CN113984922B - Quasi-in-situ X-ray photoelectron spectrum testing device and testing method thereof - Google Patents
Quasi-in-situ X-ray photoelectron spectrum testing device and testing method thereof Download PDFInfo
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Abstract
The invention relates to a quasi-in-situ X-ray photoelectron spectrum testing device and a testing method thereof, wherein the testing device comprises a gas mixing system, a stop valve, a reaction tank, a gate valve, a rapid sample injection cavity, a molecular beam epitaxy Bao Mosheng long cavity, a rapid annealing cavity, a sample transition transferring cavity, a buffer cavity, a second rapid sample injection cavity and an X-ray photoelectron spectrum analysis cavity; the gas mixing system is communicated with the reaction tank through a stop valve, each cavity is matched with an independent vacuum pump set system and mutually isolated through a gate valve, all cavities in the whole device are in vacuum interconnection through a sealing channel, and a tested sample is subjected to process treatment and detection before being tested in the device. After the reaction or the gas high-temperature treatment, the sample is transferred into an X-ray photoelectron spectroscopy analysis cavity for testing under the condition of not exposing air, so that the information which is closer to the actual final state of the tested catalytic material is obtained.
Description
Technical Field
The invention relates to a detection technology, in particular to a quasi-in-situ X-ray photoelectron spectrum testing device and a testing method thereof, wherein the quasi-in-situ X-ray photoelectron spectrum testing device is in vacuum interconnection with a high-temperature reaction tank with near normal pressure to high pressure.
Background
Catalysis and surface interface chemistry are scientific bases for energy and substance conversion, play a very important role in the development of civilization of human beings and world economy, and can convert raw materials into chemical products, fuels and the like with high added values in an efficient, green and economic manner, so that the catalyst can be widely applied to various industries such as energy, chemical industry, food, medicine, electronics and the like. Therefore, regarding the essential role of catalysis, the further understanding of the interaction between the catalytic material and the reactant in the reaction process of the reagent becomes an important theory for guiding researchers to synthesize and prepare high-performance catalysts, and the X-ray photoelectron spectroscopy, as a surface analysis means, is widely applied to the research of the element composition and valence state change of the surface interface of the catalytic material in the catalytic reaction process.
X-ray photoelectron Spectrometry (X-ray photoelectron spectroscopy, XPS) irradiates a sample with X-rays such that internal electrons or valence electrons of atoms or molecules are excited to become photoelectrons, and the chemical composition of the surface of the sample, the binding energy of individual elements and the valence state are characterized by measuring the signal of the photoelectrons. XPS is a common surface analysis technology, is widely applied to characterization of surface elements and electronic structures of materials, and is especially used for research in the field of catalysis, and is one of the main methods for researching the surface composition and chemical state of catalytic materials. However, since the detection of X-rays and photoelectrons emitted by the XPS electron gun must be performed under ultra-high vacuum, the sample is in a vacuum analysis cavity during the traditional XPS test, and the dynamic change of the catalytic material under the reaction condition is more remarkable for the characterization of the catalytic material. Moreover, in the traditional XPS test process, the catalyst material is inevitably exposed to the atmosphere in the sample preparation and transmission processes, and the property of the catalyst material is likely to be changed due to the influence of the gas component in the air, so that the property of the catalyst material cannot be truly represented. This greatly limits the dynamic change study of XPS characterization technology under catalytic reaction conditions.
Disclosure of Invention
Aiming at the problem that the performance of a catalyst material is possibly changed due to exposure to the atmospheric environment in the existing sample testing process, the quasi-in-situ X-ray photoelectron spectroscopy testing device and the testing method thereof are provided.
The technical scheme of the invention is as follows: a quasi-in-situ X-ray photoelectron spectrum testing device comprises a gas mixing system, a stop valve, a reaction tank, a gate valve, a first rapid sample injection cavity, a molecular beam epitaxy Bao Mosheng long cavity, a rapid annealing cavity, a sample transition transferring cavity, a buffer cavity, a second rapid sample injection cavity and an X-ray photoelectron spectrum analysis cavity; the gas mixing system is communicated with the reaction tank through a stop valve, the cavities are matched with an independent vacuum pump system and are isolated from each other through a gate valve, the reaction tank is communicated with the first rapid sample injection cavity through the gate valve, the sample transition transfer cavity is communicated with the first rapid sample injection cavity, the molecular beam epitaxy Bao Mosheng long cavity, the rapid annealing cavity and the buffer cavity through the respective gate valves, the buffer cavity is communicated with the second rapid sample injection cavity in the X-ray photoelectron spectroscopy analysis cavity through the gate valve, the second rapid sample injection cavity is communicated with the X-ray photoelectron spectroscopy analysis cavity through a cavity door, all cavities in the whole device are vacuum-interconnected through a sealing channel, and the measured sample is processed and detected by the process before the measurement in the device.
Preferably, the sample transition transferring cavity is provided with a sample parking table capable of placing samples, the sample parking table is arranged on a rotatable and telescopic sample rod, and the samples are transferred between different cavities through the transition of the sample transition transferring cavity.
Preferably, the molecular beam epitaxy film growth chamber is one in which the model system samples required for testing are prepared by film growth.
Preferably, the rapid annealing furnace chamber is matched with a laser heating device and an infrared thermometer to carry out high-temperature annealing treatment on the sample.
Preferably, the reaction tank comprises a sample conveying system, a reaction tank reaction cavity, a sealing system, a vacuum pump system, a heating system and a gas mixing system, wherein the gas mixing system is used for preparing a gas reaction cavity required by the reaction from near normal pressure to high pressure, the vacuum pump system and the heating system are used for respectively vacuumizing and heating the reaction cavity, the sealing system comprises a sealing valve and a blind plate sealing piece, the reaction tank reaction cavity is in sealing connection with the first rapid sample conveying cavity through the sealing valve at one end, and the reaction tank reaction cavity is in sealing connection with the sample conveying system through the blind plate sealing piece at the other end.
Preferably, the reaction cavity of the reaction tank comprises a water-cooling interlayer, a heating interlayer and a reaction cavity from outside to inside, wherein the water-cooling interlayer is communicated with a water-cooling water inlet and a water-cooling water outlet, and the external water source can fill the water-cooling interlayer with cooling water to realize the cooling of the outer wall of the reaction cavity of the reaction tank; the heating interlayer is composed of heating resistance wires, surrounds the reaction chamber and realizes uniform heating of the reaction chamber; the reaction chamber for sample reaction is communicated with the reaction gas inlet pipeline and the reaction gas outlet, and the sample reacts in the reaction chamber.
