CN112114015B - In-situ characterization method and device for electrochemical infrared spectrum combination of pollutant interface reaction - Google Patents
In-situ characterization method and device for electrochemical infrared spectrum combination of pollutant interface reaction Download PDFInfo
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Abstract
The invention relates to an in-situ characterization method and device for electrochemical infrared spectrum combination of pollutant interface reaction. The electrochemical infrared spectrum combined detection method constructed by the invention can acquire multi-dimensional information such as qualitative/quantitative, macroscopic/microscopic and the like of target reaction synchronization, so that pollutant reaction is more comprehensively known, and the multi-dimensional clarification of a pollutant interface process and a regulation mechanism is facilitated, thereby effectively solving the pollution problem. The electrochemical infrared spectrum combination device established by the invention has the advantages of simple operation, long service life, wide infrared wave number application range and more purposes, and can be widely applied to the in-situ characterization aspect of pollutant interface reaction.
Description
Technical Field
The invention belongs to the field of environmental chemistry, and particularly relates to an in-situ characterization method and device for electrochemical infrared spectrum combined use of pollutant interface reaction, which are suitable for in-situ characterization of a pollutant interface reaction process in a simulated soil/underground water system and can obtain synchronous macroscopic and microscopic, qualitative and quantitative information.
Background
With the rapid development of economy and the acceleration of industrialization and urbanization, China has a great pollution problem. In which, the interface cause of the pollution process and the mechanism of the repair process are unclear, which is a significant obstacle to pollution repair. To our knowledge, interfacial behavior is transformed throughout the migration of contaminants, and is the leading edge of research in the international environmental field. The study of the contaminant interfacial reaction is of fundamental interest since the behavior of most contaminant reactions depends on interfacial properties, such as adsorbent-adsorbate interactions upon adsorption/desorption and surface chemical properties upon oxidation/reduction.
In recent years, researchers have developed various advanced characterization techniques to explore the contaminant interface reactions. For qualitative detection of microscopic level, reliable infrared spectrum technology is adopted, and commercial instruments thereof facilitate in-situ detection. Electrochemical techniques that enable in situ detection are the primary choice when it comes to the detection of macroscopic and quantitative information. At present, electrochemical technology is used for measuring a time curve simulating open circuit potential in a soil and underground water system, and the change trend of the time curve can be used as an analysis basis for heavy metal adsorption or oxidation-reduction reaction. However, independent infrared spectra and electrochemical signals do not correspond to each other, since the same experimental conditions cannot be completely repeated. In summary, the current ectopic characterization of destructive reactions and single-information one-sided acquisition methods are not sufficient to support a comprehensive and in-depth understanding of contaminant reactions. In short, the reaction process has multi-scale signals of macro and micro, and can be described qualitatively and quantitatively, and since the current interface reaction process is limited by the in-situ characterization technology, how to obtain the information is an important problem for researching the pollution problem. In order to reliably answer the 'how microscopic and macroscopic behaviors' and 'how qualitative and quantitative description' at the same time, the development of a multi-dimensional characterization technology is urgently needed to clarify pollutant interface processes and regulation mechanisms from multiple scales, so that the pollution problem is deeply known and effectively solved.
In general, current technologies fail to provide a comprehensive and thorough understanding of the interfacial reactions of contaminants, and thus a technology combining multiple detection means is needed to obtain simultaneous quantitative/qualitative and macroscopic/microscopic information. According to previous experiments, infrared spectroscopy can detect in-situ interfacial reaction behavior at the molecular level, while electrochemical methods can be used as sensitive detectors of in-situ quantitation of macroscopic interfacial interactions. In view of these facts, combining the above two methods, the electrochemical infrared spectroscopy technology can allow us to simultaneously acquire an infrared microscopic signal and an electrochemical macroscopic signal, and simultaneously energize different interfacial properties, i.e., "1 +1> 2". To our knowledge, the electrochemical infrared spectroscopy is the first research used for the interfacial process for exploring spontaneous reactions of pollutants, which may open up new sources for the in-situ research of the interfacial reactions of environmental pollutants.
Disclosure of Invention
The invention aims to solve the technical problem of providing a pollutant interface reaction electrochemical infrared spectrum combined in-situ characterization method and a device thereof aiming at the defects of the existing pollutant interface reaction in-situ characterization technology. The method can monitor the interface reaction multidimensional signal of the pollutant in situ, and simultaneously obtain the information of a pollutant reaction mechanism, a quantitative signal, microscopic and macroscopic behaviors and the like, and the device has the advantages of simple operation, long service life, wide application range, rich functions and the like.
