A kind of static electrogenerated chemiluminescence electrolytic cell that is applicable to thin electrode
Technical field
The utility model relates to a kind of electrolytic cell, especially relates to a kind ofly detecting luminously in static systems, can be applicable to thin electrode, as the electrogenerated chemiluminescence electrolytic cell of platinized platinum, gold plaque and indium tin oxide (ITO) glass electrode etc.
Background technology
Electrogenerated chemiluminescence (electrogenerated chemiluminescence, ECL) mainly pass through electrochemical means, utilize some compound in the system to be measured in electrochemical reaction, to generate unsettled electron excitation intermediate state, when returning ground state, this material transition of excited state produces optical radiation, the light of this radiation is by behind the photomultiplier transit, by computer acquisition and record.Nineteen twenty-nine Harvey than under the electronegative potential during (2.8V) electrolysis alkalescence luminol aqueous solution first observed to have near the electrode luminescence phenomenon (Harvey E N, J.Phys.Chem., 1929,33:1456).Since mid-term in 20th century, people are to novel hydrocarbon complex (Ru, Os, transient metal complexes such as Pd) and cluster (Mo, the understanding aspect of photochemistry clusters such as W) and electrochemical properties has obtained very big progress, has meanwhile also promoted beginning to take shape of the theoretical experimental technique analytical approach of ECL.Because luminous wave spectrum of ECL and electrode potential are closely related,, can systematically study the mechanism of some typical luminescent substances therefore by writing down the variation of ECL luminous intensity (I) and electric current (i) simultaneously with electrode potential (E).
Electrolytic cell is an epochmaking part in the electrochemiluminescdetection detection system, and it mainly is made up of electrolytic cell groove and three-electrode system.Common three-electrode system is generally formed by working electrode, contrast electrode with to electrode, working electrode such as glass carbon, gold, platinum and ito glass electrode etc., and contrast electrode such as saturated calomel electrode, Ag/AgCl and filamentary silver etc. are to electrode such as platinum filament etc.
In electrochemistry experiment, the real work area of working electrode, the relative position of contrast electrode and working electrode will produce significantly influence to experimental result, and in luminescent detection system, the distance between working electrode and the optical window also influences the detection of luminous intensity.The static electrolytic cell groove of existing conventional mostly is circular, can not be well near optical window, and there is not good stationary installation to fix three-electrode system, testing measured electrode potential can not well be reappeared, thus can not with ECL spectrogram and galvanochemistry cyclic voltammetric (CV) dry straightly in conjunction with and obtain more response message.Especially slim ITO electrode in the thin electrode, because its good light transmittance, application in analytical chemistry is increasingly extensive, but because slim ITO thickness of electrode is very little, hold and can't stand pressure, therefore how to encapsulate slim ITO electrode, it is broken that it both had been difficult for, can obtain ECL spectrogram and CV figure again exactly, be the key issue of carrying out its relevant ECL research.
Summary of the invention
The purpose of this utility model is the deficiency at the existence of existing conventional electrolysis pond, a kind of practicality is provided, easy, be easy to change thin electrode, can carry out electrochemistry experiment and luminous detection simultaneously, be beneficial to the mechanism of some typical luminescent substances is better studied, be applicable to the static electrogenerated chemiluminescence electrolytic cell of thin electrode.
The utility model is provided with electrolytic cell cell body, T shape electrolytic cell main body, working electrode, contrast electrode and auxiliary electrode.The electrolytic cell cell body is rectangular parallelepiped; The T-shaped structure of T shape electrolytic cell main body, be provided with working electrode groove at the electrolytic cell bottom part body back side, be provided with light hole in the working electrode groove, the electrolytic cell main body is provided with caulking groove in the back side, be provided with 3 grooves in the middle of the electrolytic cell main body, be respectively contrast electrode groove, auxiliary electrode groove and liquid injection port.Working electrode, contrast electrode and auxiliary electrode are located at respectively in working electrode groove, contrast electrode groove and the auxiliary electrode groove.
Electrolytic cell cell body transparent surface is preferably simple glass or quartz glass, and electrolytic cell cell body side and bottom surface are preferably lead polytetrafluoroethylmaterial material side and bottom surface, so that reduce catoptrical absorption in light detects.Working electrode groove in the T shape electrolytic cell main body is preferably square groove, the degree of depth of working electrode groove is decided according to the thickness of thin slice working electrode, the light hole that the working electrode groove middle is provided with is preferably the circular hole that diameter is 2mm, its size is also decided according to needed real work electrode area, the caulking groove that is provided with in the electrolytic cell main body back side is preferably the rectangle caulking groove of wide 1cm, is used for fixing the lead that working electrode is drawn.3 grooves that are provided with in the middle of the electrolytic cell main body are preferably 3 cylindrical grooves.Working electrode is preferably thin electrode, and contrast electrode is preferably saturated calomel electrode, and auxiliary electrode is preferably platinum electrode.
