CN102590321A - Electrochemical online detector - Google Patents
Electrochemical online detector Download PDFInfo
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- CN102590321A CN102590321A CN2012100395416A CN201210039541A CN102590321A CN 102590321 A CN102590321 A CN 102590321A CN 2012100395416 A CN2012100395416 A CN 2012100395416A CN 201210039541 A CN201210039541 A CN 201210039541A CN 102590321 A CN102590321 A CN 102590321A
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Abstract
The invention belongs to the electrochemical online detector device and relates to an electrochemical online detector which does not require an additional electrolyte solution or any supporting electrolyte solution. The detector is composed of a working electrode measurement chamber and an auxiliary reference chamber with a common electrolyte solution which are separated by an ionic membrane (such as the Nafion cationic membrane); the test liquid free from a supporting electrolyte enters the measurement chamber through an in-out circulation hole, and real-time measurement is performed on the surface of a working electrode to obtain electric signals; and the detector consists of an upper polyvinyl chloride (PVC) plate and a lower PVC plate, which are sealed with screws and silicone pads, and can realize the continuous and dynamic online detection of the sample solution. The invention aims to provide an electrochemical online detection technology which does not require an additional electrolyte solution or supporting electrolyte solution and the electrochemical online detector is particularly suitable for the material detection or monitoring of the natural medicine without spectral response.
Description
Technical field
The invention belongs to a kind of compound galvanochemistry at thread detector, relate in particular to a kind of galvanochemistry of not having supporting electrolyte at thread detector.The detection of online detection, especially alkaloids substance when the present invention is particularly useful for column chromatography for separation, but should be appreciated that the present invention also can be used for the detection of other materials.
Background technology
The separation of the effective constituent in the natural drug is one of important developing direction in the current traditional Chinese medicine research with extracting purifying.In separating purification; Normal employing column chromatography etc. separates equipment such as device, need carry out the on-line monitoring of continuous real-time to the concentration of target substance in the chromatographic solution, to reduce loss of active ingredients; Improve yield; This needs a kind of special in thread detector, so that in time monitor the outflow situation of different pharmaceutical, it is an important sensing unit that separates in purifying at thread detector.Present domestic medicine is looked forward to generally adopting spectroscopic detector that chromatographic solution is carried out on-line monitoring or offline inspection, but exists cost higher relatively, to problems such as the insensitive material of some spectrum can't detect.
Advantages such as that Electrochemical Detection has is highly sensitive, equipment is simple relatively also can solve the problem that can't detect the insensitive material of spectrum, so Electrochemical Detection is another kind of desirable selection of online detection.But; Traditional electrochemical reaction detection pond does not have insulated chamber usually, working electrode, electrode and contrast electrode is placed solution to be measured simultaneously, needs to add a large amount of supporting electrolytes in the test and eliminates the solution voltage drop to reduce solution resistance; And need the response of quantity of sample solution more blunt; Do not meet the requirement of online detection, the solution of anhydrous or few water in especially separate purifying to Chinese medicine, and can not be extra online detection during the interpolation supporting electrolyte.
The present invention sets out according to actual conditions; The flow type galvanochemistry that a kind of novelty has been invented in design utilizes carbon paste electrode as working electrode at thread detector, utilizes the character of Nafion film solid acid simultaneously; Simultaneously detection zone and auxiliary region are separated; Can or not have under the situation of any supporting electrolyte and directly measure electroactive substance in not extra adding detecting liquid, and sensitive response is arranged, its apparatus structure be simple; Measure reliable results, for the online detection of natural drug effective constituent provides a kind of effective tool cheaply.The successful effective constituent that is used for measuring common natural drug such as flavone compound.
Summary of the invention
The purpose of patent of the present invention is to design a kind of online flow type detecting device of galvanochemistry that can be used for not extra adding or not have any supporting electrolyte.This galvanochemistry is at thread detector; Can directly carry out flow type to fluid sample detects; And the liquid that detects can or not have under the situation of any supporting electrolyte at not extra interpolation supporting electrolyte; Obtain corresponding Electrochemical Detection signal, can be used to not have the detection of the solution example of supporting electrolyte, also can be used to contain electrolytical solution example.
