving cathode heated portion of the work string, it is heated evenly. 当电压升至4〜5V时,绿玻璃开始软化,这时迅速增大电压,玻璃急剧受热后迅速熔化,并包裹住铂丝尖端,整个阴极工作柱落入下方烧杯中。 When the voltage is raised 4~5V, green glass starts to soften, then the voltage increases rapidly, the rapid melting of the glass is heated abruptly, and wrapped around the tip of a platinum wire, the entire operation of the cathode in the column falls below a beaker. 在体视显微镜(XTL-20,购自北京泰克仪器)观察下,确保铂丝尖端完全被绿玻璃管包裹。 Stereomicroscope (XTL-20, available from Tektronix Beijing) under observation to ensure that the tip of the platinum wire wrapped completely green glass.

[0063] 2)在工作阴极表面覆盖银层:利用具还原性的化合物(如醛、单糖、酒石酸钾钠盐等)将银氨配离子还原,使其中的金属银以紧密排列成银箱的方式在洁净的玻璃表面形成银镜。 [0063] 2) covering the silver layer on the cathode surface of the work: the use of a compound having reducing ability (such as aldehydes, monosaccharides sodium tartrate salts, etc.) The reduction of silver ammonia complex ion, wherein the metal silver is so closely arranged to form a silver tank the silver mirror is formed on the glass surface clean. 为了使金属银能在镜面上均匀析出并牢固附着,除了要用酸碱处理、洗涤,使镜面清洁外,还要对镜面进行“敏化”处理,其原因在于:镜面的硅酸钠经酸碱处理时,一部分成为硅酸。 In order for the precipitated metallic silver can be uniformly and firmly adhered to the mirror surface, in addition to use the acid and alkali treatment, washing, cleaning the outer mirror, mirror surface but also on the "sensitization" treatment, the reason is: sodium silicate by acid mirror alkali treatment, become part of silicic acid. 当镀银时,银与硅酸交换速度较慢,而镀液中的碱离子与硅酸交换速度很快,这种活性的差异就影响了镀层的均匀。 When the silver, silver silicate slow exchange, and the bath alkali silicate ion-exchange fast, this difference in activity affecting the uniformity of the coating. 因此,使用乙醇和丙酮浸泡处理工作电极,在清洁通风处晾干;晾干之后采用5%的SnCl2溶液(敏化液)处理镜面,然后用蒸馏水冲洗洁净后,才可在镜面上开始镀银, Thus, the use of ethanol and acetone soaking the working electrode, dry cleaning ventilation; after drying of 5% of the SnCl2 solution (sensitizing solution) for the mirror, and then after rinsing with distilled water cleansing should be started on the silver mirror ,

[0064] 具体步骤如下:在一支洁净的试管中,加入Iml 3%AgN03水溶液,随后逐滴滴入2%氨水,边滴边振荡,使溶液从有沉淀产生至沉淀恰好消失为止,溶液变成无色透明,再滴加适当的NaOH溶液(3-6滴,维持碱性即可),得到无色银氨溶液。 [0064] The specific steps are as follows: In a clean test tube, Iml 3% AgN03 aqueous solution was added, followed by the dropwise into 2% aqueous ammonia, while shaking drip edge, so that the resulting solution to precipitate a precipitate from just disappeared, the solution became into a colorless transparent, was added dropwise the appropriate NaOH solution (3-6 drops, can maintain the basic) to give a colorless silver ammonia solution.

[0065] 葡萄糖溶液配制:称取4g葡萄糖溶解在96g蒸馏水中混匀备用,并向溶液中添加1 〜2g酒石酸。 [0065] Glucose solution preparation: Weigh 96g 4g glucose were dissolved in distilled water and mix standby, and add 1 ~2g tartrate solution.

[0066] 把银氨溶液与葡萄糖溶液按2:1的体积比混合成上银混合液,迅速将工作电极置于混合液中悬浮,静置15〜20min。 [0066] The silver ammonia solution and glucose solution at 2: 1 volume ratio of silver mixed into the mixture, quickly placed in a suspension of the working electrode mixture was allowed to stand 15~20min. 之后将电极小心取出,用超纯水冲洗表面,在通风干燥处晾干。 After the electrode is carefully removed, rinsed with ultrapure water surface, dried in a dry place. 干燥后的银层光亮均匀,银层的厚度约为〇.5μπι。 Bright silver layer after drying uniform thickness of the silver layer is about 〇.5μπι. 工作电极制作完成之后在银层外表面使用锡焊固定银丝,用于传递电信号。 After completion of the working electrode was fixed to the surface using silver soldering the outer silver layer, for transferring electrical signals.

