CN112229812A - In-situ electrochemical cell for synchrotron radiation infrared test and detection method - Google Patents
In-situ electrochemical cell for synchrotron radiation infrared test and detection method Download PDFInfo
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- 238000011065 in-situ storage Methods 0.000 title claims abstract description 45
- 230000005469 synchrotron radiation Effects 0.000 title claims abstract description 23
- 238000001514 detection method Methods 0.000 title claims abstract description 17
- 238000010998 test method Methods 0.000 title description 3
- 239000003792 electrolyte Substances 0.000 claims abstract description 45
- 238000012360 testing method Methods 0.000 claims abstract description 26
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- 210000004027 cell Anatomy 0.000 claims description 41
- 238000002329 infrared spectrum Methods 0.000 claims description 25
- 238000007789 sealing Methods 0.000 claims description 25
- 229910021397 glassy carbon Inorganic materials 0.000 claims description 16
- 238000005086 pumping Methods 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 15
- -1 polytetrafluoroethylene Polymers 0.000 claims description 12
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- 229920006395 saturated elastomer Polymers 0.000 claims description 8
- 239000007789 gas Substances 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 5
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 4
- 239000004020 conductor Substances 0.000 claims description 3
- PFNQVRZLDWYSCW-UHFFFAOYSA-N (fluoren-9-ylideneamino) n-naphthalen-1-ylcarbamate Chemical compound C12=CC=CC=C2C2=CC=CC=C2C1=NOC(=O)NC1=CC=CC2=CC=CC=C12 PFNQVRZLDWYSCW-UHFFFAOYSA-N 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 2
- OYLGJCQECKOTOL-UHFFFAOYSA-L barium fluoride Chemical compound [F-].[F-].[Ba+2] OYLGJCQECKOTOL-UHFFFAOYSA-L 0.000 claims description 2
- 229910001632 barium fluoride Inorganic materials 0.000 claims description 2
- 229940075397 calomel Drugs 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- GTKRFUAGOKINCA-UHFFFAOYSA-M chlorosilver;silver Chemical compound [Ag].[Ag]Cl GTKRFUAGOKINCA-UHFFFAOYSA-M 0.000 claims description 2
- 229910003460 diamond Inorganic materials 0.000 claims description 2
- 239000010432 diamond Substances 0.000 claims description 2
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical compound Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 229910052732 germanium Inorganic materials 0.000 claims description 2
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims description 2
- 239000011521 glass Substances 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 238000005259 measurement Methods 0.000 claims description 2
- 229910000371 mercury(I) sulfate Inorganic materials 0.000 claims description 2
- RPZHFKHTXCZXQV-UHFFFAOYSA-N mercury(i) oxide Chemical compound O1[Hg][Hg]1 RPZHFKHTXCZXQV-UHFFFAOYSA-N 0.000 claims description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 2
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 2
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- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- 238000000835 electrochemical detection Methods 0.000 abstract description 9
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- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 2
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- 239000000126 substance Substances 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910000861 Mg alloy Inorganic materials 0.000 description 1
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- 239000008151 electrolyte solution Substances 0.000 description 1
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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
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
- G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
- G01N21/35—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light
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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
- G01N27/30—Electrodes, e.g. test electrodes; Half-cells
- G01N27/308—Electrodes, e.g. test electrodes; Half-cells at least partially made of carbon
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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
- G01N27/416—Systems
- G01N27/48—Systems using polarography, i.e. measuring changes in current under a slowly-varying voltage
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Abstract
The invention relates to an in-situ electrochemical reaction tank for synchrotron radiation infrared test and a detection method, wherein the in-situ electrochemical reaction tank comprises a working electrode table, a base, a tank body, an infrared window and an upper cover; the working electrode platform penetrates through the base and the opening of the tank body, a sample to be detected is arranged above the working electrode platform, the feeding amount of the threaded base is controlled to be attached to the planar infrared window as much as possible, and the synchronous radiation infrared testing port is coupled with the inclined plane arranged on the periphery of the central opening of the upper cover to form an infrared detection channel. One side of the base is provided with a working electrode lead, the four sides of the cell body are provided with a reference electrode slot, a counter electrode slot, an electrolyte pump-in slot and an electrolyte pump-out slot which are respectively connected with an external electrochemical working platform and a circulating device, the center of the cell body is provided with a hole, the upper end of the hole wall is provided with insections which are communicated with a liquid storage groove at the periphery of the hole, and an electrochemical detection micro-area is formed. The invention fully utilizes the advantages of the synchrotron radiation infrared light source, simulates a real electrochemical detection environment, has good coupling, convenient assembly and disassembly, simple and easy detection method and real and reliable data.
