CN113533403A - Flowing electrochemical testing device and method for simultaneous radiation XAS and mass spectrum - Google Patents
Flowing electrochemical testing device and method for simultaneous radiation XAS and mass spectrum Download PDFInfo
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- CN113533403A CN113533403A CN202110987640.6A CN202110987640A CN113533403A CN 113533403 A CN113533403 A CN 113533403A CN 202110987640 A CN202110987640 A CN 202110987640A CN 113533403 A CN113533403 A CN 113533403A
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N23/00—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00
- G01N23/22—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00 by measuring secondary emission from the material
- G01N23/223—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00 by measuring secondary emission from the material by irradiating the sample with X-rays or gamma-rays and by measuring X-ray fluorescence
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N23/00—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00
- G01N23/22—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00 by measuring secondary emission from the material
- G01N23/2206—Combination of two or more measurements, at least one measurement being that of secondary emission, e.g. combination of secondary electron [SE] measurement and back-scattered electron [BSE] measurement
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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
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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
- G01N27/62—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating the ionisation of gases, e.g. aerosols; by investigating electric discharges, e.g. emission of cathode
Abstract
The invention relates to the technical field of X-ray absorption spectrum characterization, and discloses a flowing electrochemical testing device for simultaneous radiation XAS and mass spectrum, which comprises a flange base body, a flange cover, a working electrode, an optical window and a gas-liquid separation assembly, wherein the flange base body is provided with a flange cover; the flange base member is opened there is the mass spectrum sampling channel that runs through along its axial, a side that the flange base member is close to the blind flange is opened there is the reaction chamber, the flange base member still opens reference electrode installation passageway, counter electrode installation passageway, inlet channel and the drain passage that have and communicate with the reaction chamber, the blind flange is opened and is had the light trap that runs through, the optics window covers in the light trap, working electrode is located between optics window and the reaction chamber. The invention also discloses a test method of the flowing electrochemical test device for the simultaneous radiation XAS and mass spectrometry. The beneficial effects are that: the electrochemical cell can realize the combination of X-ray spectrum and mass spectrum, and can capture X-ray fluorescence signals, mass spectrum signals and electrochemical signals simultaneously.
Description
Technical Field
The invention relates to the technical field of X-ray absorption spectrum characterization, in particular to a flowing electrochemical testing device and method for simultaneous radiation XAS and mass spectrum.
Background
With the continuous development of society, electrochemical reactions widely affect various industries such as batteries, digital products, automobiles and the like which are closely related to the life of people, so that electrochemical research attracts more attention. In order to understand the electrochemical reaction more deeply, the mechanism of the relevant reaction must be understood and known deeply, and the in situ characterization of the reaction by combining various on-line means can monitor the same reaction from multiple angles in real time, so as to help researchers understand the reaction process more comprehensively.
At present, relatively mature online characterization means are various, for example, electronic structure and atomic information of an electrode material can be accurately reflected by depending on an X-ray absorption spectrum of a synchrotron radiation light source, and the method has unique advantages in identifying the change of the electrode material in a micro-area; mass spectrometry techniques can capture the reactants, intermediates and end products of the reaction and monitor their quantities as a function of electrode potential and time. In order to carry out in-situ test on an electrochemical reaction system by combining the two measures and further deeply research an electrochemical reaction mechanism, a flow electrochemical test device combining synchrotron radiation XAS and mass spectrometry needs to be developed.
Disclosure of Invention
The invention aims to fill the blank in the field of characterization technology combination and provides a flowing electrochemical testing device for simultaneous radiation XAS and mass spectrometry. The method realizes the combined use of two characterization means of X-ray absorption spectrum and mass spectrometry, and can monitor the potential change, the structural change of electrode materials and the quantity change of various components related to the reaction near the electrode in real time in the process of the electrochemical reaction.
The invention also provides another test method of the flowing electrochemical testing device for the combination of the synchrotron radiation XAS and the mass spectrum.
