Electrochemical liquid phase product in-situ detection device

Abstract

The invention relates to the field of electrochemical in-situ characterization, in particular to an electrochemical liquid-phase product in-situ detection device. Comprising a pressure-adjustable gas source, a gas source connecting pipeline, a fine-aperture tee joint, a spray pipeline, a radio frequency electrode, an electrochemical cell, an electrochemical reaction electrode, a liquid-phase product introduction pipeline and a mass spectrometer, wherein the pressure-adjustable gas source is connected through the gas source connecting pipeline and a port of the fine-aperture tee joint; a left port of the fine-aperture tee joint is connected with the electrochemical cell through the liquid phase product introduction pipeline, a lower port of the fine-aperture tee joint is connected with the upper end of the spraying pipeline, the radio frequency electrode is arranged at the lower end of the spraying pipeline, and the spraying pipeline and a sampling port of the mass spectrometer are arranged in a spaced mode and directly face each other. Ions generated by the spraying pipeline enter a mass spectrometer for analysis under the action of voltage and airflow. Effective carrying of a liquid-phase product in the electrochemical reaction tank is realized through high-speed airflow generated by the pressure-adjustable gas source by utilizing the Venturi effect, and ionization of the product is realized by combining the induction electrode under radio frequency voltage.

Description

Technical Field

[0001] The present invention relates to the field of in-situ electrochemical characterization, and particularly to an in-situ detection device for electrochemical liquid-phase products. Background Art

[0002] Electrochemical research is of great significance for promoting the development and innovation in multiple fields such as clean energy, green chemistry, environmental protection, medicine, and materials science. The in-situ electrochemical mass spectrometry method combines electrochemistry and mass spectrometry, enabling real-time monitoring of the products in electrochemical reactions, and providing a powerful tool for in-depth understanding of reaction mechanisms and optimizing reaction conditions. This method can track the mass spectrometry information of products, reveal the reaction kinetics process, and has an important impact on fields such as battery technology, electrocatalytic material design, and drug research and development. By analyzing the concentration information of products and intermediates in real-time during the reaction process, researchers can more comprehensively and accurately grasp the real-time dynamic changes of the reaction, providing unprecedented insights for promoting scientific research and applied technologies. Currently, the detection methods for gas-phase products in electrochemical processes are relatively mature, while the in-situ detection of liquid-phase products has always been a difficult problem.

[0003] Currently, the existing in-situ monitoring devices for electrochemical reactions use an externally applied electrostatic field that does not directly contact the solution in the reactor of the electrochemical reaction, thereby achieving ionization of the solution at the tip of the reactor, thus avoiding the problem of a large difference from the ordinary electrochemical reaction environment in the laboratory caused by applying a high voltage in the reactor. However, this device does not have a clear method for introducing liquid-phase products. In addition, the existing publicly disclosed electrochemical electrospray ionization source includes an outer electrode and an inner electrode. The inner and outer electrodes can be arranged in parallel and coaxially to increase the electrode overlap area and reduce the electrode spacing. One of the electrodes applies an electrospray ionization working voltage, and the other electrode applies an electrochemical voltage relative to this electrode. When the solution sample flows into the ionization source, an electrochemical reaction occurs due to the voltage applied between the two electrodes, and the products of the electrochemical reaction then form gas-phase ions under the action of the electrospray ionization working voltage and can be analyzed by a subsequent mass spectrometer. However, this ionization source uses a spiral structure and has insufficient electrolytic cell versatility. Summary of the Invention

[0004] Aiming at the above problems, the purpose of the present invention is to provide an in-situ detection device for electrochemical liquid-phase products.

[0005] To achieve the above purpose, the present invention adopts the following technical solutions:

[0006] The present invention provides an in-situ detection device for electrochemical liquid-phase products, which includes an adjustable pressure gas source, a gas source connection pipeline, a fine-aperture three-way joint, a spray pipeline, a radio frequency electrode, an electrochemical cell, an electrochemical reaction electrode, a liquid-phase product introduction pipeline, and a mass spectrometer. The adjustable pressure gas source is connected through the gas source connection pipeline and the port of the fine-aperture three-way joint. The left port of the fine-aperture three-way joint is connected to the electrochemical cell through the liquid-phase product introduction pipeline. The lower port of the fine-aperture three-way joint is connected to the upper end of the spray pipeline. The radio frequency electrode is placed at the lower end of the spray pipeline. The spray pipeline is directly opposite and spaced from the sampling port of the mass spectrometer. The ions generated by the spray pipeline enter the mass spectrometer for analysis under the action of voltage and gas flow.

