In-situ high-temperature and high-pressure reaction mechanism and soft X-ray spectroscopy combined system and control system

Abstract

The invention discloses an in-situ high-temperature and high-pressure reaction mechanism and soft X-ray spectroscopy combined system. The system comprises an in-situ reaction support used for placing a sample; the vacuum mechanism is used for realizing a vacuum environment; the monochromatic mechanism is used for adjusting the light emitted by the light source and providing a target synchrotron radiation beam; the high-temperature high-pressure reaction mechanism is used for carrying out in-situ high-temperature high-pressure reaction treatment on the sample; and the testing mechanism is used for measuring the photoelectron signal and the photocurrent signal generated after the sample is irradiated by the synchrotron radiation beam and the intensity of the synchrotron radiation beam. According to the invention, in-situ high-temperature and high-pressure reaction treatment can be carried out on the sample, electronic structure change information of the sample under in-situ conditions can be known, two spectroscopy technologies of soft X-ray absorption spectrum and synchrotron radiation photoelectron spectroscopy are integrated at the same time, and the electronic structure of the sample can be explored in different dimensions.

Description

Technical Field

[0001] The present invention relates to the technical fields of soft X-ray absorption spectroscopy and synchrotron radiation photoelectron spectroscopy, and particularly relates to an in-situ high-temperature and high-pressure reaction mechanism and a soft X-ray spectroscopy combined system and a control system thereof. Background Art

[0002] Soft X-ray absorption spectroscopy is a spectroscopic technique based on the interaction between soft X-rays and matter. It obtains information about the electronic structure of a sample by measuring the absorption of soft X-rays by the sample. Synchrotron radiation photoelectron spectroscopy is a photoelectron spectroscopy technique using synchrotron radiation light source as the excitation source. Its energy is adjustable, and it can obtain information about the electronic structure of a sample by measuring the photoelectron signal emitted by the sample. By combining the two characterization techniques, a clear understanding of the electronic structure information of the sample can be achieved. In recent years, soft X-ray absorption spectroscopy and synchrotron radiation photoelectron spectroscopy have been widely applied in the fields of energy catalysis, nanomaterials, biomedicine, semiconductors, etc., and have very important scientific significance.

[0003] However, with the rapid development of materials science, the research on the electronic structure of materials has become more and more in-depth, and the limitations of soft X-ray absorption spectroscopy and synchrotron radiation photoelectron spectroscopy have gradually emerged. Both spectroscopic techniques require a very strict vacuum environment, which greatly hinders the implementation of in-situ experiments and makes it difficult to assist scientific researchers in studying the evolution process of the electronic structure of samples under in-situ reaction conditions. Therefore, it is of great scientific significance to develop an in-situ high-temperature and high-pressure reaction device and a soft X-ray spectroscopy combined system. Summary of the Invention

[0004] The present invention aims to solve at least one of the technical problems in the related technologies to some extent. For this purpose, an object of the present invention is to provide an in-situ high-temperature and high-pressure reaction mechanism and a soft X-ray spectroscopy combined system, which can perform in-situ high-temperature and high-pressure reaction treatment on a sample, help to understand the electronic structure change information occurring under in-situ conditions of the sample, and at the same time integrate two spectroscopic techniques of soft X-ray absorption spectroscopy and synchrotron radiation photoelectron spectroscopy, and can explore the electronic structure of the sample in different dimensions.

[0005] In a first aspect, an in-situ high-temperature and high-pressure reaction mechanism and a soft X-ray spectroscopy combined system provided by the present invention includes:

[0006] In-situ reaction holder: for placing the sample;

[0007] Vacuum mechanism: for realizing a vacuum environment;

[0008] Monochromator mechanism: adjusts the light emitted by the light source and is used to provide a target synchrotron radiation beam;

[0009] High-temperature and high-pressure reaction mechanism: for performing in-situ high-temperature and high-pressure reaction treatment on the sample;

[0010] Testing mechanism: used to measure the photoelectron signal, photocurrent signal generated after the sample is irradiated by synchrotron radiation beam, and the synchrotron radiation beam intensity;

[0011] Inside the vacuum mechanism, there are a test cavity, a transfer cavity, a rapid sampling cavity, and a monochromator mechanism cavity for installing the monochromator mechanism. The transfer cavity is respectively connected to the test cavity, the rapid sampling cavity, and the high-temperature and high-pressure reaction mechanism. The synchrotron radiation beam outlet of the monochromator mechanism cavity is connected to the synchrotron radiation beam inlet of the test cavity. A synchrotron radiation beam monitoring port of the testing mechanism is provided on the synchrotron radiation beam path where the monochromator mechanism cavity is connected to the test cavity. Inside the test cavity, there is a photoelectron detection port of the testing mechanism for detecting photoelectron signals. Outside the vacuum mechanism, there is a photocurrent detection port of the testing mechanism for detecting photocurrent signals.

