Film nozzle for free electron laser spectroscopy experiment and liquid sample environment system for hard X-ray spectroscopy

Abstract

The invention provides a film nozzle for a free electron laser spectroscopy experiment and a liquid sample environment system for hard X-ray spectroscopy, and relates to the technical field of sample environments of free electron laser experiment stations. The film nozzle provided by the invention comprises a first-stage nozzle and a second-stage nozzle which is nested in the first-stage nozzle and is detachably connected with the first-stage nozzle; a reducing channel and a spraying channel which are gradually closed up but not closed up in the flowing direction of liquid flow are sequentially arranged in the second-stage nozzle, and the cross sectional area of a liquid outlet of the spraying channel is 0.05 mm2 to 0.005 mm2. Through the arrangement, the thin film nozzle can generate a flat ultrathin liquid film of which the liquid flow thickness is less than 20 microns and the influence on the time resolution is less than 66fs, so that the strict requirement of a hard X-ray spectroscopy experiment on the thickness of a liquid sample can be met, and the precision of the time-resolved hard X-ray spectroscopy experiment is greatly improved.

Description

Technical Field

[0001] The invention relates to the technical field of sample environment of a free electron laser experimental station, in particular to a film nozzle for free electron laser spectroscopy experiments and a liquid sample environment system for hard X-ray spectroscopy. Background Art

[0002] Hard X-ray free electron laser devices are powerful tools for studying chemistry, biology, physics and materials science. Especially in the field of hard X-ray spectroscopy, they provide a powerful means for in-depth exploration of dynamic or static chemical and biological processes in solutions. In hard X-ray spectroscopy experiments, there are strict requirements on the thickness of liquid samples. The thickness of liquid samples needs to be controlled in the range of several microns to tens of microns to ensure that the experimental results are not affected by being too thick or too thin. In particular, the influence of liquid sample thickness is particularly significant for the time resolution of ultrafast spectroscopy reactions. However, the existing methods for producing flat ultra-thin liquid films have many shortcomings. For example, the method of colliding two liquid streams is difficult to align the liquid streams and the operation is cumbersome; while the liquid stream size generated by gas focusing and compressing the liquid stream is usually at the submicron scale, and the signal generated for hard X-ray spectroscopy is weak. In order to meet the needs of sample renewal in high-repetition-rate free electron laser spectroscopy experiments, the flow rate of liquid samples is usually required to be >10m / s, so the sample consumption is huge, and there is an urgent need for sample reuse.

[0003] In summary, there is an urgent need for a nozzle that can produce ultra-thin liquid films for free electron laser spectroscopy experiments. Summary of the invention

[0004] In order to solve the above problems, the first aspect of the present invention provides a thin film nozzle for free electron laser spectroscopy experiments, which can produce a flat ultra-thin liquid film with a liquid flow thickness of less than 20 μm and an impact on the time resolution of less than 66 fs.

[0005] The film nozzle provided in the first aspect of the present invention comprises a first-stage nozzle and a second-stage nozzle nested in the first-stage nozzle and detachably connected thereto; the second-stage nozzle is provided with a variable diameter channel and an injection channel which gradually converge but do not close along the flow direction of the liquid flow, and the cross-sectional area of ​​the liquid outlet of the injection channel is 0.05mm 2 ~0.005mm 2 .

[0006] In some feasible embodiments, the thickness of the ultra-thin liquid film sprayed from the thin film nozzle is less than 20 mm, and the impact of the ultra-thin liquid film on the time resolution is less than 66 fs; and / or, the flow rate of the thin film nozzle is 10 to 100 m / s, and the thin film nozzle can match the repetition frequency of 1 MHz free electron laser pulses.

[0007] In a feasible embodiment, the first-stage nozzle is provided with a liquid channel and a second-stage nozzle channel which are sequentially connected along the flow direction of the liquid flow; the second-stage nozzle can be arranged in the second-stage nozzle channel, and part of the second-stage nozzle is located outside the second-stage nozzle channel.

[0008] In some feasible embodiments, the second-stage nozzle channel gradually converges along the flow direction of the liquid flow, and the radius of the liquid outlet of the second-stage nozzle channel is 0.6-1.0 mm; and / or, the second-stage nozzle gradually converges along the flow direction of the liquid flow, and the radius of the second nozzle at one end inside the second-stage nozzle channel is 0.8 mm to 1.2 mm, and the radius of the second nozzle at one end outside the second-stage nozzle channel is 0.4 mm to 0.8 mm.