In order to achieve the purpose, the invention adopts the following technical scheme:
the device comprises a light path reflection part, wherein the light path reflection part comprises a shell and a detection window embedded in the middle above the shell, the detection window is provided with an upper surface and a lower surface, the upper surface of the detection window is plated with a conductive film, the conductive film is plated with a solid-phase reactant film as required, the upper surface and the lower surface of the detection window can reflect light, an infrared spectrum detector and a light source are respectively arranged on two sides of the light path reflection part, and incident light of the light source is received by the infrared spectrum detector after being reflected for multiple times by the upper surface and the lower surface of the detection window of the light path reflection part;
the reaction tank component comprises a reaction tank with an opening at the lower end and an opening at one side, the reaction tank is arranged on the upper surface of the detection window, and electrolyte and reactants are added into the reaction tank according to needs; the reference electrode is inserted into the reaction cell through an opening at one side of the reaction cell, and the conductive film deposited on the detection window and the solid-phase reactant film jointly serve as a working electrode.
According to the scheme, the light path reflection component can comprise a plurality of light path reflection plates, so that infrared incident light can reach the surface of the detection window, and can be received by the infrared spectrum detector after being reflected for multiple times. Incident light emitted by the light source reaches the light path reflecting plate on the other side after being reflected for multiple times by the light path reflecting plate and the interior of the detection window, is further reflected and is received by the infrared spectrum detector. The number of internal optical path reflectors may be increased appropriately to enhance the infrared spectral signal.
According to the scheme, the openings are formed in the two sides of the shell in the light path reflection component, so that a light source can conveniently enter a detection window.
According to the scheme, the detection window is made of diamond or zinc selenide. Diamond or zinc selenide as detection window, 700cm -1 The interference above the wave number is small.
According to the scheme, the detection window is a high-refractive-index transparent prism. Preferably, the refractive index is greater than 2.
According to the scheme, the conductive film can be a graphene conductive film. The conductive film plays a role in conducting electricity and can conduct the change of an electric signal of an object to be detected.
According to the scheme, the upper surface of the detection window is plated with the graphene conductive film by adopting a transfer graphene method, and the method specifically comprises the following steps: firstly, preparing graphene on a polymer film, and then transferring the graphene onto a detection window; and then, when a solid-phase reactant film is plated on the graphene conductive film, dispersing the powder by using alcohol and dropwise adding the powder above the graphene conductive film, and after the alcohol is volatilized, finishing the film plating of the solid-phase reactant film.
According to the scheme, the in-situ characterization device comprises a U-shaped frame, and a light source and an infrared spectrum detector are respectively embedded in the inner sides of 2 vertical ends of the U-shaped frame; the light path reflection component is arranged at the bottom of the U-shaped frame.
According to the scheme, the bottom of the shell of the light path reflection component is provided with a groove, the upper surface of the bottom of the U-shaped frame is correspondingly provided with matched bulges, and the light path reflection component is butted and placed in the U-shaped frame.
According to the scheme, a silica gel pad is arranged below the reaction tank part for buffering; the in-situ characterization device further comprises a pressure rod, the pressure rod is arranged on the U-shaped frame, and the pressure rod is adjusted to enable the reaction cell component and the light path reflection component to be in close contact with each other so as to prevent liquid leakage.
According to the scheme, the part of the upper surface of the detection window, which is not covered by the reaction tank, is provided with the conductive copper foil, so that the working electrode is conveniently connected with the electrochemical workstation, and the working electrode and a reference electrode arranged in the reaction tank form a loop for electrochemical analysis and detection. One end of the conductive copper foil is adhered to the surface of the working electrode, and the other end is clamped by a lead clamp led out from the electrochemical workstation. The tail end of a lead led out from the electrochemical workstation is made of rigid and thick metal and cannot be directly connected with a conductive film, the conductive copper foil can conduct electricity between the conductive copper foil and the conductive film, and the conductive copper foil is equivalent to a flexible electrode wire and can also be replaced by other flexible substances with a conductive function, such as copper wires. The middle part can be suspended and does not contact with other conductive substances, so as to avoid influencing the experimental result.
According to the scheme, the pollutant interface reaction electrochemical infrared spectrum combined in-situ characterization device further comprises an electrochemical workstation.
The infrared spectrometer can be directly used in commercial instruments, and is internally provided with a light source (for providing incident light) and a detector.
