CN113984922A - 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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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N23/00—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00
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- G01N23/227—Measuring photoelectric effect, e.g. photoelectron emission microscopy [PEEM]
- G01N23/2273—Measuring photoelectron spectrum, e.g. electron spectroscopy for chemical analysis [ESCA] or X-ray photoelectron spectroscopy [XPS]
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/62—Detectors specially adapted therefor
- G01N30/72—Mass spectrometers
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
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Abstract
The invention relates to a quasi-in-situ X-ray photoelectron spectroscopy 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 introduction cavity, a molecular beam epitaxial film growth cavity, a rapid annealing cavity, a sample transition transfer cavity, a buffer cavity, a second rapid sample introduction cavity and an X-ray photoelectron spectroscopy 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 unit system and mutually isolated through a gate valve, all the cavities in the whole device are mutually connected in a vacuum mode through a sealing channel, and a tested sample is subjected to process treatment and detection before being tested in the device. The method realizes that a sample is transferred to an X-ray photoelectron spectroscopy analysis cavity for testing under the condition of not exposing air after reaction or gas high-temperature treatment, and obtains information which is closer to the actual final state of a tested catalytic material.
Description
Technical Field
The invention relates to a detection technology, in particular to a quasi-in-situ X-ray photoelectron spectroscopy testing device and a testing method thereof, wherein the quasi-in-situ X-ray photoelectron spectroscopy testing device is in vacuum interconnection with a high-temperature reaction tank from near normal pressure to high pressure.
Background
Catalysis and surface chemistry are scientific bases for energy and substance conversion, play a very important role in human civilization progress and world economic development, 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 is widely applied to various industries such as energy, chemical industry, food, medicine, electronics and the like. Therefore, regarding the essential action of catalysis, the further understanding of the interaction between the catalytic material and the reactant in the reagent reaction process 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 spectroscopy (XPS) irradiates a sample with X-rays, so that electrons in the inner layer of atoms or molecules or valence electrons are excited to become photoelectrons, and the chemical composition of the surface of the sample, the binding energy of each element, and the valence state are characterized by measuring the signal of the photoelectrons. XPS is a common surface analysis technique, and is widely used for characterization of surface elements and electronic structures of materials, especially for research in the field of catalysis, and at present, XPS has become one of the main methods for researching surface composition and chemical state of catalytic materials. However, since the detection of X-ray and photoelectron emitted from the XPS electron gun must be performed under ultra-high vacuum, the conventional XPS test is performed in a vacuum analysis chamber, and the dynamic change of the catalytic material under the reaction conditions is more significant for the characterization of the catalytic material. In addition, in the conventional XPS test process, the sample is inevitably exposed to the atmospheric environment in the sample preparation and transfer processes, and the property of the catalyst material is possibly changed under the influence of gas components in the air in the process, so that the property of the catalyst material cannot be truly characterized. This greatly limits the research on the dynamic changes of XPS characterization technology under the catalytic reaction conditions.
Disclosure of Invention
Aiming at the problem that the performance of a catalyst material is possibly changed due to the fact that the existing sample is exposed to the atmospheric environment in the testing process, a quasi-in-situ X-ray photoelectron spectroscopy testing device and a testing method thereof are provided.
The technical scheme of the invention is as follows: a quasi-in-situ X-ray photoelectron spectroscopy testing device comprises a gas mixing system, a stop valve, a reaction tank, a gate valve, a first rapid sample introduction cavity, a molecular beam epitaxial film growth cavity, a rapid annealing cavity, a sample transition transfer cavity, a buffer cavity, a second rapid sample introduction cavity and an X-ray photoelectron spectroscopy 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 unit system and is mutually isolated through a gate valve, the reaction tank is communicated with a first rapid sample introduction cavity through the gate valve, the sample transition transfer cavity is communicated with the first rapid sample introduction cavity, the molecular beam epitaxial film growth cavity, the rapid annealing cavity and the buffer cavity respectively through respective gate valves, the buffer cavity is communicated with a second rapid sample introduction cavity in the X-ray photoelectron spectroscopy analysis cavity through the gate valve, the second rapid sample introduction 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 tested sample is subjected to process treatment and detection before testing in the device.
Preferably, the sample transition transfer cavity is provided with a sample parking platform for placing a sample, the sample parking platform is arranged on the rotatable and telescopic sample rod, and the sample is transferred between different cavities through the transition of the sample transition transfer cavity.
Preferably, the molecular beam epitaxy film growth chamber is used for preparing a model system sample required for testing through film growth.
Preferably, the cavity of the rapid annealing furnace 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 set system, a heating system and a gas mixing system, the gas mixing system is used for preparing a reaction cavity for reaction from near normal pressure to high pressure, the vacuum pump set system and the heating system are used for vacuumizing and heating the reaction cavity respectively, the sealing system comprises a closed valve and a blind plate sealing piece, the reaction tank reaction cavity is in sealing connection with the first rapid sample introduction cavity through the closed 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 chamber 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 the cooling of the outer wall of the reaction cavity of the reaction tank; the heating interlayer consists 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 exhaust port, and the sample reacts in the reaction chamber.
Preferably, the vacuum pump unit system comprises preceding stage mechanical pump and molecular pump, and through the external intercommunication reaction tank reaction cavity of stop valve, the preceding stage pump realizes the vacuum of ordinary pressure to 10-2mbar, and the collocation molecular pump can realize the vacuum degree of 10-9mbar magnitude, can find time the heating intermediate layer simultaneously.
12. 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 and distribution device and a near-normal-pressure gas inlet and distribution device, which respectively enter the reaction tank through a normal-pressure to high-pressure gas inlet end and a near-normal-pressure gas inlet end.