[0009] In a feasible implementation, the variable diameter channel includes a first-stage variable diameter channel and a second-stage variable diameter channel which are sequentially connected along the flow direction of the liquid flow, and the contraction rate of the first-stage variable diameter channel is smaller than the contraction rate of the second-stage variable diameter channel.

[0010] In some feasible embodiments, the cross-sectional shape of the injection channel is rectangular; the length of the injection channel is 0.3-0.8 mm, the width is 0.1 mm-0.01 mm, and the height is 0.05-0.2 mm; and / or, the cross-sectional shape at the liquid inlet of the first-stage variable diameter channel is rectangular, the length is 0.3-0.8 mm, and the width is 0.2-0.6 mm; and / or, the cross-sectional shape at the liquid outlet of the first-stage variable diameter channel is rectangular, the length is 0.3-0.8 mm, and the width is 0.1~0.3mm; and / or, the height of the first-stage variable diameter channel is 2.2~3.2mm; and / or, the cross-sectional shape of the liquid inlet of the second-stage variable diameter channel is rectangular, the length is 0.3~0.8mm, and the width is 0.1~0.3mm; and / or, the cross-sectional shape of the liquid outlet of the second-stage variable diameter channel is rectangular, the length is 0.3~0.8mm, and the width is 0.1mm~0.01mm; and / or, the height of the second-stage variable diameter channel is 0.1~0.25mm.

[0011] The second aspect of the present invention provides a liquid sample environment system for hard X-ray spectroscopy, comprising a sample solution storage bottle, a valve body and a liquid flow detection mechanism that are connected in sequence to form a loop; the liquid flow detection mechanism comprises a helium cavity, in which a sample transfer rod connected to the valve body, a thin film nozzle for free electron laser spectroscopy experiments as described in the first aspect of the present invention, and a liquid flow collector connected to the liquid storage bottle are sequentially arranged; the system also comprises a free electron laser light source and a spectrometer, wherein the free electron laser emitted by the free electron laser light source vertically passes through the liquid flow sheet ejected from the thin film nozzle and irradiates onto the spectrometer.

[0012] In a feasible embodiment, it also includes a water solution storage bottle for storing water solution, the sample solution storage bottle and the water solution storage bottle are connected to the valve body through different pump bodies and pipelines respectively, and the liquid flow collector is connected to the sample solution storage bottle through the pump body and the pipeline.

[0013] In a feasible implementation manner, the sample transfer rod is further provided with a posture adjustment mechanism for fine-tuning the relative position of the sample transfer rod.

[0014] The third aspect of the present invention provides a method for using the liquid sample environment system for hard X-ray spectroscopy according to the second aspect of the present invention, characterized in that it comprises at least the following steps:

[0015] Step 1) Place the second stage nozzle into the first stage nozzle in a nested manner, and apply a coating seal at the connection gap between the first stage nozzle and the second stage nozzle;

[0016] Step 2) fixing the film nozzle assembled in step 1) on the sample transfer rod;

[0017] Step 3) the sample solution in the liquid storage bottle enters the valve body through the pump body and the pipeline, and then enters the thin film nozzle through the valve body, and the liquid flow is ejected from the liquid outlet of the injection channel to form a flat ultra-thin liquid film;

[0018] Step 4) the free electron laser pulse vertically passes through the ultra-thin liquid film, and the signal generated by the interaction between the free electron laser pulse and the ultra-thin liquid film is detected and collected by the spectrometer;

[0019] Step 5) The ultra-thin liquid film is captured by the liquid flow collector and then enters the sample solution storage bottle through the pump body and pipeline.

[0020] The thin film nozzle for free electron laser spectroscopy experiments and the liquid sample environment system for hard X-ray spectroscopy provided by the present invention have the following beneficial effects:

[0021] 1) The thin film nozzle for free electron laser spectroscopy experiment provided by the present invention comprises a first-stage nozzle and a second-stage nozzle nested in the first-stage nozzle and detachably connected thereto. The second-stage nozzle is provided with a variable diameter channel and an injection channel which gradually converge along the flow direction of the liquid flow but do not close. The cross-sectional area of ​​the liquid outlet of the injection channel is 0.05mm 2 ~0.005mm 2 Through the above settings, the film nozzle can produce a flat ultra-thin liquid film with a liquid flow thickness of less than 20 μm and an impact on the time resolution of less than 66 fs, which can meet the strict requirements of hard X-ray spectroscopy experiments on the thickness of liquid samples and greatly improve the accuracy of time-resolved hard X-ray spectroscopy experiments.

