In-situ XAFS multifunctional combination device

Abstract

The utility model discloses an in-situ XAFS multifunctional combination device which comprises a water-cooling shell and a heating sleeve, and a sample holder is mounted in the heating sleeve. A sample cavity is formed in the center of the sample frame, window pieces and window pressing pieces are arranged on the two sides of the sample cavity from inside to outside, and through holes corresponding to the light path through holes are formed in the heating sleeve and the sample frame; the other two sides of the sample holder are further connected with a gas path system, and the sample holder is further connected with a heating system. According to the invention, through careful adjustment and parameter control of the experimental environment, state reproduction of the reaction system in a real environment is ensured, an experimenter can conveniently obtain highly accurate experimental data with good repeatability, the reaction dead volume can be reduced, and the optical path can be shortened; according to the invention, not only are many technical bottlenecks of traditional equipment in a multi-phase reaction system solved, but also the experiment precision and the data credibility are greatly improved, and important technical support is provided for the research of a complex reaction system.

Description

Technical Field

[0001] This utility model relates to the technical field of combined use of in-situ characterization devices, specifically to a multifunctional combined in-situ XAFS device. Background Technology

[0002] X-ray absorption fine structure spectroscopy (XAFS) and infrared spectroscopy (IR) are two important characterization techniques in materials science and chemistry, each providing crucial microscopic information, but both also have certain limitations. XAFS, by measuring the X-ray absorption edge of specific elements, provides high-precision data on the local structure and electronic states of the object under study. It can be used to analyze atomic-level chemical environments, coordination numbers, bond lengths, and valence states in samples, making it suitable for studying metal catalysts, functional materials, and electrochemical materials.

[0003] XAFS has the advantages of high element selectivity and the ability to obtain local environmental information in complex matrices, but its disadvantages lie in its difficulty in providing information on molecular vibrations and functional groups, and its low sensitivity to light elements, making it unable to fully reflect the molecular structure of the sample. On the other hand, infrared spectroscopy, as a means of detecting molecular vibrational modes, can directly provide information on functional groups, chemical bonds, and their changes in samples, and is suitable for detecting the chemical properties of organic molecules, catalyst surface adsorbates, reactants, and products. The advantages of infrared spectroscopy are its sensitivity to molecular structure and vibrational characteristics, providing direct evidence of molecular chemical composition, and its powerful capabilities, especially in the study of organic reactions and surface chemistry.

[0004] However, infrared spectroscopy also has its limitations: when the sample absorbance is too low or the matrix interference is significant, its signal quality may be affected. Furthermore, its sensitivity to elements and local atomic environments is not as high as XAFS. In practical research, a single XAFS or infrared spectroscopy characterization method is often insufficient to comprehensively resolve complex material reaction mechanisms. Therefore, the combined XAFS and infrared spectroscopy characterization approach has emerged, combining the two in the same experimental setup to simultaneously detect local structural and molecular vibrational information of the sample. This combined approach overcomes the limitations of single technologies, combining the atomic-level structural information provided by XAFS with the molecular-level chemical composition information provided by infrared spectroscopy to form a comprehensive analytical perspective of the sample. For example, in catalytic reaction research, XAFS can be used to determine the valence state and coordination environment of catalyst active sites, while infrared spectroscopy can monitor the molecular vibrational changes of reactants, products, and intermediates in real time, resolving reaction pathways and chemical changes. Combined characterization not only allows for real-time observation of multidimensional changes in samples under specific reaction conditions but also analyzes the relationship between the state changes of active centers and the chemical transformations of reactants during the reaction process. This enables researchers to more accurately understand reaction mechanisms, thus providing data support for the design of highly efficient catalysts.

[0005] Therefore, the development of XAFS coupled with infrared spectroscopy is of great significance. It not only solves the problem of insufficient information from single characterization methods in existing equipment, but also significantly improves experimental efficiency and data comprehensiveness. The coupled equipment enables simultaneous detection of two characterization methods within the same device, eliminating the problems of sample state changes and experimental data discontinuity caused by equipment switching, thus facilitating the acquisition of more accurate and realistic test results. Furthermore, the coupled equipment is highly adaptable to experiments in complex environments, enabling real-time observation of sample microstructure and chemical changes under various conditions such as high temperature, high pressure, and atmosphere control.