Because electrolytic cell main body of the present utility model adopts T shape structure, two arms by T shape are fixed on the electrolytic cell cell body, the working electrode groove at the main body back side and caulking groove be the steady job electrode well, thereby makes the relative distance of working electrode and contrast electrode keep certain.Therefore, the utility model has the advantages that: 1) device is simple, easy operating; 2) working electrode, contrast electrode and auxiliary electrode all are well fixed, and have solved the encapsulation problem of the especially slim ITO electrode of thin electrode; 3) working electrode groove and caulking groove are easy to the replacing of electrode all in the electrolytic cell body surfaces, and practicality is wide; 4) working electrode and contrast electrode are very close and distance is certain, make the experimental data that obtains more accurate, also help the miniaturization of device simultaneously; 5) the very close optical window of working electrode has effectively reduced the loss of light signal.
Description of drawings
Fig. 1 is the structural representation of the utility model embodiment.
Fig. 2 is the front view of the utility model embodiment.
Fig. 3 is the electrolytic cell cell body front view of the utility model embodiment.
Fig. 4 is the electrolytic cell main body front view of the utility model embodiment.
Fig. 5 is the electrolytic cell main body vertical view of the utility model embodiment.
Fig. 6 is the CV figure in the utility model embodiment application.Experiment condition: electrolytic solution is the phosphate buffer (pH=7.0) that contains 0.1mol/L KBr, and luminol concentration is 10
-4Mol/L, voltage scanning speed is 0.04V/s.In Fig. 6, horizontal ordinate is current potential Potential/V vs SCE, and ordinate is electric current Curret/mA.
Fig. 7 is the ECL figure in the utility model embodiment application.In Fig. 7, horizontal ordinate is current potential Potential/V vs SCE, and ordinate is electroluminescence intensity ECL Intensity/mV.
Embodiment
Referring to Fig. 1~5, the utility model is provided with electrolytic cell cell body 3, T shape electrolytic cell main body 1, working electrode, contrast electrode and auxiliary electrode (3 electrodes in the drawings do not draw).Electrolytic cell cell body 3 is rectangular parallelepiped, and transparent surface is common or quartz glass, and side and bottom surface are the lead polytetrafluoroethylmaterial material, can reduce catoptrical absorption in light detects.T shape electrolytic cell main body 1 T-shaped structure has a square working electrode groove 4 in bottom rear, and the degree of depth of groove is decided according to the thickness of thin slice working electrode.The working electrode groove middle make a call to a diameter be the circular hole of 2mm as light hole 2, its size is also decided according to needed real work electrode area.The rectangle caulking groove 5 of a wide 1cm is cut a hole in the middle at electrolytic cell main body 1 back side, is used for fixing the lead that working electrode is drawn; In the middle of the electrolytic cell main body 1 three cylindrical grooves are arranged, be respectively contrast electrode groove 6, auxiliary electrode groove 7 and liquid injection port 8.Below provide the application example of the utility model embodiment.
1. preparation electrolytic solution: get 0.25mL 10mmol/L luminol mother liquor, be diluted to 25mL, obtain 0.1mmol/L luminol liquid to be measured with the 0.05mol/L phosphate buffer (pH=7.0) that contains 0.1mol/L KBr.
2. the installation of working electrode:
A) get a lead that thickness is suitable, remove the insulation course (each about 1cm) at its two ends, cut one section sizeable copper and be adhesive in ITO one side and the exposed end of lead, and adjust test so that its contact is good.
B) conducting surface of usefulness electroprobe test I TO glass electrode, the adhesive surface of marine glue on the one side of its conduction and the working electrode groove is sticking mutually, getting a slice length of side again is the square marine glue of 1.5cm, is bonded at the ito glass electrode back side, does not contact with water with the lead exposed part to guarantee copper glue.
C) lead is pressed into the caulking groove of electrolytic cell main body, with steady job electrode better.
3. be contrast electrode with the saturated calomel electrode, the platinum filament that a thickness is suitable is an auxiliary electrode, inserts respectively in the electrolytic cell main body corresponding electrode groove.
4. get the test fluid of 2.5mL, inject the electrolytic cell cell body, mounted electrolytic cell main body is put into,, can continue to inject test fluid to get rid of by liquid injection hole if bubble is arranged.
5. connect test circuit, open electrochemical workstation, start the cyclic voltammetry scan program, start EChrom 2000 acquisition systems simultaneously, record data.Cyclic voltammetry experiment condition: sweep speed, 0.04V/s; Sweep limit ,-1.2~1.0V.
Fig. 6 and 7 provides the result of example, has obtained ECL spectrogram and CV figure simultaneously, illustrates that the utility model can be used for the mechanism research of typical luminescent substance well in conjunction with these two kinds of spectrograms, and the result has confirmed the utlity model has above-mentioned outstanding advantage.