According to the scheme, the electrode is inserted into the reaction tank through an opening on one side of the reaction tank, and the detection end at the bottom of the electrode needs to be completely immersed in the solution of the reaction tank; the electrode is sleeved with a rubber ring, so that the electrode is stably placed without shaking.
An in situ characterization method, comprising the steps of: respectively plating a conductive film and a solid-phase reactant film on a detection window by using the in-situ characterization device to be used as working electrodes, and then connecting the working electrodes with an electrochemical workstation;
adding a reference electrode, electrolyte and reactants into a reaction tank according to the requirement;
opening a light source and an infrared spectrum detector, wherein the light source emits incident light, and the incident light emitted by the light source is received by the infrared spectrum detector for infrared analysis after being reflected for multiple times by the upper surface and the lower surface of a detection window of a light path reflection component; and simultaneously, carrying out electrochemical reaction analysis on an electrochemical reaction signal in the reaction tank by using an electrochemical workstation.
According to the scheme, when the solid-phase reactant film is plated on the graphene conductive film, dispersing powder by using alcohol and dropwise adding the powder above the graphene conductive film, and volatilizing the alcohol to finish the film plating of the solid-phase reactant film;
the working electrode is connected with the electrochemical workstation through a conductive copper foil;
adjusting a pressure rod to make the reaction cell component and the light path reflection component tightly contact;
the electrochemical workstation selects an open circuit potential-time detection method to carry out electrochemical analysis.
According to the scheme, the reaction process to be detected needs to have infrared activity, and meanwhile, the target reaction needs to generate electron transfer or other changes so that an electrochemical signal is changed; according to the electrochemical and infrared spectrum signals obtained simultaneously, information such as peak intensity, peak type and peak position of the infrared spectrum is analyzed, and electrochemical signal change synchronous with attribution is understood, so that the interface reaction behavior of the pollutants is described in multiple dimensions.
According to the scheme, signals such as peak intensity, peak type and peak position of the infrared spectrum corresponding to the pollutants in the interface reaction process are analyzed, information such as pollutant groups, bonding modes and molecular structures can be obtained, and adsorption sites and coordination configurations of the pollutants can be analyzed; the information such as the dynamic condition, the adsorption and desorption proportion and the like of the interface reaction process can be obtained by combining the synchronous electrochemical signals, and the qualitative and quantitative analysis is carried out on the interface reaction processes such as the physics, the chemistry, the biology and the like of the pollutants, so that the interface reaction behavior of the pollutants can be described in multiple dimensions.
The device has multiple purposes, and can detect infrared spectrograms of solid and liquid and in-situ characterize infrared signals of reaction and solid-liquid reaction in solution when an electrochemical workstation and a conductive film are not used, namely an infrared spectrometer and a light path reflection part are only adopted and an object to be detected is fixed on a detection window.
When the reaction is carried out, corresponding infrared spectrograms can be obtained along with the change of substances or the difference of chemical bonds, so that infrared real-time analysis can be carried out; the infrared spectrum detection part is similar to a commercial in-situ infrared spectrometer, different substances at a detection window can absorb light with different wave numbers, and the rest spectrum is detected by an instrument to obtain a spectrogram of the object to be detected, which can show the information of the substances; the number of internal optical path reflectors may be increased appropriately to enhance the infrared spectral signal. The light path reflection component enables infrared incident light emitted by the instrument to reach an interface to be detected through reflection, and further reflects the infrared incident light to be received by the detector.
The invention has the advantages that:
(1) the invention constructs an electrochemical infrared spectrum combined detection method, can obtain multi-dimensional information such as qualitative/quantitative, macroscopic/microscopic and the like of target reaction synchronization, enables the pollutant reaction to be more comprehensively known, and is beneficial to multi-dimensionally clarifying the pollutant interface process and regulation mechanism, thereby effectively solving the pollution problem. The invention can be used for simulating the research of the interface reaction of pollutants in a soil/underground water system and provides technical support for the research of pollutant reaction mechanism, quantitative analysis, microscopic and macroscopic behaviors and the like. The problems that pollutant response signals cannot be identified and the mechanism is not clear are solved.
(2) The method does not need to separate and destroy the reaction process, can characterize the interface reaction of the pollutants in situ, enables people to know the behavior of the pollutants more deeply and accurately, and provides a reliable detection means for the in situ characterization of the reaction of the pollutants.