Description
Technical Field
The invention relates to the technical field of spectroelectrochemistry, in particular to an in-situ electrochemical cell for synchrotron radiation infrared testing and a detection method.
Background
In-situ monitoring of dynamic processes of the surface interface of the energy conversion catalyst, such as generation and evolution of intermediate products of each reaction, is an effective means for fully understanding the process mechanism of energy conversion, and is of great importance for reasonably designing a novel energy conversion catalyst with high efficiency, low price and stability. The infrared spectrum technology can detect the inherent molecular vibration of the catalyst surface interface functional group, provides rich surface interface chemical information, has simple and quick test method, does not need marking or carrying out damaging pretreatment on a sample, and is widely applied to the in-situ characterization of the heterogeneous catalysis mechanism research. However, in the in-situ electrochemical-infrared spectrum detection process, the liquid-phase electrolyte seriously weakens the infrared signal intensity, and the adsorption and re-adsorption interference of gas/solid/liquid multiphase complex products exists under the working condition state, so that the detection sensitivity of the infrared spectrum is extremely high. The synchrotron radiation infrared spectrum technology has the molecular fingerprint effect of the conventional infrared spectrum, has a plurality of excellent characteristics of a synchrotron radiation light source, such as high brightness, good collimation, continuous frequency spectrum and the like, and can particularly provide higher spectral signal intensity and good spatial and temporal resolution for a micro-area sample. The synchronous radiation infrared spectrum is combined with the in-situ electrochemical detection, so that the sensitivity of the in-situ electrochemical detection can be greatly improved. However, the published national invention patents in this respect are still lacking.
The currently disclosed patents generally design various light-transmitting window sheets to realize the coupling of various spectrometers and in-situ electrochemical cells, such as a multifunctional spectrum in-situ interface research detection cell (CN103115869A) and an electrochemical-optical combined in-situ research spectrum cell (CN103033474A) proposed by the university of south and middle, and a sum frequency spectrum in-situ flow thin-layer spectrum electrochemical reaction cell (CN102539328A) proposed by the chemical research institute of the chinese academy of sciences, all of which adopt semi-cylindrical light-transmitting window sheets, which can allow incident light to be continuously adjustable from a small angle, simplify the light path, but cannot be well coupled to a planar synchrotron radiation infrared test port. In order to increase infrared signals, active substances are usually directly plated on the bottom plane of a light-transmitting window to avoid the absorption of a solution on a spectrum signal by using a surface-enhanced total reflection principle, although the designs can simulate real electrochemical reactions, the processing difficulty of an in-situ electrochemical cell is increased, the diversity of samples and electrolyte limits the application range, and the detection repeatability is required to be improved. In addition, the thin layer flow electrochemical cell design is also often used for reducing secondary adsorption interference and improving signal to noise ratio, such as a thin layer flow electrolytic cell (CN105403553A) suitable for electrochemical in-situ raman spectroscopy detection proposed by the university of science and technology in china, a simulated cell device (CN110320476A) for in-situ detecting the gas production of a liquid battery proposed by the physical research of the academy of science in china, and an electrochemical thin layer flow detection cell (CN103983720A) proposed by the university of shanghai science, in the structure designed in this way, a sample to be detected is directly exposed to an electrolyte, is easily affected by an edge effect, and cannot completely simulate a real electrochemical detection environment. Therefore, there is a need for a fully optimized design of in situ electrochemical cells for synchrotron radiation infrared test ports.
Disclosure of Invention
The in-situ electrochemical cell provided by the invention can fully utilize the advantages of a synchrotron radiation infrared light source, simulate a real electrochemical process, is convenient to assemble and disassemble, is simple and feasible in detection method, and has real and reliable data.