[0012] Preferably, a grating and a plane mirror are installed inside the monochromator mechanism, and the plane mirror rotates around a fixed point to ensure that the position of the light spot emitted through the grating is fixed.

[0013] Preferably, the high-temperature and high-pressure reaction mechanism includes an external gas path and a reaction component. The reaction component includes a housing with a vacuum cavity inside, and an upper cover and a lower cover that are respectively rotatably installed at the upper and lower ends of the housing. When the upper cover and the lower cover rotate to a preset position, a sealed space can be formed and the in-situ reaction holder can be clamped and fixed. The upper cover is provided with a gas communication port for communicating with the external gas path. An electrode contact is installed on one side of the lower cover close to the reaction cavity. Inside the in-situ reaction holder, there are a resistance wire for heating the sample and a thermocouple for monitoring the temperature. Electrodes are provided outside the in-situ reaction holder and are respectively electrically connected to the resistance wire and the thermocouple. When the lower cover clamps and fixes the in-situ reaction holder, the electrodes are connected to the corresponding electrode contacts, and the electrode contacts are externally connected to a control circuit for driving the heating power of the resistance wire.

[0014] Preferably, the external gas path includes a gas cylinder and a high-pressure gas storage pipe. The gas cylinder is communicated with the inlet of the high-pressure gas storage pipe through a flow meter, and the outlet of the high-pressure gas storage pipe is communicated with the gas communication port of the upper cover through an inlet ball valve.

[0015] Preferably, a pressure relief valve for restricting the internal pressure of the reaction cavity from exceeding a preset value is installed on the housing.

[0016] Preferably, the high-temperature and high-pressure reaction mechanism further includes a vacuum pumping path. A vacuum pumping port is provided on the housing, and the vacuum pumping port is respectively connected to a molecular pump and a dry pump through a vacuum gauge and an outlet ball valve in sequence.

[0017] Preferably, the testing mechanism includes a photo - electron detection component, a photo - current detection component, and a synchrotron radiation beam monitoring component. The photo - electron detection component is installed inside the testing cavity near the photo - electron detection port of the testing mechanism. The photo - current detection component is installed outside the vacuum mechanism near the photo - current detection port of the testing mechanism. The synchrotron radiation beam monitoring component is installed inside the vacuum mechanism near the synchrotron radiation beam monitoring port of the testing mechanism.

[0018] Preferably, the synchrotron radiation beam monitoring component includes a vacuum electrode, a micro - ammeter, a gold mesh, and a linear driver for driving the gold mesh to move to the synchrotron radiation beam path. The gold mesh is installed near the synchrotron radiation beam monitoring port of the testing mechanism. The displacement end of the linear driver is connected to the gold mesh. One end of the vacuum electrode is connected to the gold mesh, and the other end of the vacuum electrode is connected to the micro - ammeter through a wire.

[0019] Preferably, the rapid - injection cavity is equipped with a first sample transfer rod. The connection between the rapid - injection cavity and the transfer cavity and the connection between the high - temperature and high - pressure reaction mechanism and the transfer cavity are both on the straight line in the conveying direction of the first sample transfer rod. The first sample transfer rod is used to transfer samples into the high - temperature and high - pressure reaction mechanism and transfer samples from the high - temperature and high - pressure reaction mechanism into the transfer cavity. A second sample transfer rod for transferring samples from the transfer cavity into the testing cavity is installed in the transfer cavity.

[0020] In a second aspect, a control system proposed by the present invention includes any one of the above - mentioned in - situ high - temperature and high - pressure reaction mechanism and soft X - ray spectroscopy combined systems, and further includes a data acquisition and control unit;

[0021] The data acquisition and control unit is respectively connected to the monochromator mechanism and the testing mechanism;

[0022] The data acquisition and control unit is used to control the monochromator mechanism to perform energy scanning, and is used to control the signals collected by the testing mechanism to generate soft X - ray absorption spectra or synchrotron radiation photoelectron energy spectra.