The purpose of the invention is realized by the following technical scheme: a flow electrochemical testing device for simultaneous radiation XAS and mass spectrometry comprises a flange matrix, a flange cover, a working electrode, an optical window and a gas-liquid separation assembly; the flange base member sets up with the flange lid relatively, the flange base member is opened there is the mass spectrum incoming line that runs through along its axial, a side that the flange base member is close to the flange lid is opened there is the reaction chamber, it has the separating tank with mass spectrum incoming line intercommunication and with the axle center to open in the reaction chamber, gas-liquid separation unit mount is in separating the groove, the flange base member still opens reference electrode installation passageway, counter electrode installation passageway, inlet channel and liquid outlet channel with the reaction chamber intercommunication, the light trap that runs through is opened to the flange lid, optical window covers in the light trap, working electrode is located between optical window and the reaction chamber to a side that is close to the flange lid with the reaction chamber is sealed, working electrode's at least part and flange lid contact.
Further, the flange base body comprises a base and a boss in a circular truncated cone shape; protruding seat is connected with a side of base, protruding seat is opened there is the mass spectrum sampling channel who link up along its axial, reference electrode installation passageway, counter electrode installation passageway, inlet channel and liquid outlet channel all set up in the round platform inclined plane of protruding seat, and reference electrode installation passageway and counter electrode installation passageway symmetry set up, inlet channel and liquid outlet channel symmetry set up, the reaction chamber has been opened to the another side of base, reference electrode installation passageway, counter electrode installation passageway, inlet channel and liquid outlet channel all communicate with the reaction chamber.
Further, the flange base body comprises a base and a boss in a circular truncated cone shape; protruding seat is connected with a side of base, protruding seat is opened there is the mass spectrum sampling channel who link up along its axial, the round platform inclined plane of protruding seat is seted up to reference electrode installation passageway and counter electrode installation passageway symmetry, the base is seted up to inlet channel and outlet channel symmetry, the another side of base is opened there is the reaction chamber, reference electrode installation passageway, counter electrode installation passageway, inlet channel and outlet channel all communicate with the reaction chamber.
Further, the liquid inlet channel and the liquid outlet channel are both L-shaped.
Further, the gas-liquid separation assembly comprises a support cover, a gas-liquid separation membrane and a porous metal support sheet; the separation groove comprises a columnar groove and an annular groove which are communicated, the annular groove surrounds the outer side of the columnar groove, the porous metal support sheet is positioned in the columnar groove, threads are formed in the annular groove, the support cover threads are arranged in the annular groove and used for extruding and supporting the porous metal support sheet, and the gas-liquid separation membrane is positioned in an inner cavity of the support cover.
Further, the support cover comprises an outer peripheral wall and a bottom cover, a through hole is formed in the bottom cover, the outer peripheral wall is connected with one side face of the bottom cover, and threads are arranged on the inner side of the outer peripheral wall.
Furthermore, the working electrode is a metal sheet, two ends of the working electrode are connected with contact pins, and the flange cover is provided with limiting grooves corresponding to the contact pins so that at least part of the working electrode is in contact with the flange cover.
Further, the working electrode is a metal thin layer plated on the surface of the optical window, and the edge of the metal thin layer is in contact with the flange cover.
The gas-liquid separation membrane is made of a porous polytetrafluoroethylene film, and the aperture range of the gas-liquid separation membrane is 0.2-10 mu m.
Further, still include the sealing washer, the flange base member is close to one side of blind flange and opens the annular groove that has the same axle center with the reaction chamber, annular groove is located the outside of reaction chamber, in the sealing washer embedding annular groove to realize that mass spectrum sampling channel is in the vacuum state when connecting the mass spectrometer.
Further, an optical window mounting groove is formed in one side face, close to the flange base, of the flange cover so as to be embedded in and fix the optical window.
The light-transmitting window is in a round table shape, the large-diameter end of the light-transmitting window is far away from the flange base body, the small-diameter end of the light-transmitting window is close to the flange base body, an optical window mounting groove is formed in one side face, provided with the small-diameter end, of the flange cover and used for mounting and fixing the optical window, the working electrode is arranged above the optical window, and protrudes out of the surface of the flange cover.
