CN102253032A - Method for analyzing electrochemiluminescence transient process - Google Patents
Method for analyzing electrochemiluminescence transient process Download PDFInfo
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- CN102253032A CN102253032A CN2011100703821A CN201110070382A CN102253032A CN 102253032 A CN102253032 A CN 102253032A CN 2011100703821 A CN2011100703821 A CN 2011100703821A CN 201110070382 A CN201110070382 A CN 201110070382A CN 102253032 A CN102253032 A CN 102253032A
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Abstract
The invention relates to a method for analyzing the electrochemiluminescence transient process. By the method, the electrochemiluminescence system transient process can be effectively analyzed; current, electric potential, light intensity and time dynamic parameters can be acquired from the electrochemiluminescence system transient process to compared with stable state measurement; mathematical formula models are converted; and a kinetics mechanism of the reaction is explained from another aspect. The method comprises the following steps of: (1) starting to measure by using an electrochemiluminescence transient analyzer, cutting off a working electrode loop and a counter electrode loop when a system is positioned at any luminescence potential, and stopping applying voltage; and (2) allowing the system to enter the transient process, detecting the endurance time and the luminous intensity from any luminescence potential to luminescence annihilation in the transient process, calculating a corresponding light intensity-time curve or a region area, and comparing with the light intensity-time curve or the region area under a closed loop in the stable state process to obtain a reaction kinetics equation of the transient process.
Description
Technical field
The present invention relates to the Electrochemiluminescprocess process method, particularly a kind of method of using electrogenerated chemiluminescence technical Analysis system transient state process kinetic parameter.
Background technology
When system external condition changed, electrode can change to another stable state from a stable state, and Jing Li a transition period unsettled, the marked change of galvanochemistry parameter is exactly a transient state process therebetween.In this transition period, any one electrode basic process does not reach new stable state, and the entire electrode process is among the transient state process.When some basic process did not reach stable state, the result who shows was exactly that the parameter of this process is among the variation.Under transient state, compare the change that essence can take place in the kinetic parameter of the each side electrochemical reaction of electrode and the stable state.Electrogenerated chemiluminescence is a kind of chemiluminescence phenomenon that produces by the electrochemical reaction that directly or indirectly applies the voltage generation on the electrode, the product that chemiluminescence combines with galvanochemistry, thereby the advantage of integrated luminesceence analysis high sensitivity and electrochemical potential controllability.Traditional electrical causes chemiluminescence analytical technique research is electrochemical reaction and chemical reaction under the steady state conditions, and very few for the research of transient state process.Therefore, diversification has great importance for the transient analysis method in the electrogenerated chemiluminescence transient analysis.
At present, mainly contain following two kinds in electrochemical field for the analytical approach of transient state process:
Control current step transient measuring method also is called galvanostatic method traditionally.Be meant that controlling the electric current that flows through the research electrode changes by certain waveform rule with abrupt current, the potential electrode electromotive force (is called the timing potentiometric method) over time simultaneously, and then the mechanism of analyzing electrode process.Calculate the numerical value that each element in related parameter or the electrode equivalent electrical circuit is arranged of electrode.In Control current step transient measuring method, the waveform that flows through the electric current of electrode has a variety of, but they all have a common characteristic, i.e. the hop of electric current generation at a time is constant on a certain numerical value in the regular hour scope then.But this transient analysis method is subjected to the interference of concentration polarization and equilibrium potential drift easily.
Control electromotive force step transient measuring method also is called potentiostatic method traditionally.Be meant that the control electrode electromotive force changes according to certain waveform rule with electromotive force hop, measure electric current simultaneously and (be called chronoamperometry) over time, perhaps measure electric weight and (be called the timing coulometry) over time, and then the mechanism of analyzing electrode process, calculate the numerical value that each element in related parameter or the electrode equivalent electrical circuit is arranged of electrode.