[0023] The beneficial effects of the present invention are as follows:

[0024] (1) The present invention can perform in - situ high - temperature and high - pressure reaction treatment on samples, and detect the soft X - ray absorption spectra and synchrotron radiation photoelectron energy spectra of samples without exposing them to air, which helps to understand the information on the electronic structure changes occurring in samples under in - situ conditions.

[0025] (2) The present invention integrates two spectroscopic techniques, soft X - ray absorption spectroscopy and synchrotron radiation photoelectron energy spectroscopy, simultaneously, and can explore the electronic structure of samples from different dimensions. BRIEF DESCRIPTION OF THE DRAWINGS

[0026] In the drawings:

[0027] Figure 1 FIG. is a schematic structural diagram of a system combining an in-situ high-temperature and high-pressure reaction mechanism with soft X-ray spectroscopy proposed by the present invention;

[0028] Figure 2 FIG. is a schematic structural diagram of a vacuum mechanism proposed by the present invention;

[0029] Figure 3 FIG. is a schematic structural diagram of a high-temperature and high-pressure reaction mechanism proposed by the present invention;

[0030] Figure 4 FIG. is a schematic diagram of the relative positions of a grating and a plane mirror in a monochromator mechanism proposed by the present invention;

[0031] Figure 5 FIG. is an in-situ synchrotron radiation photoelectron spectrum of C 1s of a zinc oxide sample obtained in an embodiment proposed by the present invention;

[0032] Figure 6 FIG. is an in-situ soft X-ray absorption spectrum of O-K-edge of a zinc oxide sample obtained in an embodiment proposed by the present invention.

[0033] In the figure:

[0034] 1. In-situ reaction holder, 2. Vacuum mechanism, 3. Monochromator mechanism, 4. High-temperature and high-pressure reaction mechanism, 5. Testing mechanism, 6. Data acquisition and control unit, 7. Sample, 8. Light source;

[0035] 2-1. Testing cavity, 2-2. Transfer cavity, 2-3. Quick injection cavity, 2-4. First sample transfer rod, 2-5. Second sample transfer rod, 2-6. Monochromator mechanism cavity;

[0036] 4-3. Control circuit, 4-1-1. Gas cylinder, 4-1-2. Flowmeter, 4-1-3. High-pressure gas storage pipe, 4-1-4. Inlet gas valve, 4-1-5. Outlet gas valve, 4-1-6. Molecular pump, 4-1-7. Vacuum gauge, 4-1-8. Pressure relief valve, 4-1-9. Dry pump, 4-2-1. Upper cover, 4-2-2. Lower cover;

[0037] 5-1. Photoelectron detection component, 5-2. Photoelectric current detection component, 5-3. Synchrotron radiation beam current monitoring component. DETAILED DESCRIPTION OF THE EMBODIMENTS

[0038] Refer to Figure 1 , a system combining an in-situ high-temperature and high-pressure reaction mechanism with soft X-ray spectroscopy, comprising:

[0039] In-situ reaction holder 1: used to place the sample 7;

[0040] Vacuum mechanism 2: used to achieve a vacuum environment;

[0041] Monochromator mechanism 3: adjusts the light emitted by the light source and is used to provide a target synchrotron radiation beam;

[0042] High-temperature and high-pressure reaction mechanism 4: used to perform in-situ high-temperature and high-pressure reaction treatment on the sample 7;

[0043] Testing mechanism 5: used to measure the photoelectron signal, photocurrent signal generated after the sample 7 is irradiated by the synchrotron radiation beam, and the intensity of the synchrotron radiation beam;

[0044] Reference Figure 2 , inside the vacuum mechanism 2, there are a test cavity 2-1, a transfer cavity 2-2, a rapid injection cavity 2-3, and a monochromator mechanism cavity 2-6 for installing the monochromator mechanism 3. The transfer cavity 2-2 is respectively connected to the test cavity 2-1, the rapid injection cavity 2-3, and the high-temperature and high-pressure reaction mechanism 4. The synchrotron radiation beam outlet of the monochromator mechanism cavity 2-6 is connected to the synchrotron radiation beam inlet of the test cavity 2-1. On the synchrotron radiation beam path connecting the monochromator mechanism cavity 2-6 and the test cavity 2-1, there is a synchrotron radiation beam monitoring port of the testing mechanism 5. Inside the test cavity 2-1, there is a photoelectron detection port of the testing mechanism 5 for detecting photoelectron signals. Outside the vacuum mechanism 2, there is a photocurrent detection port of the testing mechanism 5 for detecting photocurrent signals.