[0007] The radio frequency electrode is in the shape of a rectangular flat plate. The radio frequency electrode is connected to a power amplifier through a wire, and the power amplifier is connected to an arbitrary waveform generator through a wire. During operation, a waveform is set on the arbitrary waveform generator and amplified and applied to the radio frequency electrode through the power amplifier, so that the gas and sample in the spray pipeline are ionized under the action of the radio frequency electric field of the radio frequency electrode.

[0008] The inner diameter of the fine-aperture three-way joint is smaller than the inner diameters of the gas source connection pipeline, the liquid-phase product introduction pipeline, and the spray pipeline.

[0009] The adjustable pressure gas source can be a compressed gas cylinder or a gas generator; the gas is an inert gas.

[0010] The materials of the gas source connection pipeline, the fine-aperture three-way joint, and the liquid-phase product introduction pipeline are metal or non-metal materials; the material of the spray pipeline is a non-metal material.

[0011] The mass spectrometer is a quadrupole mass spectrometer, a time-of-flight mass spectrometer, a magnetic mass spectrometer, an ion trap mass spectrometer, an orbitrap mass spectrometer, or a tandem mass spectrometer.

[0012] The advantages and beneficial effects of the present invention are as follows: The in-situ detection device for electrochemical liquid-phase products provided by the present invention, through reasonable design, utilizes the high-speed gas flow generated by the adjustable pressure gas source by the Venturi effect to effectively carry the liquid-phase products in the electrochemical reaction cell, and combines the induction electrode under the radio frequency voltage to realize the ionization of the products. This design structure can realize the in-situ detection of electrochemical reactions without affecting the environment in the reaction cell, and has good application prospects in the in-situ characterization of electrochemical liquid phases. Description of the Drawings

[0013] The drawings further illustrate the present invention, but the content in the drawings does not constitute any limitation to the present invention.

[0014] Figure 1 It is a schematic structural diagram of an in-situ detection device for electrochemical liquid-phase products of the present invention.

[0015] In the figure: 1 - gas source connection pipeline, 2 - adjustable pressure gas source, 3 - power amplifier, 4 - arbitrary waveform generator, 5 - ion, 6 - mass spectrometer, 7 - radio frequency electrode, 8 - spray pipeline, 9 - fine aperture three, 10 - electrochemical cell, 11 - electrochemistry reaction electrode, 12 - liquid phase product introduction pipeline. Specific implementation manner

[0016] It should be noted that, without conflict, the embodiments in the present invention and the features in the embodiments can be combined with each other. The present invention will be described in detail below with reference to the drawings and in combination with the embodiments.

[0017] To make the objectives, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all of the embodiments. The description of at least one exemplary embodiment below is actually only illustrative and in no way restricts the present invention and its application or use. Based on the embodiments in the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts shall fall within the protection scope of the present invention.

[0018] It should be noted that the terms used here are only for describing specific implementation manners and are not intended to limit the exemplary embodiments of the present invention. As used here, unless the context clearly indicates otherwise, the singular form is also intended to include the plural form. In addition, it should be understood that when the terms "comprise" and / or "include" are used in this specification, they indicate the presence of features, steps, operations, devices, components and / or their combinations.

[0019] Unless otherwise specifically stated, the relative arrangements of components and steps, numerical expressions and values set forth in these embodiments do not limit the scope of the present invention. At the same time, it should be clear that, for the sake of description, the sizes of the various parts shown in the drawings are not drawn according to the actual proportional relationship. Technologies, methods and devices known to those of ordinary skill in the relevant art may not be discussed in detail, but where appropriate, the technologies, methods and devices should be regarded as part of the authorized specification. In all the examples shown and discussed here, any specific value should be construed as merely exemplary and not as a limitation. Therefore, other examples of the exemplary embodiments may have different values. It should be noted that: like reference numerals and letters denote like items in the following drawings, and therefore, once an item is defined in one drawing, it does not need to be further discussed in subsequent drawings.