The flange base body and the flange cover are both provided with corresponding bolt holes, and the flange base body and the flange cover are fixedly connected through bolts.
A test method based on the flowing electrochemical testing device for the simultaneous radiation XAS and mass spectrometry comprises the following steps:
the side surface of the flange base body, which is provided with the reaction cavity, faces upwards, a porous metal support sheet and a gas-liquid separation membrane are sequentially arranged in a columnar groove, a support cover is screwed in the annular groove and screwed, and a sealing ring is arranged in an annular groove;
placing the side surface of the flange cover provided with the optical window mounting groove upwards, and embedding the optical window into the optical window mounting groove;
depositing a catalytic material on the surface of the working electrode which is not in contact with the optical window, placing the working electrode on the optical window, and inserting a contact pin of the working electrode into a limiting groove of the flange cover or enabling the edge of the metal thin layer to be in contact with the flange cover;
fastening the flange base body and the flange cover by adopting bolts and nuts;
placing five internal screws and sealing gaskets into five channels on the upper surface and the inclined surface of the flange base body respectively, inserting a reference electrode, a counter electrode, a mass spectrum sampling pipe and a carrier liquid pipe into the corresponding channels, and screwing the internal screws;
clamping electrode clamps corresponding to the electrochemical workstation on the reference electrode and the counter electrode, and clamping the electrode clamps corresponding to the working electrode on the flange cover;
connecting the mass spectrum sampling pipe with a mass spectrum analyzer;
mounting the apparatus on a synchrotron radiation station with the flange cover at 45 ° to the incident X-rays;
the method comprises the steps of firstly testing a background signal by using a mass spectrometer and starting an instrument fluorescence mode of a synchronous radiation station, then starting an electrochemical workstation, and simultaneously obtaining a mass spectrum testing signal and an X-ray absorption spectrum heat exchange electrochemical reaction signal by adopting a working mode of a potentiodynamic potential, a constant potential or a constant current.
Compared with the prior art, the invention has the following advantages:
the electrochemical cell device can realize the combination of a synchrotron radiation station and a mass spectrometer, can simultaneously capture an X-ray fluorescence signal, a mass spectrum signal and an electrochemical signal under the electrochemical reaction condition, performs X-ray absorption spectrum analysis and mass spectrum analysis on the electrochemical reaction process, and keeps the stability of the electrolyte component in the electrochemical cell in the electrolyte flowing mode. Meanwhile, the electrochemical cell device disclosed by the invention is simple in structure, convenient to assemble, easy to obtain part materials, good in sealing property and significant for researching an electrochemical reaction mechanism.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this application, illustrate embodiments of the invention and, together with the description, serve to explain the invention and not to limit the invention. In the drawings:
fig. 1 shows an exploded view of a flow electrochemical test apparatus in which synchrotron radiation XAS is used in conjunction with mass spectrometry in example 1 according to the present invention;
fig. 2 shows a schematic configuration of a flow electrochemical test apparatus for simultaneous irradiation XAS with mass spectrometry according to example 1 of the present invention;
FIG. 3 shows a top view of FIG. 2;
FIG. 4 shows a cross-sectional view taken along line A-A of FIG. 3;
FIG. 5 is a schematic diagram showing the operation of a flow electrochemical test apparatus in which synchrotron radiation XAS is used in combination with mass spectrometry in example 1 according to the present invention;
fig. 6 is a schematic structural view showing a support cover in embodiment 1 according to the present invention;
fig. 7 shows an exploded view of a flow electrochemical test device in which synchrotron radiation XAS is used in conjunction with mass spectrometry in example 2 according to the present invention;
fig. 8 shows a schematic configuration of a flow electrochemical test apparatus for simultaneous irradiation XAS with mass spectrometry according to example 2 of the present invention;
FIG. 9 shows a top view of FIG. 8;
FIG. 10 shows a top view in the direction B-B of FIG. 9;
FIG. 11 shows a top view in the direction C-C of FIG. 9;
in the figure, 1, a flange base body; 2. a flange cover; 3. a working electrode; 4. an optical window; 5. a light transmissive window; 6. a base; 7. a boss base; 8. a support cover; 9. a gas-liquid separation membrane; 10. a porous metal support sheet; 11. an outer peripheral wall; 12. a bottom cover; 13. a contact pin; 14. a limiting groove; 15. a seal ring; 16. a bolt; 17. reference electrode internal screws; 18. a counter electrode internal screw; 19. a screw inside the liquid inlet; 20. a screw inside the liquid outlet; 21. a gasket; 22. a liquid inlet channel; 23. a liquid outlet channel; 24. an internal screw of the mass spectrum sample inlet; 25. a peristaltic pump; 26. a liquid storage tank; 27. a reaction chamber.
