CN108732215B - Electrochemical in-situ spectrum electrolytic cell and application - Google Patents
Electrochemical in-situ spectrum electrolytic cell and application Download PDFInfo
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- CN108732215B CN108732215B CN201810485137.9A CN201810485137A CN108732215B CN 108732215 B CN108732215 B CN 108732215B CN 201810485137 A CN201810485137 A CN 201810485137A CN 108732215 B CN108732215 B CN 108732215B
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/28—Electrolytic cell components
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/65—Raman scattering
Abstract
The invention discloses an electrochemical in-situ spectrum electrolytic cell and application thereof, comprising an electrolytic cell body, wherein the electrolytic cell body comprises a liquid inlet, a liquid outlet and an optical detection window, the liquid inlet and the liquid outlet are arranged on two opposite side walls of the electrolytic cell body, the liquid inlet is communicated with a flow injection device or a micro-fluidic device, and the optical detection window is arranged on the upper part of the electrolytic cell body. The electrochemical in-situ spectrum electrolytic cell has the characteristics of adaptability to a proper spectrum wavelength range, higher optical sensitivity, applicability to various solvents, smaller cell time constant, easiness in filling and cleaning, capability of realizing electrochemical method sample pretreatment and wastewater treatment and the like, and solves the technical defects of the conventional electrochemical in-situ spectrum detection device.
Description
Technical Field
The invention belongs to the technical field of electrochemical detection, and particularly relates to an electrochemical in-situ spectrum electrolytic cell and application thereof.
Background
The conventional electrochemical method has no capability of representing specific molecules, can only provide the sum of various microscopic information of electrode reaction, cannot meet the requirements of deep microscopic research, is difficult to accurately identify reactants, intermediates, products and the like on the electrode and explain the electrochemical reaction mechanism, and cannot meet the requirements of the research objects of the modern electrochemistry which are increasingly deep and expanded.
With the continuous improvement of the performance of the spectroscopic instrument and the emergence of new technologies, the application range of the spectroscopic instrument is continuously expanded, the process of researching an electrochemical system from a molecular level is greatly accelerated, the spectroscopic technologies such as Raman, infrared, ultraviolet, fluorescence spectrum and the like are combined with the electrochemical system, the information of the electrochemical system which cannot be obtained by a pure electrochemical experiment can be provided, and the detection of adsorbed species on the surface of an electrode and the change of the adsorbed species along with the change of chemical and electrochemical environments are carried out. Based on the electrochemical reaction path and the reaction kinetics can be speculated, so that the electrochemical reaction mechanism can be known on the molecular level, a spectroelectrochemical testing system combining electrochemical and spectroscopic technologies is formed, and the effectiveness of an intermediate product in an electrochemical equivalent circuit can be proved.
One of the keys to the application of spectroelectrochemical techniques in the field of electrochemical and spectroscopic research is the design of spectroelectrochemical cells. Because multi-step reactions are often involved in the chemical reaction process and step-by-step measurement in practical application, the traditional three-electrode electrochemical in-situ spectrum detection device cannot meet the measurement requirement.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provides an electrochemical in-situ spectroscopy electrolytic cell.
Another object of the present invention is to provide a method for analytical detection using the electrochemical in-situ spectroscopy electrolytic cell.
The technical scheme of the invention is as follows:
an electrochemical in-situ spectrum electrolytic cell comprises an electrolytic cell body, wherein the electrolytic cell body comprises a liquid inlet, a liquid outlet and an optical detection window, the liquid inlet and the liquid outlet are arranged on two opposite side walls of the electrolytic cell body, the liquid inlet is communicated with a flow injection device or a micro-fluidic device, and the optical detection window is arranged on the upper part of the electrolytic cell body;
the bottom wall of the electrolytic cell body is sequentially provided with at least one electrochemical pretreatment electrode, at least one electrochemical detection electrode and at least one electrochemical post-treatment electrode which are opposite to the optical detection window and are electrically connected with the constant potential rectifier along the direction from the liquid inlet to the liquid outlet;
the liquid to be detected flows from the liquid inlet to the liquid outlet at a set flow rate through the communication flow injection device or the microfluidic device, after the at least one electrochemical pretreatment electrode (sample pretreatment based on an electrochemical method) removes interfering impurities in the liquid to be detected, the liquid to be detected realizes qualitative and quantitative detection of a target object on the at least one electrochemical detection electrode, and electrochemical rear-end treatment is carried out on the at least one electrochemical post-treatment electrode to reduce or remove harmful substances which possibly pollute the environment; the spectrum detection instrument detects the electrochemical behavior generated in the area where the at least one electrochemical detection electrode is located through the optical detection window.