[0020] In the description of the present invention, it should be understood that the orientation or positional relationship indicated by orientation words such as "front, rear, upper, lower, left, right", "lateral, vertical, perpendicular, horizontal" and "top, bottom", etc. is usually based on the orientation or positional relationship shown in the drawings. It is only for the convenience of describing the present invention and simplifying the description. Without contrary explanation, these orientation words do not indicate and imply that the device or element referred to must have a specific orientation or be constructed and operated in a specific orientation. Therefore, it should not be construed as a limitation on the protection scope of the present invention: the orientation words "inside, outside" refer to the inside and outside relative to the contour of each component itself.

[0021] As Figure 1 shown, an embodiment of the present invention provides an in-situ detection device for electrochemical liquid-phase products, including an adjustable pressure gas source 2, a gas source connection pipeline 1, a fine-aperture three-way joint 9, a spray pipeline 8, a radio frequency electrode 7, an electrochemical cell 10, an electrochemical reaction electrode 11, a liquid-phase product introduction pipeline 12 and a mass spectrometer 6. Among them, the adjustable pressure gas source 2 is connected through the gas source connection pipeline 1 and the port of the fine-aperture three-way joint 9. The left port of the fine-aperture three-way joint 9 is connected to the electrochemical cell 10 through the liquid-phase product introduction pipeline 12. The lower port of the fine-aperture three-way joint 9 is connected to the upper end of the spray pipeline 8. The lower end of the spray pipeline 8 is provided with the radio frequency electrode 7. The spray pipeline 8 is placed opposite to and at a certain interval from the sampling port of the mass spectrometer 6. The ions 5 generated by the spray pipeline 8 enter the mass spectrometer 6 for analysis under the action of voltage and gas flow.

[0022] In the embodiment of the present invention, the radio frequency electrode 7 is in the shape of a rectangular flat plate. The radio frequency electrode 7 is connected to a power amplifier 3 through a wire, and the power amplifier 3 is connected to an arbitrary waveform generator 4 through a wire. During operation, a waveform is set on the arbitrary waveform generator 4 and amplified and applied to the radio frequency electrode 7 through the power amplifier 3, so that the gas and sample in the spray pipeline 8 are ionized under the action of the radio frequency electric field of the radio frequency electrode 7.

[0023] Furthermore, the inner diameter of the fine-aperture three-way joint 9 is smaller than the inner diameters of the gas source connection pipeline 1, the liquid-phase product introduction pipeline 12 and the spray pipeline 8.

[0024] In this embodiment, the adjustable pressure gas source 2 can be a compressed steel cylinder or a gas generator; the gas is an inert gas such as nitrogen, helium, argon, etc. Preferably, the gas is high-purity helium. The gas source connecting pipeline 1, the fine-pore diameter tee 9 and the liquid product introduction pipeline 12 are made of metal, such as stainless steel, copper, passivated stainless steel, etc., or non-metallic materials, such as PEEK, tetrafluoroethylene, quartz, etc.; the material of the spray pipeline 8 is a non-metallic material, such as PEEK, tetrafluoroethylene, quartz, etc. Preferably, the gas source connecting pipeline 1 is made of metal material, which can withstand higher gas pressure; the liquid product introduction pipeline 12 is made of PEEK material, which can withstand the corrosion of the electrolyte; the spray pipeline 8 is made of quartz material, with less residue; the fine-pore diameter tee 9 is made of passivated stainless steel material, which has the characteristics of corrosion resistance and good air tightness. The mass spectrometer 6 is a quadrupole mass spectrometer, a time-of-flight mass spectrometer, a magnetic mass spectrometer, an ion trap mass spectrometer, an orbital trap mass spectrometer or various tandem mass spectrometers. Preferably, the mass spectrometer 6 is a tandem orbital trap mass spectrometer, which has a higher resolution; it can also be a tandem time-of-flight mass spectrometer, which has a higher analysis speed.

[0025] An embodiment of the present invention provides an in-situ detection device for electrochemical liquid-phase products. When working, an electrolyte and an electrochemical reaction electrode 11 are placed in an electrochemical cell 10, and the electrochemical reaction electrode 11 is connected to an electrochemical workstation; the adjustable pressure gas source 2 is adjusted to generate an airflow through a fine-pore diameter tee 9; since the flow velocity of the airflow in the fine-pore diameter tee 9 increases, under the action of the Venturi effect, the liquid sample in the electrochemical cell 10 will slowly pass through the liquid-phase product introduction pipeline 12 into the fine-pore diameter tee 9, and be carried by the gas into the spray pipeline 8; a waveform is set on the arbitrary waveform generator 4, and is amplified by the power amplifier 3 and applied to the radio frequency electrode 7; thereby, the gas and sample in the spray pipeline 8 are ionized under the action of the radio frequency electric field of the radio frequency electrode 7, and the generated ions 5 enter the mass spectrometer 6 for analysis under the action of voltage and airflow, thereby realizing in-situ detection of liquid-phase products during the electrochemical reaction.