[0022] 2) In the thin film nozzle for free electron laser spectroscopy experiments provided by the present invention, the variable diameter channel includes a first-stage variable diameter channel and a second-stage variable diameter channel that are sequentially connected along the flow direction of the liquid flow, and the convergence rate of the first-stage variable diameter channel is less than the convergence rate of the second-stage variable diameter channel. Through the above arrangement, the flow rate of the thin film nozzle can reach 10 to 100 m / s, which can match the maximum repetition frequency of the free electron laser pulse of 1 MHz, ensuring high-speed liquid sample transmission.

[0023] 3) In the thin film nozzle for free electron laser spectroscopy experiments provided by the present invention, the thin film nozzle design can be assembled and sealed in a nested manner, and the first-stage nozzle and the second-stage nozzle use 3D printing technology with different precisions, which can ensure the accuracy and quality of the thin film nozzle in the free electron laser spectroscopy experiment.

[0024] 4) In the liquid sample environment system for hard X-ray spectroscopy provided by the present invention, two sets of high-pressure infusion pumps and six-way valves are used to realize convenient sample delivery and switching, which can realize the repeated use of sample solutions, and has efficient liquid flow transmission and regulation functions, which is convenient for replacing sample solutions and cleaning pipeline nozzles. At the same time, the sample trap and peristaltic pump cooperate to circulate the sample solution, reduce sample waste and reduce costs.

[0025] 5) In the liquid sample environment system for hard X-ray spectroscopy provided by the present invention, the posture adjustment mechanism can realize multi-dimensional fine adjustment of the flat ultra-thin liquid film, can effectively correct the deviation of the ultra-thin liquid film, and realize alignment with the free electron laser pulse. BRIEF DESCRIPTION OF THE DRAWINGS

[0026] Figure 1 It is a schematic diagram of the structure of the film nozzle of the present invention.

[0027] Figure 2 It is a cross-sectional view of the film nozzle of the present invention.

[0028] Figure 3 It is a schematic structural diagram of the first-stage nozzle of the present invention.

[0029] Figure 4 It is a cross-sectional view of the first-stage nozzle of the present invention.

[0030] Figure 5 It is a structural schematic diagram of the second-stage nozzle of the present invention.

[0031] Figure 6 It is a bottom view of the second-stage nozzle of the present invention.

[0032] Figure 7 It is a cross-sectional view of the second-stage nozzle of the present invention.

[0033] Figure 8Schematic diagram of the liquid sample environment system for hard X-ray spectroscopy of the present invention.

[0034] Reference numerals

[0035] First stage nozzle 1

[0036] Liquid channel 11

[0037] Second stage nozzle channel 12

[0038] Second stage nozzle 2

[0039] Variable diameter channel 21

[0040] First-stage variable diameter channel 21.1

[0041] Second stage variable diameter channel 21.2

[0042] Injection channel 22

[0043] Sample solution storage bottle 31

[0044] Aqueous solution storage bottle 32

[0045] Valve body 4

[0046] Liquid flow detection mechanism 5

[0047] Helium chamber 51

[0048] Sample transfer rod 52

[0049] Liquid flow collector 53

[0050] Free electron laser source 6

[0051] Spectrometer 7

[0052] Attitude adjustment mechanism 8

[0053] Thin film nozzle 100 DETAILED DESCRIPTION

[0054] The technical solutions in the embodiments of the present invention will be described clearly and completely below in conjunction with the drawings in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments in the present invention, all other embodiments obtained by ordinary technicians in the field without creative work belong to the scope of protection of the present invention. In the description of the present invention, it should be noted that the orientation or position relationship indicated by the terms "left side", "right side", "upper side", "lower side", "above", "below" and the like is based on the orientation or position relationship shown in the drawings, which is only for the convenience of describing the present invention and simplifying the description, rather than indicating or implying that the device or element referred to must have a specific orientation, be constructed and operated in a specific orientation, and therefore cannot be understood as a limitation on the present invention. In addition, the terms "first" and "second" are used for descriptive purposes only and cannot be understood as indicating or implying relative importance.