Patent of the present invention is characterized in that adopting ionic membrane (like the Nafion cationic membrane) that the Electrochemical Detection chamber is divided into two chambers: one is the working electrode chamber, mainly places working electrode, and working electrode adopts plane electrode, like carbon paste electrode; Another chamber is contrast electrode and auxiliary electrode (to electrode), like silver/silver chloride (contrast electrode), platinum filament (to electrode).Separated by ionic membrane between two Room, ionic membrane can be Nafion cationic membrane or other films.The surface of the working electrode in the working electrode chamber is parallel with the ionic membrane surface, and little spacing on working electrode surface and ionic membrane surface forms test chamber or claims test cabinet, sensing chamber, and the distance of this little spacing can suitably be controlled and regulate; Test solution this formed mensuration chamber of flowing through; Carry out electrochemical reaction at working electrode surface, reach real-time detection, because test solution does not have supporting electrolyte; Solution resistance is bigger; So the distance of little spacing on working electrode surface and ionic membrane surface need be controlled very for a short time, with the influence that reduces solution resistance and brought as far as possible with reduce the dead volume in the process of circulation as far as possible.In another chamber, charge into electro-chemical test general electrolyte solution commonly used in contrast electrode and the auxiliary electrode chamber, form the galvanochemistry auxiliary measurement system.One three electrode measurement system is formed in working electrode chamber and reference auxiliary electrode chamber by ionic membrane separates, because the special role of ionic membrane, this patent can be measured the electroactive substance in the circulation solution of no supporting electrolyte.
Patent of the present invention can adopt three electrodes or two electrode systems to detect or monitor when implementing to use.After can carrying out the solution injection, arrhea the electrochemical research that does not have supporting electrolyte solution again, can carry out researchs such as galvanochemistry scan round, single sweep this moment, so that investigate the spike potential that goes out of selecting different material.When carrying out online circulation detection/monitoring, can on working electrode, apply a constant potential according to the best current potential of selecting, carry out time-current signals, thereby obtain to go out under the different time galvanochemistry chromatogram of peak situation.When with other equipment couplings, can carry out the collection or the processing at sample peak according to going out the peak situation.
Description of drawings
Accompanying drawing is the concrete diagram of patent of the present invention, wherein:
Fig. 1 is the schematic cross-section of implementing at thread detector according to the galvanochemistry of patent of the present invention.
Fig. 2 is the overall schematic of implementing according to Fig. 1.
Fig. 3 is the whole exploded view of patent working of the present invention.
Fig. 4 is patent the 1st embodiment overall package figure of the present invention.
Fig. 5 is the cyclic voltammogram that patent working example of the present invention is measured.
Fig. 6 be patent working of the present invention example obtained time-current relationship figure.
Embodiment
The embodiment of patent of the present invention combines accompanying drawing to be described below:
Accompanying drawing 1 is that patent of the present invention need not the axis schematic cross-section of the galvanochemistry of supporting electrolyte at thread detector, and particular content is explained as follows:
1. working electrode can be the electrode of carbon paste electrode or other materials;
2. contrast electrode can be silver/silver chloride contrast electrode, also can adopt other contrast electrodes;
3. auxiliary electrode like platinum electrode, also can be the electrode of other precious metal materials;
4. detection/monitoring/research solution inlet port, solution can not extra addings or are not had any supporting electrolyte;
5. detection/monitoring/research taphole;
6. anti-drain gasket can adopt materials such as silicon rubber;
7. ionic membrane generally adopts the Nafion cationic membrane;
8. plastic plate/PVC sheet material;
9. auxiliary reference cell, in fill general electrolyte solution;
10. working electrode is measured chamber.
Accompanying drawing 2 is that patent of the present invention need not the overall schematic of the galvanochemistry of supporting electrolyte at thread detector, wherein:
11. working electrode lead;
12. whole mount is used screw-socket;
13. the turnover flow of solution is used emulsion tube.