More than two kinds of transient analysis methods for the CHARGE DISTRIBUTION state of interfacial electric double layer, CONCENTRATION DISTRIBUTION, electrode potential and the polarization current that the absorption of electrode interface covers in state, the diffusion layer good analysis practical application is arranged all.What people such as Baldo used that the organic electroluminescent light transient analysis has passenger's host molecule system phosphorescence buries in oblivion that (Phys.Rev.B 62,16 10967 (2000); Phys.Rev.B 62,10 958 (2000); M.A.Baldo et al., Nature 395,151 (1998)), and Gong etc. are applied to this method (Adv.Funct.Mater.2011 in the research of four aryl-silane photoluminescences, XX, 1-11), people such as Zhen are applied to this method (Adv.Funct.Mater.2011 in the research of fluorescence radiation diode, 21,699-707).But utilization electrogenerated chemiluminescence method is carried out the technology of transient analysis and was not also reported.In view of former experimental work basis, the applicant proposes to use the electrogenerated chemiluminescence technical method experimental system transient state process to be carried out the analysis of system first.When some basic process was in transient state, the result who shows was exactly that the parameter of this process is among the variation.Therefore, how further development research electrogenerated chemiluminescence transient analysis method concerns between the relevant kinetic parameter of discussion, for the development of transient analysis method, all is a very important problem.
Summary of the invention
Technical matters to be solved by this invention provides a kind of electrogenerated chemiluminescence analysis of transient process method, this method can be analyzed the electrochemical system transient state process effectively, and therefrom obtain electric current, electromotive force, light intensity, the time dynamics parameter compares with steady state measurement, conversion mathematics formula model is explained the kinetics mechanism that reacts from another side.
The technical solution adopted for the present invention to solve the technical problems is: electrogenerated chemiluminescence analysis of transient process method of the present invention, comprise the steps: 1. to begin to measure with the electrogenerated chemiluminescence transient analyser, when system is in any luminous current potential, cut off the working electrode loop and, stop to apply voltage electrode loop; 2. system enters transient state process, detect any luminous current potential of transient state process to luminous duration and the luminous intensity buried in oblivion, calculate corresponding light intensity-time curve or region area, contrast with steady-state process light intensity-time curve or region area under the closed-loop path, obtain the transient state process reaction kinetics equation.
As a preferred embodiment of the present invention, described step 1. in, cut off the working electrode loop simultaneously and to electrode loop, other electrochemical parameter conditions are constant, in the time of any luminous current potential of system, stop to apply voltage; Described cut-out working electrode loop and begin to detect transient state process light intensity and time dynamics parameter during to electrode loop synchronously.
The invention has the beneficial effects as follows, can avoid the limitation of single method transient analysis effectively, other the method for galvanochemistry transient analysis of comparing, has high sensitivity, low noise, easily the advantage of coupling can be used in follow-up research work widely.The method utilization is ripe relatively, and mathematical model is set up simple, has wide research application prospect.
Description of drawings
This instructions comprises following four width of cloth accompanying drawings:
Fig. 1 is the cyclic voltammetric figure and the light intensity-time curve of titania-potassium nitrate-ammonium persulfate coreaction system electrogenerated chemiluminescence stable state and transient state process;
Fig. 2 is the step pulse figure and the light intensity-time curve of titania-potassium nitrate-ammonium persulfate coreaction system electrogenerated chemiluminescence stable state and transient state process.
Fig. 3 is the cyclic voltammetric figure and the light intensity-time curve of bipyridyl ruthenium-hexa-methylene three diamine coreaction system electrogenerated chemiluminescence stable states and transient state process;
Fig. 4 is the step pulse figure and the light intensity-time curve of bipyridyl ruthenium-hexa-methylene three diamine coreaction system electrogenerated chemiluminescence stable states and transient state process.
Fig. 5 cuts off the power supply for flowing the relation curve of signal and corresponding overpotential response signal by a small margin.
Fig. 6 is the current step signal and the relation curve of overpotential response signal by a small margin accordingly.
Embodiment
The present invention is further described below in conjunction with drawings and Examples.
