CN204649682U - A kind of glass carbon tiny array electrode - Google Patents
A kind of glass carbon tiny array electrode Download PDFInfo
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- CN204649682U CN204649682U CN201520253704.XU CN201520253704U CN204649682U CN 204649682 U CN204649682 U CN 204649682U CN 201520253704 U CN201520253704 U CN 201520253704U CN 204649682 U CN204649682 U CN 204649682U
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Abstract
The utility model relates to a kind of glass carbon tiny array electrode, it is characterized in that described glass carbon tiny array electrode is made up of polytetrafluoroethylene electrode pipe, silica-based mould substrate, glass carbon tiny array electrode head and copper conductor, it is wherein mould with polyfluortetraethylene pipe, glass microarrays electrode tip is encapsulated into the end of polyfluortetraethylene pipe, microelectrode array outwardly, connect circular hole inwardly, insert copper conductor; Described glass carbon tiny array electrode head adopts deep ion etching technics to make on the silicon chip of silica-based mould.Described glass carbon tiny array electrode is the tiny array electrode adopting MEMS technology to make high-specific surface area, mainly for detection of trace heavy metal ion in potable water, beverage, milk or cosmetics; Detectable concentration is 0.1 μ g/L or following.
Description
Technical field
The utility model relates to a kind of glass carbon tiny array electrode, belongs to sensor technical field.
Background technology
Heavy metal refers to that atomic density is greater than 5g/cm
3metallic element, nearly 45 kinds, as copper, lead, zinc, cadmium, manganese, iron, cobalt, nickel, vanadium, mercury, gold, silver etc.Concentration of heavy metal ion is an important indicator in environmental monitoring field always, and the concentration that accurately can detect heavy metal ion in real time has great importance, and is also the final goal of various heavy metal detection method simultaneously.
The method of current detection heavy metal mainly contains following several: Atomic fluorophotometry (AFS), inductivity coupled plasma mass spectrometry analytical technology (ICP-MS), electrochemical methods, inductively coupled plasma atomic emission spectrum (ICP-AES), high performance liquid chromatography (HPLC), inhibiting AChE, immunoassay, biology sensor etc.Wherein the measuring-signal of electrochemical analysis method is the electric signal such as conductance, current potential, electric current, electricity, the conversion of Water demand signal just can direct record, so the apparatus of electrochemical analysis can accomplish simple miniaturization, easily be automated and analyze continuously, be a kind of generally acknowledged quick, sensitive, trace analysis methods accurately, this is also the theoretical foundation that the application adopts electrochemical methods.
The ultimate principle of electrochemical analysis method inserts special electrode in solution to be measured, and on electrode, apply specific voltage waveform, impel in solution and electrochemical reaction occurs, electrode will flow through the faradic currents relevant to material composition in solution, gather and analyze the configuration information that current value can obtain material composition.Electrochemical reaction electrode, especially working electrode are the core components of electrochemical analysis method.For stripping voltammetry, the general impact adopting three-electrode system to fall to eliminate iR, three electrodes comprise contrast electrode, to electrode (auxiliary electrode), working electrode.Contrast electrode generally uses saturated calomel electrode or Ag/AgCl electrode, generally uses chemically inert platinum electrode to electrode, and the kind of working electrode is then a lot, is broadly divided into mercury electrode and the large class of solid electrode two.
Solid electrode is the emphasis of at present research, and its advantage can use under the electromotive force of calibration, can by driven by motor High Rotation Speed, easy to use pollution-free in continuous flow monitoring system.The preparation of solid electrode is simple, and material shape etc. also can design as required, and common shape has plate-like, netted, thread, tubulose, spherical etc., and material aspect mostly is noble metal and various carbon electrode, as Pt, Au, Ag, carbon and graphite etc.