[0006] With the advancement of technology and the continuous improvement of characterization techniques in terms of resolution and methods, it should be clearly recognized that using a single in-situ characterization technique is insufficient to acquire information on crystal composition, structure, adsorption processes, and internal electronic structure. The combined use of multiple in-situ characterization methods has become a new research direction, enabling the acquisition of information from multiple perspectives, angles, and dimensions through the combined application of various technologies. Therefore, this patent aims to develop an in-situ high-temperature XAS infrared combined device, achieving an innovation in the field of combined use of in-situ characterization devices. Utility Model Content

[0007] The technical problem to be solved by this utility model is: how to provide an in-situ XAFS multi-functional combined device.

[0008] To solve the above-mentioned technical problems, this utility model provides the following technical solution:

[0009] An in-situ XAFS multifunctional combination device includes a water-cooled housing and a heating jacket installed inside the water-cooled housing, wherein a sample holder is installed inside the heating jacket.

[0010] A sample cavity is provided at the center of the sample holder. Window plates and window pressing plates are provided on both sides of the sample cavity from the inside out. Through holes corresponding to the optical path through holes are provided on both the heating sleeve and the sample holder.

[0011] The sample holder is also connected to a gas path system on its other two sides, and a heating system is also connected to the sample holder.

[0012] This application, by setting up a gas path system and a heating system on the sample holder, and through meticulous adjustment and parameter control of the experimental environment, ensures that the state of the reaction system is reproduced in the real environment. This facilitates the acquisition of highly accurate and reproducible experimental data by the experimenter, and also reduces the dead volume of the reaction and shortens the optical path. Therefore, the in-situ XAFS multifunctional coupled device of this application not only solves many technical bottlenecks of traditional equipment in multiphase reaction systems, but also significantly improves the accuracy of the experiment and the reliability of the data, providing important technical support for the study of complex reaction systems.

[0013] As a further embodiment of this utility model, the optical path through holes on both sides of the sample holder are in the form of an outwardly expanding trumpet-shaped structure.

[0014] As a further embodiment of this utility model: the heating system includes a thermocouple extending from the sample holder cover at the top of the sample holder into the sample cavity, a thermocouple seal is provided at the connection position between the thermocouple and the sample holder cover, and a heating element is provided inside the water-cooled shell and at the bottom of the heating sleeve.

[0015] As a further embodiment of this utility model: an electrode is connected to one side of the water-cooled shell via an electrode fixing block, the heating element is connected to the electrode, and the electrode is also connected to an external temperature control system.

[0016] As a further embodiment of this utility model: the heating element is made of stainless steel, aluminum alloy, silver or copper, and has a long cylindrical structure.

[0017] As a further embodiment of this invention, the window sheet is made of single-crystal diamond graphite or single-crystal alumina film.

[0018] As a further embodiment of this utility model: the gas path system includes a gas path connector one and a gas path connector two, wherein the gas path connector one and the gas path connector two extend from the water-cooled shell and the sample holder into the sample chamber.

[0019] As a further embodiment of this utility model: a water-cooled connector 1 and a water-cooled connector 2 located above the water-cooled connector 1 are provided on one side of the water-cooled housing, and the water-cooled connector 1 and the water-cooled connector 2 are connected through a water-cooling groove inside the water-cooled housing.

[0020] The water-cooled housing is also provided with a water-cooled connector four and a water-cooled connector three located above the water-cooled connector four. The water-cooled connector four and the water-cooled connector three are connected through a water-cooled groove inside the water-cooled housing.

[0021] As a further embodiment of this utility model: a base plate is detachably installed at the bottom of the water-cooled housing, and a top cover is installed at the top of the water-cooled housing.

[0022] As a further aspect of this utility model, the distance between the two window pieces is between 2mm and 10mm.

