Helical Feeding Tube Furnace System for Preparing Two-Dimensional Materials and Its Usage Method

Abstract

The present invention discloses a spiral feeding tube furnace system for preparing two-dimensional materials and a method for using the same. The spiral feeding tube furnace system includes a furnace tube, a feeder, a rotating motor, a spiral feeding rod, a first heating system, a second heating system, a product collection device and a by-product collection device. The feeder is connected to the furnace tube and is used for feeding powder materials into the furnace tube. The furnace tube includes a reaction chamber and a product collection chamber. The rotating motor is connected to the spiral feeding rod, and drives the powder materials to move in the furnace tube through the rotation of the spiral feeding rod, sequentially passing through the reaction chamber and the product collection chamber. The first heating system surrounds the reaction chamber, and the second heating system surrounds the product collection chamber. The product collection device is connected to the product collection chamber and is used for collecting the powder materials pushed by the spiral feeding rod. The by-product collection device is used for collecting the powder formed by the gas-phase condensation in the furnace tube. The present invention realizes continuous reaction and collection.

Description

Technical Field

[0001] The present invention relates to the field of two-dimensional materials, and in particular to a spiral feeding tube furnace system for preparing two-dimensional materials and a method for using the same. Background Art

[0002] At present, the equipment for preparing two-dimensional materials, such as MXene and transition metal chalcogenides (MoS2, MoSe2, etc.), is mainly a tube furnace. The precursor material is placed at the center of the furnace chamber of the tube furnace, and an inert gas is introduced to heat the precursor material. After reaching the reaction temperature, a reactive gas is introduced to carry out the reaction to prepare the two-dimensional material. After the reaction is completed, the tube furnace stops heating, and the two-dimensional material is taken out to complete the entire preparation process of the two-dimensional material.

[0003] However, there are the following problems in preparing two-dimensional materials using a tube furnace: First, a large amount of precursor materials will accumulate in the furnace chamber of the tube furnace, and the contact with the reactive gas is insufficient, resulting in incomplete reaction and difficulty in complete reaction. Therefore, the preparation of two-dimensional materials using a tube furnace is only limited to the research and development level and is difficult to carry out large-scale preparation; Second, a large amount of intermediates will be generated when the reactive gas reacts with the raw material precursor to prepare the two-dimensional material. The intermediates will condense at the end of the tube furnace, causing blockage of the tube furnace and posing a safety hazard of explosion. Moreover, the intermediates condense on the inner wall of the furnace tube, making it difficult to effectively collect them. When sampling, it is easy to mix with the prepared two-dimensional material, resulting in a large amount of impurities in the two-dimensional material; Third, when using a tube furnace to prepare two-dimensional materials, only a single reaction can be carried out. After the reaction is completed, the tube furnace needs to be cleaned and dried, making it difficult to achieve large-scale continuous preparation of two-dimensional materials. Summary of the Invention

[0004] In view of this, it is necessary to provide a spiral feeding tube furnace system that can continuously prepare two-dimensional materials with high purity on a large scale.

[0005] In a first aspect of the present invention, there is provided a spiral feeding tube furnace system for preparing two-dimensional materials, characterized in that the spiral feeding tube furnace system includes a furnace tube, a feeder, a rotating motor, a spiral feeding rod, a first heating system, a second heating system, a product collection device, and a by-product collection device; the feeder is connected to the furnace tube and is used to feed powder materials into the furnace tube; the furnace tube includes a reaction chamber and a product collection chamber; the rotating motor is connected to the spiral feeding rod, and the rotation of the spiral feeding rod drives the powder materials to move in the furnace tube, sequentially passing through the reaction chamber and the product collection chamber; the first heating system surrounds the reaction chamber, and the second heating system surrounds the product collection chamber; the product collection device is connected to the product collection chamber and is used to collect the powder materials pushed by the spiral feeding rod; the by-product collection device is used to collect the powder formed by the gas-phase condensation in the furnace tube.

[0006] In some embodiments, the above-mentioned furnace tube further includes a by-product collection chamber, and the above-mentioned by-product collection device is communicated with the by-product collection chamber for collecting the powder formed by gas-phase condensation in the by-product collection chamber.

[0007] In some embodiments, the above-mentioned furnace tube includes: a first connecting furnace tube, a first heating zone furnace tube, a second heating zone furnace tube, and a second connecting furnace tube; the first connecting furnace tube is connected to the above-mentioned feeder, the first heating system surrounds the first heating zone furnace tube, and the inside of the first heating zone furnace tube is defined as the above-mentioned reaction chamber; the second heating system surrounds the second heating zone furnace tube, and the inside of the second heating zone furnace tube is defined as the above-mentioned product collection chamber; the inside of the second connecting furnace tube is defined as the above-mentioned by-product collection chamber, which is communicated with the above-mentioned by-product collection device.

[0008] In some embodiments, several product discharge ports are arranged in the above-mentioned product collection chamber, and these product discharge ports are respectively connected to the storage tanks of the above-mentioned product collection device.

[0009] In some embodiments, several by-product discharge ports are arranged in the above-mentioned by-product collection chamber, and these by-product discharge ports are respectively connected to the storage tanks of the above-mentioned by-product collection device.

[0010] In some embodiments, a cooling device is arranged outside the above-mentioned second connecting furnace tube for reducing the furnace temperature of the second connecting furnace tube so that the gas phase in the furnace tube can be condensed into solid powder faster.

[0011] In some embodiments, the above-mentioned by-product collection device is communicated with the gas outlet of the furnace tube.

[0012] In some embodiments, the above-mentioned by-product collection device includes a storage container and a cooling device arranged outside the storage container.

[0013] In some embodiments, the above-mentioned spiral feed tube furnace system includes a sealed magnetohydrodynamic flange and / or a plurality of adapter flanges.

[0014] In some embodiments, the above-mentioned rotating motor and the above-mentioned spiral feed rod form a spiral feeding device, and the above-mentioned furnace tube and the spiral feeding device are connected by using a sealed magnetohydrodynamic flange to realize the sealing function when the above-mentioned spiral feed rod rotates.

[0015] In some embodiments, the above-mentioned plurality of adapter flanges are used for assembling and connecting furnace tube components, and play a role of connection and sealing.

[0016] In some embodiments, the above-mentioned feeder continuously feeds the reaction raw material powder into the above-mentioned furnace tube within a predetermined time period to realize continuous preparation.

[0017] In some embodiments, the first heating system and the second heating system are the same heating device.

[0018] The second aspect of the present invention also provides a method for using the spiral feeding tube furnace system for preparing two-dimensional materials as described above, and the steps include:

[0019] Place a certain amount of powder material in the above-mentioned feeder;

[0020] Introduce a protective gas and / or a reaction gas into the interior of the above-mentioned furnace tube;

[0021] Turn on the above-mentioned first heating system to raise the reaction chamber of the above-mentioned furnace tube to the reaction temperature required for preparation and keep it warm;

[0022] Turn on the above-mentioned feeder and the above-mentioned rotating motor, and use the rotation of the above-mentioned spiral feeding rod to send the above-mentioned powder material into the reaction chamber of the above-mentioned furnace tube to carry out a gas-phase reaction to prepare the above-mentioned two-dimensional material;

[0023] Turn on the above-mentioned second heating system to raise the reaction product collection chamber of the furnace tube to a certain temperature and keep it warm; and

[0024] Collect the reaction product powder in the above-mentioned product collection device;

[0025] Collect the powder condensed from the gas phase in the above-mentioned furnace tube in the above-mentioned by-product collection device.

[0026] The third aspect of the present invention also provides another method for using the spiral feeding tube furnace system for preparing two-dimensional materials as described above, and the steps include:

[0027] Place a certain amount of mixed material in the above-mentioned feeder, the above-mentioned mixed material includes powder material and a reactant, and the reactant can be sublimated into a gas when heated in the above-mentioned furnace tube;

[0028] Turn on the above-mentioned first heating system to raise the reaction chamber of the above-mentioned furnace tube to the reaction temperature required for preparation and keep it warm;

[0029] Turn on the above-mentioned feeder and the above-mentioned rotating motor, and use the above-mentioned spiral feeding rod to send the above-mentioned mixed material into the reaction chamber of the above-mentioned furnace tube to carry out a gas-phase reaction to prepare the above-mentioned two-dimensional material;

[0030] Turn on the above-mentioned second heating system to raise the reaction product collection chamber of the above-mentioned furnace tube to a certain temperature and keep it warm; and

[0031] Collect the reaction product powder in the above-mentioned product collection device;

[0032] Collect the powder condensed from the gas phase in the above-mentioned furnace tube in the above-mentioned by-product collection device.