Carbon is a kind of material that solid electrode is conventional, the advantage of material with carbon element is significant, it has than the more perfect crystalline network of silicon, wider electrochemical stability operation window, chemical inertness, good bio-compatibility and electrical and thermal conductivity, and its preparation method is easy simultaneously, cost is low.Traditional carbon electrode preparation is mainly based on vitreous carbon and carbon paste (vitreous carbon is called for short again glass carbon), polyacrylonitrile resin or phenolics etc. are slowly heated in an inert atmosphere high temperature (being up to 16000 DEG C) to be processed into the glass amorphous carbon of outer likeness in form, good conductivity, chemical stability is high, is suitable for making electrode material.But general directly do not use glass carbon, but as the substrate of chemically modified electrode.Carbon paste electrode (carbon paste electrode, be called for short CPE) be utilize the dag of electric conductivity (granularity 0.02mm ~ 0.01mm) to be mixed and made into pastel with the bonding agent (as paraffin, silicone oil etc.) of hydrophobic nature, be then coated in electrode bar surface or be packed into the class electrode made in electrode tube.Similar with glass-carbon electrode, simple carbon paste electrode limited capacity, but carbon paste electrode can be made to have certain function by the method for electrode modification, i.e. chemically modified carbon paste electrode.
The utility model is intended based on MEMS manufacturing process, acrylonitrile resin, phenolics or polyimide material is selected to manufacture glass carbon tiny array electrode, to significantly improve the performance of electrode, and be expected to the detection for trace heavy metal ion, thus be built into design of the present utility model.
Utility model content
The purpose of this utility model is to provide a kind of glass carbon tiny array electrode, method and application, key problem in technology to be solved of the present utility model is to provide a kind of glass carbon tiny array electrode based on MEMS manufacturing process and method for making, and based on the detection of heavy metal ion method of this electrode, overcome the shortcoming of existing detection of heavy metal ion electrode, improve detection sensitivity and shorten detection time.
Described glass carbon tiny array electrode; it is characterized in that; take silicon materials as substrate; deep reaction ion etching technique is adopted to make the mould of microelectrode array; acrylonitrile resin, phenolics or polyimide material are poured in mould; then under sample being placed in inert gas (argon gas) protection, through the carbonization of high temperature (1200-1600 DEG C) glass, glass carbon tiny array electrode is formed.Glass-carbon electrode described in the utility model is mainly made up of 4 critical components: polytetrafluoroethylene electrode rod, silica-based mould substrate, glass carbon tiny array electrode head and copper conductor.Made glass carbon tiny array electrode is as the working electrode of detection of heavy metal ion, three-electrode system is formed with platinum electrode and Ag/AgCl contrast electrode, silica-based mold base mainly carries the shaping of micron/submicron structure time prepared by glass carbon tiny array electrode, whole microelectrode head is connected with copper electric wire and conducts electricity, and access the checkout equipment of rear end, polytetrafluoroethylene electrode rod uses the specification of electrode to require fixed-type for whole electrode according to reality, and convenient reality uses.
In the common glass-carbon electrode of existing use, because electrode is plane, in steady-state current, response time, polarization current etc., there is remarkable deficiency, so need in actual use to carry out pre-service to improve performance at electrode surface, comprise overlay coating, nano-modified etc.But the electrode surface of surface modification can not polishing grinding, use so be only suitable for single, because treatment process requires high, stability is relatively poor.And the glass carbon tiny array electrode that the utility model proposes, electrode surface is micro-nano dot matrix, there is the notable feature of microelectrode array, comprise high steady-state current density, the extremely short response time, polarization current is little, ohm voltage drop is little, mass transfer velocity is high, signal to noise ratio (S/N ratio) is large, the more important thing is the microelectrode array made based on MEMS technology, there is consistance good, stability is high, cost is lower, and electrode surface does not need moditied processing, polishing grinding can be taked, take full advantage of the intrinsic advantage of glass-carbon electrode, be applicable to repeatedly using, therefore the glass carbon tiny array electrode that the application provides has significant advantage: stability is higher, sensitivity is higher, consistance is good, cost is lower.