Fig. 3, Fig. 4 specifically assemble synoptic diagram for patent of the present invention.Describe below in conjunction with the practical implementation method.
Among accompanying drawing 1,2 figure: this need not supporting electrolyte galvanochemistry at thread detector by two PVC plate base cover plates (8) and some accessories combine up and down.In the middle of the upper cover plate lower surface is a square convexity, wherein in the middle of the bossing square groove is arranged, and this groove is drilled with three through holes, and a middle through hole is filled carbon paste, as working electrode (1), and has lead (11) to draw, and can link to each other with electrochemical workstation.All the other two through hole connect two emulsion tubes (13), are respectively inlet (4) and liquid outlet (5).In the middle of the lower cover upper surface is a square groove, is encased inside one deck Nafion cationic membrane (7), can agree with mutually with the upper cover plate lower surface during use, forms working electrode and measures chamber (10).In addition, be designed with a cylindrical electrolyte tank in the lower cover upper surface third side connected in star,, can inject supporting electrolytes such as hydrochloric acid, sodium chloride solution during use for auxiliary reference cell (9).The lower cover lower surface is assisted reference cell (9) position, is connected with three holes, wherein two holes insert chlorination filamentary silver, platinum filament respectively as contrast electrode (2), to electrode (3), electrode cable can be drawn from the bottom.Surplus have a hole, for replenishing the usefulness of supporting electrolyte, uses rubber stopper seal at ordinary times.Up and down two cover plates respectively correspondence be drilled with four screw-sockets (12), available four screws, up and down two cover plates are fixed, and in addition, sandwich silicagel pad (6) between two cover plates in order to sealing.
In implementation process, the first step is filled to central aperture with thin glass bar with an amount of carbon paste, and carefully with the carbon paste compacting, makes lead (11) fully contact carbon paste.And carefully press mill with clean filter paper, and until the carbon paste exposed part metallic luster is arranged, form working electrode (1).In second step, up and down two cover plates (8) of no supporting electrolyte galvanochemistry at thread detector are fitted together, and fix with screw and hexagonal nut.In the 3rd step, in circular electrolyte tank, inject end liquid through the lower cover lower surface.The 4th step, about two emulsion tubes (13) connect the creeping motion type constant flow pump respectively, or directly connect the circulation test solution, liquid to be measured is injected working electrode through constant flow pump through emulsion tube measures chamber (10).Again through the upper cover plate lower surface, and the carbon paste working electrode (1) of flowing through, from the emulsion tube (13) of the other end, flow out, implement online detection.
These main performance and characteristics that need not the supporting electrolyte electrochemical detector have: adopt one deck Nafion cationic membrane (7) that chamber (10) is measured in the working electrode chamber and separate with auxiliary reference cell (9); When test, the proton in the auxiliary reference cell (9) can be diffused in the liquid to be measured through Nafion cationic membrane (7).Can ignore the electrolyte background concentration of the diffusion of protons amount of this part in auxiliary reference cell (9), so can carry out continuous on-line detection to liquid to be measured.Two cover plates (8) adopt the silicone gasket sealing up and down, and the lower cover lower surface has the design in a hole, and purpose is used for replenishing supporting electrolyte, and the time spent is not used rubber stopper seal at ordinary times, and the design of sealing can make whole galvanochemistry at the thread detector no leakage.This monitoring pool can carry out liquid with peristaltic pump and inject transmission.
Specific embodiment 1:
Like Fig. 5, Fig. 6.Patent equipment of the present invention is divided into A, two PVC plates of B base cover plate, is of a size of 5cm * 5cm.Two cover plates all are drilled with screw in order to fixing for four jiaos.In the middle of the A cover plate is the bossing of 3.5cm * 3.5cm, and the centre is 1cm * 2.5cm groove, and the degree of depth is 2mm.Groove is drilled with three through holes, and aperture, a middle hole is 0.5mm, fills carbon paste, and has lead to draw.All the other apertures, two holes are 2mm, connect two emulsion tubes, are respectively inlet and liquid outlet.