(3) The invention has wide application range, and a plurality of pollutant reactions have detection activity; has wide application field. At present, the traditional electrochemical infrared spectrum coupling technology is reported to be used for infrared spectrum detection of electric excitation reaction, and the electrochemical part of the technology cannot monitor spontaneous reaction. Most of the pollution and remediation processes of pollutants in the actual environment are performed spontaneously, so the method cannot be used for describing most pollution problems. Based on the functions of small influence of open circuit potential on the reaction and capability of detecting spontaneous signals, the electrochemical method is introduced to enable electrochemical infrared spectroscopy to be used for multi-signal characterization of spontaneous reactions and non-electric excitation reactions (such as photoexcited reactions).
(4) The wave number range of the reaction to be detected is expanded, and the operation is simpler. The traditional electrochemical infrared spectroscopy device needs to select different detection windows and conductive films thereof according to different wave numbers of reactants, so that spare materials and experimental technology are complicated. The reason is that the prior art for plating the conductive film is mature in the detection window(e.g. silicon most commonly used) at 1000cm -1 The interference below the wave number is large, and a detection window with small interference has no mature conductive film plating technology, and the film plating operation is complex and the repeatability is poor. The novel device established by the invention adopts a diamond or zinc selenide detection window and plates the graphene conductive film by a rapid graphene transfer method, so that the graphene conductive film is in a wider wave number range (4000-700 cm) -1 ) Has better applicability.
(5) The electrochemical infrared spectrum combination device established by the invention has the advantages of simple operation, long service life, wide infrared wave number application range and more purposes, and can be widely applied to the in-situ characterization aspect of the interface reaction of pollutants. The detection window of the traditional device is separated from the light path reflection device, the splicing and repeated installation of multiple parts lead to complex operation and damage to the service life of the parts, and the damage of the coating to the detection window is large, so that the replacement is frequent and the consumption is large. The electrochemical infrared spectrum combined device with the closed integrated style, which is established by the invention, embeds the detection window into the light path reflection component without separation, simplifies the operation and prolongs the service life of parts. The traditional device has single function and weak signal, and can only be used for achieving the purpose of electrochemical infrared spectrum combination. The device can be used for detecting infrared spectrograms of solid and liquid and in-situ characterizing infrared signals of substance reaction and solid-liquid reaction in the solution, and has multiple functions so as to reduce purchase of various parts and further reduce cost.
Drawings
FIG. 1 is a schematic diagram of an electrochemical infrared spectroscopy detection device.
FIG. 2 is an infrared spectrum of a combination method for detecting the reaction of hematite and arsenite.
FIG. 3 is a graph showing the potential change of the reaction of hematite with arsenite detected by the combined method.
FIG. 4 is an infrared spectrum of a combination method for detecting competitive adsorption reactions on hematite.
FIG. 5 is a graph of the potential change of the combined method for detecting competitive adsorption reactions on hematite.
FIG. 6 is a quasi-secondary kinetic fit of the hematite's chromate adsorbing potential.
FIG. 7 is a quasi-secondary kinetic fit of competitive adsorption reaction potentials on hematite.
Figure 8 is a quasi-second order kinetic fit of the adsorption and desorption phase potentials.
1-a reaction cell component, 2-an infrared spectrum detector, 3-an electrochemical workstation, 4-a computer, 5-an optical path reflecting component, 6-a U-shaped frame, 7-a detection window, 8-a pressure rod, 9-a conductive film, 10-a solid-phase reactant film, 11-a conductive copper foil, 12-an electrode, 13-an optical path reflecting plate, 14-a light source, 15-a bump and 16-a groove.