[0067] 镀银层的过程中,应注意:上银混合液应当一次加足,不可中途补加,否则,镜面上形成斑状、条状或漩涡痕迹等瑕疵,影响电信号,甚至造成浪费;静置过程中不可扰动,否则沉积银层会附着不牢固,颜色暗黑;电镀结束后,将工作阴极尖端缓慢靠近通电的加热丝。 Process [0067] silver layer, should be noted: a mixture of silver should add a little, not supplemented halfway, and otherwise, a plaque, strip or swirl marks and other defects on the mirror, electrical impact, or even wasted; not disturbed during standing, or deposited silver layer adheres weak, dark color; after plating, the working tip of the cathode heating wire energized slowly close. 调整电压,使包裹铂丝尖端的玻璃融化并向后缩,露出铂丝,关闭电源。 Adjusting the voltage so that the tip of the platinum wire wrapped glass melted and reduced, is exposed platinum wire, turn off the power.

[0068] 3)组装共轴型复合式氧微电极:将巴斯德管尖端拉成直径50μπι以下的毛细管,做为微电极外柱,在显微镜下观察修剪,使尖端平整;将镀银之后的工作电极伸入电极外柱, 工作电极的尖端距外柱尖端30μπι左右,同时插入AgCl/AgCl丝作为参比电极,用AB胶固定三者的相对位置,静置固化AB胶24小时后,在微电极尖端虹吸硅胶(Silastic Medical Adhensive Type A,Dow Corning Co.,美国)形成氧透过性隔膜(即娃胶层),其厚度为10〜 20μπι。 [0068] 3) coaxially assembled composite type oxygen microelectrode: drawn into the tube tip Pasteur 50μπι capillary diameter or less, as microelectrodes outer column, was observed under the microscope trimmed, the tip level; after the silvering working electrode projects into the outer column electrode, the tip of the working electrode from the tip about the outer column 30μπι, while inserting AgCl / AgCl wire as the reference electrode, the relative position of three glue AB, AB glue solidified on standing for 24 hours, in the microelectrode tip siphon silica gel (Silastic Medical Adhensive Type A, Dow Corning Co., USA) to form an oxygen permeable membrane (i.e., Wa subbing layer) having a thickness of 10~ 20μπι. 硅胶固化后,用带有0.2μπι过滤针头的注射器注入预先煮沸除氧的内参比溶液(0.1mol/L NaHC03+0.15mol/L Na2C〇3+0.5mol/L KCl的混合液);最后,用AB胶将预留孔密封。 After curing silica gel, using a syringe with a needle injection 0.2μπι filter boiled in advance internal reference oxygen (Na2C〇3 + 0.5mol / L KCl mixture of 0.1mol / L NaHC03 + 0.15mol / L) ratio of solution; Finally, AB glue prepared hole sealed. 将制作好的微电极套上胶塞,插入试管干燥保存待用,其结构示意图如图1所示: Microelectrodes will make a good plug sleeve, into the cell stored dry stand, a schematic view of the structure shown in Figure 1:

[0069] 所制备的共轴型复合式氧微电极包括如下结构: [0069] The coaxial type composite oxide prepared microelectrode comprising the following structure:

[0070] 工作阴极柱、参比电极和外部套管,工作阴极柱和Ag/AgCl参比电极平行设置于外部套管内,所述外部套管和所述工作阴极柱之间注有电解质溶液(〇. lmol/L NaHCO3+ 0.15mol/L Na2C03+0.5mol/L KCl的混合液),所述工作阴极柱的外壁镀有一层0·5μπι银层, 并在银层表面的末端焊接有银丝。 [0070] Work cathode stem, reference electrode and the outer sleeve, the working cathode stem and Ag / AgCl reference electrode disposed in parallel within the outer casing, impregnated with an electrolyte solution between the outer sleeve and the working cathode stem ( square. lmol / L NaHCO3 + 0.15mol / L Na2C03 + 0.5mol / L KCl mixed solution), an outer wall of the working cathode is coated with a layer column 0 · 5μπι silver layer, and a silver at the end of the welding surface of the silver layer.

[0071] 其中,所述工作阴极柱由白玻璃管A的尖端插入到绿玻璃管B的非尖端内首尾嵌套后烧结而成。 [0071] wherein said working tip inserted by the cathode column A to the white glass after sintering non-nested end to the tip of the glass tube B is green.