Preferably, the vacuum pump system consists of a front-stage mechanical pump and a molecular pump, the reaction cavity of the reaction tank is externally connected through a stop valve, the front-stage pump realizes the vacuum from normal pressure to 10 < -2 > mbar, the vacuum degree of 10 < -9 > mbar magnitude can be realized by matching with the molecular pump, and the heating interlayer can be evacuated.
Preferably, the gas mixing system comprises a normal pressure to high pressure gas inlet distribution device and a near normal pressure gas inlet distribution device, and the gas enters the reaction tank through a normal pressure to high pressure gas inlet end and a near normal pressure gas inlet end respectively.
Preferably, the normal-pressure to high-pressure air inlet distribution device comprises a vacuum pump set, eight air paths connected with an air bottle, an aluminum profile frame, a stop valve, a stainless steel gas mixing chamber, a flowmeter, a mass spectrum, a back pressure valve and micro-chromatography; the gas connected in the gas bottle is conveyed to a gas circuit device supported by the aluminum profile frame through eight gas circuit pipelines, the switch of a required gas circuit is controlled through a stop valve on each pipeline, then the flow rate of the gas is controlled through a flowmeter on the pipeline, the gas through the flowmeter enters a stainless steel gas mixing chamber to be fully mixed, then the gas enters a reaction tank through a reaction gas inlet pipeline, and the back pressure valve at the front end of the reaction gas inlet pipeline is used for controlling the pressure of the reaction gas so as to realize the accurate control of normal pressure to high pressure reaction gas; the mass spectrum is provided with eight detection channels, reaction products under different reaction pressures are tested, and the micro-chromatography is used for quantitatively detecting gaseous substances.
Preferably, the near-normal pressure air inlet and distribution device comprises eight air paths connected with the air cylinder, an aluminum profile supporting frame, a stop valve, a micro-leakage valve and a liquid nitrogen cold trap, wherein the air paths are connected with the air cylinder, the air paths are connected to the air path device supported by the aluminum profile supporting frame through the eight air paths, the stop valve on each air path is used for controlling the opening and closing of the air paths of the required air, then the micro-leakage valve is used for controlling the pressure and the flow rate of the air in the reaction tank, the control of the gas pressure of the lowest 0.001mbar is realized, and meanwhile, the air paths are provided with the cold trap for further purifying the air.
The quasi-in-situ X-ray photoelectron spectroscopy test method comprises the following test steps:
1) The vacuum pump system is used for realizing the vacuum of the whole interconnected cavity of the quasi-in-situ X-ray photoelectron spectroscopy testing device, and the vacuum of the cavity is better than 5X10 in the whole sample transmission process -8 mbar；
2) Fixing a sample on an external sample support, stopping a molecular pump and a backing pump of a second rapid sample injection cavity, introducing inert gas to enable the air pressure of the second rapid sample injection cavity to be recovered to normal pressure, opening a cavity door connected with a buffer cavity, placing the sample in a sample storage table of the second rapid sample injection cavity under the condition of protecting the cavity by the inert gas, closing the cavity door of the second rapid sample injection cavity, starting the backing pump, and vacuumizing to 5x10 -2 Starting a molecular pump after mbar to finish sample injection operation;
3) When the air pressure of the second rapid sample injection cavity is reduced to 5 multiplied by 10 -7 Transferring a sample to an X-ray photoelectron spectroscopy analysis cavity after mbar, removing surface pollution of the sample by argon ion etching, transferring the sample among a second rapid sample injection cavity, a buffer cavity and a sample transition transfer cavity, finally transferring the sample to an annealing furnace cavity for high-temperature annealing, and then performing a reverse transfer step to the X-ray photoelectron spectroscopy analysis cavity for testing until the surface has no obvious pollutant, and performing a pre-reaction comparison test;
4) After the analysis and test of the X-ray photoelectron spectroscopy before the reaction are completed, opening a gate valve between the X-ray photoelectron spectroscopy analysis cavity and the second rapid sample injection cavity, transferring the sample to the second rapid sample injection cavity, and closing the gate valve; opening a gate valve between the second rapid sample injection cavity and the buffer cavity which are in vacuum interconnection, transferring the sample into the buffer cavity, and closing the gate valve between the sample injection cavity and the second rapid sample injection cavity; then transferring the sample to the sample transition transferring cavity, then transferring to the first rapid sample feeding cavity directly connected with the reaction tank, and finally transferring to a sample parking table of the reaction tank to finish the sample transferring operation;
5) After the sample is smoothly placed in a sample parking table in the reaction tank, closing a closed valve, sealing the reaction cavity of the reaction tank, closing a vacuum pump set of a first rapid sample injection cavity directly connected with the reaction tank, and completing sample preparation before reaction;
6) Firstly, checking the condition of gas paths one by one to ensure that the pressure of a gas cylinder is moderate, the gas paths are free from gas leakage, then cleaning the gas paths to be used, adopting a rinsing mode to perform gas charging and gas exhausting for three times to complete gas path cleaning, simultaneously cleaning a gas mixing chamber for three times, enabling gas connected in the gas cylinder to enter a gas path device supported by an aluminum profile frame through eight paths of gas paths, controlling the opening and closing of a required gas path through a stop valve, then controlling the flow rate of the gas through a flowmeter, enabling the gas through the flowmeter to enter a gas mixing chamber to perform sufficient gas mixing, then enabling the gas to enter a reaction tank through a reaction tank gas inlet pipeline, finally controlling the pressure of the reaction gas through a back pressure valve at the front end of the reaction tank gas inlet pipeline to realize accurate control of normal pressure reaction gas, performing body flow adjustment through the flowmeter, enabling the gas through the flowmeter to perform sufficient mixing in the gas mixing chamber, using the back pressure valve to perform reaction pressure regulation, and then enabling the mixed gas with corresponding pressure to enter a closed reaction tank reaction chamber to perform reaction preparation;
7) After the gas mixing operation is completed, starting an experiment, starting a connected mass spectrum and a micro-chromatograph, starting heating after a base line is stable, controlling a heating process through a temperature programming system, heating at a set heating speed and a final required temperature, and controlling the pressure and flow ratio of the reaction gas in the whole process;
8) After the reaction is finished, closing a micro mass spectrum, performing gas evacuation operation after the temperature is reduced to below 100 ℃, closing an air inlet end, directly opening a tail gas end stop valve to release pressure, then opening a forepump to pump a reaction chamber and a tail gas end, then closing the tail gas end stop valve, opening a closed valve, opening a vacuum pump set of a first rapid sample injection cavity, evacuating a reaction cavity of a reaction tank, and performing the post-reaction exhaust operation;
9) The vacuum of the first rapid sample injection cavity connected with the reaction chamber is lower than 5x10 -8 Opening a gate valve between the cavity and the sample transition transferring cavity during mbar, transferring the sample into the sample transition transferring cavity, closing the gate valve, then opening the gate valve between the buffer cavity and the sample transition transferring cavity, transferring the sample into the buffer cavity, then transferring the sample into the second rapid sample injection cavity, closing the gate valve between the second rapid sample injection cavity and the buffer cavity, then transferring the sample into the X-ray photoelectron spectroscopy analysis cavity for reaction, and then testing, wherein the vacuum of all cavities in the whole sample transferring process is less than 5X10 -8 mbar。
The invention has the beneficial effects that: the quasi-in-situ X-ray photoelectron spectrum testing device and the testing method thereof realize that a sample is transferred into the X-ray photoelectron spectrum analysis cavity for testing under the condition of not exposing air after reacting or being subjected to gas high-temperature treatment, so that information which is more close to the actual final state of the tested catalytic material can be obtained, the problem that the actual catalytic material performance cannot be reacted due to the change of the catalytic material state caused by exposing the atmosphere in the traditional XPS testing process is solved, and meanwhile, the device can also be used for testing the catalytic reaction performance of a characterization model catalyst and a powder catalyst.