[0033] In some embodiments, the speed of the above-mentioned spiral feeding rod is from 0.01 cm / min to 100 cm / min.

[0034] In some embodiments, the set temperature of the above-mentioned first heating system is between 400 °C and 1500 °C; the set temperature of the above-mentioned second heating system is between room temperature and 1000 °C.

[0035] In some embodiments, the above-mentioned powder material is a MAX phase material and / or a MXene material.

[0036] In some embodiments, the above-mentioned reaction gas is a hydrogen halide, a halogen element, ammonia, phosphine, or a chalcogen hydride.

[0037] In some embodiments, the above-mentioned reactant is iodine, a chalcogen element, a halogen ammonium salt, or a halogen metal salt.

[0038] Compared with the prior art, the spiral feeding tube furnace system for preparing two-dimensional materials and its usage method provided by the present invention have the following advantages:

[0039] First, the use of the spiral feeding tube furnace system to prepare two-dimensional materials avoids the problem of insufficient reaction caused by the accumulation of a large amount of precursor materials in the furnace chamber of the tube furnace, and realizes the large-scale preparation of two-dimensional materials;

[0040] Second, the directional collection of the two-dimensional material products is realized, avoiding the explosion safety hazard caused by the condensation of intermediates at the tail end of the tube furnace, and making the prepared two-dimensional materials have high purity;

[0041] Third, the spiral feeding tube furnace system of the present invention includes a feeder and a product collection device for preparing two-dimensional materials, which can realize continuous reaction and collection, that is, realize the large-scale continuous preparation of two-dimensional materials. BRIEF DESCRIPTION OF THE DRAWINGS

[0042] Figure 1 FIG. is a schematic structural diagram of a spiral feeding tube furnace system for preparing two-dimensional materials provided in Embodiment 1 of the present invention.

[0043] Figure 2 FIG. is a schematic structural diagram of a spiral feeding tube furnace system for preparing two-dimensional materials provided in Embodiment 2 of the present invention.

[0044] Figure 3 FIG. is a schematic structural diagram of a spiral feeding tube furnace system for preparing two-dimensional materials provided in Embodiment 3 of the present invention.

[0045] Figure 4 10 kg of MXene Ti3C2Cl prepared by the spiral feeding tube furnace system in Specific Embodiment 1 of the present invention xOptical photograph.

[0046] Figure 5 For Specific Embodiment 1 of the present invention, the MAX phase material is Ti3AlC2 (a), and the target product MXene Ti3C2Cl is prepared by a spiral feeding tube furnace system x (b) Scanning electron microscope (SEM) photograph.

[0047] Figure 6 For Specific Embodiment 1 of the present invention, the MAX phase material is Ti3AlC2, and the target product MXene Ti3C2Cl is prepared by a spiral feeding tube furnace system x X-ray diffraction (XRD) pattern.

[0048] Figure 7 MXene Ti3C2Cl prepared by a common tube furnace provided for Comparative Example 1 of the present invention x XRD spectrum.

[0049] Explanation of main reference numerals:

[0050] 100, 200, 300 - Spiral feeding tube furnace system;

[0051] 10 - Furnace tube; 11 - First connecting furnace tube; 12 - First heating zone furnace tube; 13 - Second heating zone furnace tube; 14 - Second connecting furnace tube; 101 - First end; 102 - Second end; 103 - Gas outlet;

[0052] 20 - Feeder; 21 - Storage container; 22 - Connecting pipe; 221 - Gas valve; 23 - Damper valve; 24 - Pressure gauge;

[0053] 30 - Rotating motor;

[0054] 40 - Spiral feeding rod; 41 - Rotating bearing;

[0055] 51 - First heating system; 52 - Second heating system;

[0056] 60 - Product collection device; 61 - Storage tank; 62 - Storage tank; 63 - First discharge damper valve; 64 - Second discharge damper valve; 65 - Connection port; 651 - Ventilation valve; 66 - Connection port; 661 - Ventilation valve;

[0057] 70 - Intake device; 71 - First ventilation port; 711 - Ventilation valve; 72 - Second ventilation port; 721 - Ventilation valve; 73 - Third ventilation port; 731 - Pressure gauge;

[0058] 81 - Sealed magnetic fluid flange; 82 - Adapter flange; 83 - Adapter flange; 84 - Sealing flange; 85 - Adapter flange;

[0059] 90 - By - product collection device; 91 - By - product storage tank; 92 - Third discharge baffle valve; 93 - Connection port; 931 - Vent valve; 94 - Vent valve; 95 - Vent valve; 96 - Storage container; 961 - Exhaust valve; 97 - Cooling device. Detailed implementation manners

[0060] The technical solutions of the present invention are described below through specific embodiments. It should be understood that one or more steps mentioned in the present invention do not exclude the existence of other methods and steps before and after the combined steps, or other methods and steps can be inserted between these clearly mentioned steps. It should also be understood that these examples are only used to illustrate the present invention and not to limit the scope of the present invention. Unless otherwise specified, the numbers of each method step are only for the purpose of identifying each method step, rather than restricting the arrangement order of each method or limiting the implementation scope of the present invention. The change or adjustment of their relative relationship can also be regarded as the scope in which the present invention can be implemented under the condition of no substantial change in technical content.

[0061] The spiral - feed tube - type furnace system of the present invention is applicable to preparing two - dimensional materials including: MXene materials and / or two - dimensional transition metal chalcogenides (TDMs). Both of these two types of materials can obtain two - dimensional materials through gas - phase and solid - phase reactions.

[0062] One of the MXene materials can react with MAX - phase materials through a gas - phase etchant to etch the A component therein to obtain an accordion - like MXene material. The obtained accordion - like MXene material can obtain two - dimensional sheet - like MXene materials after further exfoliation steps. The implementation manner of small - scale preparation using a conventional tube furnace is described in the applicant's prior patent application "Method and System for Preparing Two - Dimensional Materials by Gas - Phase Method" (Application No.: 202011466046.4);

[0063] One of the transition metal chalcogenides can achieve a topological transformation reaction through chalcogen or pnictogen gases and MAX - phase materials to obtain two - dimensional transition metal chalcogenides with an accordion - like morphology or an expanded morphology. After further exfoliation steps, two - dimensional sheet - like transition metal chalcogenide materials can be obtained. The implementation manner of small - scale preparation using a conventional tube furnace and the topological transformation synthesis raw materials are described in the applicant's prior patent applications "Preparation Method of Expanded Transition Metal Chalcogenides" (Application No.: 201811080797.5) and "Synthesis Method of Two - Dimensional Transition Metal Chalcogenides" (Application No.: 201910995184.2).

[0064] The applicant summarized the characteristics and existing problems of the preparation processes of the above two types of two-dimensional materials, and proposed an apparatus for large-scale preparation of two-dimensional materials and a method for using the apparatus; the apparatus of the present invention can also be applicable to other scenarios where gas-solid powder reactions occur.

[0065] The spiral feed tube furnace system for preparing two-dimensional materials and the method for using the same provided by the present invention will be further described below with reference to the accompanying drawings.

[0066] Example 1

[0067] Please refer to Figure 1 , the first embodiment of the present invention provides a spiral feed tube furnace system 100 for preparing two-dimensional materials, which includes a furnace tube 10, a feeder 20, a rotating motor 30, a spiral feed rod 40, a first heating system 51, a second heating system 52, and a product collection device 60. Among them, the furnace tube 10 is sleeved inside the furnace body of the spiral feed tube furnace system. In this embodiment, the furnace tube 10 is composed of various pipe fittings connected by flanges, including: a first connecting furnace tube 11, a first heating zone furnace tube 12, and a second heating zone furnace tube 13; among them, the first connecting furnace tube 11 is used to connect external devices or equipment. In this embodiment, a connection port is provided on the first connecting pipe fitting, which is communicated with the storage container 21 of the feeder 20, so that the reaction raw material powder in the feeder 20 enters the furnace tube 10; the inside of the first heating zone furnace tube 12 is a reaction chamber (the preparation process of two-dimensional materials, that is, the process of gas-solid reaction, occurs in this reaction chamber), and the inside of the second heating zone furnace tube 13 is a product collection chamber.