In the middle of the B cover plate is the sunk part of 3.55cm * 3.55cm, can agree with mutually with the A cover plate during use, forms to measure chamber.In circular electrolyte tank is arranged, diameter is 1cm, the degree of depth is 4mm.Can inject electrolyte solutions such as hydrochloric acid during use.Electrolyte tank bottom is connected with three holes, wherein two holes insert filamentary silver, platinum filament respectively as contrast electrode, to electrode, and draw from the bottom by lead.Surplus have a hole, for replenishing the usefulness of supporting electrolyte, uses rubber stopper seal at ordinary times, in case leak-stopping liquid.Sandwich silicagel pad between two substrates in order to sealing, the centre sandwiches one deck Nafion cationic membrane (in the hydrochloric acid solution of pH=2, soak more than 8 hours, wash with ultrapure water before using).With the fixing parts such as emulsion tube, lead of epoxy resin.
Dag and whiteruss are pressed the mixed of 1g/1mL, stir, and make it the plasticity that keeps certain.With thin glass bar an amount of carbon paste is filled to central aperture, and, makes copper wire fully contact carbon paste carefully with the carbon paste compacting.Carefully press mill with clean filter paper, metallic luster is arranged until the carbon paste exposed part.The new system electrode is immersed ultrasonic 1min in the absolute ethyl alcohol, clean repeatedly with ultrapure water afterwards.A, the B two sides of device are fitted together, and fix, inject end liquid, inject the HCl of 1.0 * 10-3mol/L in the circular electrolyte tank with screw and hexagonal nut.Continuous scan round is carried out in energising in-0.2～1.0V potential window, stable and smooth until cyclic voltammetry scan (CV) curve.After each the use, wash successively with absolute ethyl alcohol, ultrapure water.After using a week, refill carbon paste electrode through above-mentioned treatment step.
During mensuration, will inject through emulsion tube from the liquid that the creeping motion type constant flow pump flows out and measure chamber.The sulculus of solution in the middle of A face three holes, the carbon paste of flowing through working electrode flows out from the emulsion tube of the other end.Through increasing or reduce silicon rubber pad, the distance between adjustable full employment electrode and the Nafion film.Fig. 5 is for using the present invention, to the plain ethanolic solution of the red bayberry of not adding supporting electrolyte, after solution injects detecting device; Take under the static condition of moving phase; With-0.2～1.2V is potential window, the speed of 100mV/s, the solution cyclic voltammogram that directly records; Solid line (---) among Fig. 5 is 500 μ m for the distance between working electrode and the Nafion film, and dotted line among Fig. 5 (-----) is 1000 μ m for the distance between working electrode and the Nafion film.It is thus clear that the excessive Electrochemical Detection signal of spacing will reduce.Fig. 6 is fixed on 0.53V for using the present invention with current potential, SI 0.1s, and to the chromatographic solution of the plain ethanolic solution of red bayberry, when flowing through device with different speed, the time current curve figure of the variable concentrations that records.
Claims (7)
1. the online detector means of galvanochemistry is characterized in that, is made up of two Room such as working electrode chamber and reference auxiliary electrode chambers, adopts ionic membrane to isolate between two Room, and working electrode face and ionic membrane surface laterally arrange, and its spacing is less than 1000 μ m.
2. device according to claim 1 is characterized in that, the spacing on working electrode face and ionic membrane surface is 200-500 μ m.
3. device according to claim 1 is characterized in that, test solution gets into the test chamber between working electrode and the ionic membrane through outer input media, carries out Electrochemical Detection.
4. device according to claim 1 is characterized in that, test solution can not need extra adding supporting electrolyte.
5. device according to claim 1 is characterized in that, test solution itself can not contain supporting electrolyte.
6. device according to claim 1 is characterized in that, reference auxiliary electrode chamber is made up of contrast electrode and auxiliary electrode, in its chamber, charges into electro-chemical test general electrolyte solution commonly used, forms electrochemical measurement system.