The invention provides an in-situ electrochemical cell for synchrotron radiation infrared testing, which comprises:
the working electrode table comprises a threaded base, a polytetrafluoroethylene outer sleeve and a glassy carbon electrode core, wherein the glassy carbon electrode core is arranged on the upper portion of the threaded base in a groove mode, and the polytetrafluoroethylene outer sleeve is arranged on the periphery of the glassy carbon electrode core;
preferably, the thread base material is an electric conductor;
preferably, the diameter of the glassy carbon electrode core is less than or equal to 5 mm.
The base, base central authorities trompil, downthehole wall processing screw thread, base one side sets up the working electrode lead wire, the base four corners sets up fastening bolt, the base material is the electric conductor.
The cell body is fixed on the base through fastening bolts, the cell body is square, a hole is formed in the center, insections are arranged at the upper end of the hole wall, an annular coaxial liquid storage groove is formed in the periphery of the hole wall, an annular shallow groove is formed in the periphery of the liquid storage groove, the thickness of the hole wall of the hole is about 2-5mm, the insections at the upper end of the hole wall are about 1-5mm deep and communicated with the liquid storage groove formed in the periphery of the hole wall, a sealing ring is arranged in the annular shallow groove, the diameter of the sealing ring is slightly smaller than the line diameter of the sealing ring, the depth of the sealing ring is slightly smaller than 1/2 of the line diameter of the sealing ring, reference electrode slots, counter electrode slots, electrolyte pumping slots and electrolyte pumping slots are formed;
preferably, the tank body is made of polytetrafluoroethylene, polyethylene terephthalate, polyvinyl chloride or organic glass;
preferably, the reference electrode is a calomel electrode, a silver-silver chloride electrode, a mercury-mercury oxide electrode, a mercury-mercurous sulfate electrode or a standard hydrogen electrode;
preferably, the counter electrode is a platinum wire or a carbon rod;
preferably, the reference electrode and the counter electrode are both provided with threaded sleeve heads, are respectively inserted into corresponding slots, and are fixedly sealed through threads and sealing rings;
preferably, the electrolyte pump-in guide pipe and the electrolyte pump-out guide pipe are respectively inserted into the corresponding slots and are connected with an external circulating device through a threaded sleeve head and a sealing ring on the guide pipe, and the external circulating device comprises a circulating pump, a gas flow control pump, a guide pipe and an electrolyte tank.
The beneficial effects of the liquid storage groove and the hole wall insection design are that the edge effect caused by the disturbance of the thin-layer flowing electrochemical micro-area is avoided, and the real electrochemical detection environment is simulated.
An infrared window is arranged above the tank body;
preferably, the window material is diamond, silicon, germanium, barium fluoride or zinc selenide;
preferably, the window is a planar disc having a diameter greater than the diameter of the shallow annular groove.
The working electrode platform penetrates through the base and the opening of the pool body, a sample to be detected is arranged above the working electrode platform, and the feeding amount of the working electrode platform is attached to an infrared window above the pool body as much as possible through the threaded base.
An upper cover is arranged above the infrared window, a hole is formed in the center of the upper cover, an annular coaxial inclined plane is arranged on the periphery of the hole and coupled with the synchrotron radiation infrared test port, and the upper cover and the tank body are fixed through fastening bolts;
preferably, the diameter of the central opening of the upper cover is slightly larger than that of the working electrode table;
preferably, the included angle between the inclined plane and the horizontal plane is smaller than 90 degrees, and the outer diameter of the inclined plane is larger than that of the synchronous radiation infrared test port.
The beneficial effects of the design of the plane infrared window and the inclined plane of the upper cover are that the in-situ electrochemical cell is well coupled with the synchronous radiation infrared test port, and meanwhile, the inclined plane is also favorable for the emergence of infrared signals, so that the detector can conveniently receive effective signals, and infrared spectroscopy signals with high signal-to-noise ratio can be obtained.