A kind of making of glass carbon tiny array electrode comprises the following steps: (1) silica-based mould preparation: select twin polishing Double-side hot oxidized silicon chip to be mold materials, deep reaction ion etching technique is adopted to etch the microarray hole of different size respectively in the one side of silicon chip, the connection chamber of microelectrode is etched, by the at high temperature thermal oxide of whole mould after having etched at another side; (2) at silica-based mould upper polymkeric substance: acrylonitrile resin, phenolics or polyimide material colloidal materials are cast on the silica-based mould completed, and leave standstill certain hour, fully enter in microarray hole to allow colloid; (3) high temperature pyrolysis carbonization: silicon chip is placed in high-temperature annealing furnace, under argon inert gas protection, be warmed up to 1200-1600 DEG C at a slow speed, and be incubated 6-12 hour, make filling acrylonitrile resin, phenolics or the carbonization of polyimide material glass, form vitreous carbon; (4) microelectrode encapsulation: be encapsulated in polyfluortetraethylene pipe after silica-based glass carbon tiny array electrode head is polished flat, insert dag, and be connected with copper conductor, finally complete the preparation of glass carbon tiny array electrode.
A kind of method applying described glass carbon tiny array electrode mensuration heavy metal ion, it is characterized in that: with the glass carbon tiny array electrode prepared for working electrode, be to electrode with platinum electrode, with Ag/AgCl electrode for contrast electrode forms three-electrode system, sample to be tested is added in electrolyte buffer liquid, adopt stripping volt ampere analysis method, according to the peak current strength detection concentration of heavy metal ion obtained, the kind of the current potential determination heavy metal that peak is separated out.
As can be seen here, it is that (detection sensitivity is relatively low for the deficiency of matrix that the utility model overcomes plane glass-carbon electrode, be difficult to meet and require for the high sensitivity of detection of heavy metal ion in potable water), the utility model provide a kind ofly to make simply, cost is low and highly sensitive, the glass carbon tiny array electrode of favorable reproducibility and method for making.Although glass-carbon electrode is the most common conventional electrode in Electrochemical Detection, have for detection of heavy metal ion and can detect the advantages such as heavy metal ion scope is wide, but the glass carbon tiny array electrode feature that the application proposes is: described glass carbon tiny array electrode is made up of polytetrafluoroethylene electrode pipe, silica-based mould substrate, glass carbon tiny array electrode head and copper conductor, it is wherein mould with polyfluortetraethylene pipe, glass microarrays electrode tip is encapsulated into the end of polyfluortetraethylene pipe, microelectrode array outwardly, connect circular hole inwardly, insert copper conductor; Described glass carbon tiny array electrode head adopts deep ion etching technics making as on the silicon chip of mould.Thus both utilized the advantage of glass material with carbon element, utilize again the advantage of tiny array electrode, main performance superiority is higher in detection sensitivity, is suitable for potable water, beverage, milk, the detection of trace heavy metal in cosmetics etc., and detects more accurately, and detection time is shorter.So the trace heavy metal ion that the application is mainly difficult to detect for conventional electrodes (concentration 0.1ug/L and following), obvious advantage can be demonstrated.
About the detection kind detecting heavy metal ion, need to coordinate detection damping fluid to realize detecting, the same with the electrode of routine.
On the whole: the technology of the application has some remarkable advantage following:
1) compared with conventional glass-carbon electrode, the electrode surface of the application adopts micro-nano lattice array, and detection sensitivity is higher, than conventional electrodes height 1-2 order of magnitude;
2) compared with other electrode materials, the electrode described in the application adopts glass material with carbon element to be electrode material, stable performance, and accuracy is high;
3) in manufacture method, the application's electrode adopts MEMS technology to make core component, batch micro operations, and cost is low, and consistance is good;
4) compared with Surface Modified Electrodes, this electrode surface can grind in polishing, and namely electrode surface is due to after galvanic corrosion pollution, can adopt the method for polishing, simply effectively remove surface contaminants, can reach clean requirement, is applicable to repeatedly using.
Compared with prior art, it is many that glass carbon tiny array electrode has detection heavy metal kind to the utility model, and chemical stability is high, and specific surface area is large, the advantages such as sensitivity is higher, and detection time is short.This working electrode is particularly suitable for the Voltammetry heavy metal ion in food analysis and environmental monitoring.(detailed in Example)
Accompanying drawing explanation
Fig. 1 is the utility model glass carbon tiny array electrode structural representation.
