Device and method for preparing core-shell bifunctional material

Abstract

The invention provides a preparation device and method of a core-shell bifunctional material, the preparation device of the core-shell bifunctional material comprises a vibration module (3), the vibration module (3) comprises a power part, a reset spring (31) and a vibration block (32), the power part is connected to the vibration block (32) so as to drive the vibration block (32) to rotate, and a sample loading table (2), the sample loading platform (2) is arranged above the vibration block (32), the reset spring (31) is arranged to enable the sample loading platform (2) and the vibration block (32) to be in a contact and mutual extrusion state, and the peripheral surface of the vibration block (32) is provided with a bulge, so that when the vibration block (32) rotates, the bulge of the vibration block (32) can beat or knock the sample loading platform (2), and the sample loading platform (2) is driven to rotate. The sample loading table (2) can vibrate in the vertical direction, so that materials in the sample loading table (2) can bounce and roll over.

Description

Technical Field

[0001] The present application belongs to the technical field of chemical industry, and in particular relates to a preparation device and method of a core-shell dual-functional material. Background Art

[0002] In a chemical reaction, a catalyst can change the chemical reaction rate of other substances and increase the chemical reaction rate, but its own mass and chemical properties do not change before and after the chemical reaction.

[0003] Catalysts play a vital role in the development of the chemical industry and society. According to incomplete statistics, there are about 30,000 raw materials and chemical intermediates in the world that are directly or indirectly synthesized by catalysts. In addition to being directly related to people's food, clothing, housing and transportation, these materials also involve many modern high-tech fields, such as information transmission, network technology, aerospace and bioengineering.

[0004] Heterogeneous solid catalysts are the most widely used catalysts in the industry, and they usually include catalyst active components, co-catalysts and carriers. The preparation and pretreatment process of the catalyst plays a very critical role in the properties of the catalyst. The preparation process of the catalyst should select appropriate conditions and coordinate various parameters. Commonly used catalyst preparation methods include precipitation, impregnation, ion exchange, mechanical mixing, melting, metal organic complex and freeze drying. In addition, many preparation methods in materials science, such as sol-gel method, coprecipitation, high temperature sol decomposition method, etc., can be used as methods for preparing catalysts used in catalytic wet oxidation after certain improvements. Coprecipitation and impregnation are the two most commonly used methods for preparing wet oxidation catalysts.

[0005] Bifunctional materials are a general term for catalysts or adsorbent materials that contain multiple functions. For example, bifunctional materials for CO2 capture and in-situ conversion to produce high-value chemicals are composed of adsorption sites for CO2 capture and catalytic sites for CO2 hydrogenation conversion to produce synthesis gas. Existing bifunctional materials for CO2 capture and in-situ conversion to produce high-value chemicals are usually synthesized by sol-gel method, coprecipitation method, high-temperature sol decomposition method and other methods. The adsorption sites and catalytic sites in the bifunctional materials prepared in this way often have different effects on each other, some of which result in better catalytic effects, some of which result in poor catalytic effects, some of which result in good adsorption effects, and more of which result in poor adsorption effects. Summary of the invention

[0006] The present application proposes a preparation device for a core-shell dual-functional material, aiming to make the dual-functional material have better catalytic reaction ability. The present application also proposes a preparation method for a core-shell dual-functional material.

[0007] The embodiment of the present application proposes a preparation device of a core-shell dual-functional material, comprising:

[0008] A vibration module, the vibration module comprising a power unit, a return spring, and a vibration block, the power unit being connected to the vibration block so as to drive the vibration block to rotate,

[0009] A sample loading platform, the sample loading platform is arranged above the vibration block, and the return spring is arranged to keep the sample loading platform and the vibration block in contact and mutually compressed state,

[0010] The vibrating block has a circumferential surface with protrusions, so that when the vibrating block rotates, the protrusions of the vibrating block can slap or knock the sample loading platform, and the sample loading platform can vibrate in the up and down directions, so that the material in the sample loading platform can bounce and roll.