Preferably, the normal-pressure to high-pressure air inlet and 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 air mixing chamber, a flowmeter, a mass spectrum, a back pressure valve and a micro-chromatograph; the gas connected in the gas cylinder is communicated to a gas path device supported by an aluminum profile frame through eight gas path pipelines, the on-off of a required gas path is controlled through a stop valve on each pipeline, the flow rate of the gas is controlled through a flowmeter on the pipeline, the gas passing through the flowmeter enters a stainless steel gas mixing chamber for sufficient gas mixing, then enters a reaction tank through a reaction gas inlet pipeline, and the pressure of the reaction gas is controlled through a back pressure valve at the front end of the reaction gas inlet pipeline so as to realize the accurate control from 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, nearly ordinary pressure distribution device that admits air includes eight gas circuits that link to each other with the gas cylinder, aluminium alloy braced frame, stop valve, microleak valve and liquid nitrogen cold trap, the gas circuit device that the gas that connects in the gas cylinder comes to aluminium alloy braced frame through eight gas circuits and supports, through the switch of the required gas circuit of stop valve control on each pipeline, the pressure and the velocity of flow of gas in the control reaction tank are come through the microleak valve afterwards, realize the control of minimum 0.001mbar gas pressure, the gas circuit is equipped with the cold trap and carries out further purification to gas simultaneously.
A quasi-in-situ X-ray photoelectron spectroscopy test method comprises the quasi-in-situ X-ray photoelectron spectroscopy test device, and specifically comprises the following test steps:
1) the vacuum of the whole interconnected cavity of the quasi-in-situ X-ray photoelectron spectroscopy testing device is realized through a vacuum pump set system, and the vacuum of the cavity is superior to 5X10 in the whole sample transfer process-8mbar；
2) Fixing the sample on an external sample support, stopping the molecular pump and the backing pump of the second rapid sample injection cavity, introducing inert gas to restore the air pressure of the second rapid sample injection cavity to normal pressure, opening the cavity door connecting the second rapid sample injection cavity and the buffer cavity, placing the sample in the sample storage table of the second rapid sample injection cavity under the condition of inert gas protection cavity, then closing the cavity door of the second rapid sample injection cavity, starting the backing pump, and vacuumizing to 5x10-2Starting the molecular pump after mbar to finish sampling operationMaking;
3) when the air pressure of the second rapid sample introduction cavity is reduced to 5 multiplied by 10-7After mbar, transferring the sample to an X-ray photoelectron spectroscopy analysis cavity, then removing surface pollution of the sample through argon ion etching, then transferring the sample among a second rapid sample introduction 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 carrying out reverse transfer steps to the X-ray photoelectron spectroscopy analysis cavity for testing until no obvious pollutant exists on the surface, and carrying out a comparison test before reaction;
4) after the X-ray photoelectron spectroscopy analysis and test before the reaction is finished, opening a gate valve between the X-ray photoelectron spectroscopy analysis cavity and the second rapid sample introduction cavity, transferring the sample to the second rapid sample introduction cavity, and closing the gate valve; opening a gate valve between the second rapid sample introduction cavity and the vacuum interconnected buffer cavity, transferring the sample into the buffer cavity, and closing the gate valve between the second rapid sample introduction cavity and the buffer cavity; then transferring the sample into a sample transition transfer cavity, transferring the sample into a first rapid sample introduction cavity directly connected with the reaction tank, and finally transferring the sample onto a sample parking platform of the reaction tank to finish the sample transfer operation;
5) after the sample is smoothly placed into a sample placing table in the reaction tank, closing the sealing valve, sealing the reaction cavity of the reaction tank, closing a vacuum pump set of a first rapid sample introduction cavity directly connected with the reaction tank, and completing sample preparation before reaction;
6) then the gas mixing operation before reaction is carried out, the gas circuit conditions are firstly checked one by one to ensure that the gas cylinder has moderate pressure and the gas circuit does not leak gas, then the gas circuit to be used is cleaned, the gas circuit cleaning is completed by inflating and exhausting for three times in a rinsing mode, meanwhile, the gas mixing chamber is also cleaned for three times, the gas connected in the gas cylinder is supplied to a gas circuit device supported by an aluminum profile frame through eight gas circuits, the opening and closing of the gas circuit of the required gas are controlled through a stop valve, the flow rate of the gas is controlled through a flowmeter, the gas through the flowmeter is supplied into the gas mixing chamber for full gas mixing, the gas is supplied into a reaction tank through a reaction tank gas inlet pipeline, finally the pressure of the reaction gas is controlled through a back pressure valve at the front end of a reaction tank gas inlet pipeline to realize the accurate control of the normal pressure reaction gas, the gas flow is regulated through the flowmeter, and the gas through the flowmeter is fully mixed in the gas mixing chamber, regulating and controlling reaction pressure by using a back pressure valve, and then introducing mixed gas with corresponding pressure into a reaction cavity of a closed reaction tank to finish gas preparation before reaction;
7) after the gas mixing operation is finished, starting an experiment, simultaneously starting the connected mass spectrum and the micro-chromatograph, starting heating after the baseline is stable, controlling the heating process through a programmed heating system to set the heating speed and the 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 the mass spectrum and the chromatographic gas inlet end stop valve, after the temperature is reduced to be below 100 ℃, carrying out gas evacuation operation, closing the gas inlet end, directly opening the tail gas end stop valve to release pressure, then opening a backing pump to evacuate a reaction chamber and a tail gas end, then closing the tail gas end stop valve, opening a sealing valve, opening a vacuum pump group of a first rapid sample introduction cavity, evacuating a reaction chamber of a reaction pool, and finishing exhaust operation after the reaction;
9) the vacuum of the chamber to be reacted and the first fast sample feeding cavity connected with the chamber to be reacted is lower than 5x10-8Opening the gate valve between this cavity and the sample transition transfer cavity during mbar, transferring the sample to the sample transition transfer cavity in, sealing the gate valve, opening the gate valve between buffer cavity and the sample transition transfer cavity afterwards, transferring the sample to the buffer cavity in, transfer to the second and advance kind the cavity fast afterwards, close the gate valve between second and the buffer cavity fast, transfer the sample afterwards to X ray photoelectron spectrometer analysis testing cavity and carry out the test after the reaction, all cavity vacuums all are less than 5X10 in the whole sample transfer process-8mbar。
The invention has the beneficial effects that: the quasi-in-situ X-ray photoelectron spectroscopy testing device and the testing method thereof realize that a sample is transferred to an X-ray photoelectron spectroscopy analysis cavity for testing under the condition of not exposing air after reaction or high-temperature treatment of gas, so that the information closer to the actual final state of a tested catalytic material can be obtained, the problem that the real catalytic material performance cannot be reflected due to the change of the catalytic material state caused by the exposure of the air in the traditional XPS testing process is solved, and meanwhile, the device can also be used for the catalytic reaction performance test of a characterization model catalyst and a powder catalyst.