[0068] In this embodiment, the first connecting furnace tube 11, the first heating zone furnace tube 12, and the second heating zone furnace tube 13 are respectively connected integrally through adapter flanges 82 and 83; it can be understood that in other embodiments, the first connecting furnace tube 11, the first heating zone furnace tube 12, and the second heating zone furnace tube 13 can also be integrally formed furnace tubes; or, the first heating zone furnace tube 12 and the second heating zone furnace tube 13 are integrally formed furnace tubes, that is, the first heating zone furnace tube 12 and the second heating zone furnace tube 13 are designed as two partitions of a furnace tube.

[0069] In other embodiments, the furnace tube of the present invention can also be increased with connecting pipes to achieve communication with other devices or equipment, realize the connection between the inside of the furnace tube and external components, and achieve specific functions, such as adding or removing materials.

[0070] The first connecting furnace tube 11 and the second heating zone furnace tube 13 are preferably made of a metal material that is convenient for forming. In this embodiment, the first connecting furnace tube 11 and the second heating zone furnace tube 13 are made of stainless steel. The first heating zone furnace tube 12 is made of a high-temperature and corrosion-resistant material, including quartz tubes, corundum tubes, ceramic tubes, graphite tubes, etc. In this embodiment, a quartz tube is selected.

[0071] The storage container 21 of the feeder 20 is connected to the first connecting furnace tube 11 through a connecting pipe. A baffle valve 23 is provided between the connecting pipes to control the connection or separation between the feeder 20 and the chamber of the furnace tube 10, so as to control the powder material to enter or stop entering the furnace tube 10, or control the gas to enter or be pumped out of the furnace tube 10. In this embodiment, a connecting pipe 22 is also connected in communication with the above-mentioned connecting pipe, which is used to connect a vacuum pump or a protective gas (such as argon) supply device. A gas valve 221 is provided on the connecting pipe to control the opening or closing of the connecting pipe 22. A pressure gauge 24 is also provided on the above-mentioned connecting pipe to monitor the pressure inside the feeder 20 in real time. In this embodiment, the connecting pipe 22 is connected to a vacuum pump (not shown in the figure) for vacuum pumping; in another embodiment, the connecting pipe 22 can also be connected to a protective gas supply device to introduce a protective gas into the feeder 20 or the furnace tube 10. In a preferred embodiment, the feeder 20 is an automatic feeding device that can continuously supply powder material to the furnace tube 10, so that the spiral feeding tube furnace system 100 of the present invention can realize continuous production.

[0072] The rotating motor 30 is connected to the spiral feeding rod 40 to realize the rotation of the spiral feeding rod 40, and the spiral feeding rod 40 is disposed inside the furnace tube 10. The spiral feeding rod 40 can push the powder material in the furnace tube 10 through rotation, so that the powder material continuously advances. During the forward movement of the powder material, it passes through the reaction chamber of the first heating zone furnace tube 12, and the powder material reacts with the reaction gas. The advancing speed range of the spiral feeding rod 40 is 0.01 cm / min to 100 cm / min, and the residence time of the material in the reaction chamber can be controlled by the advancing speed. The rotating motor 30 and the spiral feeding rod 40 form a spiral feeding device.

[0073] By designing the lengths of the first heating zone furnace tube 12 and the second heating zone furnace tube 13 and the rotation speed of the spiral feeding rod 40, the residence time of the powder material in the first heating zone furnace tube 12 and the second heating zone furnace tube 13 can be controlled. In some embodiments, optionally, the length of the first heating zone furnace tube 12 and / or the second heating zone furnace tube 13 can be between 0.5 m and 20 m.

[0074] The furnace tube 10 has opposite first end 101 and second end 102. The first end 101 is in communication with the intake device 70, and the second end 102 is in communication with the air outlet 103 through the sealing flange 84. In this embodiment, the first end 101 is one end of the first connecting furnace tube 11 and is connected to the screw feeding device through the sealing magnetic fluid flange 81. A rotating bearing 41 is provided at the second end and is connected to the screw feeding rod 40 to achieve sealing of the furnace body in the screw feeding tube furnace system 100 of the present invention when the screw feeding rod 40 is rotating. In some other embodiments, a plurality of rotating bearings can also be provided in the furnace tube 10 according to actual needs.

[0075] In this embodiment, the first end 101 of the furnace tube 10 is in communication with the intake device 70. The intake device 70 has a first ventilation port 71, a second ventilation port 72, and a third ventilation port 73. Among them, the first ventilation port 71 is set as a vacuum pumping port and is connected to a vacuum pump (not shown in the figure) to evacuate the reaction chamber. A ventilation valve 711 is provided at the first ventilation port 71 to control the opening or closing of the first ventilation port 71. The second ventilation port 72 is set to be connected to a protective gas supply device (not shown in the figure) to introduce a protective gas (such as argon) into the reaction chamber. A ventilation valve 721 is provided at the second ventilation port 72 to control the opening or closing of the second ventilation port 72. The third ventilation port 73 is indirectly in communication with the first end 101 of the furnace tube 10. A pressure gauge is also provided at one end close to the third ventilation port 73 to monitor the pressure in the furnace tube 10 (reaction vessel) in real time.

[0076] The first heating system 51 surrounds the first heating zone furnace tube 12 to achieve the heating function and provide the reaction temperature for the reaction chamber. The second heating system 52 surrounds the second heating zone furnace tube 13 to achieve the heating function and provide the required temperature for the product collection chamber. It can be understood that in some embodiments, the first heating system 51 and the second heating system 52 in the present invention can also be the same heating system, providing the same heating temperature to the first heating zone furnace tube 12 and the second heating zone furnace tube 13.

[0077] The product collection device 60 is connected to the product collection chamber (i.e., the furnace tube of the second heating zone) and is used to collect the powder product propelled into the product collection chamber by the spiral feed rod 40. (In the intention of the present invention, the powder of the reaction product is the target product two-dimensional material. Of course, according to different reactions, it can be other powder products). In this embodiment, the product collection device 60 includes two storage tanks 61 and 62. The two storage tanks 61 and 62 are respectively communicated with the product discharge port of the furnace tube 13 of the second heating zone. A first discharge baffle valve 63 and a second discharge baffle valve 64 are respectively arranged on the connecting pipes of the communication. Connecting ports 65 and 66 are respectively arranged on the connecting pipes of the communication and are used to connect a vacuum pump or a protective gas supply device to realize the function of evacuating the storage tanks 61 and 62 or introducing a protective gas, so as to avoid the oxidation of the product powder collected in the storage tanks 61 and 62. Vent valves 651 and 661 are respectively arranged on the connecting ports 65 and 66 to control the opening or closing of the connecting ports 65 and 66. In some embodiments, if the product powder itself has antioxidant properties or is stable in air, the treatment of evacuating or introducing an inert gas may not be provided.

[0078] In another embodiment, the product collection device 60 can also be provided with multiple storage tanks (≥3), which are connected to the product collection chamber (i.e., the furnace tube of the second heating zone). The advantage of providing more than two storage tanks is that the storage tanks can be used alternately to achieve continuous production. For example, in this embodiment, first open the first discharge baffle valve 63, close the second discharge baffle valve 64, and enable the storage tank 61. After the storage tank 61 is filled, close the first discharge baffle valve 63, open the second discharge baffle valve 64, and enable the storage tank 62. And so on, the storage tanks are used alternately to continuously collect the product powder. Of course, in another embodiment, such as in small-batch production, the product collection device 60 can also be provided with one storage tank.