7. device according to claim 1 is characterized in that, is used to have the compound test of electrochemical activity.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012100395416A CN102590321A (en) | 2012-02-20 | 2012-02-20 | Electrochemical online detector |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012100395416A CN102590321A (en) | 2012-02-20 | 2012-02-20 | Electrochemical online detector |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107817212A (en) * | 2017-10-31 | 2018-03-20 | 中国航空综合技术研究所 | A kind of micro- liquid film ion concentration sensor |
| CN109142473A (en) * | 2018-09-29 | 2019-01-04 | 厦门大学 | A kind of electrode reaction in situ detection mass spectrometric apparatus |
| CN109827898A (en) * | 2019-03-29 | 2019-05-31 | 河海大学 | A kind of metal corrosion test device |
| CN113363538A (en) * | 2021-05-25 | 2021-09-07 | 厦门大学 | Method for detecting catalytic layer intermediate product in real time under fuel cell working condition |
Citations (3)
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| EP0469830A1 (en) * | 1990-08-01 | 1992-02-05 | Mitsubishi Chemical Corporation | Electrode for a coulometric type of electrochemical detector |
| US5399256A (en) * | 1994-01-07 | 1995-03-21 | Bioanalytical Systems, Inc. | Electrochemical detector cell |
| US20070170056A1 (en) * | 2006-01-26 | 2007-07-26 | Arnold Don W | Microscale electrochemical cell and methods incorporating the cell |
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2012
- 2012-02-20 CN CN2012100395416A patent/CN102590321A/en active Pending
Patent Citations (3)
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|---|---|---|---|---|
| EP0469830A1 (en) * | 1990-08-01 | 1992-02-05 | Mitsubishi Chemical Corporation | Electrode for a coulometric type of electrochemical detector |
| US5399256A (en) * | 1994-01-07 | 1995-03-21 | Bioanalytical Systems, Inc. | Electrochemical detector cell |
| US20070170056A1 (en) * | 2006-01-26 | 2007-07-26 | Arnold Don W | Microscale electrochemical cell and methods incorporating the cell |
Non-Patent Citations (3)
| Title |
|---|
| KARIATE SUDHAKARA PRASAD ET AL: "Direct Electrocatalytic Oxidation of Cysteine and Cystine Based on Nafion/Lead Oxide-Manganese Oxide Combined Catalyst", 《ELECTROANALYSIS》, vol. 20, no. 11, 31 December 2008 (2008-12-31), pages 1167 - 1174 * |
| ROSANNA TONIOLO ET AL: "Porous Electrodes Supported on Ion-Exchange Membranes as Electrochemical Detectors for Supercritical Fluid Chromatography", 《ANAL.CHEM.》, vol. 76, no. 7, 1 April 2004 (2004-04-01), pages 2133 - 2137 * |
| THOMAS W.KALIRET ET AL: "Voltammetry without Supporting Electrolyte Using a Platinum Working Electrode Supported on an Ion Exchange Membrane", 《ANAL.CHEM.》, vol. 60, no. 7, 1 April 1988 (1988-04-01), pages 657 - 662 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107817212A (en) * | 2017-10-31 | 2018-03-20 | 中国航空综合技术研究所 | A kind of micro- liquid film ion concentration sensor |
| CN107817212B (en) * | 2017-10-31 | 2019-10-29 | 中国航空综合技术研究所 | A kind of micro- liquid film ion concentration sensor |
| CN109142473A (en) * | 2018-09-29 | 2019-01-04 | 厦门大学 | A kind of electrode reaction in situ detection mass spectrometric apparatus |
| CN109827898A (en) * | 2019-03-29 | 2019-05-31 | 河海大学 | A kind of metal corrosion test device |
| CN109827898B (en) * | 2019-03-29 | 2021-09-17 | 河海大学 | Metal corrosion test device |
| CN113363538A (en) * | 2021-05-25 | 2021-09-07 | 厦门大学 | Method for detecting catalytic layer intermediate product in real time under fuel cell working condition |
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Application publication date: 20120718 |