Detailed Description
The invention is further illustrated by the following figures and examples.
Example 1:
the flowing electrochemical testing device for the simultaneous radiation XAS and the mass spectrum, which is shown in the figures 1-4, comprises a flange base body 1, a flange cover 2, a working electrode 3, an optical window 4 and a gas-liquid separation component; flange base member 1 sets up with flange lid 2 relatively, flange base member 1 is opened there is the mass spectrum sampling channel who runs through along its axial, flange base member 1 is close to a side of flange lid 2 and is opened there is reaction chamber 27, it has the separating groove with mass spectrum sampling channel intercommunication to open in the reaction chamber 27, the gas-liquid is separated the unit mount and is in separating the groove, flange base member 1 still opens reference electrode installation passageway, counter electrode installation passageway, inlet channel 22 and outlet channel 23 with the reaction chamber intercommunication, flange lid 2 is opened has light trap 5 that runs through, optical window 4 covers in light trap 5, working electrode 3 is located between optical window 4 and the reaction chamber 27 to it seals a side that is close to flange lid 2 with reaction chamber 27, working electrode 3's contact foot 13 inserts flange lid 2's spacing groove 14.
The mass spectrum sampling tube is installed in a mass spectrum sample introduction channel through an internal screw 24 of a mass spectrum sample introduction port, the reference electrode is installed in the reference electrode installation channel through an internal screw 17 of the reference electrode, the counter electrode is installed in the counter electrode installation channel through an internal screw 18 of the counter electrode, the two liquid carrying tubes are correspondingly installed in a liquid inlet channel 22 and a liquid outlet channel 23 through an internal screw 19 of a liquid inlet and an internal screw 20 of a liquid outlet respectively, and a sealing gasket 21 for preventing liquid leakage is further arranged between the channels. The optical window 4 is made of materials with low X-ray absorption rate, such as sapphire, silicon nitride glass, Kapton film, Mylar polyester film, PET film and the like. The gas-liquid separation membrane 9 is made of a porous polytetrafluoroethylene film, the aperture range of the gas-liquid separation membrane 9 is 0.2-10 mu m, and the gas-liquid separation membrane 9 can penetrate gaseous or volatile reactants, products and intermediate products generated by electrochemical reaction of electrolyte in the flange matrix 1. The working electrode 3 is a metal sheet, two ends of the working electrode are connected with contact pins, and the flange cover 2 is provided with a limiting groove 14 corresponding to the contact pins so that at least part of the working electrode 3 is in contact with the flange cover 2. The contact pins 13 at both ends of the working electrode 3 are inserted into the metal flange cover 2, thereby realizing the communication between the working electrode 3 and the potential monitoring circuit. The flange cover 2 is provided with a light transmission window 5 which penetrates through the flange cover 2 and the optical window 4, so that X-rays can penetrate through the flange cover 2 and the optical window 4 at a specific angle to irradiate the surface of the working electrode 3. The flange base 1 and the supporting cover 8 are made of PEEK plastic or other hard, common, corrosion-resistant and easily-processed insulating materials. The porous metal support sheet 10 is made of porous metal material such as nickel foam. The flange cover 2 is made of 304 stainless steel, 316 stainless steel or other hard, common, corrosion-resistant and easily-machined metal materials. The sealing ring is a perfluoro-ether rubber sealing ring or a silica gel sealing ring.