Drawings
FIG. 1 is a schematic diagram of a quasi-in-situ X-ray photoelectron spectroscopy test device according to the present invention;
FIG. 2 is a schematic diagram of a high temperature reaction tank from near normal pressure to high pressure according to the present invention;
FIG. 3 is a schematic diagram of a combined device of the normal pressure to high pressure air inlet end and the high temperature reaction tank;
FIG. 4 is a schematic diagram of a near-normal pressure air inlet end-high temperature reaction tank combined device of the invention;
FIG. 5 is a graph showing the results of O1s and C1s spectra of quasi-in-situ X-ray photoelectron spectroscopy after high temperature and high pressure reaction of a flat ZnO model catalyst (Pristine-ZnO) by the method of the present invention;
FIG. 6 is a graph showing the results of O1s and C1s spectra of quasi-in-situ X-ray photoelectron spectroscopy after high temperature and high pressure reaction of a flat ZnO model catalyst (Pristine-ZnO) by the method of the present invention;
FIG. 7 is a graph showing the results of O1s and C1s spectra of a quasi-in-situ X-ray photoelectron spectroscopy test after high temperature and high pressure reaction of a treated ZnO model catalyst (Ar-ZnO) by the method of the present invention;
FIG. 8 is a graph showing the results of O1s and C1s spectra of a quasi-in-situ X-ray photoelectron spectroscopy test after high temperature and high pressure reaction of a treated ZnO model catalyst (Ar-ZnO) by the method of the present invention.
The attached drawings are identified: 1. the gas mixing system (comprising a near normal pressure gas inlet end and a normal pressure to high pressure gas inlet end); 2. a stop valve; 3. a reaction tank; 4. a gate valve; 5. a first rapid sample injection cavity; 6. a molecular beam epitaxy film growth cavity; 7. a rapid annealing chamber; 8. a sample transfer transition cavity; 9. a buffer cavity; 10. a second rapid sample injection cavity; 11. an X-ray photoelectron spectroscopy analysis cavity; 301. a magnetic sample transfer rod; 302. a tail gas discharge outlet; 303. a temperature measurement interface; 304. a water cooling water inlet; 305. a reaction chamber of the reaction tank; 306. water-cooling the interlayer; 307. heating the interlayer; 308. a reaction chamber; 309. a water-cooling water outlet; 310. a reaction gas inlet line; 311. closing the valve; 312. a reaction tank vacuum pump system; 314. an apertured blind plate seal; 103. eight gas paths communicated with the gas cylinder; 104. an aluminum profile frame; 105. a stop valve; 106. a stainless steel gas mixing chamber; 107. a flow meter; 108. mass spectrometry; 109. a vacuum pump system; 110. a pipeline four-way joint; 111. a three-way joint of the pipeline; 112. a back pressure valve; 113. micro-chromatography; 114. a reaction gas exhaust line; 115. eight gas paths communicated with the gas cylinder; 116. an aluminum profile frame; 117. a stop valve; 118. a three-way joint of the pipeline; 119. a micro-leakage valve; 120. a cold trap.
Detailed Description
The invention will now be described in detail with reference to the drawings and specific examples. The present embodiment is implemented on the premise of the technical scheme of the present invention, and a detailed implementation manner and a specific operation process are given, but the protection scope of the present invention is not limited to the following examples.