In a preferred embodiment of the present invention, the material of the electrolytic cell body comprises polytetrafluoroethylene, polytrifluoroethylene, glass or quartz.
In a preferred embodiment of the present invention, the material of the optical detection window includes calcium fluoride, silicon, germanium, quartz or glass.
In a preferred embodiment of the invention, the liquid inlet is in sealed communication with a flow injection device or a microfluidic device.
In a preferred embodiment of the invention, the side wall of the cell body is provided with at least one first electrode replacement opening corresponding to the at least one electrochemical pretreatment electrode.
In a preferred embodiment of the present invention, the side wall of the electrolytic cell body is provided with a second electrode replacement port corresponding to the at least one electrochemical detection electrode.
In a preferred embodiment of the invention, the side wall of the cell body is provided with a third electrode replacement opening corresponding to the at least one electrochemical aftertreatment electrode.
A method for analytical detection by using the electrochemical in-situ spectroscopy electrolytic cell, comprising the following steps:
driving the liquid to be detected to flow into the electrolytic cell body from the liquid inlet and flow out of the electrolytic cell body from the liquid outlet through a flow injection device or a micro-fluidic device, wherein the liquid to be detected sequentially passes through the at least one electrochemical pretreatment electrode, the at least one electrochemical detection electrode and the at least one electrochemical post-treatment electrode;
according to the electrochemical characteristics of the target object and the impurities, applying appropriate electrode potentials on the electrochemical pretreatment electrode, the electrochemical detection electrode and the electrochemical post-treatment electrode through a potentiostat to remove the impurities which seriously interfere on the electrochemical pretreatment electrode by the liquid to be detected at a set flow rate, realizing qualitative and quantitative detection of the target object on the electrochemical detection electrode, and removing harmful substances which possibly pollute the environment on the electrochemical post-treatment electrode;
the method is characterized in that qualitative and quantitative detection of a target object is realized on an electrochemical detection electrode, and meanwhile, a spectroscopic experiment is carried out through an optical detection window by using a spectroscopic detection instrument, so that information including a molecular state and a surface structure of the target object on the electrochemical detection electrode interface is obtained.
The invention has the beneficial effects that:
1. the electrochemical in-situ spectrum electrolytic cell has the characteristics of adaptability to a proper spectrum wavelength range, higher optical sensitivity, applicability to various solvents, smaller cell time constant, easiness in filling and cleaning, introduction of electrochemical sample treatment and the like, and solves the technical defect of the conventional electrochemical in-situ spectrum detection device in the aspect of detection of complex samples.
2. The electrochemical in-situ spectrum electrolytic cell is connected with the flow injection device or the micro-fluidic device so as to realize the accurate control of the flow speed and the flow of the solution in the flow path, has high analysis speed and is easy to automatically and continuously analyze, and the processes of sample pretreatment, measurement, post-treatment and the like of the solution analyzed on the electrode in the flow path are realized by connecting the constant potential rectifier, so that the accuracy and the reliability of the test are improved, the operation steps are simplified, and the test efficiency is obviously improved. Has wide application prospect in the aspect of analysis and detection.
3. The electrochemical in-situ spectrum electrolytic cell can be used with various spectrum instruments to achieve the purpose of in-situ detection of reaction products, intermediate products, adsorbed species and the like of a detected object, so that an electrochemical reaction approach is presumed to further master microscopic information of an interface molecular layer, and information such as a molecular state, a surface structure and the like of a target object on a working electrode interface is researched to obtain a reaction mechanism and qualitatively and quantitatively analyze and identify the target object.
4. The electrochemical in-situ spectrum electrolytic cell has the advantages of strong universality, wide application range, simple structure, convenient processing and low cost, and can simultaneously realize the detection of electrochemical response and spectrum signals on the working electrode under various conditions.
Drawings
FIG. 1 is a perspective view of a part of the structure of an electrochemical in-situ spectroscopy electrolytic cell of example 1 of the present invention.
FIG. 2 is a top perspective view of a portion of an electrochemical in-situ spectroscopy cell of example 1 of the present invention.
FIG. 3 is a graph showing the results of the experiment in example 1 of the present invention.
FIG. 4 is a second graph showing the experimental results of example 1 of the present invention.
Detailed Description
The technical solution of the present invention will be further illustrated and described below with reference to the accompanying drawings by means of specific embodiments.
