CN105388201A - Three-electrode integrated electrochemical sensor based on microelectrode array - Google Patents
Three-electrode integrated electrochemical sensor based on microelectrode array Download PDFInfo
- Publication number
- CN105388201A CN105388201A CN201510694570.XA CN201510694570A CN105388201A CN 105388201 A CN105388201 A CN 105388201A CN 201510694570 A CN201510694570 A CN 201510694570A CN 105388201 A CN105388201 A CN 105388201A
- Authority
- CN
- China
- Prior art keywords
- electrode
- silver
- platinum
- microelectrode array
- gold
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/416—Systems
- G01N27/42—Measuring deposition or liberation of materials from an electrolyte; Coulometry, i.e. measuring coulomb-equivalent of material in an electrolyte
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/416—Systems
- G01N27/48—Systems using polarography, i.e. measuring changes in current under a slowly-varying voltage
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Physics & Mathematics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Molecular Biology (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Investigating Or Analyzing Materials By The Use Of Electric Means (AREA)
Abstract
The invention discloses a three-electrode integrated electrochemical sensor based on a microelectrode array. The sensor comprises the bismuth film modified microelectrode array (gold working electrode), a silver/silver chloride electrode (reference electrode) and a platinum electrode (counter electrode). The three electrodes are prepared through a standard MEMS technology, and multiple discs at equal intervals are evenly distributed on the gold electrode to serve as the microelectrode array. In the electrochemical detection process, heavy metal gathering and dissolving-out reacting occur on the microelectrode array, and the surface of the microelectrode array is modified with a bismuth film in order to increase the detection type of heavy metal and expand the detection range of the heavy metal. The surface of the silver electrode is electroplated with silver chloride to form the Ag/AgCl reference electrode. The platinum electrode serves as the counter electrode and forms an access with the working electrode. Difference pulse stripping voltammetry is utilized for determining the concentration of the heavy metal, and a result shows that the sensor is high in detection sensitivity, low in detection limit and high in signal-to-noise ratio; the sensor is easy and convenient to operate, needs a small quantity of samples, can be used for rapidly detection heavy metal on site and is capable of efficiently monitoring environmental pollution in real time.
Description
Technical field
The present invention relates to electrochemical sensor and heavy metal analysis technical field, particularly relate to a kind of three electrode integrated electrochemical sensors based on microelectrode array.
Background technology
The safety problems such as food, potable water and ocean extensively receive the growing concern of people.Wherein, because heavy metal is in the cumulative effect of food chain, it is particularly serious that heavy metal pollution balances to human health and ecologic environment the harm caused.Therefore, the Site Detection real-time of heavy metal seems very important.
At present, the method for heavy metal analysis comprises the methods such as atomic spectroscopy, inductively coupled plasma mass spectrometry, electrochemical analysis.Atomic spectroscopy and inductively coupled plasma mass spectrometry is highly sensitive, Monitoring lower-cut is low, reproducible, but to experimental situation require high, instrument and reagent expensive, need professional to operate, be suitable for lab analysis.
Electrochemical method is easy and simple to handle, highly sensitive, reproducible, is applicable to field quick detection and Real-Time Monitoring.Wherein heavy metal ion is first reduced and is enriched in working electrode surface by Differential Pulse Stripping Voltammetry; Then in conjunction with differential pulse technology to analyze working electrode, the metal of deposition is oxidized stripping thereupon; Qualitative and quantitative analysis can be carried out by heavy metal ion according to the Stripping Voltammetry curve recorded.The method can detect the contents of many kinds of heavy metal ion existed in solution simultaneously, and has very high sensitivity and resolution.
Microelectrode has that mass transfer rate is fast, and electric double layer capacitance is little, and the advantages such as little fall in iR, but total current intensity on microelectrode is little, is generally 10
-9~ 10
-12a, increases detection difficulty.And microelectrode array is except retaining the feature of single microelectrode, do not changing under the prerequisite that RC constant and iR fall, strength of current be adding of microelectrode and, substantially increase faradic currents.In sum, microelectrode array has the advantages such as high mass transfer rate, high sensitivity, low detectability, anti-external interference, is widely studied and applied.
Electrochemical Detection mainly completes in three-electrode system.Three-electrode system is by working electrode, form electrode and contrast electrode.The microminiaturization of current research mainly working electrode, and contrast electrode and external traditional electrode is often adopted to electrode.Tradition three electrode detection required test sample is comparatively large, installs fixingly to wait sequence of operations loaded down with trivial details, and working electrode and can introduce interference to the change of electrode relative position, reduces repeatability and the accuracy of detection.
Summary of the invention
In order to improve the sensitivity of heavy metal analysis, accuracy, repeatability and detection efficiency, reduce traditional three-electrode system heavy metal and detect the external interference introduced, the present invention devises a kind of three electrode integrated electrochemical sensors based on microelectrode array, wherein working electrode adopts microelectrode array, with on one chip integrated to electrode, contrast electrode.This sensor can be used for field quick detection trace heavy metal, also can carry out the electrochemical analysis research of cellular and molecular level.