Label declaration: 1. polytetrafluoroethylene electrode pipe; 2. silica-based mould; 3. glass carbon tiny array electrode head; 4. copper conductor.
Fig. 2 is glass carbon tiny array electrode end view drawing, marks same Fig. 1.
Fig. 3 is microelectrode preparation flow figure.
Mark illustrates: 5. the silicon chip after cleaning, 6. front deep etching, 7. back side deep etching, 8. colloid cast and glass carbonization
Embodiment
Below in conjunction with accompanying drawing, the utility model is described in further detail.
Embodiment 1: a kind of glass carbon tiny array electrode preparation flow
Based on silicon deep reaction ion etching technique, on silicon chip, produce glass carbon tiny array electrode, idiographic flow as shown in Figure 3:
1, silica-based tiny array electrode mould preparation:
1) silicon chip selecting the oxidation of twin polishing Double-side hot is substrate, and oxidated layer thickness is 1 μm, and silicon wafer thickness is 400 μm;
2) carry out deep reaction ion etching to silicon chip, wherein one side carves diameter 3mm, the cylindrical cavity of dark 200 μm, and namely conveniently the working surface of electrode carries out size design and making;
3) etching is aimed at the another side of silicon chip, in cylindrical cavity, carve diameter be respectively 3 μm, 5 μm, 10 μm, 20 μm, 50 μm, 100 μm, spacing correspondence is respectively the deep hole array of 30 μm, 50 μm, 100 μm, 200 μm, 500 μm, 1000 μm, namely Circularhole diameter and gap ratio are 1: 10, run through silicon chip by etching;
4) high-temperature thermal oxidation is carried out to the silicon chip carving good perforation; in 1200 DEG C of high temperature oxidation furnaces, dissolve layer of oxide layer to protect silicon base on the surface of silicon chip mould and circular hole Surface Oxygen, play insulating effect simultaneously; oxidization time 6-8 hour, oxidated layer thickness is 1 μm.
2, in material cast such as silica-based mould upper phenolics;
The material such as phenolics is instiled on the silica-based mould of preparation, leave standstill a period of time, allow phenolics soak into all Micro-v oid on silicon chip, if due to colloid poor fluidity, colloid suitably can be diluted, or pour into a mould under certain condition of negative pressure; Described phenolics can replace with acrylonitrile resin or polyimide material, effect identical (lower same).
3, high temperature pyrolysis carbonization
Silicon chip is put into high-temperature annealing furnace, under the protection of inert gas argon gas, be slowly heated to 1200-1600 DEG C with the programming rate of 5-10 per minute DEG C/min, and be incubated 6-12 hour, make phenolic resin carbonized become vitreous carbon, progressively cool to room temperature with the cooling rate of 2 DEG C/min afterwards;
4, microelectrode encapsulation
The dimensional requirement of the conveniently electrode of the tiny array electrode on the silicon chip completed is carried out scribing, be separated out electrode unit, take polyfluortetraethylene pipe as mould, microelectrode head is encapsulated into the end of polyfluortetraethylene pipe, microelectrode array outwardly, connect circular hole inwardly, dag is inserted in connection circular hole, insert copper conductor (diameter 0.5-1.5mm) and be fully connected conducting with dag and glass carbon tiny array electrode head, finally inject polyfluortetraethylene pipe with epoxy resin, curing molding, has encapsulated electrode preparation.The dag particle diameter inserted is between 0.02-1mm.
Embodiment 2: in Application Example 1, glass carbon tiny array electrode detects the concentration of lead ion in sample
The utility model electrode (the glass carbon tiny array electrode namely described in embodiment 1) is for detecting the method for content of heavy metal lead, adopt stripping volt ampere analysis method, first, described electrode and platinum electrode and Ag/AgCl contrast electrode are formed three-electrode system, is connected with electrochemical analytical instrument; Secondly, sample to be tested is mixed with 5mL0.1M acetic acid/sodium acetate solution; Finally, solution is immersed in three electrode lower ends, start stripping volt ampere analysis method, voltammetry analytical parameters is: burning voltage+0.55V/50s, accumulating potential-0.6V/120s, equilibration time 40s, square wave amplitude 36mV, current potential step value 3mV, frequency 15Hz, operating potential window :-0.6V-+0.2V.Present good linear relationship within the scope of stripping peak current and lead concentration 0.1 ~ 500 μ g/L, relevant is 0.994, detects and is limited to 0.05 μ g/L.