Drawings
FIG. 1 is a schematic structural diagram of a quasi-in-situ X-ray photoelectron spectroscopy testing apparatus according to the present invention;
FIG. 2 is a schematic view of a high temperature reaction tank from near atmospheric pressure to high pressure according to the present invention;
FIG. 3 is a schematic view of a combined device of a normal pressure to high pressure inlet end and a high temperature reaction tank;
FIG. 4 is a schematic view of a near-atmospheric pressure inlet end-high temperature reaction tank combination device of the present invention;
FIG. 5 is a diagram showing the results of quasi-in-situ X-ray photoelectron spectroscopy tests O1s and C1s on a flat ZnO model catalyst (Pristine-ZnO) subjected to high-temperature high-pressure reaction by the method of the present invention;
FIG. 6 is a diagram showing the results of quasi-in-situ X-ray photoelectron spectroscopy tests O1s and C1s on a flat ZnO model catalyst (Pristine-ZnO) after high-temperature and high-pressure reaction by the method of the present invention;
FIG. 7 is a graph showing the results of quasi-in-situ X-ray photoelectron spectroscopy tests on O1s and C1s after the treated ZnO model catalyst (Ar-ZnO) is subjected to high-temperature high-pressure reaction by the method of the present invention;
FIG. 8 is a diagram showing the results of quasi-in-situ X-ray photoelectron spectroscopy tests on O1s and C1s after the treated ZnO model catalyst (Ar-ZnO) is subjected to high-temperature high-pressure reaction by the method of the present invention.
The attached drawings are as follows: 1. a 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 introduction cavity; 6. a molecular beam epitaxial film growth cavity; 7. a rapid annealing cavity; 8. a sample transfer transition cavity; 9. a buffer cavity; 10. a second rapid sample introduction cavity; 11. an X-ray photoelectron spectroscopy analysis cavity; 301. a magnetic sample transfer rod; 302. an exhaust gas discharge outlet; 303. a temperature measurement interface; 304. water cooling the water inlet; 305. a reaction chamber of the reaction tank; 306. a water-cooling interlayer; 307. heating the interlayer; 308. a reaction chamber; 309. water cooling water outlet; 310. a reaction gas inlet line; 311. closing the valve; 312. a reaction tank vacuum pump unit system; 314. an apertured blind 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 unit system; 110. a pipeline four-way connector; 111. a pipeline three-way connector; 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 pipeline three-way connector; 119. a microleakage valve; 120. and (5) cold trap.
Detailed Description
The invention is described in detail below with reference to the figures and specific embodiments. The present embodiment is implemented on the premise of the technical solution of the present invention, and a detailed implementation manner and a specific operation process are given, but the scope of the present invention is not limited to the following embodiments.
As shown in fig. 1, the quasi-in-situ X-ray photoelectron spectroscopy testing apparatus comprises a gas mixing system 1 (including a near-atmospheric gas inlet end and a normal-to-high pressure gas inlet end), a stop valve 2, a reaction cell 3, a gate valve 4, a first rapid sample introduction 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 introduction cavity 10, and an X-ray photoelectron spectroscopy analysis cavity 11. The gas mixing system 1 (including near-normal pressure and normal pressure to high pressure inlet end) is communicated with the reaction tank 3 through a stop valve, each cavity is matched with an independent vacuum pump unit system and mutually isolated through a gate valve, the gate valves between the two corresponding cavities are opened when a sample transmission requirement is met, and the corresponding gate valves are closed after the sample transmission is completed; a sample generally enters through the second rapid sample introduction cavity 10, then after the vacuum degree of the second rapid sample introduction cavity 10 is small and 10-8mbar, a gate valve between the second rapid sample introduction cavity 10 and the channel of the X-ray photoelectron spectroscopy analysis cavity 11 is opened, the sample is introduced into the X-ray photoelectron spectroscopy analysis cavity 11 with the vacuum degree superior to 10-9mbar, pre-reaction testing or sample pretreatment is carried out, after the test is completed, the gate valve between the X-ray photoelectron spectroscopy analysis cavity 11 and the second rapid sample introduction cavity 10 is opened, then the sample is transferred to the second rapid sample introduction 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 introduction cavity 10 is opened, the sample is transferred into the buffer cavity 9, then the gate valve between the two cavities is closed, then the sample is transferred into the sample transition transfer cavity 8 through a similar sample transfer process, and then the sample enters a molecular beam epitaxial film growth cavity 6 or a rapid annealing cavity 7 for treatment according to process requirements, and then is transmitted into the first rapid sample introduction cavity 5 through a sample transition cavity 8 and finally is transmitted to a sample parking platform of the reaction tank 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 introduction cavity 5 after high-temperature reaction in the reaction tank 3, then enters the sample transition transfer cavity 8 and enters the second rapid sample introduction cavity 10 in the X-ray photoelectron spectroscopy analysis cavity 11 through the buffer cavity 9, and the test of the X-ray photoelectron spectroscopy analysis after the reaction is carried out. All the cavities in the whole device are vacuum-interconnected by sealed channels, so that the test (X-ray photoelectron spectroscopy) of the sample can be realized without exposing the sample to the atmosphere after reaction or pretreatment.
The first rapid sample introduction cavity 5 and the second rapid sample introduction cavity 10 are both protected by inert gas, so that the cavities or samples can be prevented from being polluted by air.
The sample transition transfer cavity 8 is provided with a sample parking platform for placing a sample, and the sample parking platform is arranged on a rotatable and telescopic sample rod, so that the sample can be transferred between different cavities through the transition of the sample transition transfer cavity 8. The molecular beam epitaxy film growth cavity 6, referred to as an MBE cavity for short, can realize the growth of the film so as to prepare a model system sample required by the test; the cavity 7 of the rapid annealing furnace is matched with a laser heating device and an infrared thermometer, so that high-temperature annealing treatment of a sample can be realized; the buffer cavity 9 is directly connected with the sample transition transfer cavity 8 and the second rapid sample introduction cavity 10 matched with the XPS, so that the transfer of the sample between the two cavities can be realized.