[0055] In the description of the present invention, it should be noted that, unless otherwise clearly specified and limited, the terms "installed", "connected", and "connected" should be understood in a broad sense, for example, it can be a fixed connection, a detachable connection, or an integral connection; it can be a mechanical connection or an electrical connection; it can be a direct connection, or it can be indirectly connected through an intermediate medium, or it can be the internal communication of two components. For ordinary technicians in this field, the specific meanings of the above terms in the present invention can be understood according to specific circumstances.

[0056] Furthermore, in the description of the present invention, unless otherwise specified, “plurality” means two or more.

[0057] The present invention provides a thin film nozzle for free electron laser spectroscopy experiments, see Figure 1 , Figure 2 and Figure 7 The film nozzle 100 comprises a first-stage nozzle 1 and a second-stage nozzle 2 which is nested in the first-stage nozzle 1 and detachably connected thereto; the second-stage nozzle 2 is provided with a variable diameter channel 21 and an injection channel 22 which gradually converge along the flow direction of the liquid flow but do not close, and the cross-sectional area of ​​the liquid outlet of the injection channel 22 is 0.05 mm 2 ~0.005mm 2. Through the above settings, the thin film nozzle can produce a flat ultra-thin liquid film with a liquid flow thickness of less than 20μm and an impact on the time resolution of less than 66fs, which can meet the strict requirements of hard X-ray spectroscopy experiments on the thickness of liquid samples and greatly improve the accuracy of time-resolved hard X-ray spectroscopy experiments. As a supplementary explanation, the first-stage nozzle 1 and the second-stage nozzle 2 are made using 3D printing technology, and the printing materials of the first-stage nozzle 1 and the second-stage nozzle 2 are independently selected from resin or metal. The printing material of the first-stage nozzle 1 is preferably resin, and the printing material of the second-stage nozzle 2 is preferably metal; the printing accuracy of the first-stage nozzle 1 and the second-stage nozzle 2 is 5 to 10μm, preferably 5μm. Through the above settings, the accuracy and quality of the thin film nozzle in the free electron laser spectroscopy experiment can be ensured.

[0058] In the thin film nozzle for free electron laser spectroscopy experiment provided by the present invention, refer to Figure 1 and Figure 2 The first-stage nozzle 1 is provided with a liquid channel 11 and a second-stage nozzle channel 12 which are sequentially connected along the flow direction of the liquid flow; the second-stage nozzle 2 can be arranged in the second-stage nozzle channel 12, and part of the second-stage nozzle 2 is located outside the second-stage nozzle channel 12. As an illustration, the second-stage nozzle 2 and the second-stage nozzle channel 12 are usually sealed by coating.

[0059] In the thin film nozzle for free electron laser spectroscopy experiment provided by the present invention, refer to Figure 5 to Figure 7 , the cross-sectional shape of the injection channel 22 is a rectangle, and there is no gradient change in the size of the rectangle in the length direction of the injection channel 22. The length of the injection channel 22 is 0.3-0.8mm, preferably 0.5mm, the width is 0.1mm-0.01mm, preferably 0.01mm, and the height is 0.05-0.2mm, preferably 0.05mm. The second-stage nozzle channel 12 gradually converges along the flow direction of the liquid flow, and the radius of the liquid outlet of the second-stage nozzle channel 12 is 0.6-1.0mm, preferably 0.8mm. The second-stage nozzle 2 gradually converges along the flow direction of the liquid flow, and the radius of the second nozzle at one end inside the second-stage nozzle channel 12 is 0.8mm-1.2mm, preferably 1mm; the radius of the second nozzle at one end outside the second-stage nozzle channel 12 is 0.4mm-0.8mm, preferably 0.6mm.

[0060] As an illustration, the second nozzle and the second nozzle channel can be connected by snap-fitting. When inserting the second-stage nozzle 2, first insert the second-stage nozzle 2 from the liquid inlet of the first-stage nozzle 1. Because the radius of one end of the second-stage nozzle 2 located inside the second-stage nozzle channel 12 is larger than the radius at the liquid outlet of the second-stage nozzle channel 12, it can be ensured that the second-stage nozzle 2 will not completely fall out of the second-stage nozzle channel 12. The part larger than the radius at the liquid outlet of the second-stage nozzle channel 12 will be located inside the second-stage nozzle channel 12, and the part smaller than the radius at the liquid outlet of the second-stage nozzle channel 12 will be located outside the second-stage nozzle channel 12.