[0079] Embodiment 2

[0080] Please refer to Figure 2 , the second embodiment of the present invention provides another spiral feed tube furnace system 200 for preparing two-dimensional materials, which is similar to the spiral feed tube furnace system 100 of the first embodiment. The difference is that in this embodiment, the furnace tube 10 is composed of connecting various part pipe fittings through flanges. In addition to the first connecting furnace tube 11, the first heating zone furnace tube 12 and the second heating zone furnace tube 13, it also includes a second connecting furnace tube 14. The second connecting furnace tube 14 is connected to the second heating zone furnace tube 13 through a transfer flange 85 and is communicated with the air outlet 103 through a sealing flange 84. The spiral feed rod 40 penetrates through the furnace tube 10. The inside of the second connecting furnace tube 14 is defined as a by-product collection cavity. The second connecting furnace tube 14 is also preferably made of a metal material (such as stainless steel) that is easy to process and form.

[0081] In the spiral feed tube furnace system 200 of this embodiment, a by-product collection device 90 is further included, which is communicated with the by-product collection cavity (i.e., the second connecting furnace tube 14). Similar to the product collection device 60, the by-product collection device 90 includes a by-product storage tank 91. The by-product storage tank 91 is communicated with the second connecting furnace tube 14. Third discharge baffle valves 92 are respectively arranged on the connecting pipes of the communication, and a connection port 93 is also arranged on the communicating connecting pipe to realize the function of evacuating the by-product storage tank 91 or introducing a protective gas, so as to prevent the by-product powder collected in the by-product storage tank 91 from being oxidized; A ventilation valve 931 is also arranged on the connection port 93 to control the opening or closing of the connection port 93. In some embodiments, the by-product powder itself has antioxidant properties or is stable in air, and the treatment of evacuating or introducing a protective gas may not be provided.

[0082] In other embodiments, in order to realize the continuous collection of the by-product powder, the by-product collection device 90 can also include multiple storage tanks (≥2), so as to realize alternate use.

[0083] The added second connecting furnace tube 14 and the by-product collection device 90 in this embodiment are used to collect the powder material generated after the gas phase condensation in the furnace tube 10. In actual production, the reaction gas is introduced into the furnace tube 10 through the intake device 70, passes through the reaction cavity (the first heating zone furnace tube 12), and the reaction gas and the reaction raw material (powder material) carry out a gas-solid reaction to produce a gas phase by-product; that is, after passing through the first heating zone furnace tube 12, the gas phase components of the gas in the furnace tube 10 include the excess reaction gas and the gas phase by-product. Since the second heating system 52 is provided to provide heat to the required temperature, these gases still remain in the gas phase in the second heating zone furnace tube 13 and continue to enter the second connecting furnace tube 14 (the by-product collection cavity). In the second connecting furnace tube, some or all of these gases condense into by-product powder, and are pushed into the by-product collection device 90 by the rotation of the spiral feed rod 40, while realizing the collection of the by-product powder generated after condensation in the reaction system.

[0084] In other embodiments, in order to quickly condense the gas in the second connecting furnace tube 14, a cooling device, such as a circulating water cooling device, can also be arranged outside the second connecting furnace tube 14 to realize the rapid condensation of the by-product into powder for easy collection.

[0085] Embodiment III

[0086] Please refer to Figure 3, the third embodiment of the present invention provides another spiral feeding tubular furnace system 300 for preparing two-dimensional materials. Similar to the spiral feeding tubular furnace system 100 in the first embodiment, the difference is that in this embodiment, a by-product collection device 90 is connected to the gas outlet 103, which is used to cool and condense the gas flowing out of the gas outlet 103 of the furnace tube 10 into powder for collection. The gas phase components of this gas include excess reaction gas and gas-phase by-products. In this embodiment, the by-product collection device 90 includes a storage container 96, on which an exhaust valve 961 is provided to exhaust uncondensed gas. A cooling device 97, more specifically a circulating water cooling device, is provided outside the storage container 96. In actual production, by opening the gas valve 94 and closing the gas valve 95, the gas discharged from the gas outlet 103 can enter the by-product collection device 90 for collection.

[0087] Embodiment 4

[0088] The fourth embodiment of the present invention provides a method for using the spiral feeding tubular furnace system 200 for preparing two-dimensional materials, which includes the following steps:

[0089] S11, Place a certain amount of powder material in the feeder 20, close the baffle valve 23, open the gas valve 221, after performing vacuum treatment from the connecting pipe 22, then introduce a protective gas to normal pressure;

[0090] S12, Open the vent valve 711, perform vacuum treatment on the furnace tube 10 from the first vent 71, close the vent valve 711, then open the vent valve 721, introduce a protective gas into the furnace tube 10 from the second vent 72, after the inside of the furnace tube returns to normal pressure state, and stop introducing the protective gas;

[0091] S13, Introduce a reaction gas into the furnace tube 10 from the second vent 72, fill the inside of the furnace tube 10 with the reaction gas, then open the first heating system 51, heat the reaction chamber of the furnace tube 12 in the first heating zone to the reaction temperature required for preparing two-dimensional materials, and keep it warm;

[0092] S14, Open the feeder 20, the baffle valve 23 and the rotating motor 30, use the rotating motor 30 to drive the spiral feeding rod 40 to send the powder material in the feeder 20 into the reaction chamber of the furnace tube 12 in the first heating zone, and perform a gas-phase reaction to prepare the two-dimensional material;

[0093] S15, Open the second heating system 52, heat the product collection chamber of the furnace tube 13 in the second heating zone to a certain temperature, and keep it warm; and

[0094] S16. Open the first discharge baffle valve 63 to collect the reaction product two-dimensional material in the storage tank 61. After the storage tank 61 is full, close the first discharge baffle valve 63 and open the second discharge baffle valve 64 to collect the reaction product two-dimensional material in another storage tank 62. During continuous production, the two storage tanks can be used alternately.

[0095] S17. Open the third discharge baffle valve 92. By rotating the screw feed rod 40, the by-products and / or excess reaction gases in the gas phase that condense into powder in the second connecting furnace tube 14 are driven into the by-product storage tank 91 in the by-product collection device 90. During continuous production, multiple (≥2) by-product storage tanks can also be provided and used alternately.

[0096] Example Five

[0097] The fifth embodiment of the present invention provides another method for using the screw-feed tube furnace system 200 for preparing two-dimensional materials, which includes the following steps:

[0098] S21. Place a certain amount of mixed material in the feeder 20. The mixed material includes powder material and a reactant. The reactant powder can be sublimated into a gas when heated in the furnace tube 10 to realize the reaction between the gaseous reactant and the powder material. Close the baffle valve 23, open the gas valve 221, evacuate through the connecting pipe 22, and then introduce a protective gas to normal pressure.

[0099] S22. Open the vent valve 711 to evacuate the furnace tube 10 from the first vent 71. Close the vent valve 711, then open the vent valve 721 to introduce a protective gas into the furnace tube 10 from the second vent 72. After the inside of the furnace tube returns to normal pressure, stop introducing the protective gas.

[0100] S23. Open the first heating system 51 to raise the reaction chamber of the furnace tube 12 in the first heating zone to the reaction temperature required for preparing the two-dimensional material and keep it warm.

[0101] S24. Open the baffle valve 23 and the rotating motor 30 of the feeder 20, and use the rotating motor 30 to drive the screw feed rod 40 to send the mixed material in the feeder 20 into the reaction chamber of the furnace tube 10. In the reaction chamber, the reactant in the mixed material is heated and sublimated (vaporized) to carry out a gas-phase reaction to prepare the two-dimensional material.

[0102] S25. Open the second heating system 52 to raise the product collection chamber of the furnace tube 13 in the second heating zone to a certain temperature and keep it warm; and

[0103] S26. Open the first discharge baffle valve 63 to collect the reaction product two-dimensional material in the storage tank 61. After the storage tank 61 is full, close the first discharge baffle valve 63, open the second discharge baffle valve 64, and collect the reaction product two-dimensional material in another storage tank 62. During continuous production, the two storage tanks can be used alternately.

[0104] S27. Open the third discharge baffle valve 92. Rotate the screw feed rod 40 to drive the by-products and / or excess reaction gas in the second connecting furnace tube 14 that have condensed into powder to the by-product storage tank 91 in the by-product collection device 90. During continuous production, multiple (≥2) by-product storage tanks can also be set up and used alternately.