The flange base body 1 comprises a base 6 and a boss 7 in a circular truncated cone shape; protruding seat 7 is connected with a side of base 6, protruding seat 7 is opened there is the mass spectrum sampling channel who link up along its axial, reference electrode installation passageway, counter electrode installation passageway, inlet channel 22 and outlet channel 23 all set up in the round platform inclined plane of protruding seat 7, and reference electrode installation passageway sets up with counter electrode installation passageway symmetry, and inlet channel sets up with the outlet channel symmetry, and four passageways all are perpendicular with the round platform inclined plane to guarantee four passageways and the equal directional working electrode of mass spectrum sampling channel, the open end of four passageways all is provided with the screw and is used for installing corresponding inside screw, open the another side of base 6 has reaction chamber 27, reference electrode installation passageway, counter electrode installation passageway, inlet channel and outlet channel all communicate with reaction chamber.
The gas-liquid separation assembly comprises a support cover 8, a gas-liquid separation membrane 9 and a porous metal support sheet 10; the separation groove comprises a columnar groove and an annular groove which are communicated, the annular groove surrounds the outer side of the columnar groove, the porous metal support sheet 10 is located in the columnar groove, threads are formed in the annular groove, the support cover 8 is installed in the annular groove in a threaded mode and used for extruding and supporting the porous metal support sheet 10, and the gas-liquid separation membrane 9 is located in an inner cavity of the support cover 8. The supporting cover 8 is in threaded connection with the annular groove, the porous metal supporting sheet 10 and the gas-liquid separation membrane 9 can be fixed below the mass spectrum sample feeding channel, and the columnar groove is communicated with the mass spectrum sample feeding channel. The porous metal support sheet 10 is disposed above the gas-liquid separation membrane 9 to ensure that the gas-liquid separation membrane 9 does not deform or rupture under the working conditions of different pressures at both sides. The center of the support cover 8 is provided with a through hole to provide a channel for liquid circulation, and sealing is realized by extruding a gas-liquid separation membrane. The porous metal support sheet 10 can be made of porous metal materials such as nickel foam and the like to support the gas-liquid separation membrane 9 with a soft surface, and both the gas-liquid separation membrane 9 and the porous metal support sheet 10 are of porous structures and can penetrate gas while blocking liquid.
The support cover 8 comprises an outer peripheral wall 11 and a bottom cover 12, the bottom cover 12 is provided with a through hole, the outer peripheral wall 11 is connected with one side face of the bottom cover 12, and the inner side of the outer peripheral wall 11 is provided with threads. The through hole of the supporting cover 8 can communicate the mass spectrum sample feeding channel with the reaction cavity, so that liquid flow is realized, the supporting cover 8 is convenient to screw during installation, and the shape of the through hole can be hexagonal, linear or cross or other shapes convenient to operate.
The flange base body 1 and the flange cover 2 are both provided with corresponding bolt holes, and the flange base body 1 and the flange cover 2 are connected through bolts to form a flange structure. A sealing ring 15 is further arranged between the flange base body 1 and the flange cover 2, one side, close to the flange cover 2, of the flange base body 1 is provided with an annular groove which is coaxial with the reaction cavity, the annular groove is located on the outer side of the reaction cavity 27, and the sealing ring 15 is embedded into the annular groove. When the flange base 1 and the flange cover 2 are tightly connected, the working electrode 3 is pressed against the sealing ring 15, thereby closing the reaction chamber 27 to contain the electrolyte. In addition, by arranging the sealing ring, the mass spectrum sample inlet channel is in a vacuum state when the mass spectrum sample inlet pipe is connected with the mass spectrum sample inlet channel,
an optical window mounting groove is formed in one side surface, close to the flange base body 1, of the flange cover 2 so as to be embedded in and fix the optical window 4.