The present invention is achieved through the following technical solutions: a kind of three electrode integrated electrochemical sensors based on microelectrode array, and this sensor comprises: quartz substrate, metal level, insulation course, the first wire, the second wire and privates; Described metal level comprises platinum electrode, gold electrode, silver electrode, platinum lead-in wire, silver wire, gold wire, platinum pad, silver soldering dish and gold solder dish; Wherein, metal level attachment on a quartz substrate; Described silver electrode is cylindric, and the diameter of silver electrode is 600 ~ 1000 μm; Described gold electrode is circular, with silver electrode concentrically axle, the internal diameter of gold electrode is 1200 ~ 1600 μm, wall thickness is 100 ~ 200 μm, the upper surface of gold electrode is circumferentially uniformly distributed the identical disk of several sizes as microelectrode array, the diameter of microelectrode is 10 ~ 100 μm, and the spacing of microelectrode is greater than its 5 times of diameters; Described platinum electrode is circular, and with silver electrode concentrically axle, the internal diameter of platinum electrode is 1800 ~ 3000 μm, and wall thickness is 100 ~ 500 μm; Insulation course covers on quartz substrate and metal level, and the thickness of insulation course higher than metal level, and makes the microelectrode array of platinum electrode, silver electrode, platinum pad, silver soldering dish and gold solder dish upper surface exposed; Gold electrode, gold wire, gold solder dish and privates are connected and conducting successively, and platinum electrode, platinum lead-in wire, platinum pad are connected and conducting successively with the first wire, and silver electrode, silver wire, silver soldering dish and the second wire are connected and conducting successively.
Further, microelectrode array is electroplated bismuth film, silver electrode surface plating silver chloride; Plating bismuth microelectrode array is as working electrode, and silver electrode plating silver chloride is as Ag|AgCl contrast electrode, and platinum electrode is as to electrode.
Based on a preparation method for three electrode integrated electrochemical sensors of microelectrode array, the method comprises the following steps:
(1) gold electrode is prepared: after quartz substrate cleaning, drying, magnetron sputtering C r adhesion layer (30 ~ 50nm) and Au layer (200 ~ 400nm), spin coating positive photoresist, under ultraviolet light exposure imaging, after solidification, dry etching goes out gold electrode;
(2) prepare platinum electrode: magnetron sputtering Ti adhesion layer (30 ~ 50nm) and Pt layer (200 ~ 400nm), spin coating positive photoresist, after exposure imaging, dry etching goes out platinum to electrode;
(3) silver electrode is prepared: the positive photoresist first applying one deck 0.5 μm on chip, after abundant exposure imaging, the photoresist at silver electrode pattern position is removed clean, in high vacuum environment, with argon ion bombardment positively charged in plasma silver target (negative electrode), (anode) on quartz substrate chip is deposited on by the silver atoms that impelling goes out, form the silver layer of 100 ~ 200nm, finally by stripping (lift-off) technique, the silver metal layer beyond silver electrode and photoresist are together removed totally;
(4) insulation course is prepared: using plasma strengthens chemical vapour deposition technique (PECVD) and deposits a layer insulating Si in quartz substrate chip front side
3n
4, spin coating photoresist subsequently, through ultraviolet photoetching development, the insulation course of etching microelectrode array, platinum electrode, silver electrode, gold solder dish, platinum pad, silver soldering panel surface, other region insulation layers remain;
(5) make contrast electrode: using silver electrode as anode, platinum electrode is as negative electrode, and immersing in 0.1mMHCl solution, is 0.4mA/cm by size
2continuous current electroplate, the time is 300 ~ 600s, thus silver electrode surface plating AgCl;
(6) working electrode Modified Bismuth film: using platinum electrode as to electrode, first wire is as the signal extension line to electrode, using silver electrode and plating silver chloride as contrast electrode, second wire is as the signal extension line of contrast electrode, using microelectrode array as working electrode, privates, as the signal extension line of working electrode, forms three-electrode system thus, respectively with being connected with working electrode interface to electrode ports, contrast electrode interface of electrochemical workstation; Electrode part is all immersed in the solution of testing cassete, carries out Electrochemical Modification and measurement: at 1MH
2sO
4in solution, carry out cyclic voltammetry scanning, surface sweeping voltage range is-0.2V ~+1.5V, sweep speed 0.05V/s, repeatedly scans, and carries out electrode and cleans and activation; Be replaced with Bi (NO
3)
3solution (1mol/LKNO
3and 1%HNO
3as end liquid), Bi
3+concentration is 0.005 ~ 0.03mol/L, carries out potentiostatic method scanning, and potential range is-0.45 ~-0.3V, and electroplating time is 100 ~ 300s, and bismuth ion reduces at working electrode surface, and microelectrode array 11 is formed bismuth film, and thickness is less than 100nm.By washed with de-ionized water, and dry up with nitrogen, obtain a kind of three electrode integrated electrochemical sensors based on microelectrode array thus.