Embodiment 3: in Application Example 1, glass carbon tiny array electrode is to the assay method of copper ion in sample
Solution to be measured is immersed in described glass carbon tiny array electrode lower end, measures trace copper in beverage sample with square wave stripping voltammetry, initial potential-0.05V, electrodeposition current potential-1.30V, current potential increment 0.001V/S, square wave frequency 20Hz, square wave amplitude 0.02V, electrodeposition time 100s, equilibration time 10s.Be in the NH4C1 solution system of about 4.0 at pH, Cu
2+occur sensitive stripping peak at-0.22V, peak current is at Cu
2+concentration presents good linear relationship when being 0.1-500ug/L, detects and is limited to 0.05ug/L.
Claims (3)
1. a glass carbon tiny array electrode, it is characterized in that described glass carbon tiny array electrode is made up of polytetrafluoroethylene electrode pipe, silica-based mould substrate, glass carbon tiny array electrode head and copper conductor, it is wherein mould with polyfluortetraethylene pipe, glass microarrays electrode tip is encapsulated into the end of polyfluortetraethylene pipe, microelectrode array outwardly, connect circular hole inwardly, insert copper conductor; Described glass carbon tiny array electrode head adopts deep ion etching technics to make on the silicon chip of silica-based mould.
2., by electrode according to claim 1, it is characterized in that the electrode surface of tiny array electrode head is micro-nano dot matrix, there is the feature of microelectrode array; It makes based on MEMS technology.
3., by electrode according to claim 1, it is characterized in that:
1. in connection circular hole, insert dag, the particle diameter of dag is between 0.02-1mm;
2. the copper conductor diameter inserted is 0.5-1.5mm, and is connected conducting with dag and glass carbon tiny array electrode head;
3. injection ring epoxy resins in polyfluortetraethylene pipe, curing molding.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105319260A (en) * | 2015-11-05 | 2016-02-10 | 北京农业信息技术研究中心 | On-line plant glucose detection method and device based on microelectrode biosensing technology |
| CN105319257A (en) * | 2015-11-05 | 2016-02-10 | 北京农业信息技术研究中心 | ABA (abscisic acid) concentration detection method based on biosensing technology |
| CN104792843B (en) * | 2015-04-23 | 2017-12-12 | 能讯传感技术（上海）有限公司 | A kind of glass carbon tiny array electrode, method and application |
| US10585060B2 (en) | 2017-09-29 | 2020-03-10 | International Business Machines Corporation | On-chip biosensors with nanometer scale glass-like carbon electrodes and improved adhesive coupling |
-
2015
- 2015-04-23 CN CN201520253704.XU patent/CN204649682U/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104792843B (en) * | 2015-04-23 | 2017-12-12 | 能讯传感技术（上海）有限公司 | A kind of glass carbon tiny array electrode, method and application |
| CN105319260A (en) * | 2015-11-05 | 2016-02-10 | 北京农业信息技术研究中心 | On-line plant glucose detection method and device based on microelectrode biosensing technology |
| CN105319257A (en) * | 2015-11-05 | 2016-02-10 | 北京农业信息技术研究中心 | ABA (abscisic acid) concentration detection method based on biosensing technology |
| CN105319260B (en) * | 2015-11-05 | 2017-10-31 | 北京农业信息技术研究中心 | The online glucose sensing approach of plant and device based on microelectrode biosensing technology |
| US10585060B2 (en) | 2017-09-29 | 2020-03-10 | International Business Machines Corporation | On-chip biosensors with nanometer scale glass-like carbon electrodes and improved adhesive coupling |
| US10684246B2 (en) | 2017-09-29 | 2020-06-16 | International Business Machines Corporation | On-chip biosensors with nanometer scale glass-like carbon electrodes and improved adhesive coupling |
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| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20150916 Termination date: 20190423 |
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| CF01 | Termination of patent right due to non-payment of annual fee |