The detection method for performing the in-situ electrochemical-synchrotron radiation infrared test by using the in-situ electrochemical cell adopts a multi-step focusing measurement mode to realize the reality and reliability of data, and comprises the following steps:
(1) dropping a sample to be detected on a glassy carbon electrode core of a working electrode platform of the in-situ electrochemical cell for drying;
(2) installing a working electrode table, fixing the base and the cell body of the in-situ electrochemical cell by fastening bolts, focusing the synchronously radiated infrared light on the surface of a sample to be measured, and collecting the infrared spectrum;
(3) selecting a reference electrode and a counter electrode according to different electrochemical processes, and fixing the reference electrode and the counter electrode to the device in the step (2) through threads and a sealing ring;
(4) selecting electrolyte and saturated atmosphere according to different electrochemical processes, connecting an electrolyte pump-in guide pipe and a pump-out guide pipe with the device in the step (3) through threads and a sealing ring, starting a circulating pump of an external circulating device to pump the electrolyte saturated with gas into a liquid storage groove to form stable circulating electrolyte, refocusing synchronous radiation infrared light on the surface of the sample to be detected, and collecting infrared spectrum by taking the infrared spectrum collected in the step (2) as background;
(5) installing an infrared window, fixing an upper cover in the in-situ electrochemical cell to the device in the step (4) through a fastening bolt, adjusting the feeding amount of a threaded base of a working electrode table to control the thickness of an electrolyte film between the infrared window and a sample to be detected to be in a micron order, reducing the signal interference of the electrolyte, refocusing synchrotron radiation infrared light on the surface of the sample to be detected, and collecting infrared spectrum by taking the infrared spectrum collected in the step (4) as a background;
(6) respectively connecting the reference electrode, the counter electrode and the working electrode lead of the device in the step (5) with an external electrochemical working platform, electrifying the device, and controlling voltage, current and scanning time according to different samples to be detected to perform early-stage stable pretreatment;
(7) and (5) after the electrochemical signal on the surface of the sample to be detected is stable, controlling the voltage, the current and the scanning time, and collecting the infrared spectrums at different electrochemical stages by taking the infrared spectrums collected in the step (5) as a background.
Compared with the prior art, the invention has the advantages that:
(1) according to the invention, through the design of the plane infrared window and the inclined plane of the upper cover, good coupling with the synchronous radiation infrared test port is realized, the characteristics of high brightness, high flux and high collimation of a synchronous radiation infrared light source in a micro-area can be fully utilized, and simultaneously, the inclined plane is also beneficial to the emergence of infrared signals, so that a detector can receive effective signals conveniently, and infrared spectroscopy signals with high signal-to-noise ratio are obtained;
(2) the method can effectively avoid edge effect, simulate a real electrochemical detection environment, more intuitively identify the reaction intermediate in the energy conversion process, and can be used for in-situ research on the evolution of the reaction intermediate in the energy conversion process;
(3) the in-situ electrochemical cell has no specific window design, low processing cost and convenient assembly and disassembly;
(4) the detection method is simple and easy to implement, can gradually obtain reliable infrared signals of the sample to be detected, avoids the interference of false signals caused by the fact that a focus does not exist on the sample, and ensures the reality and reliability of the obtained data.
Drawings
FIG. 1 is a schematic diagram of an in situ electrochemical cell for synchrotron radiation infrared testing;
FIG. 2 is a schematic structural view of a working electrode stage of the present invention;
FIG. 3 is a schematic diagram of a tank body of the present invention in a top view;
FIG. 4 is a schematic view of the bottom structure of the tank body of the present invention;
FIG. 5 is a schematic view of the threaded nipples in the reference and counter electrodes of the embodiment;
FIG. 6 is a comparison of LSV curves for the in situ cell test of the conventional electrochemical cell of the example and the present invention;
fig. 7 is an infrared spectrum curve at different scan voltages for the example.
The device comprises a working electrode table 1, a base 2, a tank body 3, an infrared window 4, an upper cover 5, a working electrode lead 11, a fastening bolt 12, a sealing ring 13, a reference electrode slot 31, a counter electrode slot 32, an electrolyte pumping slot 33, an electrolyte pumping slot 34, an electrolyte pumping out slot 35, a liquid storage groove 35, an annular shallow groove 36, a threaded base 101, a polytetrafluoroethylene outer sleeve 102, a glassy carbon electrode core 103, a sample to be detected 104 and a threaded sleeve head 105.
Detailed Description
The invention is further described with reference to the following figures and specific embodiments.