The invention has the beneficial effects as follows:
1. the present invention take quartz glass as substrate, and electrode material adopts gold, silver, platinum, and adopt traditional standard MEMS processes, size is small, and material is common, is easy to mass production;
2. the present invention is on one chip integrated by three-electrode system, easy to operate, and interface is simple, can be placed in portable electrochemical instrument, for field quick detection;
3. the present invention adopts microelectrode array, highly sensitive, detection limit is low, by force anti-interference; The spacing of microelectrode is greater than its 5 times of diameters, can reduce too small by electrode distance and produce shielding effect; Microelectrode preplating bismuth film, can increase detection kind and the scope of heavy metal ion, improves the accuracy and repeatability that detect;
4. silver electrode of the present invention, gold electrode and platinum electrode concentrically axle, make each microelectrode distance contrast electrode and equal to the distance of electrode, make the working electrode that caused by solution resistance all identical with the potential difference (PD) between contrast electrode, reduce by external contrast electrode and the interference introduced electrode.
Accompanying drawing explanation
Fig. 1 is the Standard schematic diagram of the three electrode integrated electrochemical sensors based on microelectrode array, and (a) is overall diagram, and (b) is Electrochemical Detection schematic diagram, and (c) is sensor construction decomposing schematic representation;
In figure, quartz substrate 1, platinum electrode 2, gold electrode 3, silver electrode 4, platinum lead-in wire 5, silver wire 6, gold wire 7, platinum pad 8, silver soldering dish 9, gold solder dish 10, microelectrode array 11, metal level 12, bismuth film 13, silver chloride 14, insulation course 15, first wire 16, second wire 17, privates 18;
Fig. 2 is preparation method's process flow diagram of three electrode integrated electrochemical sensors; (a) quartz plate substrate, (b) deposition of adhesion and gold, (c) spin coating photoresist, (d) exposure imaging, (e) dry etching gold electrode, (f) dry etching platinum electrode, (g) spin coating photoresist, (h) exposure imaging, (i) evaporation sputtering silver layer, j () lift-off technique makes silver electrode, (k) PECVD depositing insulating layer, (l) etching insulating layer;
Fig. 3 is heavy metal analysis DPSV curve of the present invention;
The stripping peak current that Fig. 4 (a) is heavy metal analysis of the present invention and the standard calibration curve of Cd concentration; B standard calibration curve that () is stripping peak current and Pb concentration.
Embodiment
Below in conjunction with accompanying drawing and instantiation, the present invention is described in further detail.
One, in Fig. 1 (a), microelectrode array surface preplating bismuth film, forms working electrode, and silver electrode surface plating silver chloride, forms contrast electrode, and platinum electrode is as to electrode; Three kinds of electrodes are produced in one piece of quartz substrate by MEMS technology, can be connected by relevant attached wire with extraneous heavy metal Electrochemical detector.Fig. 1 (c) illustrates sensor internal structure and association, wherein gold electrode 3, gold wire 7, gold solder dish 10 and privates 18 are connected and conducting successively, platinum electrode 2, platinum lead-in wire 5, platinum pad 8 are connected and conducting successively with the first wire 16, and silver electrode 4, silver wire 6, silver soldering dish 9 and the second wire 17 are connected and conducting successively.
Two, the present invention is based on the preparation method of three electrode integrated electrochemical sensors of microelectrode array, comprise the following steps (see Fig. 2):
1. prepare gold electrode: (Fig. 2 is a) after cleaning, drying, magnetron sputtering C r adhesion layer (30 ~ 50nm) and Au layer (200 ~ 400nm) (Fig. 2 b) by quartz substrate.Spin coating positive photoresist (Fig. 2 c), under ultraviolet light exposure imaging (Fig. 2 d), after solidification, dry etching goes out gold electrode (Fig. 2 e).
2. prepare platinum electrode: magnetron sputtering Ti adhesion layer (30 ~ 50nm) and Pt layer (200 ~ 400nm).Spin coating positive photoresist, after exposure imaging, dry etching goes out platinum to electrode (Fig. 2 f).
3. prepare silver electrode: the positive photoresist (Fig. 2 g) first applying one deck 0.5 μm on chip, after abundant exposure imaging, the photoresist at silver electrode pattern position is removed clean (Fig. 2 h).In high vacuum environment, with argon ion bombardment positively charged in plasma silver target (negative electrode), (anode) on quartz substrate chip is deposited on by the silver atoms that impelling goes out, form the silver layer (Fig. 2 i) of 100 ~ 200nm, finally by lift-off technique, the silver metal layer beyond silver electrode and photoresist are together removed totally (Fig. 2 j).
4. prepare insulation course using plasma enhancing chemical vapour deposition technique (PECVD) and deposit a layer insulating Si in quartz substrate chip front side
3n
4(Fig. 2 k), subsequently spin coating photoresist, through ultraviolet photoetching development, the insulation course of etch gold microelectrode array, platinum electrode, silver electrode, gold solder dish, platinum pad, silver soldering panel surface, other region insulation layers remain, as illustrated in figure 21.
5. welding lead: with welding spun gold by the first wire and the connection of platinum pad, the second wire and gold solder dish are linked, privates and silver soldering dish are linked.
Three, contrast electrode preparation method
First use 3MHNO
3infiltrate silver-colored top layer, then using silver electrode as anode, platinum electrode, as negative electrode, is 0.4mA/cm by size in 0.1MHCl
2continuous current carry out anode polarization, the time is 300 ~ 600s.