[0023] Compared with the prior art, the beneficial effects of this utility model are:

[0024] This application, by setting up a gas path system and a heating system on the sample holder, and through meticulous adjustment and parameter control of the experimental environment, ensures the reproduction of the reaction system in the real environment. This facilitates the acquisition of highly accurate and repeatable experimental data, and also reduces the dead volume of the reaction and shortens the optical path. For the combined application of in-situ spectroscopy techniques such as XAFS, infrared, and Raman, this device also significantly simplifies the operation process of the experimental setup, reducing sample transfer steps during testing and interference from changes in the external environment. This is crucial for the real-time analysis of complex materials and multiphase reaction systems. Therefore, this in-situ XAFS multifunctional combined device not only solves many technical bottlenecks of traditional equipment in multiphase reaction systems, but also greatly improves the accuracy of experiments and the reliability of data, providing important technical support for the study of complex reaction systems.

[0025] This application sets up a water cooling tank inside the water-cooled shell and connects water cooling connector one and water cooling connector two, as well as water cooling connector three and water cooling connector four. Then, it connects to the external cooling water circulation system to directly realize the overall cooling function of the shell, thereby achieving the cooling of the external shell and preventing the internal heating jacket and sample rack from generating high temperatures on the external shell that could cause harm to people. The water cooling system can keep the equipment shell at a low temperature.

[0026] The material selection for the heating element in this application needs to meet the characteristics of excellent thermal conductivity and structural stability. Therefore, the materials selected include, but are not limited to, stainless steel, aluminum alloy, silver, copper and other materials. It is also designed as an elongated cylinder to make the heating more uniform. The thermocouple in this application is placed above the sample chamber to ensure the accuracy of the temperature. The heating element is connected to the electrode, and the electrode is directly connected to the external temperature control system to control parameters such as the temperature and heating rate inside the reaction chamber.

[0027] One of the significant advantages of this application is its excellent adaptability to multiphase reaction systems. By reducing the dead volume of the reaction, the influence of gases on reactants during the reaction process can be effectively reduced, avoiding the decrease in reaction efficiency or interference with spectral measurements caused by excessive gas retention. Furthermore, the short optical path of this device minimizes the impact of gases and impurities in the optical path on the spectrum, ensuring the stability and purity of the spectral signal, making it particularly suitable for signal-sensitive XAFS or infrared spectroscopy. By shortening the optical path and reducing the dead volume of the reaction, this type of device significantly improves the accuracy of test data, providing a more realistic and direct representation of the dynamic changes in the reaction system.

[0028] The in-situ XAFS multi-functional coupling device features a more compact structure, fully considering the actual needs of the experimental environment, making the equipment more convenient to operate and use. Especially under multiphase reaction conditions, this device can achieve in-situ spectral coupling, meaning it can accommodate multiple spectroscopic detection methods within the same device, including XAFS, infrared spectroscopy, and Raman spectroscopy, meeting the needs of researchers to explore reaction systems from multiple angles and dimensions. This coupling function has shown great value in the study of catalyst reaction mechanisms, material conversion processes, and energy storage materials, enabling in-depth analysis of the state changes, phase evolution, and physicochemical properties of materials or reactants under complex reaction environments from multiple levels, improving research efficiency and data comprehensiveness. Furthermore, the device's short optical path design ensures the stability of spectral measurements and the accuracy of data even under extreme conditions, especially in high-temperature and high-pressure environments, making it widely applicable in challenging experiments. Attached Figure Description

[0029] Figure 1 This is a schematic diagram of the structure of the in-situ XAFS multi-functional combined device according to an embodiment of the present invention;

[0030] Figure 2 This is a structural schematic diagram of the in-situ XAFS multi-functional combined device from another perspective, according to an embodiment of this utility model.