As shown in figure 1, the invention provides an in-situ electrochemical cell for synchrotron radiation infrared test, which comprises a working electrode table 1, wherein the working electrode table shown in figure 2 comprises a threaded base 101, a polytetrafluoroethylene outer sleeve 102 and a glassy carbon electrode core 103, a glassy carbon electrode core is arranged in a groove above the threaded base, and polytetrafluoroethylene is arranged at the periphery of the glassy carbon electrode coreThe threaded base is made of metal copper, and the diameter of the glassy carbon electrode core is 5 mm; a sample 104 to be detected is arranged on the working electrode platform, and a powdery NiFe-MOF material is adopted in the embodiment; the device comprises a base 2, a hole is formed in the center of the base, threads are machined on the inner wall of the hole, a working electrode lead 11 is arranged on one side of the base, fastening bolts 12 are arranged at four corners of the base, and the base is made of aluminum magnesium alloy; a tank body 3 is arranged above the base, fig. 3 is a schematic view of a overlooking structure of the tank body, the length, width and height of the tank body are 6cm multiplied by 1.5cm, a hole is formed in the center, the diameter of the hole is 1.06cm, the inner wall of the hole is 2mm thick, insections with the depth of about 4mm are arranged at the upper end of the hole, a liquid storage groove 35 is arranged on the periphery of the hole wall, the outer diameter distance of the liquid storage groove is 1.63cm from the center, the depth of the liquid storage groove is 8mm, electrolyte is arranged2An electrolyte; an annular shallow groove 36 is formed in the periphery of the liquid storage groove, the diameter of the annular shallow groove is 3.7cm, the annular shallow groove is used for placing an O-shaped sealing ring 13, the linear diameter of the sealing ring is 1.8mm, the diameter of the annular shallow groove is 1.6mm, and the depth of the annular shallow groove is 0.8 mm; the cell body is made of polytetrafluoroethylene and can resist strong alkali, reference electrode slots 31, counter electrode slots 32, electrolyte pumping slots 33 and electrolyte pumping slots 34 are respectively arranged on four sides of the cell body, in the embodiment of the invention, Ag/AgCl reference electrodes and platinum wire counter electrodes with thread sleeve heads 105 added are adopted as shown in figure 5, the electrodes are respectively inserted into corresponding slots, sealing rings are sleeved and the thread sleeve heads are screwed, electrode leads are connected with an external electrochemical working platform, the electrolyte pumping guide pipe and the electrolyte pumping guide pipe of an external circulating device are sleeved with the sealing rings, the sealing rings are inserted into corresponding slots and the threads are screwed, and the electrolyte cell is pumped into saturated atmosphere through a gas flow control pump; as shown in fig. 4, a groove is formed in the lower surface of the tank body, the depth of the groove is 5mm, the groove is used for placing a base and a lead, and fastening bolt hole positions are arranged at four corners of the groove and correspond to fastening bolts of the base; a circular plane BaF is arranged above the pool body2An infrared window 4, the diameter of which is 3.8 cm; an upper cover 5 is arranged above the infrared window, a hole is formed in the center of the upper cover, the aperture is 1cm, an inclined plane is arranged on the periphery of the hole, the included angle between the inclined plane and the horizontal plane is 20 degrees, the outer diameter distance of the inclined plane is about 4cm, a synchrotron radiation infrared test port is directly contacted with the inclined plane, and fastening bolts are arranged at four corners of the upper cover; working electrode table upper sealing ringThe micro-electrolyte tank passes through the base and the opening of the tank body, the feeding amount of the threaded base of the working electrode table is adjusted to be attached to the infrared window as much as possible, a micro-scale electrolyte thin layer is formed between a sample to be detected and the infrared window, and the base and the tank body, and the tank body and the upper cover are fixed through fastening bolts respectively.
In the specific implementation process, a sample to be detected is firstly dripped on a glassy carbon electrode core of a working electrode table to be dried, the working electrode table is installed, a base and a cell body are fixed by fastening bolts, an Ag/AgCl reference electrode and a platinum wire counter electrode are installed, and an electrolyte pump is pumped into a guide pipe and is pumped out of the guide pipe. And focusing the synchrotron radiation infrared light on the surface of a sample to be detected, and collecting the infrared spectrum as a primary background spectrum. Starting a circulating pump in an external circulating device2And pumping saturated 1M KOH electrolyte into the liquid storage groove to form stable circulating electrolyte, refocusing the synchrotron radiation infrared light on the surface of the sample to be detected, and collecting infrared spectrum as a secondary background spectrum by taking the primary background spectrum as the background. Installing an infrared window, fixing the cell body and the upper cover through a fastening bolt, adjusting the feeding amount of a threaded base of the working electrode table to control the thickness of an electrolyte film between the infrared window and a sample to be detected to be in a micron order, refocusing synchrotron radiation infrared light on the surface of the sample to be detected, and collecting infrared spectrum as a tertiary background spectrum by taking a secondary background spectrum as a background. And respectively connecting the reference electrode, the counter electrode and the working electrode lead with an external electrochemical working platform, electrifying, setting the potential to be 1.5V, scanning for 20min, modifying electrochemical detection parameters after the electrochemical signal of the sample to be detected is stable, and collecting electrochemical data.