[0105] In step S11 or S21, the powder material is the raw material for preparing the two-dimensional material and is related to the type of the two-dimensional material. In a specific embodiment, the powder material is a MAX phase material and / or an MXene material. The MAX phase material, such as Ti3AlC2, and the MXene material, such as Ti3C2T x , and of course, it can also be replaced with other types of MAX phases or MXene materials.

[0106] First, evacuate the furnace tube 10 and the feeder 20 and then fill them with a protective gas to prevent air from entering the furnace tube 10 and affecting the reaction.

[0107] In step S12, in some embodiments, a mixed gas of a reaction gas and a protective gas is introduced through the gas supply valve 721. The protective gas is an inert gas, such as argon, etc. The reaction gas is a gas that can chemically react with the powder material, including hydrogen halides (such as HCl, HBr, HI), iodine vapor, chalcogen hydrides (such as H2S, H2Se, H2Te), ammonia, phosphine, etc. In other embodiments, the protective gas and the reaction gas can also be introduced sequentially, such as first introducing the protective gas and then introducing the reactive gas. In a specific embodiment, a mixed gas of hydrogen chloride (HCl) and argon is introduced.

[0108] In step S21, in some embodiments, the powder material in the mixed material is a MAX phase material and / or an MXene material, and the reactant is a single chalcogen element powder, such as sulfur powder, selenium powder, tellurium powder, or it can also be a solid powder that decomposes to form a chalcogen hydride, such as ammonium sulfide, etc., or a metal halide with a low boiling point (boiling point < 1000°C).

[0109] In step S13 or S23, the reaction temperature is related to the type of two-dimensional material or the type of powder material. Generally, the reaction temperature ranges from 300°C to 1500°C. In a specific embodiment, the powder material is Ti3AlC2 and the reaction temperature is 700°C.

[0110] In step S14 or S24, the speed of the screw feed rod 40 is from 0.01 cm / min to 100 cm / min, which is related to the reaction rate of the reaction gas and the powder material. The residence time of the reaction raw material powder material in the furnace tube 12 of the first heating zone, that is, the reaction time, can be controlled by the speed of the screw feed rod 40. Preferably, the speed of the screw feed rod 40 is 1 cm / min, 10 cm / min, 20 cm / min, 40 cm / min, 60 cm / min, 80 cm / min, 100 cm / min. In a specific embodiment, the speed of the screw feed rod 40 is 10 cm / min, the length of the furnace tube 12 of the first heating zone is 3 m, and the residence time (reaction time) of the reaction raw material powder material in the furnace tube 12 of the first heating zone is controlled to be about 30 min; the length of the furnace tube 13 of the second heating zone is 1 m, and the residence time in the furnace tube 13 of the second heating zone is about 10 min.

[0111] In step S15 or S25, the temperature of the product collection chamber of the furnace tube 13 of the second heating zone is also related to the type of two-dimensional material or the type of powder material. The temperature of this product collection chamber should be equal to or greater than the boiling point temperature of the by-product and less than the melting point of the two-dimensional material, so as to avoid the condensation of the by-product on the tube wall at one end of the furnace tube 10 and avoid damaging the structure of the target product two-dimensional material. In a specific embodiment, the powder material is Ti3AlC2, the reaction gas is HCl, and after the reaction of Ti3AlC2 and HCl, a MXene material with an accordion morphology and a by-product AlCl3 (boiling point 178°C) are obtained. Therefore, the temperature of the product collection chamber of the furnace tube 13 of the second heating zone is set to be >178°C, and preferably the set range is from 200°C to 400°C.

[0112] Example Six

[0113] The sixth embodiment of the present invention provides another method for using the screw feed tube furnace system 300 for preparing two-dimensional materials. Similar to Embodiments Four and Five, the difference is that after the gas in the furnace tube 10 passes through the air outlet 103, it enters the by-product collection device 90, and the gaseous by-product and / or the excess reaction gas condense into powdery by-product powder and are stored in the storage container 96.

[0114] Example Seven

[0115] The seventh embodiment of the present invention provides a method for using a spiral feeding tube furnace system for continuous production and preparation of two-dimensional materials. The spiral feeding tube furnace system 200 is taken as an example, wherein the feeder 20 is an automatic feeder, which can continuously transport the powder material in the storage container 21 to the furnace tube 10 at a predetermined speed, and more specifically enter the chamber of the first connected furnace tube 11 through a connecting pipeline.

[0116] Before continuous production and preparation, the furnace tube 10 is evacuated and then a protective gas (argon) is introduced, and the first heating system 51 and the second heating system 52 are turned on to raise the furnace temperature to a predetermined temperature; the rotary motor 30 is turned on to drive the screw feed rod 40 to rotate; the first discharge damper valve 63 is opened, the second discharge damper valve 64 is closed, and the third discharge damper valve 92 is opened;

[0117] Open the feeder 20 again, and the powder material enters the furnace tube 10. As the spiral feed rod 40 rotates, it enters the reaction chamber in the furnace tube 12 in the first heating zone for gas-solid reaction. Driven by the rotation of the spiral feed rod 40, the reaction product powder enters the product collecting chamber in the furnace tube 13 in the second heating zone, and enters the storage tank 61 of the product collecting device 60 through the product collecting port. When the storage tank 61 is nearly full, close the first discharge baffle valve 63, and open the second discharge baffle valve 64, so that the reaction product powder enters the storage tank 62. The two storage tanks are used alternately to realize continuous production and preparation.

[0118] Open the third discharge baffle valve 92, and through the rotation of the spiral feed rod 40, the gaseous by-products and / or excess reaction gases in the second connecting furnace tube 14 are condensed into powder and driven to the by-product storage tank 91 in the by-product collection device 90. In this embodiment, two by-product storage tanks can also be set up for alternating use to achieve continuous production and collect by-product powder at the same time. Specific embodiment 1

[0120] The following uses the MAX phase material as Ti3AlC2 and the halogen hydride gas as commercial HCl liquefied gas as an example to illustrate the use of the spiral feeding tube furnace system 200 for preparing two-dimensional materials in the present invention, or the use of the spiral feeding tube furnace system 200 to prepare MXene Ti3C2Cl x The method of the two-dimensional material comprises the following steps:

[0121] (1) Place 2 kg of powdered MAX phase material Ti3AlC2 in the feeder 20, close the damper valve 23, open the gas valve 221, evacuate the feeder 20, and then close it;

[0122] (2) Open the vent valve 711 to evacuate the furnace tube 10;

[0123] (3) Close the ventilation valve 711 and open the ventilation valve 721. Introduce a mixed gas of argon and HCl from the second ventilation port 72 so that the interior of the furnace tube 10 is filled with the mixed gas. Preferably, the volume fraction of HCl in the mixed gas ranges from 5% to 50%. In a specific embodiment, a mixed gas with a volume fraction of HCl of 10% is selected for introduction.

[0124] (4) Turn on the first heating system 51 to raise the temperature of the reaction chamber of the first heating zone furnace tube 12 to 700 °C and perform heat preservation treatment.

[0125] (5) Turn on the feeder 20 and the rotating motor 30, adjust the speed of the spiral feeding rod 40 to 1 cm / min, and use the spiral feeding rod 40 to send the powder material in the feeder 20 into the reaction chamber of the first heating zone furnace tube 12 to carry out gas-phase reaction to prepare two-dimensional materials. Specifically, the HCl gas reacts with the MAX phase material Ti3AlC2, and the HCl etches the Al element in Ti3AlC2 to generate the MXene material Ti3C2Cl x and the by-product AlCl3 (boiling point 178 °C).

[0126] (6) Turn on the second heating system 52 to raise the temperature of the product collection chamber of the second heating zone furnace tube 13 to 400 °C and perform heat preservation treatment. At this temperature, the by-product AlCl3 is in a gaseous state.

[0127] (7) Open the first discharge baffle valve 63 to continuously collect the reaction product powder (two-dimensional material) in the storage tank 61.

[0128] (8) Open the third discharge baffle valve 92 to continuously collect the reaction by-product powder (AlCl3) in the by-product storage tank 91. In the spiral feeding tube furnace system 200 in this embodiment, the by-product AlCl3 cools in the by-product collection chamber of the second connecting furnace tube 14 and condenses into solid AlCl3 powder. By the rotation of the spiral feeding rod 40, the solid AlCl3 powder is collected in the by-product storage tank 91 to obtain high-purity AlCl3 chemicals, and the excess gas (including unreacted HCl, argon, etc.) is discharged through the gas outlet 103.