[0026] The present invention uses a reasonable design to utilize the high-speed airflow generated by the Venturi effect through an adjustable pressure gas source to achieve effective carrying of liquid phase products in the electrochemical reaction cell, and combines the induction electrode under the radio frequency voltage to achieve ionization of the product. The design structure can realize in-situ detection of electrochemical reactions without affecting the environment in the reaction cell, and has a good application prospect in in-situ characterization of electrochemical liquid phases.

[0027] The technical principle of the present invention is described above in conjunction with specific embodiments. These descriptions are only for explaining the principle of the present invention and cannot be interpreted as limiting the scope of protection of the present invention in any way. Based on the explanations herein, those skilled in the art can associate other specific embodiments of the present invention without creative work, and these equivalent variations or substitutions are all included in the scope defined by the claims of this application.

[0028] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit them; although the present invention has been described in detail with reference to the foregoing embodiments, those of ordinary skill in the art should understand that they can still modify the technical solutions described in the foregoing embodiments, or perform equivalent replacements for some or all of the technical features; and these modifications or replacements do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of the present invention.

Claims

1. An in-situ detection device for electrochemical liquid-phase products, characterized in that, it includes an adjustable pressure gas source (2), a gas source connection pipeline (1), a fine-aperture three-way joint (9), a spray pipeline (8), a radio frequency electrode (7), an electrochemical cell (10), an electrochemistry reaction electrode (11), a liquid-phase product introduction pipeline (12) and a mass spectrometer (6). The adjustable pressure gas source (2) is connected through the gas source connection pipeline (1) to the port of the fine-aperture three-way joint (9). The left port of the fine-aperture three-way joint (9) is connected to the electrochemical cell (10) through the liquid-phase product introduction pipeline (12). The lower port of the fine-aperture three-way joint (9) is connected to the upper end of the spray pipeline (8). The lower end of the spray pipeline (8) places the radio frequency electrode (7). The spray pipeline (8) is placed opposite and at a certain interval to the sampling port of the mass spectrometer (6). The ions (5) generated by the spray pipeline (8) enter the mass spectrometer (6) under the action of voltage and gas flow for analysis.

2. The in-situ detection device for electrochemical liquid-phase products according to claim 1, characterized in that, the radio frequency electrode (7) is in the shape of a rectangular flat plate. The radio frequency electrode (7) is connected to a power amplifier (3) through a wire. The power amplifier (3) is connected to an arbitrary waveform generator (4) through a wire. When working, set the waveform on the arbitrary waveform generator (4), and amplify and apply it to the radio frequency electrode (7) through the power amplifier (3), so that the gas and sample in the spray pipeline (8) are ionized under the action of the radio frequency electric field of the radio frequency electrode (7).

3. The in-situ detection device for electrochemical liquid-phase products according to claim 1, characterized in that, the inner diameter of the fine-aperture three-way joint (9) is smaller than the inner diameters of the gas source connection pipeline (1), the liquid-phase product introduction pipeline (12) and the spray pipeline (8).

4. The in-situ detection device for electrochemical liquid-phase products according to claim 1, characterized in that, the adjustable pressure gas source (2) can be a compressed gas cylinder or a gas generator; the gas is an inert gas.

5. The in-situ detection device for electrochemical liquid-phase products according to claim 1, characterized in that, the materials of the gas source connection pipeline (1), the fine-aperture three-way joint (9) and the liquid-phase product introduction pipeline (12) are metal or non-metal materials; the material of the spray pipeline (8) is a non-metal material.

6. The in-situ detection device for electrochemical liquid-phase products according to claim 1, characterized in that, the mass spectrometer (6) is a quadrupole mass spectrometer, a time-of-flight mass spectrometer, a magnetic mass spectrometer, an ion trap mass spectrometer, an orbitrap mass spectrometer or a tandem mass spectrometer.

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