CN102778449A - Analysis device and method based on combination of electrochemistry impedance and laser-raman spectrum impedance - Google Patents
Analysis device and method based on combination of electrochemistry impedance and laser-raman spectrum impedance Download PDFInfo
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- CN102778449A CN102778449A CN2012102763484A CN201210276348A CN102778449A CN 102778449 A CN102778449 A CN 102778449A CN 2012102763484 A CN2012102763484 A CN 2012102763484A CN 201210276348 A CN201210276348 A CN 201210276348A CN 102778449 A CN102778449 A CN 102778449A
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Abstract
The invention relates to an analysis device and method based on combination of electrochemistry impedance and laser-raman spectrum impedance. The device is characterized in that an existing electrochemistry working station and a raman spectrometer are connected by using a signal acquisition/analysis instrument to realize the combination, and intermediate products or adsorbates generated on an electrode surface in a complex solid/liquid interface reaction are confirmed by synchronously measuring and researching the electrochemistry impedance and the laser-raman spectrum impedance of a working electrode in a electrochemistry three-electrode system in a frequency domain, thereby providing an effective evidence to the intermediate products introduced into an electrochemistry equivalent circuit. The device and the method have a good support function to the research on reaction mechanism and reaction process of conducting high polymer doping, metal corrosion and protection and electrode solid-liquid interfaces, and thus the device and the method have a wide application prospect.
Description
Technical field
The present invention relates to a kind of conducting high polymers thing doping reaction that can be applicable to, metal corrosion and protection, the electrochemical impedance of electrode solid/liquid interfaces absorption research field and the analytical equipment and the method for laser Raman spectroscopy impedance coupling.
Background technology
Electrochemical impedance spectroscopy is the interchange electric potential signal that applies the different little amplitude of frequency to the electrochemical system that will study; Measure and exchange electromotive force with the variation of frequency and the ratio of current signal; Or the phasing degree Φ of impedance is with the variation of frequencies omega; And then can the analyzing electrode process kinetics, electrostatic double layer and diffusion etc.; Course of reaction and mechanism such as research electrode material, solid electrolyte, conducting polymer and corrosion protection, but this technology can't be identified in electrode surface forms in the course of reaction intermediate product or adsorbate.The laser Raman spectroscopy analytic approach is a kind of powerful material characterization technique, and the molecular structure information of material can be provided, and each Raman vibration peak meeting and a certain fixedly chemical bond are complementary, and these are unavailable information in the electrochemical impedance spectrometry.And the Raman scattering of water is very faint, and Raman spectrum is the ideal tools of research solid/liquid interfaces electrochemical reaction.
Therefore, if can strong support be provided electrochemical impedance spectroscopy and the dynamic coupling of Raman spectrum analysis method to the foundation of electrochemical reaction mimic channel.Because in the reaction mechanism of many complicacies, all can simulate electrochemical reaction with intermediate product, the introducing of laser Raman spectroscopy can be confirmed the intermediate product of introducing in the simulation.
Summary of the invention
The analytical equipment and the method that the purpose of this invention is to provide a kind of electrochemical impedance and laser Raman spectroscopy impedance coupling; It is characterized in that this analytical equipment is made up of electrochemical workstation, Raman spectrometer, signal collection/analyser; In frequency field, the working electrode in the galvanochemistry three-electrode system is carried out electrochemical impedance and laser Raman spectroscopy impedance measurement research simultaneously; Confirm electrode surface produces in the reaction of complicated solid/liquid interfaces intermediate product or adsorbate, evidence is provided the validity of the intermediate product introduced in the galvanochemistry equivalent electrical circuit.
For realizing above-mentioned purpose, the present invention adopts following operation steps:
The part of 1) existing Raman spectrometer being carried out instrument is changed, and selects high-NA objective for use, introduces little plane of oscillation mirror in the input path of laser.
2) carry out swarming and do integral operation with the Raman spectrum of data analyzing and processing software, and convert electric signal to and be transferred to signal analyzer instant acquisition.