[0072] 所述玻璃管B的尖端装有铂丝,所述铂丝的游离端与银丝或铜丝接触,所述铂丝的另一端被所述的玻璃管B的尖端所包裹、且有20μπι的铂丝裸露在外,且所述包裹所述铂丝后的玻璃管B的尖端直径为ΙΟμπι,长度为2cm〇 The free end of the [0072] B of the glass tube with the tip of a platinum wire, the platinum wire in contact with copper or silver, the platinum wire and the other end of the glass tube being encased tip B, and 20μπι of platinum wire exposed, and the tip diameter of the glass tube package B after the platinum wire is ΙΟμπι, length 2cm〇

[0073] 所述外部套管上端开口处和所述工作阴极柱之间、所述工作阴极柱上端开口处均由AB胶封闭。 [0073] The upper end of the outer sleeve between the opening and the working cathode column, the working end of the opening closed by the cathode column AB glue.

[0074] 所述工作阴极柱的尖端处的铂丝的裸露端距所述氧透过性隔膜的内端面30μπι。 [0074] The exposed end of the platinum wire cathode at the tip of the work string from said oxygen permeable inner end surface of the separator 30μπι.

[0075] 二、性能测试: [0075] Second, the performance test:

[0076] 其对溶解氧的检测标准曲线如图4所示,从图4可得知:本实施例中,对溶解氧的分辨率为〇.〇3mg 02/L,接通保护阴极后残余电流降低83%,与图4相对应的共轴氧微电极对不同氧分压的响应数据如表1所示。 [0076] detecting a standard curve shown in Figure 4 of dissolved oxygen can be seen from FIG 4: In this embodiment, the resolution of the dissolved oxygen was 〇.〇3mg 02 / L, the residue after turning cathodic protection 83% reduction in current, coaxial with the response data corresponding to the oxygen microelectrode 4 different oxygen partial pressures shown in table 1.

[0077] 其对溶解氧的实时响应曲线如图5所示,从图5可得知:本实施例中,达到90%最大值的响应时间为4s。 [0077] The time response curve of the dissolved oxygen which is shown in Figure 5, can be seen from Figure 5: In this embodiment, the response time to reach 90% of the maximum value of 4s.

[0078] 表1.共轴氧微电极对不同氧分压的响应数据 [0078] Table 1. Response data coaxially oxygen microelectrode different oxygen partial pressures

Figure CN104865301BD00091

Claims (5)