Electrogenerated chemiluminescence analysis of transient process method of the present invention comprises the steps:
1. begin to measure with the electrogenerated chemiluminescence transient analyser, when system is in any luminous current potential, when system is in any luminous current potential, cuts off the working electrode loop and, stop to apply voltage electrode loop;
2. system enters transient state process, detect any luminous current potential of transient state process to luminous duration and the luminous intensity buried in oblivion, calculate corresponding light intensity-time curve or region area, contrast with steady-state process light intensity-time curve or region area under the closed-loop path, obtain the transient state process reaction kinetics equation.
For the galvanochemistry that keeps whole transient state process and chemiluminescent assay synchronously can be with reference to property, described step 1. in, cut off the working electrode loop simultaneously and to electrode loop, other electrochemical parameter conditions are constant, in the time of any luminous current potential of system, stop to apply voltage.
Cut off the working electrode loop and begin to detect transient state process light intensity and time dynamics parameter during to electrode loop synchronously.Described system enters transient state moment by stable state and carries out opening with closed of related circuit.
A technology path is simple in order to set up, mathematical model ripe, that preparation is simple relatively electrogenerated chemiluminescence transient analysis circuit environment and correlation parameter.The present invention has investigated light intensity and the time dynamics parameter influence of two kinds of different electrochemical methods of cyclic voltammetry and step pulse analytic approach to electrode reaction system transient state process.Consider continuity and ease for operation that actual transient state process detects, the present invention has proposed cut-out working electrode loop simultaneously and has begun to detect transient state process light intensity and time dynamics parameter during to electrode loop synchronously.
With reference to Fig. 1 and Fig. 3, in titania-potassium nitrate-ammonium persulfate coreaction system, bipyridyl ruthenium-hexa-methylene three diamine coreaction systems, we use, and the method for cyclic voltammetric scans in the Electrochemiluminescprocess process, when being in any luminous position suddenly failure of current, with observe in the transient state process luminous intensity over time.From two width of cloth figure, can see light intensity and the changes in contrast of time in stable state and transient state.We find to enter the post-reacted luminous time that a relaxation is arranged of transient state, bury in oblivion along with cutting off electric current and light intensity can't occur.More can reflect this phenomenon in Fig. 1, the time that transient state process continues is 3 times of steady-state process duration nearly.We can be at disconnecting circuit and connect circuit on appropriate opportunity by switchgear, reaching comparing and measuring of stable state and transient state, thereby can obtain the kinetic parameter of binary states simultaneously.
With reference to Fig. 5, what reacted among the figure is outage stream waveform and corresponding electromotive force curve time response.Before outage, activation polarization is in steady state (SS).Cut off the power supply moment, electric double layer capacitance has little time discharge, therefore the moment of electrostatic double layer electric potential difference before outage and cut off the power supply after moment be identical, just the interfacial potential difference on the electrode does not change, the interface overpotential of electrode is constant, so the speed of carrying out of power-cut time electrochemical reaction does not change yet, be solution ohm voltage drop pop-off this moment, the electrode overpotential only is the activation polarization overpotential.
With reference to Fig. 2 and Fig. 4, in titania-potassium nitrate-ammonium persulfate coreaction system, bipyridyl ruthenium-hexa-methylene three diamine coreaction systems, we use, and the method for step pulse scans in the Electrochemiluminescprocess process, at the luminous arbitrary value that reaches of the moment that provides step current, cut off working electrode simultaneously and to the electric current of electrode this moment, electrode system enters transient state, observes light intensity over time.Similar with the result who works it out with cyclic voltammetry, the light intensity of system does not have the moment vanishing behind the cut-out electric current, but is reduced to baseline gradually in characteristics time and so on.See from Fig. 2 and Fig. 4 and can observe this phenomenon, the former transient state time is about 5 times of stable state; Latter's transient state time is about 4 times of stable state.We have illustrated time of cutting off electric current and connecting circuit no matter to be to cut off or connect among two width of cloth figure, and all can there be big hop electric current moment, but hop can not take place the electric potential difference on the solution electrode interface (being the interface overpotential) immediately.That is to say that changing the needed electrostatic double layer charging process of interfacial potential difference needs the regular hour, can not finish in moment, the change of interfacial potential difference also can not be finished in moment like this.Therefore, begin the foundation of electrode potential stable to the interface, must experience a transition period-transient state process from polarization.