The structure diagram of the quasi-in-situ X-ray photoelectron spectrum testing device shown in fig. 1 comprises a gas mixing system 1 (comprising a near normal pressure gas inlet end and a normal pressure to high pressure gas inlet end), a stop valve 2, a reaction tank 3, a gate valve 4, a first rapid sample injection cavity 5, a molecular beam epitaxial film growth cavity 6, a rapid annealing cavity 7, a sample transition transfer cavity 8, a buffer cavity 9, a second rapid sample injection cavity 10 and an X-ray photoelectron spectrum analysis cavity 11. The gas mixing system 1 (comprising a near normal pressure inlet end and a normal pressure inlet end to a high pressure inlet end) is communicated with the reaction tank 3 through a stop valve, each cavity is matched with an independent vacuum pump set system and isolated from each other through a gate valve, the gate valve between the corresponding two cavities is opened when sample transmission requirements exist, and the corresponding gate valve is closed after sample transmission is completed; the sample generally enters through the second rapid sample injection cavity 10, then after the vacuum degree of the second rapid sample injection cavity 10 is less than 10 < -8 > mbar, a gate valve between a channel of the second rapid sample injection cavity 10 and a channel of the X-ray photoelectron spectroscopy analysis cavity 11 is opened, the sample is transferred into the X-ray photoelectron spectroscopy analysis cavity 11 with the vacuum degree being better than 10 < -9 > mbar, pre-reaction test or sample pretreatment is carried out, after the test is finished, the gate valve between the X-ray photoelectron spectroscopy analysis cavity 11 and the second rapid sample injection cavity 10 is opened, the sample is transferred to the second rapid sample injection cavity 10, then the gate valve between the two cavities is closed, the two cavities are isolated, then the gate valve between the buffer cavity 9 and the second rapid sample injection cavity 10 is opened, the sample is transferred into the buffer cavity 9, then the sample transition transfer cavity 8 is transferred through a similar sample transfer flow, then the sample is transferred into the molecular beam epitaxy film growth cavity 6 or the rapid annealing cavity 7 according to the process requirement, the sample is transferred into the sample cell 3 after the sample is transferred into the first rapid sample injection cavity 5 after the transition cavity is closed, and finally the sample is transferred into the sample cell 3. The reaction gas is mixed in the gas mixing system 1 according to the requirement and then is introduced into the reaction tank 3, the sample is sent into the first rapid sample injection cavity 5 after the high-temperature reaction in the reaction tank 3, then enters the sample transition transfer cavity 8 and enters the second rapid sample injection cavity 10 in the X-ray photoelectron spectroscopy analysis cavity 11 through the buffer cavity 9, and the reacted X-ray photoelectron spectroscopy analysis is tested. All cavities in the whole device are connected in vacuum through a sealed channel, so that the test of the sample (X-ray photoelectron spectroscopy analysis) can be realized without exposing the sample to the atmosphere after the reaction or pretreatment.
The first rapid sample injection cavity 5 and the second rapid sample injection cavity 10 are protected by inert gas, so that the cavity or the sample can be prevented from being polluted by air.
The sample transition transferring cavity 8 is provided with a sample parking table capable of placing a sample, and the sample parking table is arranged on a rotatable and telescopic sample rod, so that the transfer of the sample among different cavities can be realized through the transition of the sample transition transferring cavity 8. The molecular beam epitaxy film growth cavity 6, which is simply called MBE cavity, can realize the growth of the film so as to prepare a model system sample required by the test; the rapid annealing furnace chamber 7 is matched with a laser heating device and an infrared thermometer, so that high-temperature annealing treatment of the sample can be realized; the buffer cavity 9 is directly connected with the sample transition transfer cavity 8 and the XPS matched second rapid sample injection cavity 10, so that the transfer of the sample between the two cavities can be realized.
The device schematic diagram of the reaction tank is shown in fig. 2, and comprises a sample conveying system, a reaction cavity, a sealing system, a vacuum pump system, a heating system and a gas mixing system, wherein the whole device comprises a magnetic sample conveying rod 301, a tail gas discharging pipeline 302, a temperature measuring interface 303, a water cooling water inlet 304, a reaction cavity 305 of the reaction tank, a water cooling interlayer 306, a heating interlayer 307, a reaction cavity 308, a water cooling water outlet 309, a reaction gas inlet pipeline 310, a sealing valve 311, a reaction tank vacuum pump system 312 and an open-pore blind plate sealing member 314, wherein the reaction inlet pipeline 310 comprises a near-normal pressure inlet end and a normal pressure to high pressure inlet end; the sample transmission system comprises a magnetic sample transmission rod 301, wherein the magnetic sample transmission rod 301 is orthogonal to the magnetic sample transmission rod in the first rapid sample injection cavity 5, a square sample parking table is arranged on the magnetic sample transmission rod 301 and can be used for storing a tested sample, and meanwhile, mutual transmission is realized between all vacuum interconnection devices through the orthogonal transmission rod and a sample rod below the sample parking table; the reaction tank reaction cavity 305 is respectively sealed by a closed valve 311 at two ends and a blind plate sealing piece 314 connected with the magnetic sample transmission rod 301, vacuum is obtained by a reaction tank vacuum pump set system 312, the reaction tank reaction cavity 305 comprises a water-cooling interlayer 306, a heating interlayer 307 and a reaction chamber 308 from outside to inside, the water-cooling interlayer 306 is communicated with a water-cooling water inlet 304 and a water-cooling water outlet 309, and cooling water can be filled in the water-cooling interlayer 306 by an external water source, so that the outer wall of the reaction tank reaction cavity 305 can be cooled; the heating interlayer 307 mainly comprises heating resistance wires, surrounds the reaction chamber 308, and can realize uniform heating of the reaction chamber 308; a reaction chamber 308 for sample reaction, which communicates with the reaction gas inlet line 310 and the reaction gas outlet 302, in which the sample reacts; the reaction tank vacuum pump system 312 consists of a front-stage mechanical pump and a molecular pump, the whole reaction cavity system is externally connected through a stop valve, the front-stage pump can realize the vacuum from normal pressure to 10 < -2 > mbar, the vacuum degree of 10 < -9 > mbar magnitude can be realized by matching with the molecular pump, the heating interlayer 307 can be evacuated, and the service life of the heating resistance wire is prolonged.
The heating system consists of a heating interlayer 307 surrounding a reaction chamber 308, the interlayer is in a rough vacuum (10 < -2 > mbar) state, the heating interlayer 308 surrounds a heating resistance wire, and the heating resistance wire is heated and controlled by an external control system, so that the temperature control with the temperature difference range within 0.1 ℃ can be realized; the gas mixing system is connected to the reaction chamber 305 through a reaction gas inlet pipe 310, and comprises a gas inlet system and a gas outlet system, wherein the gas inlet system comprises a near-normal pressure gas inlet end (shown in fig. 4) and a normal pressure to high pressure gas inlet end (shown in fig. 3), and is directly communicated with the reaction chamber 308 through the reaction gas inlet pipe 310.