As shown in fig. 1 and fig. 2, an electrochemical in-situ spectroscopy electrolytic cell comprises an electrolytic cell body 1, wherein the electrolytic cell body 1 comprises a liquid inlet 11, a liquid outlet 12 and an optical detection window 13, the liquid inlet 11 and the liquid outlet 12 are arranged on two opposite side walls of the electrolytic cell body 1, the liquid inlet 11 is hermetically communicated with a flow injection device or a microfluidic device, and the optical detection window 13 is arranged on the upper part of the electrolytic cell body 1;
an electrochemical pretreatment electrode 14, an electrochemical detection electrode 15 and an electrochemical post-treatment electrode 16 which are opposite to the optical detection window 13 and are electrically connected with the constant potential rectifier are sequentially arranged on the bottom wall of the electrolytic cell body 1 along the direction from the liquid inlet 11 to the liquid outlet 12, and the electrochemical pretreatment electrode 14, the electrochemical detection electrode 15 and the electrochemical post-treatment electrode 16 are screen printing electrodes; the side wall of the electrolytic cell body 1 is provided with a first electrode replacing port 141 corresponding to the electrochemical pretreatment electrode 14, a second electrode replacing port 151 corresponding to the electrochemical detection electrode 15 and a third electrode replacing port 161 corresponding to the electrochemical post-treatment electrode 16;
the liquid to be detected flows from the liquid inlet 11 to the liquid outlet 12 at a set flow rate through a communicating flow injection device or a micro-fluidic device, after the electrochemical pretreatment electrode 14 removes interfering impurities in the liquid to be detected, the liquid to be detected realizes qualitative and quantitative detection of a target object on the electrochemical detection electrode 15, and harmful substances which possibly pollute the environment are removed on the post-treatment electrode; the spectroscopic measuring instrument detects the electrochemical behavior occurring in the region where the electrochemical detection electrode 15 is present through the optical detection window 13.
The material of the electrolytic cell body 1 comprises polytetrafluoroethylene, polytrifluoroethylene, glass or quartz. The material of the optical detection window 13 includes calcium fluoride, silicon, germanium, quartz or glass.
In this embodiment, the analyzing and detecting of the pollution of the bivalent mercury ions in the water body by using the electrochemical in-situ spectroscopy electrolytic cell includes:
driving the liquid to be detected to flow into the electrolytic cell body 1 from the liquid inlet 11 and flow out of the electrolytic cell body 1 from the liquid outlet 12 through a flow injection device or a micro-fluidic device, wherein the flow rate of the liquid to be detected is controlled to be 1mL/min and the liquid to be detected sequentially passes through the electrochemical pretreatment electrode 14, the electrochemical detection electrode 15 and the electrochemical post-treatment electrode 16;
according to the electrochemical characteristics of the target and the impurities, a constant potential rectifier is applied to the electrochemical pretreatment electrode 14, the electrochemical detection electrode 15 and the electrochemical post-treatment electrode 16 to ensure that the liquid to be detected completes the removal of the impurities with serious interference on the electrochemical pretreatment electrode 14 at a set flow rate, the qualitative and quantitative detection of the target is realized on the electrochemical detection electrode 15, and harmful substances which may pollute the environment are removed on the electrochemical post-treatment electrode 16, specifically:
applying a 1.2V potential to the electrochemical pretreatment electrode 14 to complete oxidation of organic matters and the like in the water body so as to avoid interference on the detection electrode, as shown in FIG. 3; firstly applying a potential of-0.1V to the electrochemical detection electrode 15 to enrich bivalent mercury ions in the water body on the surface of the electrochemical detection electrode 15, and then sweeping the bivalent mercury ions to 0.8V from 0V by using a square wave anodic stripping voltammetry to obtain a stripping peak of the mercury ions, as shown in FIG. 4; applying a potential of-0.5V to the electrochemical post-treatment electrode 16 to enrich the divalent mercury ions on the surface of the electrochemical post-treatment electrode 16 so as to avoid environmental pollution;
while realizing qualitative and quantitative detection of the target object on the electrochemical detection electrode 15, the electrochemical in-situ spectroscopy electrolytic cell is placed under a microscope of a Raman spectrometer, the laser wavelength is adjusted to 785nm, the reaction generated on one of the electrochemical pre-treatment electrode 14, the electrochemical detection electrode 15 and the electrochemical post-treatment electrode 16 is detected in situ through the optical detection window 13, and a spectroscopy experiment is carried out, so that the information of the target object on the electrochemical detection electrode 15 interface, including the molecular state and the surface structure, is researched.
Through comparison, the water sample subjected to pretreatment can detect trace mercury ions contained in the water body compared with the water sample not subjected to pretreatment, as shown in fig. 3. And opening the Raman spectrometer to obtain a Raman spectrum signal, and carrying out in-situ monitoring on the chemical reaction process on the surface of the electrode so as to obtain the information of the target object on the electrode interface, including the molecular state and the surface structure.