3) electro-chemical systems is set up equivalent-circuit model;
4) the electrochemical impedance parameter in the equivalent circuit model is carried out numerical simulation;
5) numerical simulation is carried out in the Raman spectrum impedance, the intermediate product that occurs in the equivalent circuit is confirmed;
6) analog result of the above-mentioned two kinds of impedances of contrast, the update the system reaction mechanism mechanism of reaction.
Among the present invention, be according to Randle circuit rule to the foundation of electro-chemical systems equivalent-circuit model.
Among the present invention, the numerical simulation of the electrochemical impedance parameter in the equivalent circuit model (resistance, electric capacity, inductance) is to adopt the least square fitting principle.
Among the present invention, data analyzing and processing software can directly read the spectral information of the ccd sensor in the raman spectroscopy instrument, and the Raman spectrum that is obtained is deducted noise background, swarming, integration, digital-to-analog conversion computing.
Among the present invention, select high-NA objective for use, these object lens can directly immerse in the solution, effectively improve the Raman spectrum peak intensity of sample, improve signal to noise ratio (S/N ratio).
Among the present invention, introduce little plane of oscillation mirror, make the laser that is radiated on the sample come flyback retrace (line mode), reduce the irreversible lesion of the thermal effect of laser the sample generation by setpoint frequency in the input path of laser.
Among the present invention, raman spectral signal (Δ Raman) is with applying voltage (Δ U=U on the working electrode
0Sin ω t) causality condition, linear conditions and stability condition are observed in variation and changing, raman spectral signal and voltage signal simultaneously.
Among the present invention, electro-chemical systems adopts the standard three-electrode system, working electrode, contrast electrode and electrode is connected to electrochemical workstation after add electrolytic solution, working electrode is applied polarizing voltage.The object lens of the burnt Raman spectrometer of copolymerization are immersed in the electrolytic solution, regulate the focusing hot spot and focus, sample exposure is set carries out spectrogram after the time and obtain in working electrode surface.
Among the present invention; Signal collection/analyser measurements and calculations respectively exchanges electromotive force and alternating current; The ratio with sine wave freuqency ω variation of electromotive force and raman spectral signal; Electromotive force and alternating current ratio are the electrochemical impedance Δ E/ Δ I of system, and electromotive force and raman spectral signal ratio are the Raman spectrum impedance Δ E/ Δ Raman of system.
The present invention obtains the laser Raman spectroscopy impedance of corresponding frequencies immediately in the process of measuring electrochemical impedance, be the present electrochemical impedance of initiative at home and abroad and the characterizing method of Raman spectrum impedance coupling.The present invention has good support effect for the electrochemical reaction of complicacy like the reaction mechanism of the doping of conducting high polymers thing, metal corrosion and protection, electrode solid/liquid interfaces and the research of the reaction mechanism mechanism of reaction, is with a wide range of applications.
Description of drawings
Fig. 1 is an electrochemical in-situ raman spectroscopy device synoptic diagram; Among the figure: 1, laser, 2, the Notch filter, 3, oil immersion objective, 4, ccd sensor, 5, diffraction grating, 6, the Raman spectrum spectrogram, 7, electrochemical workstation, 8, contrast electrode, 9, working electrode, 10, to electrode, 11, the in-situ electrolysis pond.
Fig. 2 is the synoptic diagram of the analytical equipment of electrochemical impedance and laser Raman spectroscopy impedance coupling.Among the figure: 1, Raman spectrometer, 2, Raman peaks intensity/voltage transitions appearance, 3, electrochemical workstation, 4, signal analysis/collection instrument, 5, signal generator, 6, electrochemical cell.