Four, preplating bismuth film
Using gold microelectrode array as working electrode, platinum electrode is as to electrode, and Ag|AgCl, as contrast electrode, forms three-electrode system, and the electrode interface corresponding with analytical instrument is connected.
A electrode activation
At 1MH
2sO
4solution in, carry out cyclic voltammetry scan, parameter is in table 1.Repeatedly scan, until occur stablizing waveform.
Table 1 gold microelectrode activates
| Parameter name | Parameter value |
| Initial potential | 0.05V |
| Noble potential | +1.5V |
| Electronegative potential | -0.2V |
| Sweep speed | 0.05V/s |
B preplating bismuth film
Be replaced by Bi (NO
3)
3solution (1mol/LKNO
3and 1%HNO
3as end liquid), wherein Bi
3+concentration is 0.005 ~ 0.03mol/L, carries out potentiostatic method scanning, and current potential is between-0.45 ~-0.3V, and electroplating time is 100 ~ 300s, and parameter is in table 2.
Table 2 preplating bismuth film
| Parameter name | Parameter value |
| Initial potential | -0.45～-0.3V |
| Time | 100～300s |
Five, heavy metal analysis
The bismuth film microelectrode array more than prepared is as working electrode, silver silver chloride electrode is as contrast electrode, platinum electrode is as to electrode, together constitute three electrode integrated electrochemical sensors, go between first of sensor, the second lead-in wire and the 3rd lead-in wire be connected with to electrode interface with the working electrode interface of electrochemical analyser, contrast electrode interface respectively, be configured damping fluid, setting stripping voltammetry parameter, complete the heavy metal analysis to lead, cadmium or nickel, wherein
1.PH buffer solution configures:
Ka＝[H
+][Ac
-]/[HAc]；pH＝pKa+lg([Ac
-]/[HAc])；pKa＝4.76(25℃)
Get 2.72g sodium acetate crystal, 2.62mL glacial acetic acid (0.0458mol) is dissolved in 200mL deionized water, joins to obtain the NaAc_HAc buffer solution of PH=4.4.
2. stripping voltammetry setting parameter is as table 3
Table 3 Differential Pulse Stripping Voltammetry detects heavy metal
| Parameter name | Parameter value | Parameter name | Parameter value |
| Accumulating potential | -1.35V | Sweep velocity | 0.05V/s |
| Enrichment time | 60s | Recurrence interval | 0.2s |
| Resting potential | -1.2V | Pulse height | 50mV |
| Settling time | 10s | Pulse width | 0.06s |
| Scanning voltage scope | -1.2V～-0.01V | Sampling period | 0.02s |
3. measurement result as shown in Figure 4, and experimental result shows that this three electrode sensor can be used for heavy metal and detects analysis fast, and has the good linearity and sensitivity, and detection limit is low.
Claims (3)
1. three electrode integrated electrochemical sensors based on microelectrode array, it is characterized in that, this sensor comprises: quartz substrate (1), metal level (12), insulation course (15), the first wire (16), the second wire (17) and privates (18); Described metal level (12) comprises platinum electrode (2), gold electrode (3), silver electrode (4), platinum lead-in wire (5), silver wire (6), gold wire (7), platinum pad (8), silver soldering dish (9) and gold solder dish (10); Wherein, metal level (12) is attached in quartz substrate (1); Described silver electrode (4) is for cylindric, and the diameter of silver electrode (4) is 600 ~ 1000 μm; Described gold electrode (3) is for circular, with silver electrode (4) concentrically axle, the internal diameter of gold electrode (3) is 1200 ~ 1600 μm, wall thickness is 100 ~ 200 μm, the upper surface of gold electrode (3) is circumferentially uniformly distributed the identical disk of several sizes as microelectrode array (11), the diameter of microelectrode is 10 ~ 100 μm, and the spacing of microelectrode is greater than its 5 times of diameters; Described platinum electrode (2) is for circular, and with silver electrode (4) concentrically axle, the internal diameter of platinum electrode (2) is 1800 ~ 3000 μm, and wall thickness is 100 ~ 500 μm; Insulation course (15) covers on quartz substrate (1) and metal level (12), the thickness of insulation course (15) higher than metal level (12), and makes the microelectrode array (11) of platinum electrode (2), silver electrode (4), platinum pad (8), silver soldering dish (9) and gold solder dish (10) upper surface exposed; Gold electrode (3), gold wire (7), gold solder dish (10) and privates (18) are connected and conducting successively, platinum electrode (2), platinum lead-in wire (5), platinum pad (8) and the first wire (16) are connected and conducting successively, and silver electrode (4), silver wire (6), silver soldering dish (9) and the second wire (17) are connected and conducting successively.
2. a kind of three electrode integrated electrochemical sensors based on microelectrode array according to claim 1, it is characterized in that, microelectrode array (11) is coated with bismuth film (13), and described silver electrode (4) upper surface is coated with silver chloride (14); Microelectrode array (11) plating bismuth film (13) is as working electrode, and silver electrode (4) plating silver chloride (14) is as Ag|AgCl contrast electrode, and platinum electrode (2) conduct is to electrode.