Fig. 2 is a schematic diagram of an apparatus of a reaction cell, which includes a sample transfer system, a reaction chamber, a sealing system, a vacuum pump set system, a heating system and a gas mixing system, and the entire apparatus includes a magnetic sample transfer rod 301, a tail gas exhaust pipeline 302, a temperature measurement interface 303, a water-cooling water inlet 304, a reaction cell reaction chamber 305, a water-cooling interlayer 306, a heating interlayer 307, a reaction chamber 308, a water-cooling water outlet 309, a reaction gas inlet pipeline 310, a sealing valve 311, a reaction cell vacuum pump set system 312 and an open-hole blind plate sealing element 314, wherein the reaction gas inlet pipeline 310 includes a near-normal pressure gas inlet end and a normal pressure to high pressure gas inlet end; the sample transmission system comprises a magnetic sample transmission rod 301, the magnetic sample transmission rod 301 is orthogonal to the magnetic sample transmission rod in the first rapid sample introduction cavity 5, a square sample parking platform is arranged on the magnetic sample transmission rod 301 and can be used for storing a tested sample, and meanwhile, the vacuum interconnection devices are mutually transmitted through the orthogonal transmission rod and the sample rod below the sample parking platform; the reaction tank reaction cavity 305 is sealed through the sealing valves 311 at two ends and the blind plate sealing element 314 connected with the magnetic transmission rod 301, vacuum is obtained through the reaction tank vacuum pump unit 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, an external water source can fill the water-cooling interlayer 306 with cooling water, and 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, where the sample is reacted; reaction tank vacuum pump unit system 312 comprises preceding stage mechanical pump and molecular pump, switches on whole reaction chamber system outward through the stop valve, and the preceding stage pump can realize the ordinary pressure to 10-2 mbar's vacuum, and the collocation molecular pump can realize the vacuum degree of 10-9mbar magnitude, can find time the heating intermediate layer 307 of managing simultaneously, prolongs the life of heating resistance wire.
The heating system consists of a heating interlayer 307 surrounding the reaction chamber 308, the interlayer is in a rough vacuum (10-2mbar) state, the heating interlayer 308 surrounds the heating resistance wires, and the heating control is carried out on the heating resistance wires through an external control system, so that the temperature control within the temperature difference range of 0.1 ℃ can be realized; the gas mixing system is connected to the reaction chamber 305 through a reaction gas inlet pipe 310, and includes a gas inlet system and an exhaust system, wherein the gas inlet system includes a near-atmospheric gas inlet (as shown in fig. 4) and an atmospheric-to-high-pressure gas inlet (as shown in fig. 3), and is directly communicated with the reaction chamber 308 through the reaction gas inlet pipe 310.
Fig. 3 is a schematic diagram of a normal pressure to high pressure air inlet end device, which comprises a vacuum pump set 109, eight air channels 103 connected with an air bottle, an aluminum profile frame 104, a stop valve 105, a stainless steel gas 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 that connects in the gas cylinder comes to the gas circuit device that aluminium alloy frame 104 supported through eight gas circuit pipelines 103, the switch of the required gas circuit of stop valve 105 control on each pipeline, flow rate through flowmeter 107 on the pipeline control gas afterwards, gas through flowmeter 107 gets into and carries out abundant gas mixing in the stainless steel gas mixing chamber 106, in the reaction tank 3 is got into through reaction gas inlet line 310 afterwards, at last, the accurate bar (1 bar-10) of atmospheric pressure to high-pressure reaction gas is realized to reaction gas's pressure of control through reaction gas inlet line front end back pressure valve 112. The mass spectrum 108 has eight detection channels, can detect eight different gas substances simultaneously, and also has a normal pressure sample injection system and a vacuum sample injection system, so that reaction product testing under different reaction pressures can be realized, and the vacuum pump unit system 109 comprises a backing mechanical pump and a molecular pump, and can realize 10-9The micro-chromatograph 113 is calibrated by standard gas under the vacuum degree of mbar magnitude, and can quantitatively detect gaseous substances such as carbon dioxide, hydrogen, carbon monoxide, methane, low-carbon alkane, low-carbon olefin and the like.
Fig. 4 is a schematic diagram of a near-atmospheric pressure gas inlet end device, which comprises eight gas paths 115 connected with a gas cylinder, an aluminum profile frame 116, a stop valve 117, a pipeline three-way joint 118, a microleak valve 119, a liquid nitrogen cold trap 120 and a high-temperature reaction tank. The gas circuit device that the aluminium alloy frame 116 supported is come to through eight gas circuit pipelines 115 to the gas of connecting in the gas cylinder, through the switch of the required gas circuit of stop valve 117 control on each pipeline, controls gaseous pressure and velocity of flow in the reaction tank through three little hourglass valve 119 afterwards, can realize the control of minimum 0.001mbar gas pressure, and the gas circuit is equipped with cold trap 120 simultaneously, can carry out further purification to gas.