Specific embodiments
Embodiment 1:
Use vacuum vapour deposition in the gold thin film of fresh mica sheet surface deposition one layer thickness that dissociates, subsequently at 0.5M H as 100nm
2SO
4, use electrochemical method deposit thickness on gold thin film to be the polyaniline film of 50nm in the solution of 0.15M aniline.After polyaniline film rinsed well with the sulfuric acid solution of pH 1 and 3 successively, transfer in the electrochemical in-situ spectrum electrolytic cell, and inject 0.01M K
2SO
4(pH=3) electrolytic solution; Mode according to Fig. 2 connects spectrum electrolytic cell, electrochemical workstation, Raman spectrometer and signal collection/analyser; Start electrochemical impedance and Raman spectrum impedance procedure; The spectrum time of taking the photograph that Raman spectrometer is set is 0.1s, Laser Measurement Raman spectrum impedance when electrochemical impedance is measured, and experiment parameter is voltage amplitude 10mV; Frequency 60k-0.01Hz, respectively-0.1 ,-0.2 ,-0.3 ,-measure electrochemical impedance and laser Raman spectroscopy impedance simultaneously under the 0.4V vs Ag/AgCl voltage.The electrochemical impedance result of p-poly-phenyl amine carries out numerical simulation according to the galvanochemistry equivalent electrical circuit, identifies the intermediate product of introducing in the galvanochemistry equivalent electrical circuit with the Raman spectrum impedance results, confirms reaction mechanism and the course of polyaniline redox reaction under pH=3.
Claims (8)
1. the analytical equipment and the method for electrochemical impedance and laser Raman spectroscopy impedance coupling; It is characterized in that this analytical equipment comprises electrochemical workstation, laser Raman spectrometer, spectrum electrolytic cell and microcomputer; Through in frequency field, the working electrode in the galvanochemistry three-electrode system being measured electrochemical impedance and Raman spectrum impedance simultaneously; Confirm electrode surface produces in the reaction of complicated solid/liquid interfaces intermediate product or adsorbate, evidence is provided the validity of the intermediate product introduced in the galvanochemistry equivalent electrical circuit.
2. by the analytical equipment of described electrochemical impedance of claim 1 and laser Raman spectroscopy impedance coupling, its characterization step is following successively:
The part of 1) existing Raman spectrometer being carried out instrument is changed, and selects high-NA objective for use, introduces little plane of oscillation mirror in the input path of laser;
2) carry out swarming and do integral operation with the Raman spectrum of data analyzing and processing software, and convert electric signal to and be transferred to signal analyzer instant acquisition;
3) electro-chemical systems is set up equivalent-circuit model;
4) the electrochemical impedance parameter in the equivalent circuit model is carried out numerical simulation;
5) numerical simulation is carried out in the Raman spectrum impedance, the intermediate product that occurs in the equivalent circuit carries out really;
6) analog result of the above-mentioned two kinds of impedances of contrast, the update the system reaction mechanism mechanism of reaction.
3. press the analytical equipment and the method for claim 1 or 2 described a kind of electrochemical impedances and laser Raman spectroscopy impedance coupling; It is characterized in that; Use from the development data interpretation software and can directly read the ccd sensor spectral information in the raman spectroscopy instrument; The Raman spectrum that obtains is deducted noise background, swarming, integration, digital-to-analog conversion computing, be transferred to signal analyzer.
4. press the analytical equipment and the method for claim 1 or 2 described a kind of electrochemical impedances and laser Raman spectroscopy impedance coupling; It is characterized in that; Select high-NA objective for use, these object lens can directly immerse in the solution, effectively improve the Raman spectrum peak intensity and the signal to noise ratio (S/N ratio) of sample.
5. press the analytical equipment and the method for claim 1 or 2 described a kind of electrochemical impedances and laser Raman spectroscopy impedance coupling; It is characterized in that; Introduce little plane of oscillation mirror in the input path of laser; Make the laser that focuses on the sample come flyback retrace, reduce the irreversible lesion that laser thermal effect produces sample by setpoint frequency.
6. by the analytical equipment and the method for claim 1 or 2 described a kind of electrochemical impedances and laser Raman spectroscopy impedance coupling, it is characterized in that laser Raman spectroscopy signal (Δ Raman) is with applying voltage (Δ U=U on the working electrode
0Sin ω t) variation and changing.
7. by the analytical equipment and the method for claim 1 or 2 described a kind of electrochemical impedances and laser Raman spectroscopy impedance coupling, it is characterized in that, in the process of measuring electrochemical impedance, obtain the laser Raman spectroscopy impedance of corresponding frequencies immediately.