The technical principle of the invention is as follows:
the invention utilizes the method of combining electrochemical infrared spectroscopy to obtain electrochemical and infrared spectroscopy signals which are synchronous in the reaction process in situ, thereby obtaining qualitative/quantitative, macroscopic/microscopic information of target reaction. The specific principle is as follows: the light source 14 in the infrared spectrometer 6 emits infrared incident light, the infrared incident light is reflected by the light path reflection plate 13 and then reaches the working electrode, the infrared incident light is partially absorbed by the working electrode, the infrared incident light is reflected by the light path reflection plate 13 and then reaches the infrared spectrum detector, and therefore representation of infrared spectrum signals at the working electrode is achieved. At the same time, the open circuit potential signal of the above reaction is monitored throughout. Microscopic qualitative information can be obtained from the infrared spectrogram, chemical bonds can be identified by the shape and the position of an infrared peak, and the peak intensity can judge the enhancement/weakening, appearance/disappearance of different chemical bonds. The open circuit potential can reveal macroscopic quantitative information and can show the direction and the amount of electron transfer in the spontaneous reaction process, the potential rise shows that the working electrode loses electrons, and the decline is opposite. By combining infrared spectrum and electrochemistry, qualitative/quantitative and macroscopic/microscopic information of target reaction can be obtained simultaneously. The electrochemical function of the traditional electrochemical infrared spectrum combined method cannot obtain spontaneous reaction and non-electric excitation reaction signals. The introduction of the electrochemical method enables electrochemical infrared spectroscopy to be used for multi-signal characterization of spontaneous reactions and non-electric excitation reactions (e.g., photoexcited reactions) based on the small influence of open-circuit potential on the reactions and the capability of detecting spontaneous signals. In addition, the conventional method usually uses silicon as a detection window, which is 1000cm for each detection window -1 Infrared spectrum detection interference below wave numberLarge and the method of overcoming the wavenumber interference through a complex detection window (e.g., Si/ZnSe) is difficult to implement and complicated to operate. Therefore 700cm was used in this study -1 The diamond or zinc selenide with less interference above the wave number is used as a detection window, and the conductive film is deposited by a fast transfer graphene method, so that the operation is simple.
In addition, the detection window and the light path reflection device of the traditional device are separated, the splicing and repeated installation of multiple parts cause complex operation and damage to the service life of the parts, and the damage of the coating to the detection window is large, so that the replacement is frequent and the consumption is large. The device of the invention has longer service life and multiple purposes, can be used for detecting infrared spectrograms of solid and liquid and in-situ characterizing infrared signals of substance reaction and solid-liquid reaction in solution, and is mainly due to the following reasons: the infrared light reflected by the integrated light path reflection component has less loss and strong signal, so that the enhancement function of a conductive film is not needed, and the infrared spectrum detection without the conductive film can be realized; meanwhile, the integrated light path reflection component does not need to be assembled, and the influence of repeated use on the service life of the component is small.
Detailed Description
The present invention will be described in detail with reference to specific examples, which are provided for illustration only and are not intended to limit the scope of the present invention.
Example 1: research on infrared wave number larger than 1000cm by electrochemical infrared spectrum combined method -1 Reaction of contaminants
An electrochemical infrared spectrum combination device is set up according to the mode of figure 1, a reaction detection window selects diamond and is conductive
An in-situ characterization device for electrochemical infrared spectroscopy of a pollutant interface reaction is shown in fig. 1: the optical path reflection component comprises a shell, wherein two sides in the shell of the optical path reflection componentIs divided intoAnd the two sides of the shell are provided with openings, so that a light source can be incident on the detection window. The infrared spectrum detector 2 and the light source 14 are respectively arranged at two sides of the light path reflection component, and the incident light emitted by the light sourceAfter being reflected for multiple times by the light path reflecting plate of the light path reflecting component and the upper and lower surfaces of the detection window, the infrared spectrum detector receives the light; the middle of casing top is inlayed and is established detection window high refractive index transparent prism 7, the detection window has upper surface and lower surface, the upper surface and the lower surface homoenergetic reflected light of detection window, plate graphite alkene conductive thin film in proper order on the upper surface of detection window, plate solid phase reactant film as required on the graphite alkene conductive thin film, the part that the upper surface of detection window is not covered by the reaction tank is provided with conductive copper foil 11, during the use, conductive thin film and the solid phase reactant film of deposit on the detection window are as working electrode jointly, accessible conductive copper foil 11 links to each other with electrochemical workstation 3.
The reaction tank component comprises a reaction tank 1 with an opening at the lower end and an opening 12 at one side, the reaction tank is arranged on the upper surface of the detection window, and solution is added into the reaction tank according to the requirement; the reference electrode 12 is inserted into the reaction tank through an opening at one side of the reaction tank, the detection end at the bottom of the electrode needs to be completely immersed in the solution of the reaction tank, and a rubber ring is sleeved on the electrode, so that the electrode is stably placed without shaking. The conductive film deposited on the detection window and the solid-phase reactant film are jointly used as working electrodes, a conductive copper foil is arranged on the part, which is not covered by the reaction tank, of the upper surface of the detection window, so that the working electrodes are conveniently connected with the electrochemical workstation, and the working electrodes and the reference electrodes arranged in the reaction tank form a loop for electrochemical analysis and detection.