A quasi-in-situ X-ray photoelectron spectroscopy test method vacuum-interconnected with a high-temperature reaction tank from near normal pressure to high pressure comprises the following steps:
1) the quasi-in-situ photoelectron spectroscopy testing device which is vacuum interconnected with the high-temperature reaction tank from near normal pressure to high pressure is built, the vacuum of the whole interconnected cavity is realized through a vacuum pump set system, and the vacuum of the cavity is superior to 5x10 in the whole sample transfer process- 8mbar；
2) The sample is fixed to the magnetic sample transfer rod 301 of the reaction well 3 (in this case, a flat sample transfer rod is used)
Single crystal face), then stopping the molecular pump and the backing pump of the second rapid sample introduction cavity 10, introducing argon to restore the air pressure to normal pressure, then opening the cavity door, putting a sample into the sample storage platform of the second rapid sample introduction cavity 10 under the condition of argon protection, then closing the cavity door, starting the backing pump, and vacuumizing to 5x10-2After mbar, starting a molecular pump to finish sample injection operation;
3) when the air pressure of the second rapid sample introduction cavity 10 is reduced to 5 multiplied by 10-7After mbar, the sample is transferred to an X-ray photoelectron spectroscopy analysis cavity 11, then ZnO sample surface pollution is eliminated through argon ion etching, then sample transfer is carried out among a second rapid sample introduction cavity 10, a buffer cavity 9 and a sample transition transfer cavity 8, and finally the sample is transferred to an annealing furnace cavity 7 for high-temperature annealing, and then opposite transfer steps are carried out to the X-ray photoelectron spectroscopy analysis cavity 11Testing until the surface has no obvious pollutant, and performing a pre-reaction contrast test;
4) after the X-ray photoelectron spectroscopy analysis and test before the reaction is finished, opening a gate valve 4 between an X-ray photoelectron spectroscopy analysis cavity 11 and a second rapid sample introduction cavity 10, transferring the sample to the second rapid sample introduction cavity 10, and closing the gate valve; opening a gate valve between the second rapid sample introduction cavity 10 and the buffer cavity 9 which is connected with each other in vacuum, transferring the sample into the buffer cavity 9, and closing the gate valve between the second rapid sample introduction cavity 10 and the sample; then transferring the sample into a sample transition transfer cavity 8, transferring the sample into a first rapid sample introduction cavity 5 directly connected with the reaction tank 3, and finally transferring the sample onto a sample parking platform of the reaction tank 3 to finish the ZnO sample transfer operation;
5) after the ZnO sample is smoothly put into the sample placing table in the reaction tank 3, closing the sealing valve 311, sealing the reaction tank reaction cavity 305, closing the vacuum pump group of the first rapid sample introduction cavity 5 directly connected with the reaction tank 3, and completing the preparation before reaction;
6) then the gas mixing operation before reaction is carried out, the gas path conditions are checked one by one to ensure that the gas cylinder pressure is moderate, the gas path does not generate gas leakage, and then H is used for cleaning2And a CO gas path, wherein the gas path is cleaned by adopting a rinsing mode, the gas is inflated and exhausted for three times, and the gas mixing chamber is cleaned for three times. H2 and CO connected in the gas cylinder come to the gas circuit device that aluminium alloy frame 104 supported through eight way gas circuit 103 wherein two ways, the switch of the required gas circuit of stop valve 105 control, the velocity of flow of gas is controlled through flowmeter 107 afterwards, gas through the flowmeter gets into and mixes gas in the gas chamber 106 and carry out abundant gas mixing, get into reaction tank 3 through reaction tank air inlet pipeline 310 afterwards, control reaction gas's pressure through back pressure valve 112 at last in order to realize the accurate control of ordinary pressure reaction gas, carry out CO and H through the flowmeter and carry out the accurate control of CO and H and frame2Adjusting the gas flow (1: 3), fully mixing the gas in the gas mixing chamber through the gas of the flow meter, adjusting and controlling the reaction pressure by using a back pressure valve, then introducing the mixed gas with corresponding pressure into a closed reaction tank reaction cavity 305, and preparing before reaction;
7) after the gas mixing operation is finished, an experiment is started, meanwhile, the mass spectrum 108 and the micro-chromatograph 113 connected with the tail gas end are started, after the base line is stable, the temperature is raised, the temperature raising process is controlled through a programmed temperature raising system, the temperature is raised at the temperature raising speed of 10 ℃/min, the reaction is stopped for 10 min at intervals of 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 process2Pressure and flow ratio of (a).
8) After the reaction is finished, closing the mass spectrum and the chromatographic gas inlet end stop valve, after the temperature is reduced to be below 100 ℃, carrying out gas evacuation operation, closing the gas inlet end, directly opening the tail gas end stop valve to release the pressure, then opening the backing pump to evacuate the reaction chamber 308 and the tail gas end, then closing the tail gas end stop valve, opening the sealing valve 311, opening the vacuum pump set of the first rapid sample introduction cavity 5, evacuating the reaction chamber 305 of the reaction tank, and finishing the exhaust operation after the reaction;
9) the vacuum of the chamber to be reacted and the first fast sample feeding cavity 5 connected with the chamber to be reacted is lower than 5x10-8Open the push-pull valve between this cavity and the sample transition transfer cavity 8 during mbar, transfer the sample to the sample transition in the cavity 8, seal the push-pull valve, open the push-pull valve between buffer cavity 9 and the sample transition transfer cavity 8 afterwards, transfer the sample to the buffer cavity 9 in, transfer to the second fast sampling cavity 10 afterwards, close the push-pull valve between second fast sampling cavity 10 and the buffer cavity 9, transfer the sample to X ray photoelectron spectrometer analysis testing cavity 11 afterwards and test after the reaction, all cavity vacuums all are less than 5X10 in the whole sample transfer process-8mbar。
The resulting C1s and O1s are shown in fig. 5 and 6, with low surface oxygen vacancy concentration and no presence of formate species before reaction, and with formate formation on the catalyst surface after reaction, with disappearance of oxygen vacancies. The test result error caused by surface carbon pollution when the test is not originally XPS experiment test can be obviously eliminated.
