CN102980924B - Ampere type electrochemical detector for analyzing flow system - Google Patents
Ampere type electrochemical detector for analyzing flow system Download PDFInfo
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- CN102980924B CN102980924B CN201210477903.XA CN201210477903A CN102980924B CN 102980924 B CN102980924 B CN 102980924B CN 201210477903 A CN201210477903 A CN 201210477903A CN 102980924 B CN102980924 B CN 102980924B
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Abstract
The invention discloses an ampere type electrochemical detector for analyzing a flow system. The ampere type electrochemical detector comprises a container with a liquid outlet, wherein the upper part of the container is respectively provided with a work electrode, a reference electrode and a counter electrode, the bottom of the container is fixedly provided with a flat surface baffle, and the bottom parts of the flat surface baffle and the container are respectively provided with a hole; the holes are provided with an outlet pipe with a high performance liquid chromatograph or a flow injection instrument, the tail end of the outlet pipe and the upper surface of the flat surface baffle are positioned on the same flat surface, the work electrode is pressed onto the flat surface baffle, and the center of the work electrode aims at the outlet pipe; a thin layer is formed between the surface of the work electrode and the flat surface baffle, and the thickness of the thin layer is less than or equal to 300 micrometers; and the work electrode can preferably catch and electrolyze the object to be measured, and a pre-added flowing phase solution and/or an inert electrolyte solution in the container can conduct the electrode. The ampere type electrochemical detector provided by the invention has the advantages that the structure is simple, the ampere type electrochemical detector has the combined advantages of the thin layer type and spray wall type electrolysis, the electrolytic efficiency is improved, the current signal is strengthened, the sensitivity is improved, and the electrode is also easy to clean and replace.
Description
Technical field
The present invention relates to and a kind of analyze electrochemical detector for current system, especially relate to a kind of ampere-type electrochemical detector for high performance liquid chromatography and Flow Injection Analysis.
Background technology
Electrochemical detector is because it is highly sensitive, selectivity is good, equipment is simple and with low cost, often be used to high performance liquid chromatography be separated after in the detection of electroactive material and Flow Injection Analysis, mainly comprise conductivity type, capacitor type, electromotive force type, coulomb type and ampere-type.Wherein, ampere-type detecting device take solid electrode as working electrode, and the electric current produced when electrochemical reaction occurs measurement measured object on electrode, with the change of measured object concentration, is electrochemical detector the most frequently used in recent years.Distinguish from fluid dynamic angle, ampere-type detecting device can be divided into 4 types, i.e. thin layer formula, spray wall type, tubular type and probe-type, and wherein thin layer formula and spray wall type are two the most frequently used types.During thin layer formula ampere detector detects for high performance liquid chromatography, current commodity ampere detector also adopts this type mostly, as the HP1049A of hewlette-packard and the L-ECD-6A of Japanese Shimadzu Corporation, but thin layer formula configuration is not easy to cleaning or the replacing of electrode.Spray wall type ampere detector makes sample be injected in working electrode surface and electrolysis occur and generation current signal, contributes to the cleaning of electrode, but sample spray wall liquid of short duration on electrode can cause current signal more weak, and sensitivity is not high.
Summary of the invention
Technical matters to be solved by this invention is, provides a kind of electrode easy cleaning and replacing, the highly sensitive ampere-type electrochemical detector analyzed for current system.
The technical scheme that the present invention solves the employing of its technical matters is: a kind of ampere-type electrochemical detector analyzed for current system, comprise the container being provided with leakage fluid dram, working electrode is equipped with respectively in the top of described container, contrast electrode and to electrode, the bottom of described container is fixed with a plane shuttering panels, described plane shuttering panels, the bottom of container is equipped with the hole that a diameter is 0.5-2 millimeter, the outlet of high performance liquid chromatograph or flow injection instruments is housed in hole, the end of described outlet and the upper surface of plane shuttering panels are in same plane, and be fixed in plane shuttering panels, described working electrode is pressed on plane shuttering panels, and make the center of working electrode aim at outlet, skim is formed between the surface of working electrode and plane shuttering panels, thickness≤300 micron of thin layer, working electrode can be caught and electrolysis determinand better, pre-add mobile phase solution and/or indifferent electrolyte solution in described container conduction electrode, in testing process, determinand detects with the pattern of spraying wall and thin layer electrolysis and combining, the solution that container receipt continuously outflows from high performance liquid chromatograph or flow injection instruments outlet, unnecessary solution flows out from leakage fluid dram.