[0061] In the thin film nozzle for free electron laser spectroscopy experiment provided by the present invention, refer to Figure 7 The variable diameter channel 21 includes a first-stage variable diameter channel 21.1 and a second-stage variable diameter channel 21.2 which are connected in sequence along the flow direction of the liquid flow. The convergence rate of the first-stage variable diameter channel 21.1 is less than that of the second-stage variable diameter channel 21.2. The so-called convergence rate can be understood as the degree of inclination. That is, the degree of inclination of the first-stage variable diameter channel 21.1 is less than that of the second-stage variable diameter channel 21.2. As an illustration, the first-stage variable diameter channel 21.1 and the second-stage variable diameter channel 21.2 are gradually converged along the flow direction of the liquid flow, but the shape of the cross section is always kept as a rectangle. The maximum cross section of the first-stage variable diameter channel 21.1 and the second-stage variable diameter channel 21.2 is at the liquid inlet, and the minimum cross section is at the liquid outlet. The length of the first-stage variable diameter channel 21.1 at the liquid inlet is 0.3-0.8mm, preferably 0.5mm, the width is 0.2-0.6mm, preferably 0.4mm, and the height is 2.2-3.2mm, preferably 2.7mm; the length of the first-stage variable diameter channel 21.1 at the liquid outlet is 0.3-0.8mm, preferably 0.5mm, the width is 0.1-0.3mm, preferably 0.2mm. The length of the second-stage variable diameter channel 21.2 at the liquid inlet is 0.3-0.8mm, preferably 0.5mm, the width is 0.1-0.3mm, preferably 0.2mm; the length of the second-stage variable diameter channel 21.2 at the liquid outlet is 0.3-0.8mm, preferably 0.5mm, the width is 0.1-0.01mm, preferably 0.01mm, and the height is 0.1-0.25mm, preferably 0.1mm. Through the above settings, the flow rate of the film nozzle can reach 10 to 100 m / s, which can match the maximum repetition frequency of the free electron laser pulse of 1 MHz, ensuring high-speed liquid sample transmission.

[0062] Embodiment 2

[0063] The present invention also provides a liquid sample environment system for hard X-ray spectroscopy, see Figure 8, including a sample solution storage bottle 31, a valve body 4 and a liquid flow detection mechanism 5 which are connected in sequence to form a loop. The liquid flow detection mechanism 5 includes a helium cavity 51, in which a sample transfer rod 52 connected to the valve body 4, a thin film nozzle for free electron laser spectroscopy experiment as described in Example 1 and a liquid flow collector 53 are sequentially arranged; the liquid flow collector 53 is connected to the sample solution storage bottle 31 through a pump body and a pipeline. The liquid sample environment system also includes a free electron laser light source 6 and a spectrometer 7, and the free electron laser emitted by the free electron laser light source 6 vertically passes through the liquid flow sheet ejected from the thin film nozzle and irradiates the spectrometer 7. In addition, the sample solution storage bottle 31 and the valve body 4 are connected through a pipeline and a pump body, and the pump body between the sample solution storage bottle 31 and the valve body 4 is preferably a high-pressure infusion pump, the valve body 4 is preferably a six-way valve, and the pipeline between the sample solution storage bottle 31 and the valve body 4 is preferably a 1 / 16 metal pipeline. The pump body between the liquid flow trap 53 and the sample solution storage bottle 31 is preferably a peristaltic pump, and the pipeline between the liquid flow trap 53 and the sample solution storage bottle 3 is preferably a 1 / 16 metal pipeline. The liquid inlet end of the thin film nozzle is usually also equipped with a Luer adapter (external Luer to 10-32 internal PEEK) assembly, and the 10-32 threaded connector is connected to the valve body 4 through a 1 / 16 peek pipeline.

[0064] In the liquid sample environment system for hard X-ray spectroscopy provided by the present invention, refer to Figure 8 , and also includes a water solution storage bottle 32 for storing water solution; the sample solution storage bottle 31 and the water solution storage bottle 32 are connected to the valve body 4 through different pump bodies and pipelines, respectively, and the liquid flow collector 53 is connected to the sample solution storage bottle 31 through a pump body and a pipeline.