Further, the in-situ characterization device comprises a U-shaped frame, and the light source and the infrared spectrum detector are respectively embedded inside 2 vertical ends of the U-shaped frame; the light path reflection component is arranged at the bottom of the U-shaped frame. The bottom of the light path reflecting component shell is provided with a groove, the upper surface of the bottom of the U-shaped frame is correspondingly provided with matched bulges, and the light path reflecting component is butted and placed in the U-shaped frame.
A silica gel pad is arranged below the reaction tank part for buffering; the in-situ characterization device further comprises a pressure rod, the pressure rod is arranged on the U-shaped frame, and the pressure rod is adjusted to enable the reaction cell component and the light path reflection component to be in close contact with each other so as to prevent liquid leakage.
First, it is confirmed that the infrared spectrum detector 2 and the light source 14 are normally disposed on both sides of the U-shaped frame 6 with the pressure bar 8 being located above, and the bottom recess 16 of the optical path reflecting member 5 is gradually brought close to the bottom projection 15 of the U-shaped frame 6 until they are fitted. Then, a conductive film 9 and a solid-phase reactant film 10 are respectively plated on the detection window 7, and are connected with the electrochemical workstation 3 through a conductive copper foil 11, and the pressure rod 8 is adjusted to make the reaction cell component 1 and the optical path reflection component 5 tightly contact. Finally, the electrodes 12, electrolyte and reactants are added to the cell component 1 as needed. The power is turned on, the light source 14 emits incident light, the infrared spectrum detector 2 collects the emitted light, and infrared analysis is performed using computer 4 software. Meanwhile, the software of the computer 4 of the electrochemical workstation 3 is controlled to select an open circuit potential-time detection method, so that the electrochemical reaction signal is analyzed. The reactants can be added on the way to monitor the change of the reaction.
Arsenic (As) and its compounds are commonly used in pesticides and herbicides, are carcinogenic, and belong to highly toxic substances, wherein the infrared wave number of arsenite is more than 1000cm -1 . Meanwhile, hematite is a common mineral in the nature. Therefore, this section studies the adsorption reaction of hematite solids with arsenite solutions. Electrochemical selective detection of open circuit potential changes. The working electrode is constructed by plating a graphene film and then a hematite film on a detection window, and the reference electrode adopts a silver/silver chloride electrode without a counter electrode. The reaction process was monitored by electrochemical infrared spectroscopy to obtain the following information.
The reaction of hematite solids and sodium arsenite solution in sodium sulfate electrolyte was detected by in situ characterization as follows:
according to the requirements of target reaction, the electrolyte is sodium sulfate, the solid-phase reactant is hematite, and the liquid-phase reactant is sodium arsenite. The working electrode is constructed by plating a graphene film and then a hematite film on a detection window, and the reference electrode adopts a silver/silver chloride electrode without a counter electrode.
Specifically, the optical path reflecting member 5 is butted in an infrared spectrometer 6, and a conductive thin film 9 (graphene film) and a solid-phase reactant hematite thin film 10 are respectively plated on a detection window 7. And plating the graphene film by using a rapid graphene transfer method, namely tearing off the graphene film protection paper in water by using tweezers, then pasting the graphene film on a detection window, uncovering the protection paper on the other side, heating on a heater at 300 ℃ for 20 minutes to remove possible residual organic matters, and cooling at room temperature. The deposition of the solid-phase reactant film requires that 0.5 g of hematite powder is firstly dispersed in 2 ml of ethanol, the dispersion liquid is absorbed by a rubber head dropper and is dripped above the graphene film on the detection window, and the construction of the working electrode is completed after the ethanol is volatilized. The working electrode was connected to the electrochemical workstation 3 using a 3 cm conductive copper foil 11, one end of which was glued to the working electrode surface and the other end was clamped by a wire clamp leading from the electrochemical workstation. The pressure rod 8 is adjusted to make the reaction cell component 1 and the light path reflection component 5 closely contact with each other at intervals of a silica gel pad, and a silver/silver chloride electrode 12 and sodium sulfate electrolyte are added. Turning on software 'CHI 1200B' for controlling electrochemical workstation in computer, selecting 'open circuit potential-time' detection method, inputting '50000's for running time, inputting '0.2's for sampling interval time, inputting '1' and '-1' V for highest potential and lowest potential respectively, clicking the button for starting detection, and generating real-time open circuit potential monitoring graph along with time. In addition, turning on the software 'OMNIC' for controlling the infrared spectrometer in the computer, clicking the parameter setting icon, selecting the ATR mode, and selecting the diamond window. Clicking a background sampling icon to start background deduction, clicking a sample detection icon to start sampling after background sampling is finished, adding a sodium arsenite solution after the first sampling is finished, and recording the adding time. And then, multiple times of automatic sampling are set, so that the sampling is automatically carried out. For the signal of the open circuit potential, the change of the open circuit potential along with the time can be observed in real time in the reaction process, and other operations are not needed. And analyzing electrochemical and infrared spectrum signals obtained by the reaction so as to analyze the reaction behavior in multiple dimensions.