3. a preparation method for three electrode integrated electrochemical sensors according to claim 1, it is characterized in that, the method comprises the following steps:
(1) gold electrode is prepared: after quartz substrate cleaning, drying, magnetron sputtering C r adhesion layer (30 ~ 50nm) and Au layer (200 ~ 400nm), spin coating positive photoresist, under ultraviolet light exposure imaging, after solidification, dry etching goes out gold electrode;
(2) prepare platinum electrode: magnetron sputtering Ti adhesion layer (30 ~ 50nm) and Pt layer (200 ~ 400nm), spin coating positive photoresist, after exposure imaging, dry etching goes out platinum to electrode;
(3) silver electrode is prepared: the positive photoresist first applying one deck 0.5 μm on chip, after abundant exposure imaging, the photoresist at silver electrode pattern position is removed clean, in high vacuum environment, with argon ion bombardment positively charged in plasma silver target (negative electrode), (anode) on quartz substrate chip is deposited on by the silver atoms that impelling goes out, form the silver layer of 100 ~ 200nm, finally by stripping (lift-off) technique, the silver metal layer beyond silver electrode and attached wire pad and photoresist are together removed totally;
(4) insulation course is prepared: using plasma strengthens chemical vapour deposition technique (PECVD) and deposits a layer insulating Si in quartz substrate chip front side
3n
4, spin coating photoresist subsequently, through ultraviolet photoetching development, the insulation course of etching microelectrode array, platinum electrode, silver electrode, gold solder dish, platinum pad, silver soldering panel surface, other region insulation layers remain;
(5) make contrast electrode: using silver electrode (4) as anode, platinum electrode (2) is as negative electrode, and immersing in 0.1mMHCl solution, is 0.4mA/cm by size
2continuous current electroplate, the time is 300 ~ 600s, thus silver electrode surface plating AgCl;
(6) working electrode Modified Bismuth film: using platinum electrode (2) as to electrode, first wire (16) is as the signal extension line to electrode, using silver electrode (4) and plating silver chloride (14) as contrast electrode, second wire (17) is as the signal extension line of contrast electrode, using microelectrode array (11) as working electrode, privates (18) is as the signal extension line of working electrode, form three-electrode system thus, respectively with being connected with working electrode interface to electrode ports, contrast electrode interface of electrochemical workstation; Electrode part is all immersed in the solution of testing cassete, carries out Electrochemical Modification and measurement: at 1MH
2sO
4in solution, carry out cyclic voltammetry scanning, surface sweeping voltage range is-0.2V ~+1.5V, sweep speed 0.05V/s, repeatedly scans, thus completes the clean and activation of electrode; Be replaced with Bi (NO
3)
3solution (1mol/LKNO
3and 1%HNO
3as end liquid), Bi
3+concentration is 0.005 ~ 0.03mol/L, carries out potentiostatic method scanning, and potential range is-0.45 ~-0.3V, electroplating time is 100 ~ 300s, bismuth ion reduces on the working electrode (s, and at microelectrode array (11) upper formation bismuth film, thickness is less than 100nm.By washed with de-ionized water, and dry up with nitrogen, obtain a kind of three electrode integrated electrochemical sensors based on microelectrode array thus.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510694570.XA CN105388201A (en) | 2015-10-21 | 2015-10-21 | Three-electrode integrated electrochemical sensor based on microelectrode array |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510694570.XA CN105388201A (en) | 2015-10-21 | 2015-10-21 | Three-electrode integrated electrochemical sensor based on microelectrode array |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN105388201A true CN105388201A (en) | 2016-03-09 |
Family
ID=55420724
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510694570.XA Pending CN105388201A (en) | 2015-10-21 | 2015-10-21 | Three-electrode integrated electrochemical sensor based on microelectrode array |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105388201A (en) |
Cited By (23)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105891192A (en) * | 2016-06-24 | 2016-08-24 | 大连理工大学 | Electrochemical and electrochemical luminescence detection method based on integrated three-electrode system microchip |
| CN106979969A (en) * | 2017-02-25 | 2017-07-25 | 深圳市赛亿科技开发有限公司 | The Intelligent bowl of concentration of heavy metal ion in a kind of detection food liquid |
| CN107192665A (en) * | 2017-06-05 | 2017-09-22 | 中国石油大学(华东) | The test system and method for the heterogeneous texture local corrosion of multi-electrode coupling |