The light-transmitting window 5 is in a round table shape, the flange base body 1 is far away from the large-diameter end of the light-transmitting window, the small-diameter end of the light-transmitting window is close to the flange base body 1, an optical window mounting groove is formed in one side face, provided with the small-diameter end, of the flange cover 2 and used for mounting and fixing the optical window 4, the working electrode 3 is arranged above the optical window 4, and the working electrode 3 protrudes out of the surface of the flange cover 2, so that the working electrode 3 can extrude the sealing ring 15, and the sealing of the reaction cavity 27 is realized.
A test method based on the flowing electrochemical testing device for the simultaneous radiation XAS and mass spectrometry comprises the following steps:
(1) assembling the flow electrochemical cell: the side surface of the flange base body, which is provided with the reaction cavity, faces upwards, a porous metal support sheet and a gas-liquid separation membrane are sequentially arranged in a columnar groove, a support cover is screwed in the annular groove and screwed, and a sealing ring is arranged in an annular groove;
placing the side surface of the flange cover provided with the optical window mounting groove upwards, and embedding the optical window into the optical window mounting groove;
depositing a catalytic material on the surface of the working electrode which is not in contact with the optical window, and placing the working electrode on the optical window to enable the contact pin of the working electrode to be inserted into the limit groove of the flange cover;
fastening the flange base body and the flange cover by adopting bolts and nuts;
placing five internal screws and sealing gaskets into five channels on the upper surface and the inclined surface of the flange base body respectively, inserting a reference electrode, a counter electrode, a mass spectrum sampling pipe and a carrier liquid pipe into the corresponding channels, and fixing the internal screws;
(2) assembling a three-electrode system: clamping electrode clamps corresponding to the electrochemical workstation on the reference electrode and the counter electrode, and clamping the electrode clamps corresponding to the working electrode on the flange cover;
(3) connecting a mass spectrum analyzer: connecting the mass spectrum sampling pipe with a mass spectrum analyzer;
(4) connecting a liquid supplementing system: one end of each liquid carrying pipe is connected into two opposite pore channels on the inclined plane of the flange base body, the other end of each liquid carrying pipe is placed into an empty liquid storage pool, electrolyte (which can be acid solution, alkali solution or organic solution) is injected into the liquid storage pools, and peristaltic pumps are respectively arranged on the two liquid carrying pipes.
(5) Placing a device: mounting the apparatus on a synchrotron radiation station with the flange cover at 45 ° to the incident X-rays;
(6) and (3) system testing: the peristaltic pumps 25 are activated and allowed to co-current with the electrolyte. When the two liquid carrying pipes are filled with electrolyte, a mass spectrum analyzer is used for testing a background signal and starting a fluorescence mode of the synchronous radiation station, then an electrochemical workstation is started, and a working mode of potentiodynamic potential, constant potential or constant current is adopted to obtain a mass spectrum testing signal, an X-ray absorption spectrum and an electrochemical reaction signal at the same time.
(7) And after the test is finished, the instrument is closed, the power supply is turned off, and the experiment is finished. And pouring the residual electrolyte into a waste liquid barrel, and cleaning the liquid storage tank, the liquid carrying pipe and the flowing electrochemical cell so as to be reused.
As the reference electrode, various commercially available reference electrodes such as a silver chloride electrode (Ag/AgCl), a mercury oxide electrode (Hg/HgO) and a reversible hydrogen electrode can be used. The counter electrode can be an acid solution, an alkali solution or an organic solution by using an electrolyte such as a platinum wire electrode, a graphite rod electrode and the like.
The flange base body 1 in the embodiment is provided with a plurality of channels, so that a reference electrode, a counter electrode, a mass spectrum sampling pipe and a carrier liquid pipe can be inserted into the reaction cavity 27 from a plurality of directions and focused on the center of the working electrode 3; the porous metal support sheet 10 and the gas-liquid separation membrane 9 are fixed between the reaction cavity 27 and the mass spectrum sampling tube by the support cover 8, so that a mass spectrometer can capture reactants, products and intermediate products related to the reaction in time; the working electrode 3 is arranged on the optical window 4, and incident X rays can be absorbed by the catalyst on the working electrode 3 and excite fluorescence, so that the bulk phase change of the catalyst in the electrochemical reaction can be monitored; the liquid carrying pipe is connected with the liquid supplementing system, and the relative stability of the components of the electrolyte in the reaction cavity is kept through the circulation of the electrolyte.