Referring to fig. 3, a schematic diagram of a normal pressure to high pressure air inlet end device comprises a vacuum pump set 109, eight air paths 103 connected with an air bottle, an aluminum profile frame 104, a stop valve 105, a stainless steel air mixing chamber 106, a flowmeter 107, a mass spectrum 108, a pipeline four-way joint 110, a pipeline three-way joint 111, a back pressure valve 112 and a micro chromatograph 113. The gas connected in the gas cylinder goes to the gas circuit device supported by the aluminum profile frame 104 through eight gas circuit pipelines 103, the switch of the gas circuit of the required gas is controlled through the stop valve 105 on each pipeline, then the flow rate of the gas is controlled through the flowmeter 107 on the pipeline, the gas passing through the flowmeter 107 enters the stainless steel gas mixing chamber 106 to be fully mixed, then the gas enters the reaction tank 3 through the reaction gas inlet pipeline 310, and finally the pressure of the reaction gas is controlled through the back pressure valve 112 at the front end of the reaction gas inlet pipeline to realize the accurate control of the reaction gas from normal pressure to high pressure (1 bar-10 bar). The mass spectrum 108 has eight detection channels, can detect eight different gas substances simultaneously, and has an atmospheric pressure sample injection system and a vacuum sample injection system, so that the reaction product test under different reaction pressures can be realized, and the vacuum pump system 109 is composed of a front-stage mechanical pump and a molecular pump, and can realize 10 -9 The vacuum degree of the mbar magnitude is calibrated by the micro-chromatograph 113 through standard gas, and the quantitative detection of gaseous substances such as carbon dioxide, hydrogen, carbon monoxide, methane, low-carbon alkane, low-carbon alkene and the like can be carried out.
Fig. 4 is a schematic diagram of a near-normal pressure air inlet end device, which comprises eight air channels 115 connected with an air bottle, an aluminum profile frame 116, a stop valve 117, a pipeline three-way joint 118, a micro-leakage valve 119, a liquid nitrogen cold trap 120 and a high-temperature reaction tank. The gas connected in the gas bottle is supplied to a gas circuit device supported by an aluminum profile frame 116 through eight gas circuit pipelines 115, the switch of a gas circuit of the required gas is controlled through stop valves 117 on each pipeline, then the pressure and the flow rate of the gas in the reaction tank are controlled through three micro-leakage valves 119, the control of the gas pressure of the lowest 0.001mbar can be realized, and meanwhile, the gas circuit is provided with a cold trap 120, so that the gas can be further purified.
The method for testing the quasi-in-situ X-ray photoelectron spectroscopy in vacuum interconnection with the high-temperature reaction tank from near normal pressure to high pressure comprises the following steps:
1) Setting up a quasi-in-situ photoelectron spectrum testing device which is in vacuum interconnection with a high-temperature reaction tank with near normal pressure to high pressure, realizing the vacuum of the whole interconnection cavity through a vacuum pump system, wherein the vacuum of the cavity is better than 5x10 in the whole sample transmission process - 8 mbar；
2) The sample is fixed on the magnetic sample transfer rod 301 of the reaction cell 3 (in this case flat is usedSingle crystal face), then stopping the molecular pump and the backing pump of the second rapid sample injection cavity 10, introducing argon gas to restore the air pressure to normal pressure, then opening a cavity door, placing a sample into a sample storage table of the second rapid sample injection cavity 10 under the condition of an argon gas protection cavity, then closing the cavity door, opening the backing pump, and vacuumizing to 5x10 -2 Starting a molecular pump after mbar to finish sample injection operation;
3) When the air pressure of the second rapid sample injection cavity 10 is reduced to 5 multiplied by 10 -7 After mbar, transferring a sample to an X-ray photoelectron spectroscopy analysis cavity 11, removing ZnO sample surface pollution by argon ion etching, transferring the sample among a second rapid sample introduction cavity 10, a buffer cavity 9 and a sample transition transfer cavity 8, finally transferring the sample to an annealing furnace cavity 7 for high-temperature annealing, and then performing an opposite transfer step to the X-ray photoelectron spectroscopy analysis cavity 11 for testing until no obvious pollutant exists on the surface, and performing a pre-reaction comparison test; 4) After the analysis and test of the X-ray photoelectron spectroscopy before the reaction are completed, opening a gate valve 4 between an X-ray photoelectron spectroscopy analysis cavity 11 and a second rapid sample injection cavity 10, transferring a sample to the second rapid sample injection cavity 10, and closing the gate valve; opening a gate valve between the second rapid sample injection cavity 10 and the buffer cavity 9 which is in vacuum interconnection, transferring the sample into the buffer cavity 9, and closing the gate valve between the sample injection cavity and the second rapid sample injection cavity 10; the sample is then transferred into the sample transition transfer chamber 8 and then to the sample transfer chamber The reaction tank 3 is directly connected with the first rapid sample injection cavity 5, and finally the sample is transferred to a sample parking table of the reaction tank 3 to finish ZnO sample transfer operation;
5) After the ZnO sample is smoothly placed in a sample parking platform in the reaction tank 3, closing a closed valve 311, sealing the reaction cavity 305 of the reaction tank, closing a vacuum pump set of a first rapid sample injection cavity 5 directly connected with the reaction tank 3, and completing preparation before reaction;
6) Then the gas mixing operation before reaction is carried out, firstly, the gas path conditions are checked one by one, the moderate pressure of the gas cylinder is ensured, the gas path is free from gas leakage, and then H is used for cleaning 2 And the CO gas path adopts a rinsing mode, the gas path is cleaned by inflating and exhausting three times, and the gas mixing chamber is cleaned for three times. The H2 and CO connected in the gas cylinder are delivered to the gas path device supported by the aluminum profile frame 104 through two of eight gas paths 103, the switch of the gas path of the required gas is controlled through a stop valve 105, then the flow rate of the gas is controlled through a flowmeter 107, the gas passing through the flowmeter enters a gas mixing chamber 106 to be fully mixed, then enters a reaction tank 3 through a reaction tank gas inlet pipeline 310, finally the pressure of the reaction gas is controlled through a back pressure valve 112 to realize the accurate control of the normal pressure reaction gas, and the CO and the H are carried out through the flowmeter 2 The gas flow is regulated (1:3), the gas passing through the flowmeter is fully mixed in the gas mixing chamber, the back pressure valve is used for regulating and controlling the reaction pressure, and then the mixed gas with the corresponding pressure is introduced into the closed reaction chamber 305 of the reaction tank, so that the preparation before the reaction is completed;
7) After the gas mixing operation is completed, the experiment is started, the mass spectrum 108 and the micro chromatograph 113 which are connected with the tail gas end are started at the same time, after the base line is stable, the temperature is raised, the temperature raising process is controlled by a temperature programming system, the temperature is raised at the temperature raising speed of 10 ℃/min, the temperature stays for 10 minutes at 50 ℃ after 200 ℃, and finally the reaction is finished after the temperature is raised to 500 ℃. The reaction gases CO and H are strictly controlled in the whole process 2 Pressure and flow ratio of (c).