| CN107991370A (en) * | 2017-10-27 | 2018-05-04 | 宁波大学 | Water sample heavy metal analysis apparatus and method and its micro-nano sensor |
| CN107991227A (en) * | 2018-01-08 | 2018-05-04 | 东北大学 | A kind of embedded type sensor device suitable for the detection of corrosion-inhibiting coating electrochemistry noise |
| CN108511600A (en) * | 2018-02-28 | 2018-09-07 | 云南中烟工业有限责任公司 | A kind of sound causes the preparation method of atomization chip |
| CN108680627A (en) * | 2018-06-27 | 2018-10-19 | 宁波大学 | Micro-nano sensor and preparation method thereof for detecting Organic substance in water content |
| CN108802127A (en) * | 2018-05-03 | 2018-11-13 | 佛山科学技术学院 | A kind of removable electrochemical sensor |
| CN109632909A (en) * | 2018-12-14 | 2019-04-16 | 惠州市金百泽电路科技有限公司 | A kind of production method of ceramic base sensing electrode surface fine-line |
| CN110558993A (en) * | 2019-09-19 | 2019-12-13 | 中国科学技术大学 | Prussian blue microneedle electrode for blood glucose monitoring, preparation method of prussian blue microneedle electrode, blood glucose monitoring patch and preparation method of blood glucose monitoring patch |
| CN107843633B (en) * | 2017-11-03 | 2020-05-19 | 大连大学 | Flexible electrode for copper ion determination and determination method thereof |
| CN111323365A (en) * | 2020-04-09 | 2020-06-23 | 北京国网弘泰科技有限公司 | Three-electrode corrosion sensor and manufacturing method thereof |
| CN111398542A (en) * | 2020-04-03 | 2020-07-10 | 长沙军民先进技术研究有限公司 | Wireless acquisition node and method based on water body environment monitoring |
| CN111413255A (en) * | 2020-03-31 | 2020-07-14 | 浙江大学 | Micro-electrode system and method for testing oxygen mass transfer coefficient of proton exchange membrane |
| CN112595763A (en) * | 2020-12-09 | 2021-04-02 | 华中科技大学 | Chemically modified electrode array sensor for detecting heavy metal ions in water body |
| CN112666235A (en) * | 2021-01-19 | 2021-04-16 | 郑州轻工业大学 | PtNi bimetal-based two-electrode integrated enzyme-free glucose sensor and preparation method thereof |
| CN113109408A (en) * | 2021-04-08 | 2021-07-13 | 海南师范大学 | Portable palm electrochemical sensor for detecting enzyme concentration based on chip electrode and preparation method and detection method thereof |
| CN113640356A (en) * | 2021-09-09 | 2021-11-12 | 杭州超钜科技有限公司 | Chloride ion detection sensor |
| CN113970584A (en) * | 2021-10-26 | 2022-01-25 | 河海大学常州校区 | Heavy metal ion detection method and system |
| CN114113250A (en) * | 2021-12-24 | 2022-03-01 | 中国科学院空天信息创新研究院 | Multi-parameter sensor integrated chip and preparation method thereof |
| CN114930165A (en) * | 2019-12-06 | 2022-08-19 | 创新水护理有限责任公司 | Amperometric sensor for measuring free chlorine with a reference electrode having a gold electrode surface consisting of a series of electrically connected, spaced apart surface portions |
| CN116337971A (en) * | 2023-03-21 | 2023-06-27 | 深圳市雷诺华科技实业有限公司 | Reference electrode-free micro-matrix biosensor |
| US11846597B2 (en) | 2018-01-03 | 2023-12-19 | Corning Incorporated | Methods for making electrodes and providing electrical connections in sensors |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN2155019Y (en) * | 1993-04-12 | 1994-02-02 | 中国科学院上海冶金研究所 | Diamond-platinum film electrode |
| CN201060198Y (en) * | 2007-06-07 | 2008-05-14 | 复旦大学 | Integrated forming disposable electrochemical sensor for determining blood lead concentration |
| CN102135518A (en) * | 2011-01-07 | 2011-07-27 | 上海交通大学 | Detection electrode of trace lead in drinking water and preparation method thereof |
| CN102323314A (en) * | 2011-05-27 | 2012-01-18 | 中国科学院上海微系统与信息技术研究所 | Production and detection method of plated bismuth gold micro-array electrode for detecting heavy metals |
| KR20120126977A (en) * | 2011-05-13 | 2012-11-21 | 고려대학교 산학협력단 | CNT-based three electrode system, fabrication of the same and electrochemical biosensor using the same |
| CN103149265A (en) * | 2012-12-31 | 2013-06-12 | 北京师范大学 | Quick copper-testing method based on linear sweep voltammetry and three-electrode sensor |
| CN103913502A (en) * | 2012-12-31 | 2014-07-09 | 北京师范大学 | Copper rapid determination method based on square-wave stripping voltammetry and three-electrode sensor |
| CN103913501A (en) * | 2012-12-31 | 2014-07-09 | 北京师范大学 | Copper rapid determination method based on differential pulse voltammetry and three-electrode sensor |
| CN104777199A (en) * | 2015-03-27 | 2015-07-15 | 浙江大学 | Nanometer material-based miniaturized electrochemical insulin sensor and preparation method thereof |
-
2015
- 2015-10-21 CN CN201510694570.XA patent/CN105388201A/en active Pending
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN2155019Y (en) * | 1993-04-12 | 1994-02-02 | 中国科学院上海冶金研究所 | Diamond-platinum film electrode |