The above description is only a preferred embodiment of the present invention, and therefore should not be taken as limiting the scope of the invention, which is defined by the appended claims.
Claims (7)
1. An electrochemical in-situ spectroscopy electrolytic cell, characterized in that: the device comprises an electrolytic cell body, wherein the electrolytic cell body comprises a liquid inlet, a liquid outlet and an optical detection window, the liquid inlet and the liquid outlet are arranged on two opposite side walls of the electrolytic cell body, the liquid inlet is communicated with a flow injection device or a micro-fluidic device, and the optical detection window is arranged on the upper part of the electrolytic cell body;
the bottom wall of the electrolytic cell body is sequentially provided with at least one electrochemical pretreatment electrode, at least one electrochemical detection electrode and at least one electrochemical post-treatment electrode which are opposite to the optical detection window and are electrically connected with the constant potential rectifier along the direction from the liquid inlet to the liquid outlet;
the liquid to be detected flows from the liquid inlet to the liquid outlet at a set flow rate through the communication flow injection device or the micro-fluidic device, after the at least one electrochemical pretreatment electrode removes interfering impurities in the liquid to be detected, the liquid to be detected realizes qualitative and quantitative detection of a target object on the at least one electrochemical detection electrode, and harmful substances which possibly pollute the environment are removed on the at least one electrochemical post-treatment electrode; the spectrum detection instrument detects the electrochemical behavior generated in the area where the at least one electrochemical detection electrode is located through the optical detection window;
the method for analyzing and detecting by using the reagent comprises the following steps:
driving the liquid to be detected to flow into the electrolytic cell body from the liquid inlet and flow out of the electrolytic cell body from the liquid outlet through a flow injection device or a micro-fluidic device, wherein the liquid to be detected sequentially passes through the at least one electrochemical pretreatment electrode, the at least one electrochemical detection electrode and the at least one electrochemical post-treatment electrode;
according to the electrochemical characteristics of the target object and the impurities, applying appropriate electrode potentials on the electrochemical pretreatment electrode, the electrochemical detection electrode and the electrochemical post-treatment electrode through a potentiostat to remove the impurities which seriously interfere on the electrochemical pretreatment electrode by the liquid to be detected at a set flow rate, realizing qualitative and quantitative detection of the target object on the electrochemical detection electrode, and removing harmful substances which possibly pollute the environment on the electrochemical post-treatment electrode;
the method is characterized in that qualitative and quantitative detection of a target object is realized on an electrochemical detection electrode, and meanwhile, a spectroscopic experiment is carried out through an optical detection window by using a spectroscopic detection instrument, so that thermodynamic and kinetic information including a molecular state and a surface structure of the target object on the electrochemical detection electrode interface is obtained.
2. An electrochemical in situ spectroscopy cell according to claim 1 wherein: the material of the electrolytic cell body comprises polytetrafluoroethylene, polytrifluoroethylene, glass or quartz.
3. An electrochemical in situ spectroscopy cell according to claim 1 wherein: the optical detection window is made of calcium fluoride, silicon, germanium, quartz or glass.
4. An electrochemical in situ spectroscopy cell according to claim 1 wherein: the liquid inlet is communicated with the flow injection device or the micro-fluidic device in a sealing way.
5. An electrochemical in situ spectroscopy cell according to claim 1 wherein: the side wall of the electrolytic cell body is provided with at least one first electrode replacing opening corresponding to the at least one electrochemical pretreatment electrode.
6. An electrochemical in situ spectroscopy cell according to claim 1 wherein: and a second electrode replacing opening corresponding to the at least one electrochemical detection electrode is formed in the side wall of the electrolytic cell body.
7. An electrochemical in situ spectroscopy cell according to claim 1 wherein: and a third electrode replacing opening corresponding to the at least one electrochemical post-treatment electrode is formed in the side wall of the electrolytic cell body.
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| CN102411021A (en) * | 2011-08-23 | 2012-04-11 | 深圳市中兴环境仪器有限公司 | Electrochemical electrolytic cell |
| CN103389280A (en) * | 2013-08-07 | 2013-11-13 | 苏州扬清芯片科技有限公司 | Flow electrolytic cell for ultraviolet-visible spectrum |
| CN204439523U (en) * | 2014-08-15 | 2015-07-01 | 中国科学院过程工程研究所 | A kind of controlling temp type flowing thin layer and frequently spectroelectrochemistry reaction in-situ pond |
| CN104502322B (en) * | 2014-09-18 | 2017-07-28 | 浙江工业大学 | Electrochemical in-situ SERS chip and its production method |
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