8) After the reaction is finished, closing a mass spectrum, performing gas evacuation operation after the temperature is reduced to below 100 ℃, closing an air inlet end, directly opening a tail gas end stop valve for pressure relief, then opening a forepump to pump a reaction chamber 308 and a tail gas end, then closing the tail gas end stop valve, opening a sealing valve 311, opening a vacuum pump group of a first rapid sample injection cavity 5, evacuating a reaction tank reaction cavity 305, and completing the post-reaction exhaust operation;
9) The vacuum of the first rapid sample injection cavity 5 connected with the reaction cavity is lower than 5x10 -8 Opening a gate valve between the cavity and the sample transition transferring cavity 8 during mbar, transferring the sample into the sample transition transferring cavity 8, closing the gate valve, then opening a gate valve between the buffer cavity 9 and the sample transition transferring cavity 8, transferring the sample into the buffer cavity 9, then transferring the sample into the second rapid sample injection cavity 10, closing the gate valve between the second rapid sample injection cavity 10 and the buffer cavity 9, then transferring the sample into the X-ray photoelectron spectroscopy analysis cavity 11 for reaction, and then testing, wherein the vacuum of all cavities in the whole sample transferring process is less than 5X10 -8 mbar。
The C1s and O1s obtained are shown in figures 5 and 6, the concentration of oxygen vacancies on the surface before the reaction is low and no formate species exist, formate is formed on the surface of the catalyst after the reaction, and the oxygen vacancies disappear. The test result error caused by surface carbon pollution in the XPS experiment test can be obviously eliminated.
Example 2
The method for testing the quasi-in-situ X-ray photoelectron spectroscopy comprises the following steps:
1) The quasi-in-situ X-ray photoelectron spectrum testing device is built, the vacuum of the whole interconnected cavity is realized through a vacuum pump set, and the vacuum of the cavity is better than 5X10 in the whole sample transmission process -8 mbar；
2) Fixing the sample on a sample holder (in this case using surface roughness formed after ion implantation)Single crystal face), then stopping the second rapid sample injection cavity 10 molecular pump and the backing pump, introducing argon gas to restore the air pressure to normal pressure, then opening the cavity door, and putting in under the condition of argon protectionThe sample is put into a sample parking table of a second rapid sample introduction cavity 10, then a cavity door is closed, a backing pump is started, and the sample is vacuumized to 5x10 -2 Starting a molecular pump after mbar to finish sample injection operation;
3) When the air pressure of the second rapid sample injection cavity 10 is reduced to 5 multiplied by 10 -7 After mbar, transferring the sample to an X-ray photoelectron spectroscopy analysis cavity 11, removing ZnO sample surface pollution by argon ion etching, transferring the sample among a second rapid sample introduction cavity 10, a buffer cavity 9 and a sample transition transfer cavity 8, finally transferring the sample to an annealing furnace cavity 7 for high-temperature annealing, and then performing opposite transfer steps to the X-ray photoelectron spectroscopy analysis cavity for testing until the surface has no obvious pollutant, and performing a pre-reaction comparison test;
4) After the analysis and test of the X-ray photoelectron spectroscopy before the reaction are completed, opening a gate valve between the X-ray photoelectron spectroscopy analysis cavity and the second rapid sample injection cavity 10, transferring the sample to the second rapid sample injection cavity 10, and closing the gate valve; opening a gate valve between the second rapid sample injection cavity 10 and the buffer cavity 9 which is in vacuum interconnection, transferring the sample into the buffer cavity 9, and closing the gate valve between the sample injection cavity and the second rapid sample injection cavity 10; then transferring the sample to the sample transition transferring cavity 8, then transferring to the first rapid sample feeding cavity 5 directly connected with the reaction tank 3, and finally transferring to a sample parking table of the reaction tank 3 to finish ZnO sample transferring operation;
5) After the ZnO sample is smoothly placed in the sample storage platform in the reaction cavity, closing the sealing valve 311, sealing the reaction cavity 305 of the reaction tank, closing the vacuum pump set of the first rapid sample injection cavity 5 directly connected with the reaction tank 3, and completing preparation before reaction;
6) Then the gas mixing operation before reaction is carried out, firstly, the gas path conditions are checked one by one, the moderate pressure of the gas cylinder is ensured, the gas path is free from gas leakage, and then H is used for cleaning 2 And the CO gas path adopts a rinsing mode, the gas path is cleaned by inflating and exhausting three times, and the gas mixing chamber is cleaned for three times. H2 and CO connected in the gas cylinder are delivered to the gas circuit device supported by the aluminum profile frame 104 through two of eight gas circuits 103, and are cut offThe stop valve 105 controls the opening and closing of the gas path of the required gas, then the flow rate of the gas is controlled through the flowmeter 107, the gas passing through the flowmeter enters the gas mixing chamber 106 to be fully mixed, then the gas enters the reaction tank 3 through the reaction tank inlet pipeline 310, finally the pressure of the reaction gas is controlled through the back pressure valve 112 to realize the accurate control of the normal pressure reaction gas, and the CO and the H are carried out through the flowmeter 2 The gas flow is regulated (1:3), the gas passing through the flowmeter is fully mixed in the gas mixing chamber, the back pressure valve is used for regulating and controlling the reaction pressure, and then the mixed gas with the corresponding pressure is introduced into the closed reaction chamber 305 of the reaction tank, so that the preparation before the reaction is completed;
7) After the gas mixing operation is completed, the experiment is started, the mass spectrum 108 and the micro chromatograph 113 which are connected with the tail gas end are started at the same time, after the base line is stable, the temperature is raised, the temperature raising process is controlled by a temperature programming system, the temperature is raised at the temperature raising speed of 10 ℃/min, the temperature stays for 10 minutes at 50 ℃ after 200 ℃, and finally the reaction is finished after the temperature is raised to 500 ℃. The reaction gases CO and H are strictly controlled in the whole process 2 Pressure and flow ratio of (c).