Further, described container is plastic cup or beaker.
Further, the cross sectional shape of described plane shuttering panels is square or circular.
Further, described plane shuttering panels is made up of materials such as organic glass, simple glass or plastics, preferred organic glass.
Described indifferent electrolyte solution can be the solution such as sodium sulphate, potassium chloride or sodium perchlorate.
Spray wall type and the electrolysis of thin layer formula combine by the present invention, skim is formed between working electrode surface and plane shuttering panels, namely by electrolysis generation current after determinand molecule is sprayed onto the center of working electrode from outlet, then flow away along the thin layer limited between the surface and plane shuttering panels of working electrode (within 300 microns) to surrounding, determinand molecule is caused to continue by electrolysis, produce larger current signal, to increase sensitivity.
Compared with prior art, structure of the present invention is simple, and not only have the advantage of thin layer formula and the electrolysis of spray wall type concurrently, and can improve electrolytic efficiency, strengthen current signal, improve sensitivity, electrode is easy cleaning and replacing also.
The present invention can be used for the multiple current system such as efficient liquid phase chromatographic analysis and Flow Injection Analysis, can analyze detection many kinds of substance simultaneously.
Accompanying drawing explanation
Fig. 1 is the structural representation of the embodiment of the present invention;
Fig. 2 is the canonical plotting of dopamine;
Fig. 3 is the canonical plotting of homovanillic acid;
Fig. 4 is the chromatogram of the standard mixed liquor of dopamine (retention time 2.39 min) and homovanillic acid (retention time 4.12 min);
Fig. 5 is the response signal figure that Using Flow Injection Analysis detects potassium ferrocyanide;
Fig. 6 is the typical curve that Using Flow Injection Analysis detects potassium ferrocyanide.
Embodiment
Below in conjunction with drawings and Examples, the invention will be further described.
With reference to accompanying drawing 1, the present embodiment comprises the plastic cup 7 being provided with leakage fluid dram 6, described plastic cup 7 is equipped with working electrode 3, contrast electrode 4 and to electrode 5, the bottom of described plastic cup 7 is fixed with one piece of square poly (methyl methacrylate) plate 1, the hole that a diameter is 1 millimeter is all worn bottom poly (methyl methacrylate) plate 1 and plastic cup 7, the outlet 2 of high performance liquid chromatography is housed in hole, the end of described outlet 2 and the upper surface of poly (methyl methacrylate) plate 1 are in same plane, and be fixed in poly (methyl methacrylate) plate 1, described working electrode 3 is pressed on poly (methyl methacrylate) plate 1, and make the center of working electrode 3 aim at outlet 2, skim is formed between the surface of working electrode 3 and poly (methyl methacrylate) plate 1, thickness of thin layer is 180 microns, working electrode can be made to catch well and electrolysis determinand, pre-add mobile phase solution in described plastic cup 7 conduction electrode, in testing process, determinand detects with the pattern of spraying wall and thin layer electrolysis and combining, and plastic cup 7 receives the solution continuously outflowed from the outlet 2 of high performance liquid chromatograph, and unnecessary solution flows out from leakage fluid dram 6.Certainly, described mobile phase solution also can use indifferent electrolyte (as sodium sulphate, potassium chloride or sodium perchlorate etc.) solution, or substitutes with the mixed solution of mobile phase solution and indifferent electrolyte solution.
During detection, namely by electrolysis generation current after determinand molecule is sprayed onto the center of working electrode 3 from outlet 2, the surface then along working electrode 3 flows away to surrounding, causes more determinand molecule by electrolysis, produces larger current signal, increases sensitivity.
Measurement and analysis example 1(is with reference to accompanying drawing 2,3,4 and table 1): high performance liquid chromatography Electrochemical Detection dopamine and homovanillic acid standard model
Standard model is prepared: with 0.02 mol L
-1perchloric acid prepares 0.01 mol L respectively
-1dopamine and the standard reserving solution of homovanillic acid, by this solution mobile phase (0.10 mol L during use
-1phosphate buffer+methyl alcohol, volume ratio is 85:15, pH 6) dilution is the standard working solution of a series of concentration.