| CN201060198Y (en) * | 2007-06-07 | 2008-05-14 | 复旦大学 | Integrated forming disposable electrochemical sensor for determining blood lead concentration |
| CN102135518A (en) * | 2011-01-07 | 2011-07-27 | 上海交通大学 | Detection electrode of trace lead in drinking water and preparation method thereof |
| KR20120126977A (en) * | 2011-05-13 | 2012-11-21 | 고려대학교 산학협력단 | CNT-based three electrode system, fabrication of the same and electrochemical biosensor using the same |
| CN102323314A (en) * | 2011-05-27 | 2012-01-18 | 中国科学院上海微系统与信息技术研究所 | Production and detection method of plated bismuth gold micro-array electrode for detecting heavy metals |
| CN103149265A (en) * | 2012-12-31 | 2013-06-12 | 北京师范大学 | Quick copper-testing method based on linear sweep voltammetry and three-electrode sensor |
| CN103913502A (en) * | 2012-12-31 | 2014-07-09 | 北京师范大学 | Copper rapid determination method based on square-wave stripping voltammetry and three-electrode sensor |
| CN103913501A (en) * | 2012-12-31 | 2014-07-09 | 北京师范大学 | Copper rapid determination method based on differential pulse voltammetry and three-electrode sensor |
| CN104777199A (en) * | 2015-03-27 | 2015-07-15 | 浙江大学 | Nanometer material-based miniaturized electrochemical insulin sensor and preparation method thereof |
Non-Patent Citations (5)
| Title |
|---|
| CHRISTOS KOKKINOS ET.AL: "Disposable lithographically fabricated bismuth microelectrode arrays for stripping voltammetric detection of trace metals", 《ELECTROCHEMISTRY COMMUNICATIONS》 * |
| CHRISTOS KOKKINOS ET.AL: "Disposable microfabricated bismuth microelectrode arrays for trace metal analysis by stripping voltammetry", 《PROCEDIA ENGINEERING》 * |
| CHRISTOS KOKKINOS ET.AL: "Microfabricated disposable lab-on-a-chip sensors with integrated bismuth microelectrode arrays for voltammetric determination of trace metals", 《ANALYTICA CHIMICA ACTA》 * |
| VLASTIMIL REHACEK ET.AL: "Bismuth-coated diamond-like carbon microelectrodes for heavy metals determination", 《SENSORS AND ACTUATORS B: CHEMICAL》 * |
| 刘德盟 等: "基于溶出伏安法的铋微阵列电极检测饮料中的铅和镉", 《分析化学》 * |
Cited By (30)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105891192A (en) * | 2016-06-24 | 2016-08-24 | 大连理工大学 | Electrochemical and electrochemical luminescence detection method based on integrated three-electrode system microchip |
| CN106979969A (en) * | 2017-02-25 | 2017-07-25 | 深圳市赛亿科技开发有限公司 | The Intelligent bowl of concentration of heavy metal ion in a kind of detection food liquid |
| CN107192665A (en) * | 2017-06-05 | 2017-09-22 | 中国石油大学(华东) | The test system and method for the heterogeneous texture local corrosion of multi-electrode coupling |
| CN107991370A (en) * | 2017-10-27 | 2018-05-04 | 宁波大学 | Water sample heavy metal analysis apparatus and method and its micro-nano sensor |
| CN107843633B (en) * | 2017-11-03 | 2020-05-19 | 大连大学 | Flexible electrode for copper ion determination and determination method thereof |
| US11846597B2 (en) | 2018-01-03 | 2023-12-19 | Corning Incorporated | Methods for making electrodes and providing electrical connections in sensors |
| CN107991227A (en) * | 2018-01-08 | 2018-05-04 | 东北大学 | A kind of embedded type sensor device suitable for the detection of corrosion-inhibiting coating electrochemistry noise |
| CN107991227B (en) * | 2018-01-08 | 2023-11-03 | 东北大学 | Implanted sensor device suitable for electrochemical noise detection of anti-corrosion coating |
| CN108511600A (en) * | 2018-02-28 | 2018-09-07 | 云南中烟工业有限责任公司 | A kind of sound causes the preparation method of atomization chip |
| CN108802127B (en) * | 2018-05-03 | 2020-07-07 | 佛山科学技术学院 | Detachable electrochemical sensor |
| CN108802127A (en) * | 2018-05-03 | 2018-11-13 | 佛山科学技术学院 | A kind of removable electrochemical sensor |
| CN108680627A (en) * | 2018-06-27 | 2018-10-19 | 宁波大学 | Micro-nano sensor and preparation method thereof for detecting Organic substance in water content |
| CN108680627B (en) * | 2018-06-27 | 2023-09-12 | 宁波大学 | Micro-nano sensor for detecting organic matter content in water and manufacturing method thereof |
| CN109632909A (en) * | 2018-12-14 | 2019-04-16 | 惠州市金百泽电路科技有限公司 | A kind of production method of ceramic base sensing electrode surface fine-line |
| CN110558993A (en) * | 2019-09-19 | 2019-12-13 | 中国科学技术大学 | Prussian blue microneedle electrode for blood glucose monitoring, preparation method of prussian blue microneedle electrode, blood glucose monitoring patch and preparation method of blood glucose monitoring patch |
| CN114930165A (en) * | 2019-12-06 | 2022-08-19 | 创新水护理有限责任公司 | Amperometric sensor for measuring free chlorine with a reference electrode having a gold electrode surface consisting of a series of electrically connected, spaced apart surface portions |
| CN111413255A (en) * | 2020-03-31 | 2020-07-14 | 浙江大学 | Micro-electrode system and method for testing oxygen mass transfer coefficient of proton exchange membrane |