8) After the reaction is finished, closing a mass spectrum, performing gas evacuation operation after the temperature is reduced to below 100 ℃, closing an air inlet end, directly opening a tail gas end stop valve for pressure relief, then opening a backing pump for pumping a reaction chamber and a tail gas end, then closing the tail gas end stop valve, opening a sealing valve 311, opening a vacuum pump group of a first rapid sample injection cavity 5, evacuating a reaction tank reaction cavity 305, and performing post-reaction exhaust operation; 9) The vacuum of the first rapid sample injection cavity 5 connected with the reaction cavity is lower than 5x10 -8 Opening a gate valve between the cavity and the sample transition transferring cavity 8 during mbar, transferring the sample into the sample transition transferring cavity 8, closing the gate valve, then opening a gate valve between the buffer cavity 9 and the sample transition transferring cavity 8, transferring the sample into the buffer cavity 9, then transferring the sample into the second rapid sample injection cavity 10, closing the gate valve between the second rapid sample injection cavity 10 and the buffer cavity 9, then transferring the sample into the X-ray photoelectron spectroscopy analysis cavity 11 for reaction and then testing, and the whole sample All cavity vacuum in the transmission process is less than 5x10 -8 mbar；
The obtained C1s and O1s are shown in figures 7 and 8, the surface of the sample before the reaction has no obvious C species, is not polluted by the atmosphere, the surface state of the sample before and after the reaction has obvious change, and the concentration of oxygen vacancies on the surface is obviously more than that of the surfaceAnd (3) a sample.
The above examples illustrate only a few embodiments of the invention, which are described in detail and are not to be construed as limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. Accordingly, the scope of protection of the present invention is to be determined by the appended claims.
Claims (11)
1. The quasi-in-situ X-ray photoelectron spectrum testing device is characterized by comprising a gas mixing system, a stop valve, a reaction tank, a gate valve, a first rapid sample injection cavity, a molecular beam epitaxy Bao Mosheng long cavity, a rapid annealing cavity, a sample transition transferring cavity, a buffer cavity, a second rapid sample injection cavity and an X-ray photoelectron spectrum analysis cavity; the gas mixing system is communicated with the reaction tank through a stop valve, the cavities are matched with an independent vacuum pump system and are isolated from each other through a gate valve, the reaction tank is communicated with the first rapid sample injection cavity through the gate valve, the sample transition transfer cavity is communicated with the first rapid sample injection cavity, the molecular beam epitaxy Bao Mosheng long cavity, the rapid annealing cavity and the buffer cavity through the respective gate valves, the buffer cavity is communicated with the second rapid sample injection cavity in the X-ray photoelectron spectroscopy analysis cavity through the gate valve, the second rapid sample injection cavity is communicated with the X-ray photoelectron spectroscopy analysis cavity through a cavity door, all cavities in the whole device are vacuum-interconnected through a sealing channel, and the measured sample is processed and detected by the process before the measurement in the device.
2. The quasi-in-situ X-ray photoelectron spectroscopy test device of claim 1, wherein the sample transition transfer cavity is provided with a sample parking table capable of placing a sample, the sample parking table is arranged on a rotatable and telescopic sample rod, and the transition of the sample transition transfer cavity is used for transferring the sample between different cavities.
3. The quasi-in-situ X-ray photoelectron spectroscopy apparatus of claim 1 or 2, wherein the molecular beam epitaxy film growth chamber is one in which a model system sample required for the test is prepared by growth of a film.
4. The quasi-in-situ X-ray photoelectron spectroscopy test device of claim 1 or 2, wherein the rapid annealing chamber is matched with a laser heating device and an infrared thermometer to perform high-temperature annealing treatment on the sample in the rapid annealing chamber.
5. The quasi-in-situ X-ray photoelectron spectroscopy test device according to claim 1, wherein the reaction tank comprises a sample conveying system, a reaction tank reaction cavity, a sealing system, a vacuum pump system, a heating system and a gas mixing system, the gas mixing system is used for preparing a reaction cavity of gas required by near normal pressure to high pressure reaction, the vacuum pump system and the heating system are used for vacuumizing and heating the reaction cavity respectively, the sealing system comprises a sealing valve and a blind plate sealing piece, the reaction tank reaction cavity is in sealing connection with the first rapid sample feeding cavity through the sealing valve at one end, and the reaction tank reaction cavity is in sealing connection with the sample conveying system through the blind plate sealing piece at the other end.
6. The quasi-in-situ X-ray photoelectron spectroscopy test device according to claim 5, wherein the reaction cavity of the reaction tank comprises a water-cooling interlayer, a heating interlayer and a reaction cavity from outside to inside, the water-cooling interlayer is communicated with a water-cooling water inlet and a water-cooling water outlet, and an external water source can fill the water-cooling interlayer with cooling water to realize cooling of the outer wall of the reaction cavity of the reaction tank; the heating interlayer is composed of heating resistance wires, surrounds the reaction chamber and realizes uniform heating of the reaction chamber; the reaction chamber for sample reaction is communicated with the reaction gas inlet pipeline and the reaction gas outlet, and the sample reacts in the reaction chamber.
7. The quasi-in-situ X-ray photoelectron spectroscopy test device according to claim 6, wherein the vacuum pump system consists of a front-stage mechanical pump and a molecular pump, the front-stage pump is externally connected with a reaction cavity of the reaction tank through a stop valve, the front-stage pump realizes vacuum from normal pressure to 10 < -2 > mbar, and the vacuum degree of 10 < -9 > mbar magnitude can be realized by matching with the molecular pump, and meanwhile, the heating interlayer can be evacuated.
8. The quasi-in-situ X-ray photoelectron spectroscopy test device of claim 1, wherein the gas mixing system comprises a normal pressure to high pressure gas inlet distribution device and a near normal pressure gas inlet distribution device, which enter the reaction tank through a normal pressure to high pressure gas inlet end and a near normal pressure gas inlet end respectively.
9. The quasi-in-situ X-ray photoelectron spectroscopy test device according to claim 8, wherein the normal pressure to high pressure air inlet distribution device comprises a vacuum pump set, eight air paths connected with an air bottle, an aluminum profile frame, a stop valve, a stainless steel gas mixing chamber, a flowmeter, a mass spectrum, a back pressure valve and a micro chromatograph; the gas connected in the gas bottle is conveyed to a gas circuit device supported by the aluminum profile frame through eight gas circuit pipelines, the switch of a required gas circuit is controlled through a stop valve on each pipeline, then the flow rate of the gas is controlled through a flowmeter on the pipeline, the gas through the flowmeter enters a stainless steel gas mixing chamber to be fully mixed, then the gas enters a reaction tank through a reaction gas inlet pipeline, and the back pressure valve at the front end of the reaction gas inlet pipeline is used for controlling the pressure of the reaction gas so as to realize the accurate control of normal pressure to high pressure reaction gas; the mass spectrum is provided with eight detection channels, reaction products under different reaction pressures are tested, and the micro-chromatography is used for quantitatively detecting gaseous substances.