[0045] Obviously, based on the above, in this application, the target synchrotron radiation beam is provided by the monochromator mechanism 3, the in-situ high-temperature and high-pressure reaction treatment is performed on the sample 7 by the high-temperature and high-pressure reaction mechanism 4. After the in-situ high-temperature and high-pressure reaction treatment, the sample can be transferred to the test cavity 2-1 without exposure to air. After being irradiated by the target synchrotron radiation beam, the generated photoelectron signal and photocurrent signal are obtained through the testing mechanism 5, and the synchrotron radiation photoelectron energy spectrum or soft X-ray absorption spectrum results are generated.

[0046] Specifically, gate valves are provided at the connections between the transfer cavity 2-2 and the test cavity 2-1 and the rapid injection cavity 2-3;

[0047] The rapid injection cavity 2-3 is equipped with a dry pump and a molecular pump to achieve the cavity vacuum, and at the same time, the vacuum degree is measured through a vacuum gauge tube;

[0048] The test cavity 2-1 is equipped with a dry pump, a molecular pump, and an ion pump to achieve the cavity vacuum, and at the same time, the vacuum degree is measured through a vacuum gauge tube. The test cavity 2-1 is connected to the ion pump through a gate valve. Inside the test cavity 2-1, there is a sample holder for placing the in-situ reaction holder 1;

[0049] The monochromator mechanism cavity 2-6 is connected to the test cavity 2-1 through a gate valve. The monochromator device cavity 2-6 is equipped with an ion pump to achieve the cavity vacuum, and at the same time, the vacuum degree is measured through a vacuum gauge tube. The monochromator device cavity 2-6 is connected to the ion pump through a gate valve.

[0050] The vacuum degree of this embodiment is maintained at 5×10 -9 to 5×10 -10 mbar.

[0051] In this embodiment, referring to Figure 4 , a grating and a flat mirror that rotates around a fixed point to ensure the fixed position of the light spot emitted from the grating are installed inside the monochromator mechanism 3.

[0052] Obviously, based on the above, the grating uses the principle of multi-slit diffraction to disperse light, thereby adjusting the photon energy of the synchrotron radiation beam.

[0053] The grating uses the principle of multi-slit diffraction to disperse light, and the flat mirror is used for the transmission of the synchrotron radiation beam to ensure the fixed position of the light spot of the output synchrotron radiation beam.

[0054] There are rulings on the surface of the grating, and the dispersion effect of the grating is described by the grating equation: d(sinθ + sinα) = mλ

[0055] d: Grating constant, the distance between adjacent rulings.

[0056] θ: Angle between the incident light ray and the grating normal.

[0057] α: Diffraction angle, the angle between the diffracted light and the normal.

[0058] m: Diffraction order, an integer, such as ±1, ±2.

[0059] λ: Wavelength of light.

[0060] When the grating rotates, α changes, and lights of different wavelengths pass through the exit slit in turn to achieve wavelength selection.

[0061] Referring to Figure 4 , the flat mirror rotates around point M with a vertical distance of 31.2 mm. When rotating, the grating rotates accordingly, and a coordinate system is established with the center of the plane grating as the coordinate origin O, the outgoing light as the x-axis, and the vertical direction as the y-axis. The coordinates of point M are Xm = 0 mm; Ym = -15.7 mm.

[0062] The light spot size of the synchrotron radiation beam in this embodiment is 1 mm × 1 mm; the energy range of the synchrotron radiation beam is 100 - 1000 eV; the energy resolution range of the synchrotron radiation beam is 1000 - 3000.

[0063] In this embodiment, referring toFigure 3 , the high-temperature and high-pressure reaction mechanism includes an external gas path and a reaction component. The reaction component includes a housing with a vacuum cavity inside, and an upper cover 4-2-1 and a lower cover 4-2-2 that are rotatably installed at the upper and lower ends of the housing respectively. When the upper cover 4-2-1 and the lower cover 4-2-2 are rotated to a preset position, a sealed space can be formed and the in-situ reaction support 1 can be clamped and fixed. The upper cover 4-2-1 is provided with a gas communication port for connecting the external gas path. On one side of the lower cover 4-2-2 close to the reaction cavity, electrode contacts are installed. Inside the in-situ reaction support 1, there are heating wires for heating the sample 7 and thermocouples for monitoring the temperature. Outside the in-situ reaction support 1, there are electrodes electrically connected to the heating wires and thermocouples respectively. When the lower cover 4-2-2 clamps and fixes the in-situ reaction support 1, the electrodes are connected to the corresponding electrode contacts, and the electrode contacts are externally connected to a control circuit 4-3 for driving the heating power of the heating wires.