Example 2
A quasi-in-situ X-ray photoelectron spectroscopy test method comprises the following steps:
1) building the quasi-normal position XThe ray photoelectron spectrum tester realizes the vacuum of the whole interconnected cavity through the vacuum pump set, and the vacuum of the cavity is superior to 5x10 in the whole sample transfer process-8mbar；
2) The sample is fixed on a sample holder (in this case, the surface roughness formed after ion implantation is used
Single crystal face), then stopping the molecular pump and the backing pump of the second rapid sample injection cavity 10, introducing argon to restore the air pressure to normal pressure, then opening the cavity door, putting the sample into the sample parking platform of the second rapid sample injection cavity 10 under the condition of argon protection, then closing the cavity door, starting the backing pump, and vacuumizing to 5x10-2After mbar, starting a molecular pump to finish sample injection operation;
3) when the air pressure of the second rapid sample introduction cavity 10 is reduced to 5 multiplied by 10-7After mbar, transferring the sample to an X-ray photoelectron spectroscopy analysis cavity 11, then removing surface pollution of the ZnO sample by argon ion etching, then transferring the sample among a second rapid sample introduction cavity 10, a buffer cavity 9 and a sample transition transfer cavity 8, and 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 pollutants, and performing a comparison test before reaction;
4) after the X-ray photoelectron spectroscopy analysis and test before the reaction is finished, opening a gate valve between the X-ray photoelectron spectroscopy analysis cavity and the second rapid sample introduction cavity 10, transferring the sample to the second rapid sample introduction cavity 10, and closing the gate valve; opening a gate valve between the second rapid sample introduction cavity 10 and the buffer cavity 9 which is connected with each other in vacuum, transferring the sample into the buffer cavity 9, and closing the gate valve between the second rapid sample introduction cavity 10 and the sample; then transferring the sample into a sample transition transfer cavity 8, transferring the sample into a first rapid sample introduction cavity 5 directly connected with the reaction tank 3, and finally transferring the sample onto a sample parking platform of the reaction tank 3 to finish the ZnO sample transfer operation;
5) after the ZnO sample is smoothly put into the sample storage table in the reaction cavity, closing the sealing valve 311, sealing the reaction cavity 305 of the reaction tank, closing a vacuum pump group of the first rapid sample introduction cavity 5 directly connected with the reaction tank 3, and completing the preparation before reaction;
6) then the gas mixing operation before reaction is carried out, the gas path conditions are checked one by one to ensure that the gas cylinder pressure is moderate, the gas path does not generate gas leakage, and then H is used for cleaning2And a CO gas path, wherein the gas path is cleaned by adopting a rinsing mode, the gas is inflated and exhausted for three times, and the gas mixing chamber is cleaned for three times. H2 and CO connected in the gas cylinder come to the gas circuit device that aluminium alloy frame 104 supported through two ways in the eight way gas circuit 103, switch through the required gas circuit of stop valve 105 control, the velocity of flow of gas is controlled through flowmeter 107 afterwards, gas through the flowmeter gets into and mixes gas in the gas chamber 106 and carry out abundant gas mixing, get into reaction tank 3 through reaction tank air inlet pipe 310 afterwards, control reaction gas's pressure through back pressure valve 112 at last in order to realize the accurate control of ordinary pressure reaction gas, carry out CO and H through the flowmeter and react gaseous accurate control2Adjusting the gas flow (1: 3), fully mixing the gas in the gas mixing chamber through the gas of the flow meter, adjusting and controlling the reaction pressure by using a back pressure valve, then introducing the mixed gas with corresponding pressure into a closed reaction tank reaction cavity 305, and preparing before reaction;
7) after the gas mixing operation is finished, an experiment is started, meanwhile, the mass spectrum 108 and the micro-chromatograph 113 connected with the tail gas end are started, after the base line is stable, the temperature is raised, the temperature raising process is controlled through a programmed temperature raising system, the temperature is raised at the temperature raising speed of 10 ℃/min, the reaction is stopped for 10 min at intervals of 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 process2Pressure and flow ratio of (a).
8) After the reaction is finished, closing the mass spectrum and the chromatographic gas inlet end stop valve, after the temperature is reduced to be below 100 ℃, carrying out gas evacuation operation, closing the gas inlet end, directly opening the tail gas end stop valve to release the pressure, then opening a backing pump to evacuate 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 the first rapid sample introduction cavity 5, evacuating a reaction chamber 305 of a reaction pool, and finishing the exhaust operation after the reaction;
9) the vacuum of the chamber to be reacted and the first fast sample feeding cavity 5 connected with the chamber to be reacted is lower than 5x10-8Open the push-pull valve between this cavity and the sample transition transfer cavity 8 during mbar, transfer the sample to the sample transition in the cavity 8, seal the push-pull valve, open the push-pull valve between buffer cavity 9 and the sample transition transfer cavity 8 afterwards, transfer the sample to the buffer cavity 9 in, transfer to the second fast sampling cavity 10 afterwards, close the push-pull valve between second fast sampling cavity 10 and the buffer cavity 9, transfer the sample to X ray photoelectron spectrometer analysis testing cavity 11 afterwards and test after the reaction, all cavity vacuums all are less than 5X10 in the whole sample transfer process-8mbar；
The obtained C1s and O1s are shown in FIGS. 7 and 8, the surface of the sample before reaction has no obvious C species and is not polluted by the atmosphere, the surface state of the sample before and after reaction has obvious change, and the surface oxygen vacancy concentration is obviously higher than that of the sample which is flat
And (3) sampling.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (11)
1. A quasi-in-situ X-ray photoelectron spectroscopy testing device is characterized by comprising a gas mixing system, a stop valve, a reaction tank, a gate valve, a first rapid sample introduction cavity, a molecular beam epitaxial film growth cavity, a rapid annealing cavity, a sample transition transfer cavity, a buffer cavity, a second rapid sample introduction cavity and an X-ray photoelectron spectroscopy 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 unit system and is mutually isolated through a gate valve, the reaction tank is communicated with a first rapid sample introduction cavity through the gate valve, the sample transition transfer cavity is communicated with the first rapid sample introduction cavity, the molecular beam epitaxial film growth cavity, the rapid annealing cavity and the buffer cavity respectively through respective gate valves, the buffer cavity is communicated with a second rapid sample introduction cavity in the X-ray photoelectron spectroscopy analysis cavity through the gate valve, the second rapid sample introduction 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 tested sample is subjected to process treatment and detection before testing in the device.
2. The quasi-in-situ X-ray photoelectron spectroscopy testing apparatus of claim 1, wherein the sample transition transfer cavity is provided with a sample parking platform for placing the sample thereon, the sample parking platform is arranged on a rotatable and telescopic sample rod, and the sample is transferred between different cavities through the transition of the sample transition transfer cavity.
3. The quasi-in-situ X-ray photoelectron spectroscopy apparatus of claim 1 or 2, wherein the molecular beam epitaxy film growth chamber is used for preparing a model system sample required for testing by film growth.