| CN111413255B (en) * | 2020-03-31 | 2020-12-18 | 浙江大学 | Micro-electrode system and method for testing oxygen mass transfer coefficient of proton exchange membrane |
| CN111398542A (en) * | 2020-04-03 | 2020-07-10 | 长沙军民先进技术研究有限公司 | Wireless acquisition node and method based on water body environment monitoring |
| CN111323365A (en) * | 2020-04-09 | 2020-06-23 | 北京国网弘泰科技有限公司 | Three-electrode corrosion sensor and manufacturing method thereof |
| CN112595763A (en) * | 2020-12-09 | 2021-04-02 | 华中科技大学 | Chemically modified electrode array sensor for detecting heavy metal ions in water body |
| CN112666235B (en) * | 2021-01-19 | 2023-03-10 | 郑州轻工业大学 | PtNi bimetal-based two-electrode integrated enzyme-free glucose sensor and preparation method thereof |
| CN112666235A (en) * | 2021-01-19 | 2021-04-16 | 郑州轻工业大学 | PtNi bimetal-based two-electrode integrated enzyme-free glucose sensor and preparation method thereof |
| CN113109408A (en) * | 2021-04-08 | 2021-07-13 | 海南师范大学 | Portable palm electrochemical sensor for detecting enzyme concentration based on chip electrode and preparation method and detection method thereof |
| CN113640356A (en) * | 2021-09-09 | 2021-11-12 | 杭州超钜科技有限公司 | Chloride ion detection sensor |
| CN113970584A (en) * | 2021-10-26 | 2022-01-25 | 河海大学常州校区 | Heavy metal ion detection method and system |
| CN114113250A (en) * | 2021-12-24 | 2022-03-01 | 中国科学院空天信息创新研究院 | Multi-parameter sensor integrated chip and preparation method thereof |
| CN114113250B (en) * | 2021-12-24 | 2024-01-09 | 中国科学院空天信息创新研究院 | Multi-parameter sensor integrated chip and preparation method thereof |
| CN116337971A (en) * | 2023-03-21 | 2023-06-27 | 深圳市雷诺华科技实业有限公司 | Reference electrode-free micro-matrix biosensor |
| CN116337971B (en) * | 2023-03-21 | 2023-11-10 | 深圳市雷诺华科技实业有限公司 | Reference electrode-free micro-matrix biosensor |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105388201A (en) | Three-electrode integrated electrochemical sensor based on microelectrode array | |
| CN101609063B (en) | Microelectrode array chip sensor for electrochemical immunological detection | |
| Kovacs et al. | Microfabricated heavy metal ion sensor | |
| CN103454426B (en) | Preparation method of nanogold/chitosan-graphene-methylene blue modified immunosensor | |
| CN102621199B (en) | Grapheme-modified Pt electrode and method for detecting trace amount heavy metal | |
| CN102495119A (en) | Multi-parameter water quality monitoring integrated microarray electrodes and preparation method | |
| CN106841353B (en) | A kind of preparation method and applications of no enzyme electrochemica biological sensor electrode | |
| Batley | Electroanalytical techniques for the determination of heavy metals in seawater | |
| CN104965011A (en) | Photoelectric integrated potential sensor for detecting extracellular biochemical parameters, and production method thereof | |
| CN112763555A (en) | Multi-target heavy metal microfluidic electrochemical sensor and preparation and application thereof | |
| CN103743804A (en) | Organic phosphorus electrochemical biosensor based on adsorption of nano particles | |
| CN102636538A (en) | Microelectrode array sensor as well as preparation method and stripping voltmeter detection method thereof | |
| DeAngelis et al. | Thin-layer differential pulse voltammetry | |
| CN101358941A (en) | Double-face nanometer band electrode array integration sensor capable of being cut and method for manufacturing same | |
| CN103063842A (en) | Preparation method of immunosensor for detecting Carbofuran pesticide residues | |
| CN105067695A (en) | Nanogold autocatalytic growth-based unmarked okadaic acid sensor | |
| CN104777199A (en) | Nanometer material-based miniaturized electrochemical insulin sensor and preparation method thereof | |
| CN111579598A (en) | Portable microcystin detector and using method thereof | |
| CN102901759A (en) | Thin layer detection pool for detecting serotonins and metabolites in urine sample, and its manufacturing method | |
| CN114894868B (en) | Preparation method and application of composite material modified electrode for detecting glutamic acid | |
| CN104122312A (en) | Bioelectrode and preparation method thereof | |
| CN108845121A (en) | A kind of preparation method of okadaic acid three-dimensional gold nanorod array immunization electrode | |
| CN201289468Y (en) | Two-sided nanometer belt electrode array integrated sensor capable of being cut up | |
| CN107843636A (en) | A kind of method with heavy metal fast-field evaluation in ship rivers and lakes and ocean | |
| CN202522538U (en) | Microelectrode array sensor |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20160309 |
|
| WD01 | Invention patent application deemed withdrawn after publication |