[0065] In the liquid sample environment system for hard X-ray spectroscopy provided by the present invention, refer to Figure 1 The sample transfer rod 52 is also provided with a posture adjustment mechanism 8 for fine-tuning the relative position of the sample transfer rod 52. As an illustration, the posture adjustment mechanism 8 can drive the sample transfer rod 52 to move in the XYZ three-dimensional directions and drive the sample transfer rod 52 to rotate around its own axial direction. The posture adjustment mechanism 8 can adopt a FERROVAC XYZ Boomerax Manipulator.

[0066] The present invention also provides a method for using a liquid sample environment system for hard X-ray spectroscopy, characterized in that the method comprises at least the following steps:

[0067] Step 1) Place the second-stage nozzle 2 into the first-stage nozzle 1 in a nested manner, and apply a coating seal at the joint gap between the first-stage nozzle 1 and the second-stage nozzle 2; Place the second-stage nozzle 2 into the second-stage nozzle channel 12, and the portion of the second-stage nozzle 2 containing the liquid outlet is located outside the second-stage nozzle channel 12, and the portion of the second-stage nozzle 2 containing the liquid inlet is located inside the second-stage nozzle channel 12;

[0068] Step 2) Fix the film nozzle 100 assembled in step 1) on the sample transfer rod 52; the sample transfer rod 52 is fixed on the posture adjustment structure, and the posture adjustment mechanism 8 can drive the sample transfer rod 52 to move in the XYZ three-dimensional direction and drive the sample transfer rod 52 to rotate around its own axial direction;

[0069] Step 3) the sample solution in the liquid storage bottle 3 enters the valve body 4 through the pump body and the pipeline, and then enters the thin film nozzle through the valve body 4, and the liquid flow is ejected from the liquid outlet of the injection channel 22 to form a flat ultra-thin liquid film;

[0070] Step 4) The free electron laser pulse passes through the ultra-thin liquid film vertically, and the signal generated by the interaction between the free electron laser pulse and the ultra-thin liquid film is detected and collected by the spectrometer 7; at this time, the attitude adjustment mechanism 8 can be controlled to keep the free electron laser pulse and the ultra-thin liquid film vertical;

[0071] Step 5) The ultra-thin liquid film is captured by the liquid flow collector 53, and then enters the sample solution outlet bottle 31 through the pump body and the pipeline; then, the valve body 4 is controlled and the pipeline is switched to the aqueous solution storage bottle 32, and the aqueous solution passes through the part passed in the above steps again, and the part it passes is rinsed for the next experiment.

[0072] The above is only a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and substitutions can be made without departing from the technical principles of the present invention. These improvements and substitutions should also be regarded as the scope of protection of the present invention.

Claims

1. A thin film nozzle for free electron laser spectroscopy experiments, characterized in that: The film nozzle (100) comprises a first-stage nozzle (1) and a second-stage nozzle (2) nested in the first-stage nozzle (1) and detachably connected thereto; The second-stage nozzle (2) is provided with a variable diameter channel (21) and an injection channel (22) which gradually converge but do not close along the flow direction of the liquid flow, and the cross-sectional area of ​​the injection channel (22) at the liquid outlet is 0.05 mm 2 ~0.005mm 2 .

2. The thin film nozzle for free electron laser spectroscopy experiment according to claim 1, characterized in that: The thickness of the ultra-thin liquid film sprayed by the thin film nozzle (100) is less than 20 mm, and the influence of the ultra-thin liquid film on the time resolution is less than 66 fs; And / or, the flow rate of the thin film nozzle (100) is 10 to 100 m / s, and the thin film nozzle (100) can match the repetition frequency of 1 MHz free electron laser pulses.

3. The thin film nozzle for free electron laser spectroscopy experiment according to claim 1, characterized in that: The first-stage nozzle (1) is provided with a liquid channel (11) and a second-stage nozzle channel (12) which are sequentially connected along the flow direction of the liquid flow; the second-stage nozzle (2) can be arranged in the second-stage nozzle channel (12), and part of the second-stage nozzle (2) is located outside the second-stage nozzle channel (12).

4. The thin film nozzle for free electron laser spectroscopy experiment according to claim 3, characterized in that: The second-stage nozzle channel (12) gradually converges along the flow direction of the liquid flow, and the radius of the liquid outlet of the second-stage nozzle channel (12) is 0.6 to 1.0 mm; And / or, the second-stage nozzle (2) gradually converges along the flow direction of the liquid flow, the radius of the end of the second-stage nozzle (2) located inside the second-stage nozzle channel (12) is 0.8 mm to 1.2 mm, and the radius of the end of the second-stage nozzle (2) located outside the second-stage nozzle channel (12) is 0.4 mm to 0.8 mm.