[0129] In specific embodiment 1, after the reactants in the feeder 20 are completely fed and all the precursors have reacted, the reaction device is cooled down, and then the target product MXene Ti3C2Cl in the storage tank 61 is taken out. x . Figure 4 Figure 10 is a photograph of 10 kg of MXene Ti3C2Cl prepared using the spiral feeding tube furnace system 200. For the MAX phase material Ti3AlC2 and the target product MXene Ti3C2Cl x x ​Scanning electron microscopy (SEM) tests were carried out separately, and the results are as Figure 5 shown. Figure 5 In a, it is the SEM photo of the MAX phase material Ti3AlC2, Figure 5 and in b, it is the SEM photo of MXene Ti3C2Clx. By comparing Figure 5 a and b in it, it can be seen that the morphology of Ti3AlC2 is a three-dimensional block structure, while the target product MXene Ti3C2Cl x shows an obvious accordion-like layered structure.

[0130] X-ray diffraction (XRD) analysis was carried out on the MAX phase material Ti3AlC2 and the target product MXene Ti3C2Cl x , and the results are as Figure 6 shown. The (002) peak in the raw material Ti3AlC2 appears at the position of 9.5°, while the (002) peak in the target product MXene Ti3C2Cl x after reaction with hydrogen chloride (HCl) shifts to a lower angle to 8.0°. This indicates that the HCl gas completely etched the Al element in Ti3AlC2 during the gas-phase etching reaction, generating the accordion-like structured Ti3C2Cl x MXene, resulting in an expansion of the interlayer spacing, which is consistent with the results of the scanning electron microscopy photos of Ti3C2T x . It can also be seen from the XRD test of the target product that the product does not contain the characteristic peaks of the raw material MAX phase material, indicating the high purity of the obtained product.

[0131] Comparing Example 1

[0132] The method for preparing MXene Ti3C2Cl x two-dimensional material by using a common tube furnace includes the following steps:

[0133] (1) Place 2 kg of powdered Ti3AlC2 inside the common tube furnace;

[0134] (2) Continuously introduce HCl gas into the tube furnace to fill the reaction chamber inside the tube furnace with HCl gas;

[0135] (3) Heat the tube furnace to 700 °C for gas-phase reaction to obtain the target product.

[0136] Furthermore, XRD characterization was carried out on the material obtained in Comparative Example 1, as Figure 7 shown. The product prepared in Comparative Example 1 shows the corresponding peaks of Ti3AlC2 and Ti3C2Cl at the positions of 9.5° and 8.0° simultaneously xThe (002) characteristic diffraction peak of MXene indicates that both Ti3AlC2 and Ti3C2Cl coexist in the product. x This shows that it is difficult to achieve complete conversion of a large amount of MAX phase to MXene in a common tube furnace. Specific Example 2

[0138] This example provides a method for preparing MXene Ti3C2I x using the spiral feeding tube furnace system 200 for two-dimensional materials, or a method for preparing MXene Ti3C2I x using the spiral feeding tube furnace system 300 for two-dimensional materials, which includes the following steps:

[0139] (1) Place 2 kg of a mixed material of powdered MAX phase material Ti3AlC2 and solid iodine powder (the mass ratio of Ti3AlC2 to iodine powder is 1:10) in the feeder 20. Open the gas valve 221, evacuate the feeder 20 and then close it.

[0140] (2) Open the ventilation valve 711, evacuate the furnace tube 10, close the ventilation valve 711, open the ventilation valve 721, and introduce argon from the second ventilation port 72 until the furnace tube 10 returns to normal pressure.

[0141] (3) Open the first heating system 51 to heat the reaction chamber of the furnace tube 12 in the first heating zone to 700 °C and keep it warm.

[0142] (4) Open the feeder 20 and the spiral feeding rod 40, adjust the speed of the spiral feeding rod 40 to 1 cm / min, and use the spiral feeding rod 40 to send the mixed material in the feeder 20 into the reaction chamber of the furnace tube 12 in the first heating zone to carry out a gas-phase reaction to prepare the two-dimensional material. Specifically, the iodine powder sublimes into iodine vapor and reacts with the MAX phase material Ti3AlC2. The iodine vapor etches the Al element in Ti3AlC2 to generate the MXene material Ti3C2I x and the by-product AlI3 (boiling point 382 °C).

[0143] (5) Open the second heating system 52 to heat the product collection chamber of the furnace tube 13 in the second heating zone to 600 °C and keep it warm. At this temperature, the by-product AlI3 is in a gaseous state.

[0144] (6) Open the first discharge baffle valve 63 and / or the second discharge baffle valve 64 to continuously collect the reaction product two-dimensional material in the storage tank 61 and / or the storage tank 62.

[0145] (7) Open the third discharge baffle valve 92, continuously collect the reaction intermediate (by-product AlI3) in the by-product storage tank 91. When the gas in the furnace tube 10 passes through the second connecting furnace tube 14, due to the decrease in furnace temperature, the by-product AlI3 condenses into solid powder, and is pushed into the by-product storage tank 91 for collection as the spiral feed rod 40 rotates, obtaining high-purity AlI3 chemical.

[0146] In some embodiments, the evacuation treatment in this embodiment can also be replaced by introducing a protective gas to exclude the air in the furnace tube 10 and / or the feeder 20.

[0147] In some embodiments, the reactant in this embodiment can also be replaced by other chemicals that can sublime or vaporize by heating. For the powder material being MAX phase material, such reactants with etching effect can also be ammonium halides (such as NH4Cl, NH4I, etc.), metal halide salts (such as ZnCl2, CuCl2, etc.). Adjust the temperatures of the first and second heating systems according to the characteristics of different reactants to achieve the preparation of two-dimensional materials. Specific Embodiment 3

[0149] The method of this embodiment is similar to that of Specific Embodiment 2, the difference being that the mixed material selects Ti3AlC2 and ZnCl2 elemental powders. In step 3, open the first heating system 51 to raise the temperature of the reaction chamber of the first heating zone furnace tube 12 to 1000 °C and perform heat preservation treatment; in step 5, open the second heating system 52 to raise the temperature of the product collection chamber of the second heating zone furnace tube 13 to 800 °C and perform heat preservation treatment. At this temperature, the by-product AlCl3 and the excess ZnCl2 are in a gaseous state. Specific Embodiment 4

[0151] This embodiment provides a method for using the spiral feed tube furnace system 100 for preparing two-dimensional transition metal chalcogenide materials, or a method for preparing two-dimensional transition metal chalcogenide materials using the spiral feed tube furnace system 100. Taking the preparation of MoS2 as an example, it includes the following steps:

[0152] (1) Place 2 kg of powdered MAX phase material Mo2GeC in the feeder 20;

[0153] (2) Introduce a mixed gas of argon and H2S from the gas inlet valve 721 to fill the inside of the furnace tube 10 with the mixed gas; preferably, the volume fraction of H2S in the mixed gas is between 5% and 50%. In a specific implementation, a mixed gas with a volume fraction of H2S of 10% is selected to be introduced;

[0154] (3) Turn on the first heating system 51 to raise the temperature of the reaction chamber of the furnace tube 12 in the first heating zone to 800 °C and perform heat preservation treatment;

[0155] (4) Turn on the feeder 20 and the spiral feeding rod 40, adjust the speed of the spiral feeding rod 40 to 0.2 cm / min, and use the spiral feeding rod 40 to send the powder material in the feeder 20 into the reaction chamber of the furnace tube 12 in the first heating zone to carry out a gas-phase reaction to prepare the two-dimensional material. Specifically, the H2S gas undergoes a topological transformation reaction with the MAX phase material Mo2GeC, and the S element replaces the Ge element and the C element in Mo2GeC to generate MoS2 and a by-product germanium hydride (GeH4, gaseous at room temperature);

[0156] (5) Open the first discharge baffle valve 63 and / or the second discharge baffle valve 64 to continuously collect the reaction product two-dimensional material in the storage tank 61 and / or the storage tank 62;

[0157] (6) Continuously discharge the reaction intermediate (by-product GeH4) through the air outlet 103.