The polarization curve of the sample is tested by using the in-situ electrochemical cell provided by the invention, the test voltage range is 1.2-1.8V vs RHE, the sweep rate is 20mV/s, the polarization curve of the sample is scanned by using the conventional electrochemical cell under the same detection condition, as shown in figure 6, the polarization curve of the sample detected by using the in-situ electrochemical cell provided by the invention is better matched with the polarization curve of the sample detected by using the conventional electrochemical cell, and the in-situ electrochemical cell provided by the invention can simulate a real electrochemical detection environment. In order to detect the infrared spectrum signal under the electrochemical working condition, a constant potential method is adopted in this embodiment, and the voltages are respectively fixed as follows: 1.2V, 1.4V and 1.6V and held under applied voltage for 10min, with three background spectra as background for infrared spectral acquisition.
As shown in FIG. 7, a wave number of 1050cm to 1050cm has been observed at a voltage of 1.4V-1An infrared signal peak appears and may correspond to a reaction intermediate product-O-O-, and the infrared signal peak is increased in intensity at 1.6V, which indicates that the infrared signal peak corresponds to the reaction intermediate product of the sample to be detected in the electrochemical process. To verify the above conclusions, saturated atmosphere electrolyte solutions may also be isotopically substituted, such as by H2O18By replacement with H2O16Or O to be saturated18 2Atmosphere is changed to O16 2By performing the same operation as described above, the infrared signal peak of oxygen adsorption can be eliminated from the appearance position and displacement of the infrared signal peak of the isotope with the applied voltage, the structure of the reaction intermediate product can be further clarified, and the evolution of the reaction intermediate product can be estimated.
The above description is only a preferred embodiment of the present invention, and should not be construed as limiting the scope of the invention, i.e., the equivalent variations and modifications made in the patent scope and the specification of the present invention should be covered by the present invention.
Claims (8)
1. An in-situ electrochemical cell for synchrotron radiation infrared testing, comprising: comprises a working electrode table, a base, a tank body, an infrared window and an upper cover; the base and the tank body, and the tank body and the upper cover are respectively fixed through fastening bolts; the center of the base is provided with a hole, one side of the base is provided with a working electrode lead, and four corners of the base are provided with fastening bolts; the center of the tank body is provided with a hole, the upper end of the hole wall is provided with insections, the periphery of the hole wall is provided with an annular coaxial liquid storage groove, the periphery of the liquid storage groove is provided with an annular shallow groove, the four sides of the tank body are provided with reference electrode slots, counter electrode slots, electrolyte pumping slots and electrolyte pumping slots, the upper surface and the lower surface are respectively provided with fastening bolt hole sites corresponding to the fastening bolts of the upper cover and the base; the working electrode platform penetrates through the base and the opening of the tank body, a sample to be detected is arranged above the working electrode platform, and the working electrode platform is attached to an infrared window above the tank body as much as possible through the feeding amount of the threaded base; the center of the upper cover is provided with a hole, the periphery of the hole is provided with an annular coaxial inclined plane coupled with the synchrotron radiation infrared test port, and four corners of the upper cover are provided with fastening bolts.
2. The in situ electrochemical cell for synchrotron infrared testing of claim 1, wherein: the working electrode stage includes: the device comprises a threaded base, a polytetrafluoroethylene outer sleeve and a glassy carbon electrode core; a groove is formed above the threaded base and provided with a glassy carbon electrode core, and a polytetrafluoroethylene outer sleeve is arranged on the periphery of the glassy carbon electrode core; the threaded base is a conductor; the diameter of the glassy carbon electrode core is less than or equal to 5 mm.
3. The in situ electrochemical cell for synchrotron infrared testing of claim 1, wherein: the inner wall of the central hole of the base is provided with threads, and the base is made of a conductive body.