[0031] Figure 3 This is an exploded view of the in-situ XAFS multi-functional combined device according to an embodiment of this utility model;

[0032] Figure 4 This is a partial exploded view of the in-situ XAFS multi-functional combined device according to an embodiment of this utility model;

[0033] Figure 5 This is a bottom view of the in-situ XAFS multi-functional combined device according to an embodiment of this utility model;

[0034] Figure 6 This is an embodiment of the present utility model. Figure 5 Sectional view along line AA;

[0035] Explanation of reference numerals in the attached figures:

[0036] 1. Base plate; 2. Water-cooled connector one; 3. Water-cooled connector two; 4. Top cover; 5. Water-cooled connector three; 6. Water-cooled connector four; 7. Electrode fixing block one; 8. Electrode fixing block two; 9. Electrode; 10. Gas connection connector one; 11. Thermocouple; 12. Gas connection connector two; 13. Water-cooled outer shell; 14. Water-cooled tank; 15. Heating element; 16. Heating jacket; 17. Window pressure plate; 18. Sample holder top cover; 19. Thermocouple seal; 20. Sealing ring; 21. Sealing gasket; 22. Window plate; 23. Sample holder. Detailed Implementation

[0037] To make the objectives, technical solutions, and advantages of the embodiments of this utility model clearer, the technical solutions of the embodiments of this utility model will be clearly and completely described below in conjunction with the embodiments of this utility model. Obviously, the described embodiments are only some embodiments of this utility model, not all embodiments. Based on the embodiments of this utility model, all other embodiments obtained by those skilled in the art without creative effort are within the protection scope of this utility model.

[0038] Reference Figure 1 and Figure 2 An in-situ XAFS multi-functional coupling device is a multi-spectral coupling testing device adapted to multiphase reaction systems. In addition to providing reaction environment atmospheres such as high temperature and high pressure, it can also be adapted to multi-functional coupling devices for various characterization spectra such as XAFS spectroscopy, infrared spectroscopy, and Raman spectroscopy.

[0039] Specifically, it includes a base plate 1, a water-cooled housing 13, and a top cover 4. The base plate 1 is detachably installed at the bottom of the water-cooled housing 13 by bolts or pins, and the top cover 4 is also detachably installed at the top of the water-cooled housing 13 by bolts or pins. The top of the water-cooled housing 13 is open, and the top cover 4 is symmetrically installed on both sides of the top of the water-cooled housing 13, with a space reserved between the two top covers 4 for the thermocouple 11 to pass through.

[0040] Reference Figure 1 , Figure 2 and Figure 6 The water-cooled housing 13 itself can be water-cooled. A water-cooled connector 12 and a water-cooled connector 23 located above the water-cooled connector 12 are provided on one side of the water-cooled housing 13. The water-cooled connector 12 and the water-cooled connector 23 are connected through the water-cooled channel 14 inside the water-cooled housing 13. The water-cooled channel 14 has a side-standing "U" shaped structure.

[0041] Furthermore, a water-cooled connector 4 6 and a water-cooled connector 3 5 located above the water-cooled connector 4 6 are provided on one side of the water-cooled housing 13. The water-cooled connector 4 6 and the water-cooled connector 3 5 are connected through a water-cooled channel 14 inside the water-cooled housing 13. The water-cooled channel 14 has a side-standing "U" shaped structure.

[0042] The overall water cooling principle is as follows: Water enters the water cooling tank 14 inside the water-cooled shell 13 through water-cooled connector 12 on the side of the water-cooled shell 13, flows into the corresponding water cooling tank 14 through water-cooled connector 12, and then flows out from water-cooled connector 23; then water-cooled connector 23 and water-cooled connector 46 are connected, the water flowing out of water-cooled connector 23 enters water-cooled connector 46, then flows into the corresponding water cooling tank 14 from water-cooled connector 46, and finally flows out from water-cooled connector 35, forming a loop; water-cooled connector 12 and water-cooled connector 35 are connected to the external cooling water circulation system to directly realize the overall cooling function of the water-cooled shell 13; the water cooling system can keep the equipment shell at a low temperature and avoid the temperature from being too high and causing harm to people.

[0043] Reference Figure 3 and Figure 4 The water-cooled housing 13 has flared through holes on both its front and rear sides, serving as optical path through holes. Inside the water-cooled housing 13, between the two through holes, are two heating sleeves 16. Each heating sleeve 16 has a flared through hole in its center, corresponding to the through hole on the water-cooled housing 13. A sample holder 23 is installed between the two heating sleeves 16, and window pressure plates 17 are installed on both the front and rear sides of the sample holder 23. Each of the two sets of window pressure plates 17 has a window piece 22 on its inner side, and the sample is ultimately placed between the two window pieces 22. It should be noted that, for ease of understanding, the front and rear directions here are... Figure 3 Based on this, the forward and backward directions mentioned below are similar and should not be construed as limitations on this application.