With reference to Fig. 6, what reflected among the figure is single current step method response curve.At t=0 constantly, occurring an electromotive force on the overpotential response curve dashes forward more.This extremely short in a flash in, very little by the electric weight of electrode, be not enough to change the state-of-charge at interface, electric double layer capacitance has little time charging, the electric potential difference on the interface has little time to change.The electric double layer capacitance branch road that is equivalent to the electrode equivalent electrical circuit is by short circuit.And the solution ohm voltage drop has the current following characteristic, can occur simultaneously along with the more prominent of electric current.Electromotive force on the response curve is prominent to be exactly the ohm voltage drop of solution more.After current step, interfacial electric double layer electric capacity begins charging, has electrochemical reaction to take place simultaneously.The total electric current that flows through electrode comprises this two parts.Begin moment in the electrostatic double layer charging, all electric currents all are used for the electrostatic double layer charging.Subsequently, along with the carrying out of charging process, the interfacial potential difference constantly changes, i.e. activation polarization overpotential η
eSet up (η gradually
e) increase impel the increase of electric current.(η
e) continuous increase, its that is shared ratio in total current constantly rises, and reaches steady state (SS) up to electrochemical reaction, (η
e) reach stationary value, no longer change, at this moment, the electrostatic double layer charging process finishes, and all electric current is used for electrochemical reaction.
The present invention can use electrogenerated chemiluminescence technical research analysis system transient state process effectively, obtain light intensity in this transient state process and various kinetic parameters of time carry out after the statistical procedures with stable state under the correlation parameter that obtains compare, set up numerical relationship model, and this method and additive method can be organically combined coupling to system transient state process diversification transient analysis, avoided the limitation of single method transient analysis, compare other the method for galvanochemistry transient analysis, the utilization electrogenerated chemiluminescence has high sensitivity, low noise, easily the various advantages of coupling can be used in follow-up research work widely.The method utilization is ripe relatively, and mathematical model is set up simple, has wide research application prospect.
Claims (2)
1. electrogenerated chemiluminescence analysis of transient process method comprises the steps:
1. begin to measure with the electrogenerated chemiluminescence transient analyser, when system is in any luminous current potential, cuts off the working electrode loop and, stop to apply voltage electrode loop;
2. system enters transient state process, detect any luminous current potential of transient state process to luminous duration and the luminous intensity buried in oblivion, calculate corresponding light intensity-time curve or region area, contrast with steady-state process light intensity-time curve or region area under the closed-loop path, obtain the transient state process reaction kinetics equation.
2. electrogenerated chemiluminescence analysis of transient process method as claimed in claim 1, it is characterized in that: described step 1. in, cut off the working electrode loop simultaneously and to electrode loop, other electrochemical parameter conditions are constant, in the time of any luminous current potential of system, stop to apply voltage.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000036387A (en) * | 1998-07-16 | 2000-02-02 | Matsushita Electric Ind Co Ltd | Organic light emitting panel |
| CN101911335A (en) * | 2007-11-09 | 2010-12-08 | 通用显示公司 | Stable blue phosphorescent organic light emitting devices |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000036387A (en) * | 1998-07-16 | 2000-02-02 | Matsushita Electric Ind Co Ltd | Organic light emitting panel |
| CN101911335A (en) * | 2007-11-09 | 2010-12-08 | 通用显示公司 | Stable blue phosphorescent organic light emitting devices |
Non-Patent Citations (1)
| Title |
|---|
| 张志林等,1: "薄膜电致发光瞬态过程的物理模型及定量计算", 《发光学报》 * |
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Application publication date: 20111123 |