Example 2:
the present example is the same as example 1 except for the following technical features:
the flange base body 1 comprises a base 6 and a boss 7 in a circular truncated cone shape; protruding seat 7 is connected with a side of base 6, protruding seat 7 is opened there is the mass spectrum sampling channel who link up along its axial, the round platform inclined plane of protruding seat 7 is seted up with counter electrode installation passageway symmetry to reference electrode installation passageway, inlet channel 22 and outlet channel 23 symmetry are seted up in base 6, open the another side of base 6 has reaction chamber 27, reference electrode installation passageway, counter electrode installation passageway, inlet channel and outlet channel all communicate with reaction chamber 27. The liquid inlet channel 22 and the liquid outlet channel 23 are both L-shaped. In addition, the structure of the flange base body can also have other forms.
The working electrode 3 may also be a thin metal layer plated on the surface of the optical window 4 in this embodiment, and the edge of the thin metal layer is in contact with the flange cover 2.
The above-mentioned embodiments are preferred embodiments of the present invention, and the present invention is not limited thereto, and any other modifications or equivalent substitutions that do not depart from the technical spirit of the present invention are included in the scope of the present invention.
Claims (10)
1. A flow electrochemical testing device for simultaneous radiation XAS and mass spectrum is characterized in that: the device comprises a flange base body, a flange cover, a working electrode, an optical window and a gas-liquid separation assembly; the flange base member sets up with the flange lid relatively, the flange base member is opened there is the mass spectrum incoming line that runs through along its axial, a side that the flange base member is close to the flange lid is opened there is the reaction chamber, open the separating tank that has with mass spectrum incoming line intercommunication in the reaction chamber, the gas-liquid is separated the unit mount and is in separating the groove, the flange base member still opens reference electrode installation passageway, counter electrode installation passageway, inlet channel and the drain passage with the reaction chamber intercommunication, the flange lid is opened there is the light trap that runs through, optical window covers in the light trap, working electrode is located between optical window and the reaction chamber to a side that is close to the flange lid with the reaction chamber is sealed, working electrode's at least part and flange lid contact.
2. A flow electrochemical test apparatus for simultaneous radiation XAS and mass spectrometry according to claim 1, wherein: the flange base body comprises a base and a boss seat in a circular truncated cone shape; protruding seat is connected with a side of base, protruding seat is opened there is the mass spectrum sampling channel who link up along its axial, reference electrode installation passageway, counter electrode installation passageway, inlet channel and liquid outlet channel all set up in the round platform inclined plane of protruding seat, and reference electrode installation passageway and counter electrode installation passageway symmetry set up, inlet channel and liquid outlet channel symmetry set up, the reaction chamber has been opened to the another side of base, reference electrode installation passageway, counter electrode installation passageway, inlet channel and liquid outlet channel all communicate with the reaction chamber.
3. A flow electrochemical test apparatus for simultaneous radiation XAS and mass spectrometry according to claim 1, wherein: the flange base body comprises a base and a boss seat in a circular truncated cone shape; protruding seat is connected with a side of base, protruding seat is opened there is the mass spectrum sampling channel who link up along its axial, the round platform inclined plane of protruding seat is seted up to reference electrode installation passageway and counter electrode installation passageway symmetry, the base is seted up to inlet channel and outlet channel symmetry, the another side of base is opened there is the reaction chamber, reference electrode installation passageway, counter electrode installation passageway, inlet channel and outlet channel all communicate with the reaction chamber.