[0044] Furthermore, the two heating sleeves 16 can be detachably connected by bolts or pins, and the cavity formed between them is used to place the sample holder 23. The second funnel-shaped through hole opened between the two heating sleeves 16 serves as an optical path through hole, and its diameter is smaller than the diameter of the first through hole on the water-cooled outer shell 13.

[0045] Furthermore, a sample cover 18 can be installed on the top of the sample holder 23 by bolts or pins. A funnel-shaped through hole three is also provided on the front and rear sides of the sample holder 23. The diameter of the through hole three is smaller than that of the through hole two, and the diameters of the through hole three, through hole two, and through hole one are all located on the same central axis. Two window pressure plates 17 are installed into the through hole three from both sides. A window piece 22 is provided on the inner side of the window pressure plate 17. The distance between the two window pieces 22 is the sample cavity used to store the sample.

[0046] Furthermore, to make the overall structure of the device more compact, the sample holder 23, which serves as the main reaction component, is designed as a cuboid structure, with the optical path following the smallest possible cuboid shape. Meanwhile, to accommodate the actual operating space of various spectrometers, the overall dimensions of the sample holder 23 and the sample holder cover 18 should be ≤35*20*45mm (length*width*height); the distance between the two windows 22 can be designed to be between 2mm and 10mm. The material of the windows 22 must meet the requirement of high transmittance in the X-ray, infrared, and visible light bands; therefore, the material selection for the windows 22 includes, but is not limited to, single-crystal diamond graphite and single-crystal alumina film.

[0047] Reference Figure 3 and Figure 4 The left and right ends of the sample holder 23 are connected to gas path connector 10 and gas path connector 22, respectively. Gas enters the cavity through gas path connectors 10 and 22 and is blown onto the sample. After flowing through the sample, the gas flows out from above. The internal gas path design of the cavity allows the gas to pass fully through the sample, ensuring the smooth flow of the entire gas path. It should be noted that, for ease of understanding, the front-back direction here is... Figure 3 Based on this, the forward and backward directions mentioned below are similar and should not be construed as limitations on this application.

[0048] Reference Figure 3 and Figure 4 A thermocouple 11 is installed on the top of the sample holder 23. The thermocouple 11 extends from the top cover 18 of the sample holder into the sample chamber. A thermocouple seal 19 is provided at the connection position between the thermocouple 11 and the top cover 18 of the sample holder, and a sealing ring 20 is provided at the bottom of the thermocouple seal 19. An annular sealing gasket 21 is provided at the position where the outer side of the window 22 contacts the sample holder 23. A heating element 15 is provided inside the water-cooled shell 13 and at the bottom of the heating sleeve 16. An electrode 9 is connected to the outer side of the water-cooled shell 13 through electrode fixing block 1 7 and electrode fixing block 2 8. The heating element 15 is connected to the electrode 9, and the electrode 9 is also connected to an external temperature control system.

[0049] It is important to note that the material selection for the heating element 15 must meet the requirements of excellent thermal conductivity and structural stability. Therefore, the materials selected for the heating element 15 include, but are not limited to, stainless steel, aluminum alloy, silver, copper, etc. The heating element 15 adopts a long cylindrical shape to make the heating more uniform. The thermocouple 11 is placed above the sample chamber to ensure the accuracy of the temperature. The heating element 15 is connected to the electrode 9, and the electrode 9 is directly connected to the external temperature control system to control parameters such as the temperature and heating rate inside the reaction chamber.

[0050] The specific operating principle of this application is as follows:

[0051] Use an Allen wrench to remove the screws on the sample holder cover 18 of the sample holder 23, then place the sample into the sample chamber, and then reinstall the sample holder cover 18. Install it on the spectrometer and operate it. Observe the transmittance of the Raman beam, XAFS beam and FTIR beam emitted by the spectrometer, thus enabling compatibility with multiple spectral functions.