As shown in FIG. 2, immediately after arsenite is added, a distinct characteristic peak appears, and the peak shape and the peak position of the peak are consistent with those of hematite which adsorbs arsenite by double-tooth double-core. The characteristic peaks described above gradually decrease as the reaction proceeds. The infrared spectrum results show that: arsenite can adsorb onto hematite as a bidentate double core, and this adsorption then decreases. To further elucidate the reaction progress, we investigated simultaneous electrochemical signals. As shown in fig. 3, after arsenite is added, the potential drops, i.e. the working electrode (hematite) gets electrons and the arsenite loses electrons. Combining infrared spectroscopy with electrochemical results to obtain: during the reaction process, arsenite is firstly adsorbed to hematite in a bidentate and binuclear configuration, and then part of the adsorbed arsenite is oxidized to be stable by the hematite, and the whole process takes about 75 minutes. Therefore, the invention can obtain the microscopic bonding condition and regular change of the reaction, can also obtain the multi-dimensional information such as synchronous electron transfer and the like, and provides help for people to deeply understand the reaction process.
Example 2: electrochemical infrared spectrum combined method for researching infrared wave number less than 1000cm -1 Reaction of contaminants of
Based on the influence of some detection windows, the electrochemical infrared spectrum combined device is 1000cm -1 Since the following is greatly disturbed, the wave number is limited, and 1000cm was studied in this section -1 The following contaminants react. Waste water discharged from leather factories, printing and dyeing factories and other factories often contains heavy metal chromium which can cause renal failure and even cause cancer, and the infrared wave number of chromate is less than 1000cm -1 . This section therefore investigated the reactions associated with chromate contamination. Hematite (HNC) as solid-phase reactant is sequentially mixed with infrared wave number less than 1000cm -1 Chromate radical (Cr) and wave number of more than 1000cm -1 To explore the applicability of the process to reactants of different wavenumbers. Similar to the example 1, an electrochemical infrared spectroscopy combined device is set up, a reaction detection window selects zinc selenide, and the reaction process is monitored.
As shown in FIG. 4, 1000cm after addition of chromate to the system -1 To 700cm -1 Has obvious peak and is consistent with the spectrum of hematite single-tooth single-core bonding chromate. After the addition of oxalate, the early peak is obviously reduced, and 1000cm -1 The characteristic peak of the hematite double-tooth double-core five-membered ring bonded oxalate appears above. The infrared spectrum result shows that: the hematite firstly absorbs chromate in a monodentate mononuclear mode, and the later absorbs oxalate in a bidentate binuclear five-membered ringPart of the chromate adsorbed earlier is desorbed. The right side of the map is a synchronous potential value, and the rule that the potential is firstly gradually increased and then decreased can be observed. The specific potential results are shown in fig. 5, and the reaction process has obvious potential rise before fall. Since the adsorption of oxalate does not substantially cause a potential change, the effect thereof can be ignored, and it is considered that the potential change is caused by chromate reaction. Further, by combining the conclusion of the infrared spectrum, the proportion of the later-period drop of the potential to the earlier-period rise is calculated, and the following results can be found: the chromate desorbed from the oxalate accounts for 30% of the earlier adsorbed part. Finally, kinetic fitting is carried out on potential change in the reaction process, as shown in fig. 6 and 7, darker thick points are experimental detection values of potential, light and thinner lines are fitting results, it is found that both the adsorption and desorption stages well meet the quasi-second-order kinetics, and fitting parameters are shown in fig. 8.
It was thus concluded that: the electrochemical infrared spectrum combination method and the novel device thereof can be used for obtaining in-situ infrared spectrograms and potential changes of reactants with different wave numbers, so that macroscopic and microscopic behaviors of the reaction are obtained, qualitative and quantitative analysis is carried out on the reaction, and the method is helpful for people to comprehensively and deeply understand the pollutant reaction from multiple dimensions.