4. The quasi-in-situ X-ray photoelectron spectroscopy testing device of claim 1 or 2, wherein the cavity of the rapid annealing furnace is matched with a laser heating device and an infrared thermometer to carry out high-temperature annealing treatment on the sample.
5. The quasi-in-situ X-ray photoelectron spectroscopy test device of claim 1, wherein the reaction cell comprises a sample transfer system, a reaction cell reaction cavity, a sealing system, a vacuum pump set system, a heating system and a gas mixing system, the gas mixing system is used for preparing a gas reaction cavity required by reaction from near normal pressure to high pressure, the vacuum pump set system and the heating system are used for respectively vacuumizing and heating the reaction cavity, the sealing system comprises a closed valve and a blind plate sealing member, the reaction cell reaction cavity is hermetically connected with the first rapid sample injection cavity through the closed valve at one end, and the reaction cell reaction cavity is hermetically connected with the sample transfer system through the blind plate sealing member at the other end.
6. The quasi-in-situ X-ray photoelectron spectroscopy testing device according to claim 5, wherein the reaction chamber of the reaction tank comprises a water-cooling interlayer, a heating interlayer and a reaction chamber 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 the cooling of the outer wall of the reaction chamber of the reaction tank; the heating interlayer consists 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 exhaust port, and the sample reacts in the reaction chamber.
7. The quasi-in-situ X-ray photoelectron spectroscopy testing apparatus of claim 6, wherein the vacuum pump set system comprises a pre-mechanical pump and a molecular pump, the reaction chamber is communicated with the outside of the stop valve, the pre-mechanical pump realizes vacuum from normal pressure to 10-2mbar, the molecular pump is matched to realize vacuum degree of 10-9mbar, and 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 and distribution device and a near-normal-pressure gas inlet and distribution device, which respectively enter the reaction tank through a normal-pressure to high-pressure gas inlet end and a near-normal-pressure gas inlet end.
9. The quasi-in-situ X-ray photoelectron spectroscopy testing device of claim 8, wherein the normal-pressure to high-pressure gas inlet and distribution device comprises a vacuum pump set, eight gas paths connected with a gas cylinder, an aluminum profile frame, a stop valve, a stainless steel gas mixing chamber, a flow meter, a mass spectrum, a back pressure valve and a micro-chromatograph; the gas connected in the gas cylinder is communicated to a gas path device supported by an aluminum profile frame through eight gas path pipelines, the on-off of a required gas path is controlled through a stop valve on each pipeline, the flow rate of the gas is controlled through a flowmeter on the pipeline, the gas passing through the flowmeter enters a stainless steel gas mixing chamber for sufficient gas mixing, then enters a reaction tank through a reaction gas inlet pipeline, and the pressure of the reaction gas is controlled through a back pressure valve at the front end of the reaction gas inlet pipeline so as to realize the accurate control from 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 spectroscopy testing device of claim 8, wherein the near-normal pressure gas inlet and distribution device comprises eight gas circuits connected with a gas cylinder, an aluminum profile supporting frame, a stop valve, a microleak valve and a liquid nitrogen cold trap, gas connected in the gas cylinder is supplied to the gas circuit device supported by the aluminum profile supporting frame through the eight gas circuits, the stop valve on each pipeline is used for controlling the on-off of the gas circuit of the required gas, then the pressure and the flow rate of the gas in the reaction tank are controlled through the microleak valve, the control of the gas pressure of the lowest 0.001mbar is realized, and meanwhile, the gas circuits are provided with the cold traps to further purify the gas.
11. A quasi-in-situ X-ray photoelectron spectroscopy test method comprises the quasi-in-situ X-ray photoelectron spectroscopy test device, and is characterized by comprising the following test steps:
1) the vacuum of the whole interconnected cavity of the quasi-in-situ X-ray photoelectron spectroscopy testing device is realized through a vacuum pump set system, and the vacuum of the cavity is superior to 5X10 in the whole sample transfer process-8mbar；
2) Fixing the sample on an external sample support, stopping the molecular pump and the backing pump of the second rapid sample injection cavity, introducing inert gas to restore the air pressure of the second rapid sample injection cavity to normal pressure, opening the door of the cavity connecting the second rapid sample injection cavity and the buffer cavity, placing the sample in the sample storage table of the second rapid sample injection cavity under the condition of inert gas protection cavity, and placing the sample in the sample storage table of the second rapid sample injection cavity along with the protection of the inert gasThen the chamber door of the second rapid sampling chamber is closed, the backing pump is started, and the vacuum pumping is carried out till 5x10-2After mbar, starting a molecular pump to finish sample injection operation;
3) when the air pressure of the second rapid sample introduction cavity is reduced to 5 multiplied by 10-7After mbar, transferring the sample to an X-ray photoelectron spectroscopy analysis cavity, then removing surface pollution of the sample through argon ion etching, then transferring the sample among a second rapid sample introduction 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 carrying out reverse transfer steps to the X-ray photoelectron spectroscopy analysis cavity for testing until no obvious pollutant exists on the surface, and carrying out a comparison test before reaction;
4) after the X-ray photoelectron spectroscopy analysis and test before the reaction is finished, opening a gate valve between the X-ray photoelectron spectroscopy analysis cavity and the second rapid sample introduction cavity, transferring the sample to the second rapid sample introduction cavity, and closing the gate valve; opening a gate valve between the second rapid sample introduction cavity and the vacuum interconnected buffer cavity, transferring the sample into the buffer cavity, and closing the gate valve between the second rapid sample introduction cavity and the buffer cavity; then transferring the sample into a sample transition transfer cavity, transferring the sample into a first rapid sample introduction cavity directly connected with the reaction tank, and finally transferring the sample onto a sample parking platform of the reaction tank to finish the sample transfer operation;