[0052] To protect the gas source or apply pressure, gas connector 10 and gas connector 2 12 should be connected to the gas source and waste gas recovery interfaces respectively. The gas source is introduced into the sample chamber through gas connector 10, allowing the gas to pass through the sample fully and ensuring the smooth flow of the entire gas path. Then the gas is discharged through gas connector 2 12 and then connected to the waste gas recovery interface.

[0053] To introduce illumination parameters, a light source can be applied to the front of the cavity window 22; to apply temperature parameters, the cooling water circulation system can be turned on first to cool down the water-cooled shell 13, and then the temperature control system can be turned on. At this time, the heating element 15 will start heating. After the temperature reaches the target value, photothermal structure characterization can be performed.

[0054] The above embodiments are only used to illustrate the technical solutions of this utility model, and are not intended to limit it. Although this utility model has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some of the technical features. Such modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the spirit and scope of the technical solutions of the embodiments of this utility model.

Claims

1. An in-situ XAFS multi-functional combined device, characterized in that, It is compatible with multiple spectral detections, including a water-cooled housing (13) and a heating jacket (16) installed inside the water-cooled housing (13), with a sample holder (23) installed inside the heating jacket (16). A sample chamber is provided at the center of the sample holder (23). Window plates (22) and window pressing plates (17) are provided on both sides of the sample chamber from the inside out. Through holes corresponding to the optical path through holes are provided on the heating sleeve (16) and the sample holder (23). The other two sides of the sample holder (23) are connected to the gas path system, and the sample holder (23) is also connected to the heating system; The heating system includes a thermocouple (11), a thermocouple seal (19) is provided at the connection position between the thermocouple (11) and the sample holder cover 18, and a sealing ring is provided at the bottom of the thermocouple seal (19). An annular sealing gasket is provided at the position where the outer side of the window (22) contacts the sample holder (23). A heating element (15) is provided inside the water-cooled outer shell (13) and at the bottom of the heating sleeve (16).

2. The in-situ XAFS multifunctional combined device according to claim 1, characterized in that: The optical path through holes on both sides of the sample holder (23) are in the shape of an outwardly expanding trumpet.

3. The in-situ XAFS multifunctional combined device according to claim 1, characterized in that: The thermocouple (11) extends into the sample chamber from the sample holder cover (18) at the top of the sample holder (23).

4. The in-situ XAFS multifunctional combined device according to claim 3, characterized in that: An electrode (9) is connected to one side of the water-cooled outer shell (13) via an electrode fixing block. The heating element (15) is connected to the electrode (9), and the electrode (9) is also connected to an external temperature control system.

5. The in-situ XAFS multifunctional combined device according to claim 3, characterized in that: The heating element (15) is made of stainless steel, aluminum alloy, silver or copper and has a long cylindrical structure.

6. The in-situ XAFS multifunctional combined device according to claim 1, characterized in that: The window (22) is made of single-crystal diamond graphite or single-crystal alumina film.

7. The in-situ XAFS multifunctional combined device according to claim 1, characterized in that: The gas path system includes a gas path connector one (10) and a gas path connector two (12), which extend from the water-cooled shell (13) and the sample holder (23) into the sample chamber.

8. The in-situ XAFS multifunctional combined device according to claim 1, characterized in that: A water-cooled connector 1 (2) and a water-cooled connector 2 (3) located above the water-cooled connector 1 (2) are provided on one side of the water-cooled housing (13). The water-cooled connector 1 (2) and the water-cooled connector 2 (3) are connected through the water-cooled tank inside the water-cooled housing (13). The water-cooled outer shell (13) is also provided with a water-cooled connector four (6) and a water-cooled connector three (5) located above the water-cooled connector four (6). The water-cooled connector four (6) and the water-cooled connector three (5) are connected through the water-cooled tank inside the water-cooled outer shell (13).

9. The in-situ XAFS multifunctional combined device according to claim 1, characterized in that: The bottom of the water-cooled housing (13) is detachably fitted with a base plate (1), and the top of the water-cooled housing (13) is fitted with a top cover (4).

10. The in-situ XAFS multifunctional combined device according to claim 1, characterized in that: The spacing between the two window pieces (22) is between 2mm and 10mm.

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