Claims (9)
1. The utility model provides a pollutant interfacial reaction electrochemistry infrared spectroscopy allies oneself with uses normal position characterization device which characterized in that: the device comprises a light path reflection part, a reaction tank part, a U-shaped frame and a pressure rod, wherein the light path reflection part is arranged at the bottom of the U-shaped frame and comprises a shell and a detection window embedded in the middle above the shell, the detection window is provided with an upper surface and a lower surface, a graphene conductive film is plated on the upper surface of the detection window, a solid-phase reactant film is plated on the graphene conductive film as required, the upper surface and the lower surface of the detection window can reflect light, a spectrum detector and a light source are positioned on two sides of the light path reflection part and are respectively embedded inside 2 vertical ends of the U-shaped frame, and incident light emitted by the light source is received by an infrared spectrum detector after being reflected for multiple times by the upper surface and the lower surface of the light path reflection part detection window;
the reaction tank component comprises a reaction tank with an opening at the lower end and an opening at one side, the reaction tank is arranged on the upper surface of the detection window, and electrolyte and reactants are added into the reaction tank according to needs; the reference electrode is inserted into the reaction tank through an opening on one side of the reaction tank, and the conductive film deposited on the detection window and the solid-phase reactant film are jointly used as working electrodes;
the pressure rod is arranged on the U-shaped frame, and the pressure rod is adjusted to enable the reaction cell component and the light path reflection component to be in close contact with each other so as to prevent liquid leakage.
2. The in-situ characterization device according to claim 1, wherein: the light path reflection component comprises a plurality of light path reflection plates, and can ensure that infrared incident light can reach the surface of the detection window and can be received by the infrared spectrum detector after being reflected for multiple times; and openings are formed in two sides of the shell in the light path reflecting component, so that a light source can conveniently enter the detection window.
3. The in-situ characterization device according to claim 1, wherein: the detection window is a high-refractive-index transparent prism; the detection window is made of diamond or zinc selenide.
4. The in-situ characterization device according to claim 1, wherein: the graphene conductive film is coated by adopting a transfer graphene method, and specifically comprises the following steps: the preparation of graphene is completed on a polymer film, and then the graphene is transferred to a detection window.
5. The in-situ characterization device according to claim 1, wherein: the bottom of the light path reflecting component shell is provided with a groove, the upper surface of the bottom of the U-shaped frame is correspondingly provided with matched bulges, and the light path reflecting component is butted and placed in the U-shaped frame.
6. The in-situ characterization device according to claim 1, wherein: a silica gel pad is arranged below the reaction tank part for buffering; the in-situ characterization device further comprises an electrochemical workstation, wherein a conductive copper foil is arranged on the part, which is not covered by the reaction cell, of the upper surface of the detection window, so that the working electrode is conveniently connected with the electrochemical workstation, and forms a loop with a reference electrode arranged in the reaction cell for electrochemical analysis and detection.
7. An in-situ characterization method, characterized by: the method comprises the following steps: using the in-situ characterization device of claim 1, plating a conductive film and a solid-phase reactant film on the detection window respectively as working electrodes, and then connecting the working electrodes with an electrochemical workstation;
adding a reference electrode, electrolyte and reactants into the reaction tank according to the requirement;
turning on a light source and an infrared spectrum detector, wherein the light source emits incident light, and the incident light emitted by the light source is received by the infrared spectrum detector for infrared analysis after being reflected for multiple times by the upper surface and the lower surface of a detection window of a light path reflection part; and meanwhile, carrying out electrochemical reaction analysis on an electrochemical reaction signal in the reaction tank by utilizing an electrochemical workstation.
8. The in-situ characterization method according to claim 7, wherein: when a solid-phase reactant film is plated on the graphene conductive film, dispersing powder by using alcohol and dropwise adding the powder above the graphene conductive film, and completing the film plating of the solid-phase reactant film after the alcohol is volatilized; the working electrode is connected with the electrochemical workstation through a conductive copper foil; adjusting a pressure rod to make the reaction cell component and the light path reflection component tightly contact; the electrochemical workstation selects an open circuit potential-time detection method to carry out electrochemical analysis.
9. The in-situ characterization method according to claim 7, wherein: the reaction process to be detected needs to have infrared activity, and meanwhile, the target reaction needs to generate electron transfer or other changes so that the electrochemical signal is changed; according to the electrochemical and infrared spectrum signals obtained simultaneously, peak intensity, peak type and peak position information of the infrared spectrum are analyzed, and electrochemical signal changes synchronous with attribution are understood, so that the interface reaction behavior of the pollutants is described in multiple dimensions.
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