10. The quasi-in-situ X-ray photoelectron spectrum test device according to claim 8, wherein the near-normal pressure air inlet and distribution device comprises eight air paths connected with an air bottle, an aluminum profile supporting frame, a stop valve, a micro-leakage valve and a liquid nitrogen cold trap, wherein the air paths are arranged on the air bottle, the air paths are supported by the aluminum profile supporting frame, the stop valve on each pipeline is used for controlling the opening and closing of the air paths of the required air, and then the micro-leakage valve is used for controlling the pressure and the flow rate of the air in the reaction tank, so that the control of the minimum gas pressure of 0.001mbar is realized, and meanwhile, the air paths are provided with the cold trap for further purifying the air.
11. A quasi-in-situ X-ray photoelectron spectroscopy test method comprising a quasi-in-situ X-ray photoelectron spectroscopy test device according to any one of claims 1 to 10, comprising the specific steps of:
1) The vacuum pump system is used for realizing the vacuum of the whole interconnected cavity of the quasi-in-situ X-ray photoelectron spectroscopy testing device, and the vacuum of the cavity is better than 5X10 in the whole sample transmission process -8 mbar；
2) Fixing a sample on an external sample support, stopping a molecular pump and a backing pump of a second rapid sample injection cavity, introducing inert gas to enable the air pressure of the second rapid sample injection cavity to be recovered to normal pressure, opening a cavity door connected with a buffer cavity, placing the sample in a sample storage table of the second rapid sample injection cavity under the condition of protecting the cavity by the inert gas, closing the cavity door of the second rapid sample injection cavity, starting the backing pump, and vacuumizing to 5x10 -2 Starting a molecular pump after mbar to finish sample injection operation;
3) When the air pressure of the second rapid sample injection cavity is reduced to 5 multiplied by 10 -7 After mbar, transferring the sample to an X-ray photoelectron spectroscopy analysis cavity, removing the surface pollution of the sample by argon ion etching, transferring the sample between a second rapid sample feeding cavity, a buffer cavity and a sample transition transfer cavity, finally transferring the sample to an annealing furnace cavity for high-temperature annealing, and then performing the opposite transfer step to the X-ray photoelectron spectroscopy analysis cavity Performing a pre-reaction control test until the surface is free of obvious pollutants;
4) After the analysis and test of the X-ray photoelectron spectroscopy before the reaction are completed, opening a gate valve between the X-ray photoelectron spectroscopy analysis cavity and the second rapid sample injection cavity, transferring the sample to the second rapid sample injection cavity, and closing the gate valve; opening a gate valve between the second rapid sample injection cavity and the buffer cavity which are in vacuum interconnection, transferring the sample into the buffer cavity, and closing the gate valve between the sample injection cavity and the second rapid sample injection cavity; then transferring the sample to the sample transition transferring cavity, then transferring to the first rapid sample feeding cavity directly connected with the reaction tank, and finally transferring to a sample parking table of the reaction tank to finish the sample transferring operation;
5) After the sample is smoothly placed in a sample parking table in the reaction tank, closing a closed valve, sealing the reaction cavity of the reaction tank, closing a vacuum pump set of a first rapid sample injection cavity directly connected with the reaction tank, and completing sample preparation before reaction;
6) Firstly, checking the condition of gas paths one by one to ensure that the pressure of a gas cylinder is moderate, the gas paths are free from gas leakage, then cleaning the gas paths to be used, adopting a rinsing mode to perform gas charging and gas exhausting for three times to complete gas path cleaning, simultaneously cleaning a gas mixing chamber for three times, enabling gas connected in the gas cylinder to enter a gas path device supported by an aluminum profile frame through eight paths of gas paths, controlling the opening and closing of a required gas path through a stop valve, then controlling the flow rate of the gas through a flowmeter, enabling the gas through the flowmeter to enter a gas mixing chamber to perform sufficient gas mixing, then enabling the gas to enter a reaction tank through a reaction tank gas inlet pipeline, finally controlling the pressure of the reaction gas through a back pressure valve at the front end of the reaction tank gas inlet pipeline to realize accurate control of normal pressure reaction gas, performing body flow adjustment through the flowmeter, enabling the gas through the flowmeter to perform sufficient mixing in the gas mixing chamber, using the back pressure valve to perform reaction pressure regulation, and then enabling the mixed gas with corresponding pressure to enter a closed reaction tank reaction chamber to perform reaction preparation;
7) After the gas mixing operation is completed, starting an experiment, starting a connected mass spectrum and a micro-chromatograph, starting heating after a base line is stable, controlling a heating process through a temperature programming system, heating at a set heating speed and a final required temperature, and controlling the pressure and flow ratio of the reaction gas in the whole process;
8) After the reaction is finished, closing a micro mass spectrum, performing gas evacuation operation after the temperature is reduced to below 100 ℃, closing an air inlet end, directly opening a tail gas end stop valve to release pressure, then opening a forepump to pump a reaction chamber and a tail gas end, then closing the tail gas end stop valve, opening a closed valve, opening a vacuum pump set of a first rapid sample injection cavity, evacuating a reaction cavity of a reaction tank, and performing the post-reaction exhaust operation;
9) The vacuum of the first rapid sample injection cavity connected with the reaction chamber is lower than 5x10 -8 Opening a gate valve between the cavity and the sample transition transferring cavity during mbar, transferring the sample into the sample transition transferring cavity, closing the gate valve, then opening the gate valve between the buffer cavity and the sample transition transferring cavity, transferring the sample into the buffer cavity, then transferring the sample into the second rapid sample injection cavity, closing the gate valve between the second rapid sample injection cavity and the buffer cavity, then transferring the sample into the X-ray photoelectron spectroscopy analysis cavity for reaction, and then testing, wherein the vacuum of all cavities in the whole sample transferring process is less than 5X10 - 8 mbar。
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