4. A flow electrochemical test apparatus for simultaneous radiation XAS and mass spectrometry according to claim 1, wherein: the gas-liquid separation assembly comprises a support cover, a gas-liquid separation membrane and a porous metal support sheet; the separation groove comprises a columnar groove and an annular groove which are communicated, the annular groove surrounds the outer side of the columnar groove, the porous metal support sheet is positioned in the columnar groove, threads are formed in the annular groove, the support cover threads are arranged in the annular groove and used for extruding and supporting the porous metal support sheet, and the gas-liquid separation membrane is positioned in an inner cavity of the support cover.
5. A flow electrochemical test apparatus for simultaneous radiation XAS and mass spectrometry according to claim 1, wherein: the support cover comprises an outer peripheral wall and a bottom cover, a through hole is formed in the bottom cover, the outer peripheral wall is connected with one side face of the bottom cover, and threads are arranged on the inner side of the outer peripheral wall.
6. A flow electrochemical test apparatus for simultaneous radiation XAS and mass spectrometry according to claim 1, wherein: the working electrode is a metal sheet, contact pins are connected to two ends of the working electrode, and limiting grooves corresponding to the contact pins are formed in the flange cover so that at least part of the working electrode is in contact with the flange cover.
7. A flow electrochemical test apparatus for simultaneous radiation XAS and mass spectrometry according to claim 1, wherein: the working electrode is a metal thin layer plated on the surface of the optical window, and the edge of the metal thin layer is in contact with the flange cover.
8. A flow electrochemical test apparatus for simultaneous radiation XAS and mass spectrometry according to claim 1, wherein: still include the sealing washer, the flange base member is close to one side of blind flange and opens the annular groove that has the same axle center with the reaction chamber, the annular groove is located the outside of reaction chamber, in the sealing washer embedding annular groove to realize that mass spectrum sampling channel is in the vacuum state when connecting the mass spectrometer.
9. A flow electrochemical test apparatus for simultaneous radiation XAS and mass spectrometry according to claim 1, wherein: and one side surface of the flange cover, which is close to the flange base body, is provided with an optical window mounting groove so as to be embedded and fixed with an optical window.
10. An assay method based on a flow electrochemical test apparatus for simultaneous irradiation XAS and mass spectrometry according to any of claims 1 to 9, comprising the steps of:
the side surface of the flange base body, which is provided with the reaction cavity, faces upwards, a porous metal support sheet and a gas-liquid separation membrane are sequentially arranged in a columnar groove, a support cover is screwed in the annular groove and screwed, and a sealing ring is arranged in an annular groove;
placing the side surface of the flange cover provided with the optical window mounting groove upwards, and embedding the optical window into the optical window mounting groove;
depositing a catalytic material on a surface of the working electrode not in contact with the optical window and placing the working electrode over the optical window with at least a portion of the working electrode in contact with the flange cover;
fastening the flange base body and the flange cover by adopting bolts and nuts;
placing five internal screws and sealing gaskets into five channels on the upper surface and the inclined surface of the flange base body respectively, inserting a reference electrode, a counter electrode, a mass spectrum sampling pipe and a carrier liquid pipe into the corresponding channels, and screwing the internal screws;
clamping electrode clamps corresponding to the electrochemical workstation on the reference electrode and the counter electrode, and clamping the electrode clamps corresponding to the working electrode on the flange cover;
connecting the mass spectrum sampling pipe with a mass spectrum analyzer;
mounting the apparatus on a synchrotron radiation station with the flange cover at 45 ° to the incident X-rays;
the method comprises the steps of firstly testing a background signal by using a mass spectrometer and starting a fluorescence mode of a synchronous radiation station, then starting an electrochemical workstation, and simultaneously obtaining a mass spectrum test signal, an X-ray absorption spectrum and an electrochemical reaction signal by adopting a working mode of a potentiodynamic potential, a constant potential or a constant current.
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| CN114486736A (en) * | 2022-01-10 | 2022-05-13 | 山东大学 | Multifunctional spectrum and X-ray diffraction in-situ reaction chamber and application |
| CN114486736B (en) * | 2022-01-10 | 2023-10-10 | 山东大学 | Multifunctional spectrum and X-ray diffraction in-situ reaction chamber and application |
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