8. press the analytical equipment and the method for claim 1 or 2 described a kind of electrochemical impedances and laser Raman spectroscopy impedance coupling; It is characterized in that; The method is the electrochemical impedance at home and abroad initiated and the characterizing method of laser Raman spectroscopy impedance coupling; For the electrochemical reaction of complicacy, like the reaction mechanism of the doping of conducting high polymers thing, metal corrosion and protection, electrode solid/liquid interfaces and the research of the reaction mechanism mechanism of reaction good support effect is arranged, be with a wide range of applications.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103389330A (en) * | 2013-08-07 | 2013-11-13 | 苏州扬清芯片科技有限公司 | Electrochemical impedance and quartz crystal microbalance combined analysis device and method |
| CN103852461A (en) * | 2014-03-28 | 2014-06-11 | 厦门大学 | Electrochemical needle point enhanced Raman spectrometry instrument based on scanning probe microscope |
| CN103901247A (en) * | 2012-12-28 | 2014-07-02 | 清华大学 | Electric potential difference measurement method |
| CN104569090A (en) * | 2014-12-26 | 2015-04-29 | 浙江清华长三角研究院萧山生物工程中心 | Electrochemical impedance and ultraviolet visible absorption spectrum combined analysis device and method |
| CN106885801A (en) * | 2017-03-01 | 2017-06-23 | 东南大学 | A kind of method for monitoring electrochemical luminescence intensity and wavelength |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102435315A (en) * | 2011-10-14 | 2012-05-02 | 深圳市世纪天源环保技术有限公司 | Photon counting Raman spectrometer capable of realizing full spectrum direct-reading performance |
| CN101581688B (en) * | 2009-03-12 | 2012-06-27 | 西北师范大学 | Electrochemical detection method for dihydrogen phosphate ions in water system |
-
2012
- 2012-08-06 CN CN2012102763484A patent/CN102778449A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101581688B (en) * | 2009-03-12 | 2012-06-27 | 西北师范大学 | Electrochemical detection method for dihydrogen phosphate ions in water system |
| CN102435315A (en) * | 2011-10-14 | 2012-05-02 | 深圳市世纪天源环保技术有限公司 | Photon counting Raman spectrometer capable of realizing full spectrum direct-reading performance |
Non-Patent Citations (5)
| Title |
|---|
| 宋巍等: "银电极上植酸钠/2-氨基-5-巯基-1,3,4-噻二唑混合自组装层的表面增强拉曼光谱和电化学研究", 《化学学报》 * |
| 张颖怀 等: "用电化学阻抗谱(EIs)研究环氧树脂涂层的防腐蚀性能", 《腐蚀与防护》 * |
| 曹晓卫 等: "银电极表面异亮氨酸单分子膜结构和表面性质的表面增强拉曼光谱研究", 《化学学报》 * |
| 田中群: "Raman-STM联用系统及其初步实验", 《物理化学学报》 * |
| 田中群: "电化学原位拉曼光谱的应用及进展", 《电化学》 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103901247A (en) * | 2012-12-28 | 2014-07-02 | 清华大学 | Electric potential difference measurement method |
| CN103901247B (en) * | 2012-12-28 | 2016-08-31 | 清华大学 | Potential difference measurements method |
| CN103389330A (en) * | 2013-08-07 | 2013-11-13 | 苏州扬清芯片科技有限公司 | Electrochemical impedance and quartz crystal microbalance combined analysis device and method |
| CN103852461A (en) * | 2014-03-28 | 2014-06-11 | 厦门大学 | Electrochemical needle point enhanced Raman spectrometry instrument based on scanning probe microscope |
| CN103852461B (en) * | 2014-03-28 | 2016-01-20 | 厦门大学 | A kind of galvanochemistry Tip-Enhanced Raman Spectroscopy instrument based on scanning probe microscopy |
| CN104569090A (en) * | 2014-12-26 | 2015-04-29 | 浙江清华长三角研究院萧山生物工程中心 | Electrochemical impedance and ultraviolet visible absorption spectrum combined analysis device and method |
| CN106885801A (en) * | 2017-03-01 | 2017-06-23 | 东南大学 | A kind of method for monitoring electrochemical luminescence intensity and wavelength |
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