[0064] Obviously, based on the above, in the high-temperature and high-pressure reaction mechanism, a high-pressure environment is provided for the sealed space formed between the upper cover 4-2-1 and the lower cover 4-2-2 through the external gas path, and a high-temperature environment is provided by the heating wires controlled by the control circuit 4-3, so as to realize the in-situ high-temperature and high-pressure reaction treatment of the sample.

[0065] In this embodiment, a torque wrench of 25 N·m is used to rotate the upper cover 4-2-1 until the upper cover 4-2-1 and the lower cover 4-2-2 clamp the in-situ sample support 1, and the temperature range of the in-situ high-temperature and high-pressure reaction is 0° to 500°.

[0066] In this embodiment, the external gas path includes a gas cylinder 4-1-1 and a high-pressure gas storage pipe 4-1-3. The gas cylinder 4-1-1 is connected to the intake port of the high-pressure gas storage pipe 4-1-3 through a flow meter 4-1-2, and the outlet of the high-pressure gas storage pipe 4-1-3 is connected to the gas communication port of the upper cover 4-2-1 through an intake ball valve 4-1-4.

[0067] A pressure relief valve 4-1-8 for restricting the internal pressure of the reaction cavity from exceeding a preset value is installed at the housing.

[0068] The high-temperature and high-pressure reaction mechanism further includes a vacuum pumping gas path. A vacuum pumping port is opened at the housing, and the vacuum pumping port is connected to a molecular pump 4-1-6 and a dry pump 4-1-9 through a vacuum gauge 4-1-7 and an outlet ball valve 4-1-5 in sequence.

[0069] Specifically, the gas cylinder 4-1-1 is connected to the high-pressure gas storage pipe 4-1-3 through a stainless steel pipe, and a flowmeter 4-1-2 is installed in the middle. The flowmeter 4-1-2 can control the flow rate of the gas in the gas cylinder 4-1-1 entering the high-pressure gas storage pipe 4-1-3. The upper end of the high-pressure gas storage pipe 4-1-3 is connected to the outer shell through a stainless steel pipe, and an intake ball valve 4-1-4 is installed in the middle. The intake ball valve 4-1-4 can be opened and closed to control whether the gas enters the high-temperature and high-pressure reaction mechanism 4. The lower end of the high-pressure gas storage pipe 4-1-3 is connected to a four-way valve. One of the paths is connected to the high-temperature and high-pressure reaction mechanism 4, and an outlet ball valve 4-1-5 and a vacuum gauge 4-1-7 are installed in the middle. The outlet ball valve 4-1-5 can be opened and closed to control whether the gas flows out of the high-temperature and high-pressure reaction mechanism 4. The vacuum gauge 4-1-7 can detect the vacuum condition in the pipeline. A three-way valve is also installed between the vacuum gauge 4-1-7 and the outer shell, and a pressure relief valve 4-1-8 is installed at the last end. When the pressure in the high-temperature and high-pressure reaction mechanism 4 is greater than the set pressure of the pressure relief valve 4-1-8, the pressure relief valve 4-1-8 starts automatically to protect the high-temperature and high-pressure reaction mechanism 4. For the other two paths of the four-way valve, one path is connected to the dry pump 4-1-9, and the last path is connected to the molecular pump 4-1-6. The molecular pump 4-1-6 is also connected to the high-temperature and high-pressure reaction mechanism 4 through a gate valve.

[0070] In this embodiment, the flow rate range that the flowmeter can control is from 10 ml / min to 200 ml / min; the set pressure of the pressure relief valve is 10 bar. When the pressure in the pipeline exceeds 10 bar, the pressure relief valve starts automatically, and the vacuum degree of the reaction cavity is maintained at 5×10 -7 to 5×10 -8 mbar.

[0071] In this embodiment, the testing mechanism 5 includes a photoelectron detection component 5-1, a photocurrent detection component 5-2, and a synchrotron radiation beam monitoring component 5-3. The photoelectron detection component 5-1 is installed inside the testing cavity 2-1 near the photoelectron detection port of the testing mechanism 5. The photocurrent detection component 5-2 is installed outside the vacuum mechanism 2 near the photocurrent detection port of the testing mechanism 5. The synchrotron radiation beam monitoring component 5-3 is installed inside the vacuum mechanism 2 near the synchrotron radiation beam monitoring port of the testing mechanism 5.