5) after the sample is smoothly placed into a sample placing table in the reaction tank, closing the sealing valve, sealing the reaction cavity of the reaction tank, closing a vacuum pump set of a first rapid sample introduction cavity directly connected with the reaction tank, and completing sample preparation before reaction;
6) then the gas mixing operation before reaction is carried out, the gas circuit conditions are firstly checked one by one to ensure that the gas cylinder has moderate pressure and the gas circuit does not leak gas, then the gas circuit to be used is cleaned, the gas circuit cleaning is completed by inflating and exhausting for three times in a rinsing mode, meanwhile, the gas mixing chamber is also cleaned for three times, the gas connected in the gas cylinder is supplied to a gas circuit device supported by an aluminum profile frame through eight gas circuits, the opening and closing of the gas circuit of the required gas are controlled through a stop valve, the flow rate of the gas is controlled through a flowmeter, the gas through the flowmeter is supplied into the gas mixing chamber for full gas mixing, the gas is supplied into a reaction tank through a reaction tank gas inlet pipeline, finally the pressure of the reaction gas is controlled through a back pressure valve at the front end of a reaction tank gas inlet pipeline to realize the accurate control of the normal pressure reaction gas, the gas flow is regulated through the flowmeter, and the gas through the flowmeter is fully mixed in the gas mixing chamber, regulating and controlling reaction pressure by using a back pressure valve, and then introducing mixed gas with corresponding pressure into a reaction cavity of a closed reaction tank to finish gas preparation before reaction;
7) after the gas mixing operation is finished, starting an experiment, simultaneously starting the connected mass spectrum and the micro-chromatograph, starting heating after the baseline is stable, controlling the heating process through a programmed heating system to set the heating speed and the 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 the mass spectrum and the chromatographic gas inlet end stop valve, after the temperature is reduced to be below 100 ℃, carrying out gas evacuation operation, closing the gas inlet end, directly opening the tail gas end stop valve to release pressure, then opening a backing pump to evacuate a reaction chamber and a tail gas end, then closing the tail gas end stop valve, opening a sealing valve, opening a vacuum pump group of a first rapid sample introduction cavity, evacuating a reaction chamber of a reaction pool, and finishing exhaust operation after the reaction;
9) the vacuum of the chamber to be reacted and the first fast sample feeding cavity connected with the chamber to be reacted is lower than 5x10-8Opening the gate valve between this cavity and the sample transition transfer cavity during mbar, transferring the sample to the sample transition transfer cavity in, sealing the gate valve, opening the gate valve between buffer cavity and the sample transition transfer cavity afterwards, transferring the sample to the buffer cavity in, transfer to the second and advance kind the cavity fast afterwards, close the gate valve between second and the buffer cavity fast, transfer the sample afterwards to X ray photoelectron spectrometer analysis testing cavity and carry out the test after the reaction, all cavity vacuums all are less than 5X10 in the whole sample transfer process-8mbar。
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN201066334Y (en) * | 2007-07-30 | 2008-05-28 | 厦门大学 | Analysis and pre-processing device for electronic energy spectrum instrument sample |
| CN104062312A (en) * | 2014-06-09 | 2014-09-24 | 清华大学 | X-ray photoelectron spectroscopy (XPS) analysis method and system for researching interaction of plasma and material surface |
| CN203965347U (en) * | 2014-07-08 | 2014-11-26 | 费密仪器科技（上海）有限公司 | The pretreated reaction unit of electron spectroscopy measurement sample in-situ in early stage |
| WO2018088771A1 (en) * | 2016-11-09 | 2018-05-17 | 고려대학교 산학협력단 | X-ray fluorescence analysis atomic layer deposition apparatus and x-ray fluorescence analysis atomic layer deposition method |
| CN110967363A (en) * | 2018-10-01 | 2020-04-07 | 盛达欧米科有限公司 | Hard X-ray photoelectron spectroscopy apparatus and system |
| CN113325022A (en) * | 2021-07-08 | 2021-08-31 | 上海科技大学 | Quasi-in-situ photoelectron spectroscopy testing device and testing method thereof |
-
2021
- 2021-10-21 CN CN202111225240.8A patent/CN113984922B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN201066334Y (en) * | 2007-07-30 | 2008-05-28 | 厦门大学 | Analysis and pre-processing device for electronic energy spectrum instrument sample |
| CN104062312A (en) * | 2014-06-09 | 2014-09-24 | 清华大学 | X-ray photoelectron spectroscopy (XPS) analysis method and system for researching interaction of plasma and material surface |
| CN203965347U (en) * | 2014-07-08 | 2014-11-26 | 费密仪器科技（上海）有限公司 | The pretreated reaction unit of electron spectroscopy measurement sample in-situ in early stage |
| WO2018088771A1 (en) * | 2016-11-09 | 2018-05-17 | 고려대학교 산학협력단 | X-ray fluorescence analysis atomic layer deposition apparatus and x-ray fluorescence analysis atomic layer deposition method |
| CN110967363A (en) * | 2018-10-01 | 2020-04-07 | 盛达欧米科有限公司 | Hard X-ray photoelectron spectroscopy apparatus and system |
| JP2020056789A (en) * | 2018-10-01 | 2020-04-09 | シエンタ・オミクロン・アーベー | Hard x-ray photoelectron spectroscopy device and system |
| CN113325022A (en) * | 2021-07-08 | 2021-08-31 | 上海科技大学 | Quasi-in-situ photoelectron spectroscopy testing device and testing method thereof |
Non-Patent Citations (3)
| Title |
|---|
| WUGEN HUANG等: "Atomic structures and electronic properties of Cr‐doped ZnO(10¯10) surfaces", 《CHINESE JOURNAL OF CATALYSIS》, vol. 42, no. 6, pages 971 * |
| 刘强等: "利用原位APXPS与STM研究H2在ZnO(10-10)表面的活化", 《物理化学学报》, vol. 34, no. 12, pages 1366 * |
| 赵冉等: "原子层沉积机理的原位光电子能谱研究进展", 《中国科学: 化学》, vol. 50, no. 6, pages 669 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116519727A (en) * | 2023-03-21 | 2023-08-01 | 浙江大学 | Scanning electron microscope and observation method for microstructure evolution of sample thereof |
| CN116519727B (en) * | 2023-03-21 | 2024-03-26 | 浙江大学 | Scanning electron microscope and observation method for microstructure evolution of sample thereof |
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