5. The thin film nozzle for free electron laser spectroscopy experiment according to claim 1, characterized in that: The variable diameter channel (21) comprises a first-stage variable diameter channel (21.1) and a second-stage variable diameter channel (21.2) which are sequentially connected along the flow direction of the liquid flow, and the contraction rate of the first-stage variable diameter channel (21.1) is smaller than the contraction rate of the second-stage variable diameter channel (21.2).

6. The thin film nozzle for free electron laser spectroscopy experiment according to claim 4, characterized in that: The cross-sectional shape of the injection channel (22) is rectangular; the length of the injection channel (22) is 0.3-0.8 mm, the width is 0.1 mm-0.01 mm, and the height is 0.05-0.2 mm; and / or, the cross-sectional shape of the liquid inlet of the first-stage variable diameter channel (21.1) is rectangular, with a length of 0.3 to 0.8 mm and a width of 0.2 to 0.6 mm; and / or, the cross-sectional shape of the liquid outlet of the first-stage variable diameter channel (21.1) is rectangular, with a length of 0.3 to 0.8 mm and a width of 0.1 to 0.3 mm; and / or, the height of the first-stage variable diameter channel (21.1) is 2.2 to 3.2 mm; And / or, the cross-sectional shape of the liquid inlet of the second-stage variable diameter channel (21.2) is rectangular, with a length of 0.3 to 0.8 mm and a width of 0.1 to 0.3 mm; and / or, the cross-sectional shape of the liquid outlet of the second-stage variable diameter channel (21.2) is rectangular, with a length of 0.3 to 0.8 mm and a width of 0.1 to 0.01 mm; and / or, the height of the second-stage variable diameter channel (21.2) is 0.1 to 0.25 mm.

7. A liquid sample environment system for hard X-ray spectroscopy, characterized in that: It comprises a sample solution storage bottle (31), a valve body (4) and a liquid flow detection mechanism (5) which are connected in sequence to form a loop; The liquid flow detection mechanism (5) comprises a helium cavity (51), in which a sample transfer rod (52) connected to the valve body (4), a thin film nozzle for free electron laser spectroscopy experiment according to any one of claims 1 to 6, and a liquid flow collector (53) connected to the sample solution storage bottle (31) are sequentially arranged; It also comprises a free electron laser light source (6) and a spectrometer (7), wherein the free electron laser emitted by the free electron laser light source (6) vertically passes through the liquid flow sheet ejected from the film nozzle and irradiates the spectrometer (7).

8. The liquid sample environment system for hard X-ray spectroscopy according to claim 7, characterized in that: It also includes a water solution storage bottle (32) for storing water solution; the sample solution storage bottle (31) and the water solution storage bottle (32) are connected to the valve body (4) through different pump bodies and pipelines, respectively, and the liquid flow collector (53) is connected to the sample solution storage bottle (31) through the pump body and the pipeline.

9. The liquid sample environment system for hard X-ray spectroscopy according to claim 7, characterized in that: The sample transfer rod (52) is also provided with a posture adjustment mechanism (8) for finely adjusting the relative position of the sample transfer rod (52).

10. A method for using the liquid sample environment system for hard X-ray spectroscopy according to claims 7 to 9, characterized in that: At least the following steps are included: Step 1) inserting the second-stage nozzle (2) into the first-stage nozzle (1) in a nested manner, and applying a coating and sealing at the connecting gap between the first-stage nozzle (1) and the second-stage nozzle (2); Step 2) fixing the film nozzle (100) assembled in step 1) on the sample transfer rod (52); Step 3) the sample solution in the liquid storage bottle (3) enters the valve body (4) through the pump body and the pipeline, and then enters the thin film nozzle through the valve body (4), and the liquid flow is ejected from the liquid outlet of the injection channel (22) to form a flat ultra-thin liquid film; Step 4) The free electron laser pulse vertically passes through the ultra-thin liquid film, and the signal generated by the interaction between the free electron laser pulse and the ultra-thin liquid film is detected and collected by the spectrometer (7); Step 5) The ultra-thin liquid film is captured by the liquid flow collector (53), and then enters the sample solution storage bottle (31) through the pump body and pipeline.

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