[0072] Obviously, based on the above, the photoelectron detection component 5-1 can detect the photoelectron signal generated after the sample is irradiated by the synchrotron radiation beam, analyze the kinetic energy of the photoelectrons. The photocurrent detection component 5-2 is connected to the in-situ sample holder 1 through the test cavity 2-1. Specifically, the in-situ sample holder 1 is located on the sample rack. The electrode at the bottom of the in-situ sample holder 1 is connected to the electrode on the sample rack, and the electrode on the sample rack is connected to the photocurrent detection component 5-2. When the sample is irradiated by light, electrons will be lost, and this process can be detected and quantified by the photocurrent detection component 5-2, and the photocurrent signal generated after the sample is irradiated by the synchrotron radiation beam can be detected. The synchrotron radiation beam monitoring component 5-3 is used to measure the intensity of the synchrotron radiation beam in real time, so as to calibrate the photocurrent signal detected by the photocurrent detection component 5-2.

[0073] In this embodiment, the energy range detected by the photoelectron detection component 5-1 is 12.5 - 3000 eV; the current range detected by the photocurrent detection component 5-2 is 10 -4 to 10 -16 A.

[0074] In this embodiment, the synchrotron radiation beam monitoring component 5-3 includes a vacuum electrode, a microammeter, a gold mesh, and a linear driver for driving the gold mesh to move to the optical path of the synchrotron radiation beam. The gold mesh is installed at a position close to the synchrotron radiation beam monitoring port of the test mechanism 5. The displacement end of the linear driver is connected to the gold mesh, one end of the vacuum electrode is connected to the gold mesh, and the other end of the vacuum electrode is connected to the microammeter through a wire.

[0075] Obviously, based on the above, when the gold mesh is irradiated by the synchrotron radiation beam, electron escape will occur, and its intensity is positively correlated with the intensity of the synchrotron radiation beam. By using the microammeter to detect the current loss of the gold mesh, the intensity of the synchrotron radiation beam can be judged.

[0076] Specifically, in this application, the microammeter is manufactured by KEITHLEY, model: 6517A;

[0077] The gold mesh is manufactured by Precisionefor ming, model: MG49 117.6LPI Au Mesh 11”x11”;

[0078] The linear driver is manufactured by Femto, model: LTM35L200M.

[0079] In this embodiment, a first sample transfer rod 2-4 is installed in the rapid injection cavity 2-3. The connection between the rapid injection cavity 2-3 and the transfer cavity 2-2 and the connection between the high-temperature and high-pressure reaction mechanism 4 and the transfer cavity 2-2 are both on the straight line in the conveying direction of the first sample transfer rod 2-4. The first sample transfer rod 2-4 is used to transfer the sample 7 into the high-temperature and high-pressure reaction mechanism 4 and transfer the sample 7 from the high-temperature and high-pressure reaction mechanism 4 into the transfer cavity 2-2. A second sample transfer rod 2-5 for transferring the sample 7 from the transfer cavity 2-2 into the test cavity 2-1 is installed in the transfer cavity 2-2.

[0080] Obviously, based on the above, the setting of the sample transfer rod can realize the rapid transfer of the sample on the in-situ reaction support 1 to the target position.

[0081] As another embodiment of the present application, this embodiment proposes a control system, which includes any one of the above-mentioned in-situ high-temperature and high-pressure reaction mechanism and soft X-ray spectroscopy combined system, and further includes a data acquisition and control unit 6;

[0082] The data acquisition and control unit 6 is respectively connected to the monochromator mechanism 3 and the test mechanism 5;

[0083] The data acquisition and control unit 6 is used to control the monochromator mechanism 3 to perform energy scanning, and is used to control the signals collected by the test mechanism 5 to generate synchrotron radiation photoelectron spectroscopy or soft X-ray absorption spectroscopy results.

[0084] To more clearly illustrate the solutions and effects of this embodiment, the following is an example in combination with the accompanying drawings:

[0085] First, vent the rapid injection chamber 2-3. Subsequently, place the in-situ reaction carrier loaded with the sample on the sample clamp in the rapid injection chamber 2-3, and start vacuum pumping. When the vacuum condition meets the requirements, use the first sample transfer rod 2-4 to transfer the in-situ reaction carrier 1 to the high-temperature and high-pressure reaction mechanism 4. Then, use a torque wrench to rotate the upper cover 4-2-1 to clamp the in-situ reaction carrier 1 between the upper cover 4-2-1 and the lower cover 4-2-2, forming an internal sealed environment. Open the gas cylinder 4-1-1, the flowmeter 4-1-2, and the inlet ball valve 4-1-4, and close the outlet ball valve 4-1-5. When the internal environment pressure meets the reaction requirements, close the inlet ball valve 4-1-4, the flowmeter 4-1-2, and the gas cylinder 4-1-1. Use the control circuit 4-3 to control the temperature of the in-situ reaction carrier 1 until the temperature condition meets the reaction requirements. When the reaction time is reached, open the dry pump 4-1-9 and the corresponding valves, pump for a period of time, then open the molecular pump 4-1-6 and its valve. When the gas in the high-pressure gas storage pipe 4-1-3 is pumped out, open the inlet ball valve 4-1-4 and the outlet ball valve 4-1-5, and pump for another period of time. Then, use a torque wrench to rotate the upper cover 4-2-1 and continue vacuum pumping. When the vacuum meets the sample transfer condition, use the first sample transfer rod 2-4 to transfer the in-situ reaction carrier 1 to the transfer chamber, and then use the second sample transfer rod 2-5 to transfer the in-situ reaction carrier 1 to the test chamber for testing.

[0086] More specifically, referring to Figure 5 and Figure 6 , the sample to be tested is zinc oxide, the vacuum degree of the test chamber is 4×10 -9 mbar, the gas cylinder is high-purity carbon monoxide gas with a purity of 99.999%, the flow rate of the flowmeter is 50 ml / min, the reaction pressure is 1 bar, the in-situ reaction temperature is 20 °C, the reaction time is 1 hour, Figure 5 is the in-situ synchrotron radiation photoelectron spectrum of C 1s of the zinc oxide sample obtained under the conditions of this embodiment, Figure 6 is the in-situ soft X-ray absorption spectrum of O-K-edge of the zinc oxide sample obtained under the conditions of this embodiment, which proves that the in-situ high-temperature and high-pressure reaction device and the soft X-ray spectroscopy combined system work normally.

Claims

1. An in-situ high-temperature and high-pressure reaction mechanism and soft X-ray spectroscopy combined system, characterized in that Comprising: In-situ reaction holder (1): for placing the sample (7); Vacuum mechanism (2): for achieving a vacuum environment; Monochromator mechanism (3): for adjusting the light emitted by the light source and used to provide the target synchrotron radiation beam; High-temperature and high-pressure reaction mechanism (4): for performing in-situ high-temperature and high-pressure reaction treatment on the sample (7); Testing mechanism (5): for measuring the photoelectron signal, photocurrent signal generated after the sample (7) is irradiated by the synchrotron radiation beam, and the intensity of the synchrotron radiation beam; A test cavity (2-1), a transfer cavity (2-2), a rapid sampling cavity (2-3), and a monochromator cavity (2-6) for installing the monochromator mechanism (3) are provided inside the vacuum mechanism (2). The transfer cavity (2-2) is respectively connected to the test cavity (2-1), the rapid sampling cavity (2-3), and the high-temperature and high-pressure reaction mechanism (4). The synchrotron radiation beam outlet of the monochromator cavity (2-6) is connected to the synchrotron radiation beam inlet of the test cavity (2-1). A synchrotron radiation beam monitoring port of the testing mechanism (5) is provided on the synchrotron radiation beam path connecting the monochromator cavity (2-6) and the test cavity (2-1). A photoelectron detection port of the testing mechanism (5) for detecting the photoelectron signal is provided inside the test cavity (2-1). A photocurrent detection port of the testing mechanism (5) for detecting the photocurrent signal is provided outside the vacuum mechanism (2).

2. The in-situ high-temperature and high-pressure reaction mechanism and soft X-ray spectroscopy combined system according to claim 1, wherein: A grating and a flat mirror that rotates around a fixed point to ensure the fixed position of the light spot emitted through the grating are installed inside the monochromator mechanism (3).

3. The in-situ high-temperature and high-pressure reaction mechanism and soft X-ray spectroscopy combined system according to claim 1, characterized in that: The high-temperature and high-pressure reaction mechanism includes an external gas path and a reaction assembly. The reaction assembly includes a housing with a vacuum cavity inside, and an upper cover (4-2-1) and a lower cover (4-2-2) that are respectively rotatably installed at the upper and lower ends of the housing. When the upper cover (4-2-1) and the lower cover (4-2-2) are rotated to a preset position, a sealed space can be formed and the in-situ reaction holder (1) can be clamped and fixed. The upper cover (4-2-1) is provided with a gas communication port for connecting to the external gas path. An electrode contact is installed on one side of the lower cover (4-2-2) close to the reaction cavity. A resistance wire for heating the sample (7) and a thermocouple for monitoring the temperature are provided inside the in-situ reaction holder (1). Electrodes respectively electrically connected to the resistance wire and the thermocouple are provided outside the in-situ reaction holder (1). When the lower cover (4-2-2) clamps and fixes the in-situ reaction holder (1), the electrodes are connected to the corresponding electrode contacts, and the electrode contacts are externally connected to a control circuit (4-3) for driving the heating power of the resistance wire.