Sample determination: be working electrode with the glass-carbon electrode of diameter 5 mm, saturated calomel electrode is contrast electrode, and carbon-point is to electrode, and the titer of dopamine and homovanillic acid is injected chromatographic system respectively, detects under 0.7 V vs SCE current potential.With peak current to concentration mapping preparation standard curve (for dopamine, Fig. 3 is homovanillic acid to Fig. 2), it is at 0.01 ~ 100 μm of ol L
-1concentration ranges internal linear very well (
r 2> 0.999), detectability is respectively 1.1(dopamine) and 0.7 nM(homovanillic acid), all lower than the result that UV-detector (Shimadzu SPD-20AV) and commercial electrochemical detector (Shimadzu L-ECD-6A) obtain.Fig. 4 is the chromatogram of the dopamine (retention time 2.39 min) of 40 μMs and the standard mixed liquor of homovanillic acid (retention time 4.12 min).
The linear regression analysis parameter that table 1 obtains for different detecting device and detectability.
In regression equation
ywith
xrepresent peak height (in electrochemical detector of the present invention, unit is nA, and in UV-detector and commercial electrochemical detector, unit is μ V) respectively and analyze the concentration (μM) of thing.
Measurement and analysis example 2(is with reference to accompanying drawing 5,6): Using Flow Injection Analysis detects potassium ferrocyanide
Standard model is prepared: with 0.10 mol L
-1aqueous sodium persulfate solution prepares the potassium ferrocyanide titer of a series of concentration.
Standard model measures: be working electrode with the glass-carbon electrode of diameter 3 mm, saturated calomel electrode is contrast electrode, carbon-point is to electrode, by potassium ferrocyanide Injection Flow Injection Spectrophotometry instrument, detect under 0.5 V vs SCE current potential, obtain flow injection response diagram (Fig. 5,40 μMs of potassium ferrocyanides), peak current is obtained canonical plotting (Fig. 6) to concentration mapping.
Claims (4)
1. the ampere-type electrochemical detector analyzed for current system, comprise the container being provided with leakage fluid dram, working electrode is equipped with respectively in the top of described container, contrast electrode and to electrode, it is characterized in that: the bottom of described container is fixed with a plane shuttering panels, described plane shuttering panels, the bottom of container is equipped with the hole that a diameter is 0.5-2 millimeter, the outlet of high performance liquid chromatograph or flow injection instruments is housed in hole, the end of described outlet and the upper surface of plane shuttering panels are in same plane, and be fixed in plane shuttering panels, described working electrode is pressed on plane shuttering panels, and make the center of working electrode aim at outlet, skim is formed between the surface of working electrode and plane shuttering panels, thickness≤300 micron of thin layer, working electrode can be caught and electrolysis determinand better, pre-add mobile phase solution and/or indifferent electrolyte solution in described container conduction electrode, in testing process, determinand detects with the pattern of spraying wall and thin layer electrolysis and combining, the solution that container receipt continuously outflows from high performance liquid chromatograph or flow injection instruments outlet, unnecessary solution flows out from leakage fluid dram.
2. the ampere-type electrochemical detector analyzed for current system according to claim 1, is characterized in that: described container is plastic cup or beaker.
3. the ampere-type electrochemical detector analyzed for current system according to claim 1 and 2, is characterized in that: the cross sectional shape of described plane shuttering panels is square or circular.
4. the ampere-type electrochemical detector analyzed for current system according to claim 1 and 2, is characterized in that: described plane shuttering panels is made up of organic glass, simple glass or plastics.
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| CN104359960B (en) * | 2014-11-17 | 2016-11-30 | 中国科学院长春应用化学研究所 | A kind of open type electrochemistry flow detection pond based on affinity |
| CN105116032B (en) * | 2015-07-09 | 2019-09-20 | 上海小海龟科技有限公司 | Flow control reference electrode system and the biochemical analysis method for applying it |
| CN105092676A (en) * | 2015-09-10 | 2015-11-25 | 鞠文军 | Electrochemical detection cell |
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Non-Patent Citations (2)
| Title |
|---|
| Large-volume wall-jet cells as electrochemical detectors for high-performance liquid chromatography;H.GUNASINGHAM;《Analytica Chimica Acta》;19841231;第159卷;第139-147页 * |
| The Use of Silver Solid Amalgam Working Electrode for Determination of Nitrophenols by HPLC with Electrochemical Detection;Ales Danhel等;《Electroanalysis》;20091231;第21卷(第3-5期);第304页以及图1 * |
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