4. The in situ electrochemical cell for synchrotron infrared testing of claim 1, wherein: the cell body is a cube, threads are machined on the inner walls of the reference electrode slot, the counter electrode slot, the electrolyte pumping slot and the electrolyte pumping slot, the thickness of a hole wall of a central hole of the cell body is about 2-5mm, the depth of a tooth pattern on the upper end of the hole wall is about 1-5mm, the tooth pattern is communicated with a liquid storage groove arranged on the periphery of the hole wall, a sealing ring is arranged in the annular shallow groove, the diameter of the sealing ring is slightly smaller than the line diameter of the sealing ring, and the depth of the sealing ring is slightly.
The tank body is made of polytetrafluoroethylene, polyethylene terephthalate, polyvinyl chloride or organic glass;
the reference electrode is a calomel electrode, a silver-silver chloride electrode, a mercury-mercury oxide electrode, a mercury-mercurous sulfate electrode or a standard hydrogen electrode;
the counter electrode is a platinum wire or a carbon rod;
the reference electrode and the counter electrode are both provided with threaded sleeve heads, are respectively inserted into corresponding slots and are fixedly sealed through threads and sealing rings;
the electrolyte pump is gone into the pipe and is gone out the pipe and insert corresponding slot respectively, is connected with external circulation device through screw thread pullover and sealing washer on the pipe, external circulation device contains circulating pump, gas flow control pump, pipe and electrolyte pond.
5. The in situ electrochemical cell for synchrotron infrared testing of claim 1, wherein: the infrared window material is diamond, silicon, germanium, barium fluoride or zinc selenide; the infrared window is a plane wafer, and the diameter of the infrared window is larger than that of the annular shallow groove.
6. The in situ electrochemical cell for synchrotron infrared testing of claim 1, wherein: the diameter of the central opening of the upper cover is slightly larger than that of the working electrode table; the included angle between the inclined plane and the horizontal plane is smaller than 90 degrees, and the outer diameter of the inclined plane is larger than that of the synchronous radiation infrared test port.
7. The in situ electrochemical cell for synchrotron infrared testing of claim 1, wherein: and a sealing ring is arranged between the working electrode platform and the central hole of the pool body.
8. An in-situ electrochemical cell detection method for synchrotron radiation infrared testing according to any of claims 1 to 7, comprising: the method adopts a multi-step focusing measurement mode to realize the trueness and reliability of data, and comprises the following steps:
(1) dropping a sample to be detected on a glassy carbon electrode core of a working electrode platform of the in-situ electrochemical cell for drying;
(2) installing a working electrode table, fixing the base and the cell body of the in-situ electrochemical cell by fastening bolts, focusing the synchronously radiated infrared light on the surface of a sample to be measured, and collecting the infrared spectrum;
(3) selecting a reference electrode and a counter electrode according to different electrochemical processes, and fixing the reference electrode and the counter electrode to the device in the step (2) through threads and a sealing ring;
(4) selecting electrolyte and saturated atmosphere according to different electrochemical processes, connecting the electrolyte pumping guide pipe and the electrolyte pumping guide pipe with the device in the step (3) through threads and a sealing ring, starting a circulating pump of an external circulating device to pump the electrolyte with saturated atmosphere into a liquid storage groove to form stable circulating electrolyte, refocusing synchronous radiation infrared light on the surface of the sample to be detected, and collecting infrared spectrum by taking the infrared spectrum collected in the step (2) as background;
(5) installing an infrared window, fixing an upper cover in the in-situ electrochemical cell to the device in the step (4) through a fastening bolt, adjusting the feeding amount of a threaded base of a working electrode table to control the thickness of an electrolyte film between the infrared window and a sample to be detected to be in a micron order, reducing the signal interference of the electrolyte, refocusing synchrotron radiation infrared light on the surface of the sample to be detected, and collecting infrared spectrum by taking the infrared spectrum collected in the step (4) as a background;
(6) respectively connecting the reference electrode, the counter electrode and the working electric lead of the device in the step (5) with an external electrochemical working platform, electrifying the device, and controlling voltage, current and scanning time according to different samples to be detected to perform early-stage stable pretreatment;
(7) and (5) after the electrochemical signal on the surface of the sample to be detected is stable, controlling the voltage, the current and the scanning time, and collecting the infrared spectrums at different electrochemical stages by taking the infrared spectrums collected in the step (5) as a background.
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