4. An in-situ high-temperature and high-pressure reaction mechanism and soft X-ray spectroscopy combined system according to claim 3, characterized in that: The external gas path includes a gas cylinder (4-1-1) and a high-pressure gas storage pipe (4-1-3). The gas cylinder (4-1-1) is connected to the inlet of the high-pressure gas storage pipe (4-1-3) through a flow meter (4-1-2). The outlet of the high-pressure gas storage pipe (4-1-3) is connected to the gas communication port of the upper cover (4-2-1) through an inlet ball valve (4-1-4).

5. An in-situ high-temperature and high-pressure reaction mechanism and soft X-ray spectroscopy combined system according to claim 4, characterized in that: A pressure relief valve (4-1-8) for restricting the internal pressure of the reaction cavity from exceeding a preset value is installed on the outer shell.

6. An in-situ high-temperature and high-pressure reaction mechanism and soft X-ray spectroscopy combined system according to claim 3, characterized in that: The high-temperature and high-pressure reaction mechanism further includes a vacuum pumping circuit. A vacuum pumping port is provided on the outer shell, and the vacuum pumping port is respectively connected to a molecular pump (4-1-6) and a dry pump (4-1-9) through a vacuum gauge (4-1-7) and an outlet balloon valve (4-1-5) in sequence.

7. An in-situ high-temperature and high-pressure reaction mechanism and soft X-ray spectroscopy combined system according to claim 1, characterized in that: The testing mechanism (5) includes a photoelectron detection component (5-1), a photocurrent detection component (5-2), and a synchrotron radiation beam monitoring component (5-3). The photoelectron detection component (5-1) is installed inside the testing cavity (2-1) near the photoelectron detection port of the testing mechanism (5). The photocurrent detection component (5-2) is installed outside the vacuum mechanism (2) near the photocurrent detection port of the testing mechanism (5). The synchrotron radiation beam monitoring component (5-3) is installed inside the vacuum mechanism (2) near the synchrotron radiation beam monitoring port of the testing mechanism (5).

8. An in-situ high-temperature and high-pressure reaction mechanism and soft X-ray spectroscopy combined system according to claim 7, characterized in that: The synchrotron radiation beam monitoring component (5-3) includes a vacuum electrode, a microammeter, a gold mesh, and a linear driver for driving the gold mesh to move to the synchrotron radiation beam optical path. The gold mesh is installed near the synchrotron radiation beam monitoring port of the testing mechanism (5). The driving displacement end of the linear driver is connected to the gold mesh. One end of the vacuum electrode is connected to the gold mesh, and the other end of the vacuum electrode is connected to the microammeter through a wire.

9. An in-situ high-temperature and high-pressure reaction mechanism and soft X-ray spectroscopy combined system according to claim 1, characterized in that: A first sample transfer rod (2-4) is installed in the rapid sampling cavity (2-3). The connection between the rapid sampling cavity (2-3) and the transfer cavity (2-2) and the connection between the high-temperature and high-pressure reaction mechanism (4) and the transfer cavity (2-2) are both on the straight line in the conveying direction of the first sample transfer rod (2-4). The first sample transfer rod (2-4) is used to transfer the sample (7) into the high-temperature and high-pressure reaction mechanism (4) and transfer the sample (7) from the high-temperature and high-pressure reaction mechanism (4) into the transfer cavity (2-2). A second sample transfer rod (2-5) for transferring the sample (7) from the transfer cavity (2-2) into the testing cavity (2-1) is installed in the transfer cavity (2-2).

10. A control system, characterized in that: An in-situ high-temperature and high-pressure reaction mechanism and soft X-ray spectroscopy combined system comprising the one described in any one of claims 1-9 further includes a data acquisition and control unit (6); The data acquisition and control unit (6) is respectively connected to the monochromator mechanism (3) and the testing mechanism (5); The data acquisition and control unit (6) is used to control the monochromator mechanism (3) to perform energy scanning, and is used to control the signals collected by the testing mechanism (5) to generate soft X-ray absorption spectra or synchrotron radiation photoelectron energy spectra.

Images