[0158] In this embodiment, the second heating system 52 is not required, or it can be understood that the temperature set by the second heating system 52 is room temperature. Specific Example 5

[0160] This embodiment provides a method for using the spiral feeding tube furnace system 300 for preparing transition metal chalcogenide two-dimensional materials, or a method for preparing transition metal chalcogenide two-dimensional materials using the spiral feeding tube furnace system 300. Taking the preparation of MoS2 as an example, it includes the following steps:

[0161] (1) Place 2 kg of a mixed material of powdered MXene material Mo2C and elemental sulfur powder in the feeder 20, and the molar ratio of Mo2C to elemental sulfur powder is 1:(1 - 1.5);

[0162] (2) Introduce argon gas through the gas vent valve 721 to fill the inside of the furnace tube 10 with argon gas;

[0163] (3) Turn on the first heating system 51 to raise the temperature of the reaction chamber of the furnace tube 12 in the first heating zone to 800 °C and perform heat preservation treatment;

[0164] (4) Turn on the feeder 20 and the spiral feeding rod 40, adjust the speed of the spiral feeding rod 40 to 0.5 cm / min, and use the spiral feeding rod 40 to send the mixed material in the feeder 20 into the reaction chamber of the furnace tube 12 in the first heating zone to carry out a gas-phase reaction to prepare the two-dimensional material. Specifically, the elemental sulfur powder sublimes into a gas state and undergoes a topological transformation reaction with the MXene material Mo2C, and the S element replaces the C element to generate MoS2;

[0165] (5) Turn on the second heating system 52 to raise the temperature of the product collection chamber of the furnace tube 13 in the second heating zone to 200 °C and perform heat preservation treatment. At this temperature, elemental sulfur is in a gaseous state;

[0166] (6) Open the first discharge baffle valve 63 and / or the second discharge baffle valve 64 to continuously collect the reaction product two-dimensional material in the storage tank 61 and / or the storage tank 62;

[0167] (7) Open the third discharge baffle valve 92, and the gas in the furnace tube 10 enters the storage container 96 through the gas outlet 103. Since a cooling device 97 is provided outside the storage container 96, the gaseous sulfur therein condenses into solid elemental sulfur powder in the storage container 96 and can be recycled, and the excess gas is discharged through the exhaust valve 961.

[0168] In this embodiment, the sulfur powder can also be replaced with other elemental powder of chalcogen elements, such as selenium powder, tellurium powder, etc., to obtain two-dimensional transition metal chalcogenide.

[0169] The foregoing description of the specific exemplary embodiments of the present invention is for purposes of illustration and exemplification. These descriptions are not intended to limit the present invention to the precise forms disclosed, and obviously, many changes and variations are possible in light of the above teachings. The purpose of selecting and describing the exemplary embodiments is to explain the specific principles of the present invention and its practical applications, so that those skilled in the art can implement and utilize various different exemplary embodiments of the present invention, as well as various different selections and changes. The scope of the present invention is intended to be defined by the claims and their equivalents.

Claims

1. A method for using a spiral feeding tube furnace system for preparing two-dimensional materials, characterized in that, The spiral feed tube furnace system includes a furnace tube, a feeder, a rotating motor, a spiral feed rod, a first heating system, a second heating system, a product collection device, and a by-product collection device; The feeder is connected to the furnace tube and is used to feed powder materials into the furnace tube; The furnace tube includes a reaction chamber and a product collection chamber; The rotating motor is connected to the spiral feed rod, and the rotation of the spiral feed rod drives the powder material to move in the furnace tube, sequentially passing through the reaction chamber and the product collection chamber; The first heating system surrounds the reaction chamber, and the second heating system surrounds the product collection chamber; The product collection device is connected to the product collection chamber and is used to collect the powder pushed by the spiral feed rod; The by-product collection device is used to collect the powder formed by the condensation of the gas phase in the furnace tube; The furnace tube further includes a by-product collection chamber, and the by-product collection device is communicated with the by-product collection chamber and is used to collect the powder formed by the condensation of the gas phase in the by-product collection chamber; The furnace tube includes: a first connecting furnace tube, a first heating zone furnace tube, a second heating zone furnace tube, and a second connecting furnace tube; the first connecting furnace tube is connected to the feeder, the first heating system surrounds the first heating zone furnace tube, and the inside of the first heating zone furnace tube is defined as the reaction chamber; the second heating system surrounds the second heating zone furnace tube, and the inside of the second heating zone furnace tube is defined as the product collection chamber; the inside of the second connecting furnace tube is defined as the by-product collection chamber and is communicated with the by-product collection device; The usage method includes the following steps: Place a certain amount of powder materials in the feeder; Introduce a protective gas and / or a reaction gas into the inside of the furnace tube; Turn on the first heating system to heat the reaction chamber of the furnace tube to the required reaction temperature for preparation and keep it warm; Turn on the feeder and the rotating motor, and use the rotation of the spiral feed rod to send the powder materials into the reaction chamber of the furnace tube to carry out a gas-phase reaction to prepare the two-dimensional material; Turn on the second heating system to heat the reaction product collection chamber of the furnace tube to a certain temperature and keep it warm; and Collect the reaction product powder in the product collection device; Collect the powder formed by the condensation of the gas phase in the furnace tube in the by-product collection device.

2. The method of using the spiral feeding tubular furnace system for preparing two-dimensional materials as claimed in claim 1, wherein Several product discharge ports are provided in the product collection chamber, and the product discharge ports are respectively connected to the storage tanks of the product collection device; And / or, several by-product discharge ports are provided in the by-product collection chamber, and the by-product discharge ports are respectively connected to the storage tanks of the by-product collection device.

3. The method of using the spiral feeding tube furnace system for preparing two-dimensional materials according to claim 1, characterized in that, A cooling device is provided outside the second connecting furnace tube.

4. The method of using a spiral feeding tube furnace system for preparing two-dimensional materials according to claim 1, characterized in that, The by-product collection device is communicated with the gas outlet of the furnace tube.

5. The method for using the spiral feeding tube furnace system for preparing two-dimensional materials according to claim 4, wherein, The by-product collection device includes a storage container and a cooling device provided outside the storage container.

6. The method of using a spiral feeding tube furnace system for preparing two-dimensional materials according to claim 1, characterized in that, The spiral feed tube furnace system includes a sealed magnetic fluid flange and / or a plurality of adapter flanges.

7. The method of using the spiral feeding tube furnace system for preparing two-dimensional materials according to claim 6, characterized in that, The rotary motor and the spiral feeding rod form a spiral feeding device, and the sealed magneto-fluid flange is used to connect the furnace tube and the spiral feeding device to achieve the sealing effect when the spiral feeding rod rotates; And / or, the multiple adapter flanges are used for assembling and connecting the furnace tube components, playing the roles of connection and sealing.

8. The method of using the spiral feeding tube furnace system for preparing two-dimensional materials according to claim 1, characterized in that, The feeder continuously feeds the reaction raw material powder into the furnace tube within a predetermined period of time to achieve continuous preparation; And / or, the first heating system and the second heating system are the same heating device.

9. The method of using a spiral feed tube furnace system for preparing two-dimensional materials according to any one of claims 1 to 8, characterized in that, The speed of the spiral feeding rod is from 0.01 cm / min to 100 cm / min; And / or, the set temperature of the first heating system is between 400°C and 1500°C; the set temperature of the second heating system is between room temperature and 1000°C.

10. The method of using a spiral feeding tube furnace system for preparing two-dimensional materials according to any one of claims 1 to 8, characterized in that, The powder material is a MAX phase material and / or a MXene material; And / or, the reaction gas is a hydrogen halide, a halogen element, ammonia, phosphine, or a chalcogen hydride.