  1. 1. 一种共轴型复合式氧微电极,包括工作阴极柱(3)、参比电极(9)和外部套管(I),工作阴极柱(3)和参比电极(9)平行设置于外部套管内,所述外部套管(1)和所述工作阴极柱(3)之间注有电解质溶液(10),其特征在于:所述工作阴极柱(3)的外壁或所述外部套管(1) 的内壁镀有一层银层(7),并在所述银层(7)表面焊接有导电金属丝(8); 所述银层(7)的厚度为0.1-lMi; 所述导电金属丝(8)选自银丝、铜丝和铂丝中任一种; 在所述银层(7)表面的末端焊接有导电金属丝(8); 所述工作阴极柱(3)由玻璃管A (4)的尖端插入到玻璃管B (5)的非尖端内首尾嵌套后烧结而成; 所述玻璃管B (5)的尖端装有铂丝(6),所述铂丝(6)的游离端与银丝或铜丝(I 1)接触, 所述铂丝(6)的另一端被所述的玻璃管B (5)的尖端所包裹、且有部分铂丝裸露在外; 所述外部套管(1)上端开口处和所述工作阴极柱(3)之 A coaxial type oxygen microelectrode composite, comprising a cathode working column (3), reference electrode (9) and the outer sleeve (the I), the working cathode stem (3) and a reference electrode (9) arranged parallel within the outer casing, impregnated with an electrolyte solution (10) between the outer sleeve (1) and the working cathode column (3), wherein: the outer wall of the working cathode stem (3) or the external the inner wall of the sleeve (1) is coated with a layer of silver layer (7), and (7) the surface of a conductive wire welded (8) in said silver layer; thickness of the silver layer (7) is a 0.1-lMi; the said conductive wire (8) is selected from silver, copper and platinum wire of any one of; the silver layer (7) welding the end surface of the conductive wire (8); the working cathode stem (3) after insertion of the tip end to end within a glass tube nest a (4) to a glass tube B (5) of the non-sintered tip; tip of the glass tube B (5) is provided with a platinum wire (6), said platinum filaments (6) the free end of the silver or copper (I 1) in contact with the tip of the platinum wire and the other end (6) of the glass tube is B (5) of the package, and some platinum wire exposed out; the outer sleeve (1) and an upper end opening of the working cathode stem (3) of the 、所述工作阴极柱(3)上端开口处均由环氧树脂(12)封闭; 所述外部套管(1)的一端为尖状且尖端末尾注有透氧硅胶(2),形成氧透过性隔膜; 所述参比电极(9)为Ag/AgCl参比电极; 所述电解质溶液(1 〇)为NaHCO3、Na2CO3和KC1的混合液,其中,所述电解质溶液中NaHCO3、 Na2CO3和KCl的摩尔浓度分别为0.01-1 mol/L、0.01-1 mol/L和0.01-3 mol/L; 所述包裹所述铂丝(6)后的玻璃管B (5)的尖端直径为7〜12μπι,长度为1.5-3.0cm; 所述铂丝(6)伸入所述玻璃管B (5)的尖端的长度为1.5〜2cm; 所述铂丝(6)的非游离端的未被包裹而裸露在外的铂丝长度为10-30μπι; 所述外部套管(1)的尖端的直径小于50μπι; 所述工作阴极柱(3)的尖端(13)处的铂丝的裸露端距所述氧透过性隔膜的内端面20-50μπι; 所述透氧娃胶(2)的厚度为10〜20μηι。 The working cathode column (3) an epoxy resin by an upper end opening (12) is closed; end of the outer sleeve (1) is tapered and the tip end of the silica gel impregnated with oxygen (2), forming an oxygen permeability through the diaphragm; the reference electrode (9) is a Ag / AgCl reference electrode; the electrolyte solution (1 billion) of NaHCO3, Na2CO3 and the mixture KC1, wherein said electrolyte solution NaHCO3, Na2CO3 and KCl the molar concentration of 0.01-1 mol / L, 0.01-1 mol / L and 0.01-3 mol / L; tip diameter of the glass tube B (5) after the wrapping of the platinum wire (6) is July to 12μπι, the length of 1.5-3.0cm; the platinum wire (6) extending into the tip of the glass tube length B (5) is 1.5~2cm; unencapsulated non-free end of the platinum wire (6) being platinum wire exposed length 10-30μπι; tip diameter of the outer sleeve (1) is less than 50μπι; platinum wire exposed at the end of the working tip of the cathode stem (3) (13) from said oxygen 20-50μπι pervious inner end surface of the separator; the oxygen baby gum (2) has a thickness 10~20μηι.
  2. 2. 权利要求1所述的共轴型复合式氧微电极的制备方法,包括如下步骤: 1) 制作工作阴极:(a)将铀丝插入王水中l_2cm,腐蚀80-90min,使铀丝插入端腐蚀至直径为5〜ΙΟμπι; (b) 取玻璃管A⑷和玻璃管B (5)均拉制成尖嘴玻璃管,并将已腐蚀的铂丝端插入到玻璃管B (5)的尖端中,使其插入长度为1.5〜2cm,再将玻璃管A (4)尖端插入玻璃管B (5)非尖端中,烧结; (c) 将步骤(b)中得到的玻璃管B (5)的尖端固定在加热线圈中间位置,增大电热丝两端电压,使玻璃管B (5)的尖端熔化包裹住铂丝,得到工作阴极; 2) 工作阴极表面镀银层:将银氨溶液和还原性化合物混合得到上银混合液,并将所述工作阴极悬浮于上银混合液中,在工作阴极表面镀上一层银层,并在银层的上端表面处焊接导电金属丝; 3) 组装共轴型复合式氧微电极:将巴斯德管一端拉制成直径50μπι以下的尖端, Preparing composite coaxial type oxygen microelectrode according to claim 1, comprising the following steps: 1) production work Cathode: (a) the wire into aqua regia uranium l_2cm, corrosion 80-90min, uranium wire is inserted corrosion end to a diameter of 5~ΙΟμπι; (b) take A⑷ glass and glass B (5) are drawn into a glass tube beak, and corroded platinum wire end is inserted into a glass tube B (5) of the tip and allowed the insertion length of 1.5~2cm, and then the glass tube a (4) inserting the tip of a glass tube B (5) the tip of the non-sintered; (c) the step (b) obtained glass tube B (5) the tip of the heating coil is fixed intermediate position, increasing the voltage across the heating wire, the glass tube B (5) of the wrap tip melt platinum wire cathode to obtain work; 2) working cathode surface layer of silver: silver and ammonia solution mixing the reducing compound to give a mixture of silver, and the working cathode suspended in a mixture of silver, the working surface of the cathode layer is coated with a layer of silver, and a conductive wire welded on the upper end surface of the silver layer; 3) assembling composite coaxial type oxygen microelectrode: one end of the pipe is drawn into the tip Pasteur 50μπι diameter or less, 将镀银层的工作阴极装入其中心部位,同时,在其中装入参比电极,用环氧树脂封口,并将巴斯德管尖端虹吸透氧硅胶,形成氧透过性隔膜,最后,在巴斯德管内注入电解质溶液,即得到共轴型复合式氧微电极。 The silver layer on the cathode charged working center thereof, while the reference electrode was charged therein, sealed with an epoxy resin, and the siphon tube tip Pasteur silica oxygen, oxygen-permeable membrane is formed, and finally, injecting an electrolyte solution in the tube Pasteur, to obtain composite coaxial type oxygen microelectrode.
  3. 3. 根据权利要求2所述的制备方法,其特征在于:步骤I) (a)中,所述铂丝的直径为O·05-0·2mm; 所述王水由体积比4:1:3的H20、HN〇3和HCl组成; 步骤1)⑹中,所述玻璃管A (4)的尖端外径为1.5-2.0cm; 所述玻璃管B (5)的尖端外径为0.3-0.7mm; 所述加热线圈为O型镍铁丝; 步骤I) (c)中,还包括对工作阴极的尖端进行加热,使玻璃熔化并向后缩,露出铂丝的步骤; 所述包裹所述铂丝(6)后的玻璃管B (5)的尖端直径为7〜12μπι,长度为1.5-3.0cm。 3. The production method according to claim 2, wherein: in step I) (a), the diameter of the platinum wire is O · 05-0 · 2mm; aqua regia, the volume ratio of 4: 1: H20 3, and HCl HN〇3 composition; step 1) ⑹, the glass tube a (4) tip outer diameter of 1.5-2.0cm; the outer diameter of the tip of the glass tube B (5) is 0.3 0.7mm; the heating wire coil is a nickel O; step I) (c), further comprising a cathode tip to the work by heating, and the molten glass after condensing, step platinum wire exposed; the said parcel platinum wire glass B (5) after (6) tip diameter 7~12μπι, a length of 1.5-3.0cm.
  4. 4. 根据权利要求2或3所述的制备方法,其特征在于:步骤2)中,所述银氨溶液和还原性化合物的体积比为2:1; 所述还原性化合物为含醛基化合物,所述含醛基化合物为甲醛、乙醛和葡萄糖中的至少一种; 所述悬浮的时间为15〜20min; 所述上银混合液应当一次加足,不能中途补加。 The production method of claim 2 or claim 3, wherein: in step 2), the volume ratio of the ammonia solution of silver and a reducing compound is 2: 1; the reducing compound is an aldehyde group-containing compound the aldehyde group-containing compound is at least one of formaldehyde, acetaldehyde and glucose; and the suspension time is 15~20min; on the mixture should add a little silver, the process can not supplemented.
  5. 5. 根据权利要求2或3所述的制备方法,其特征在于:步骤3)中,所述铂丝的裸露端距所述氧透过性隔膜的内端面20-50μπι; 所述氧透过性隔膜的厚度为10〜20μπι; 所述电解质溶液为NaHCO3、Na2TO3和KCl的混合液,其中,所述电解质溶液中NaHCO3、 Na2CO3和KCl的摩尔浓度分别为0.01-1 mol/L、0.01-1 mol/L和0.01-3 mol/L。 The production method of claim 2 or claim 3, wherein: the step 3), the exposed end of the platinum wire from the oxygen-permeable inner end surface of the separator 20-50μπι; the oxygen permeation the thickness of the separator is 10~20μπι; the electrolyte solution is NaHCO3, Na2TO3 and KCl mixture, wherein the electrolyte solution NaHCO3, Na2CO3 and KCl molar concentration were 0.01-1 mol / L, 0.01-1 mol / L, and 0.01-3 mol / L.
CN 201510204564 2015-04-27 2015-04-27 A co-axial oxygen microelectrode composite type and preparation method CN104865301B (en)

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EP0078590A1 (en) * 1981-10-31 1983-05-11 Corning Glass Works Microelectronic sensor assembly
US4908115A (en) * 1986-04-22 1990-03-13 Toray Industries, Inc. Minute electrode for electrochemical analysis
CN101408526A (en) * 2008-11-14 2009-04-15 西安建筑科技大学 Dissolved oxygen micro electrode and preparing method thereof

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EP0078590A1 (en) * 1981-10-31 1983-05-11 Corning Glass Works Microelectronic sensor assembly
US4908115A (en) * 1986-04-22 1990-03-13 Toray Industries, Inc. Minute electrode for electrochemical analysis
CN101408526A (en) * 2008-11-14 2009-04-15 西安建筑科技大学 Dissolved oxygen micro electrode and preparing method thereof

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