11. A method for using a spiral feeding tube furnace system for preparing two-dimensional materials, characterized in that, The spiral feeding tube furnace system includes a furnace tube, a feeder, a rotary motor, a spiral feeding rod, a first heating system, a second heating system, a product collection device, and a by-product collection device; The feeder is connected to the furnace tube and is used to feed the powder material into the furnace tube; The furnace tube includes a reaction chamber and a product collection chamber; The rotary motor is connected to the spiral feeding rod, and the rotation of the spiral feeding rod drives the powder material to move in the furnace tube, sequentially passing through the reaction chamber and the product collection chamber; The first heating system surrounds the reaction chamber, and the second heating system surrounds the product collection chamber; The product collection device is connected to the product collection chamber and is used to collect the powder pushed by the spiral feeding rod; The by-product collection device is used to collect the powder formed by the gas-phase condensation in the furnace tube; The furnace tube further includes a by-product collection chamber, and the by-product collection device is communicated with the by-product collection chamber and is used to collect the powder formed by the gas-phase condensation in the by-product collection chamber; The furnace tube includes: a first connecting furnace tube, a first heating zone furnace tube, a second heating zone furnace tube, and a second connecting furnace tube; the first connecting furnace tube is connected to the feeder, the first heating system surrounds the first heating zone furnace tube, and the inside of the first heating zone furnace tube is defined as the reaction chamber; the second heating system surrounds the second heating zone furnace tube, and the inside of the second heating zone furnace tube is defined as the product collection chamber; the inside of the second connecting furnace tube is defined as the by-product collection chamber and is communicated with the by-product collection device; The usage method includes the steps of: Placing a certain amount of mixed material in the feeder, the mixed material including a powder material and a reactant, and the reactant can be sublimated into a gas when heated in the furnace tube; Turning on the first heating system to raise the temperature of the reaction chamber of the furnace tube to the reaction temperature required for preparation and keeping it warm; Turning on the feeder and the rotary motor, and using the rotation of the spiral feeding rod to send the mixed material into the reaction chamber of the furnace tube to carry out a gas-phase reaction to prepare the two-dimensional material; Turn on the second heating system to raise the temperature of the reaction product collection chamber of the furnace tube to a certain temperature and keep it insulated; and Collect the reaction product powder in the product collection device; Collect the powder condensed from the gas phase in the furnace tube in the by-product collection device.

12. The method of using the spiral feeding tubular furnace system for preparing two-dimensional materials according to claim 11, characterized in that, Several product discharge ports are provided in the product collection chamber, and these product discharge ports are respectively connected to the storage tanks of the product collection device; And / or, several by-product discharge ports are provided in the by-product collection chamber, and these by-product discharge ports are respectively connected to the storage tanks of the by-product collection device.

13. The method of using the spiral feeding tube furnace system for preparing two-dimensional materials according to claim 11, characterized in that, A cooling device is provided outside the second connecting furnace tube.

14. The method of using a spiral feeding tube furnace system for preparing two-dimensional materials according to claim 11, characterized in that, The by-product collection device is communicated with the gas outlet of the furnace tube.

15. The method of using the spiral feeding tubular furnace system for preparing two-dimensional materials according to claim 14, characterized in that The by-product collection device includes a storage container and a cooling device provided outside the storage container.

16. The method of using the spiral feeding tube furnace system for preparing two-dimensional materials as claimed in claim 11, wherein, The spiral feed tube furnace system includes a sealed magnetic fluid flange and / or a plurality of adapter flanges.

17. The method of using the spiral feeding tube furnace system for preparing two-dimensional materials according to claim 16, characterized in that, The rotary motor and the spiral feed rod form a spiral feeding device, and the sealed magnetic fluid flange is used to connect the furnace tube and the spiral feeding device to achieve the sealing function under the rotation of the spiral feed rod; And / or, the plurality of adapter flanges are used to assemble and connect the furnace tube components, playing a role of connection and sealing.

18. The method of using the spiral feeding tube furnace system for preparing two-dimensional materials according to claim 11, characterized in that, The feeder continuously feeds the reaction raw material powder into the furnace tube within a predetermined period of time to achieve continuous preparation; And / or, the first heating system and the second heating system are the same heating device.

19. The method of using a spiral feeding tube furnace system for preparing two-dimensional materials according to any one of claims 11 to 18, characterized in that, The speed of the spiral feed rod is 0.01 cm / min to 100 cm / min; And / or, the set temperature of the first heating system is between 400°C and 1500°C; the set temperature of the second heating system is between room temperature and 1000°C.

20. The method of using a spiral feed tube furnace system for preparing two-dimensional materials according to any one of claims 11 to 18, characterized in that, The powder material is a MAX phase material and / or a MXene material; And / or, the reactant is iodine, chalcogen, halogen ammonium salt, halogen metal salt.

21. A spiral feeding tube furnace system for preparing two-dimensional materials, characterized in that, The spiral feed tube furnace system includes a furnace tube, a feeder, a rotary motor, a spiral feed rod, a first heating system, a second heating system, a product collection device and a by-product collection device; The feeder is connected to the furnace tube and is used to feed the powder material into the furnace tube; The furnace tube includes a reaction chamber and a product collection chamber; The rotary motor is connected to the spiral feed rod, and the rotation of the spiral feed rod drives the powder material to move in the furnace tube, sequentially passing through the reaction chamber and the product collection chamber; The first heating system surrounds the reaction chamber, and the second heating system surrounds the product collection chamber; The product collection device is connected to the product collection chamber and is used to collect the powder pushed by the spiral feed rod; The by-product collection device is used to collect the powder condensed from the gas phase in the furnace tube; The furnace tube further includes a by-product collection chamber, and the by-product collection device is communicated with the by-product collection chamber and is used to collect the powder condensed from the gas phase in the by-product collection chamber; The furnace tube includes: a first connecting furnace tube, a first heating zone furnace tube, a second heating zone furnace tube, and a second connecting furnace tube; the first connecting furnace tube is connected to the feeder, the first heating system surrounds the first heating zone furnace tube, and the interior of the first heating zone furnace tube is defined as the reaction chamber; the second heating system surrounds the second heating zone furnace tube, and the interior of the second heating zone furnace tube is defined as the product collection chamber; the interior of the second connecting furnace tube is defined as the by-product collection chamber and is communicated with the by-product collection device; The first heating zone furnace tube and the second heating zone furnace tube are designed to be non - the same furnace tube.

22. The spiral feeding tube furnace system for preparing two-dimensional materials according to claim 21, wherein, The first connecting furnace tube and / or the second heating zone furnace tube is made of metal material; the first heating zone furnace tube is selected from one of quartz tube, corundum tube, ceramic tube, and graphite tube.

23. The spiral feed tube furnace system for preparing two-dimensional materials according to claim 21, wherein The first connecting furnace tube and / or the second heating zone furnace tube is made of stainless steel material; the first heating zone furnace tube is selected as a quartz tube.

24. The spiral feeding tube furnace system for preparing two-dimensional materials according to claim 21, characterized in that, Several product discharge ports are arranged in the product collection chamber, and these product discharge ports are respectively connected to the storage tanks of the product collection device; And / or, several by - product discharge ports are arranged in the by - product collection chamber, and these by - product discharge ports are respectively connected to the storage tanks of the by - product collection device.

25. The spiral feeding tube furnace system for preparing two-dimensional materials according to claim 21, wherein, A cooling device is arranged outside the second connecting furnace tube.

26. The spiral feeding tube furnace system for preparing two-dimensional materials according to claim 21, characterized in that, The by - product collection device is communicated with the gas outlet of the furnace tube.

27. The spiral feeding tube furnace system for preparing two-dimensional materials according to claim 26, wherein The by - product collection device includes a storage container and a cooling device arranged outside the storage container.

28. The spiral feeding tube furnace system for preparing two-dimensional materials according to claim 21, characterized in that, The spiral feed tube furnace system includes a sealed magneto - fluid flange and / or a plurality of adapter flanges.

29. The spiral feeding tube furnace system for preparing two-dimensional materials according to claim 28, wherein The rotating motor and the spiral feed rod form a spiral feeding device, and the sealed magneto - fluid flange is used to connect the furnace tube and the spiral feeding device to achieve the sealing effect when the spiral feed rod rotates; And / or, the plurality of adapter flanges are used for assembling and connecting furnace tube components to play a connecting and sealing role.

30. The spiral feeding tube furnace system for preparing two-dimensional materials according to claim 21, characterized in that, The feeder continuously feeds the reaction raw material powder into the furnace tube within a predetermined period to achieve continuous preparation.

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