[0011] In at least one possible implementation manner, a cross section of the vibration block is a polygon.

[0012] In at least one possible implementation manner, a cross section of the vibration block is square.

[0013] In at least one possible embodiment, the vibration amplitude of the sample loading platform in the up and down directions is 0.6 cm to 1.7 cm.

[0014] In at least one possible implementation, the preparation device further includes a vacuum chamber, which can form a vacuum environment, and the sample loading platform and the vibration module are both disposed inside the vacuum chamber.

[0015] In at least one possible embodiment, a magnetron sputtering device is further included in the vacuum chamber, and the magnetron sputtering device is used to sputter a sputtering target material onto a sputtered material in the sample loading station to form a core-shell dual-functional material.

[0016] The present application also proposes a method for preparing a core-shell dual-functional material, the preparation method using a preparation device described in any one of the above technical solutions, the preparation method comprising:

[0017] S1: a granular sputtered material is loaded on the sample loading platform, and the sputtered material in the sample loading platform is continuously rolled by repeatedly impacting the bottom of the sample loading platform;

[0018] S2: The sputtering target is bombarded with high-energy particles so that the atoms on the surface of the sputtering target obtain the energy of the incident particles and are excited to be emitted from the surface of the sputtering target and toward the sputtered material. The sputtering target is deposited on the surface of the sputtered material to form a coating layer.

[0019] In at least one possible implementation, the sputtered material is a mixture of calcium and aluminum, and the sputtering target is a metal.

[0020] In at least one possible embodiment, the particle size of the sputtered material is 250 to 450 microns; and / or

[0021] The sputtered material is impacted at a frequency of 80 to 200 times per minute.

[0022] In at least one possible embodiment, the device for bombarding the sputtering target with high-energy particles is a magnetron sputtering device, and the sputtering power of the magnetron sputtering device is 250 to 300 watts, and the sputtering time is 30 to 120 minutes.

[0023] By adopting the above technical solution, the particles of the sputtered material are violently rolled in the loading platform through the vibration module, so that the particles of the sputtered material can be evenly coated with a coating layer of the sputtering target material, thereby forming a core-shell dual-functional material. In the chemical utilization process, the core-shell dual-functional material has a more significant catalytic reaction ability due to the spatial confinement of the core-shell dual-functional material. BRIEF DESCRIPTION OF THE DRAWINGS

[0024] Figure 1 A schematic structural diagram of a vibration block in a first position of a device for preparing a core-shell dual-functional material according to an embodiment of the present application is shown.

[0025] Figure 2 A schematic structural diagram of a vibration block in a second position of a device for preparing a core-shell dual-functional material according to an embodiment of the present application is shown.

[0026] Description of Reference Numerals

[0027] 1 substrate table

[0028] 2 Sample loading platform 21 Stabilizing block 22 Sample pot

[0029] 3 vibration module 31 return spring 32 vibration block 33 rotation axis

[0030] 100Sputtered material

[0031] 200 sputtering target 201 first sputtering target 202 second sputtering target DETAILED DESCRIPTION

[0032] In order to more clearly explain the above-mentioned purposes, features and advantages of the present application, the specific implementation methods of the present application are described in detail in this section in conjunction with the accompanying drawings. In addition to the various implementation methods described in this section, the present application can also be implemented in other different ways. Without violating the spirit of the present application, those skilled in the art can make corresponding improvements, deformations and substitutions, so the present application is not limited by the specific embodiments disclosed in this section. The scope of protection of the present application shall be subject to the claims.

[0033] Magnetron sputtering is an effective film material preparation method used in industry. It is a type of physical vapor deposition (PVD). Magnetron sputtering can bombard a solid cathode target with high-energy particles with an energy of more than tens of electron volts, so that the atoms on the surface of the cathode target obtain the energy of the incident particles and are excited and emitted from the solid surface, and are deposited on the surface of the substrate to form a thin film. The particles that bombard the surface of the target in magnetron sputtering are ions. The process of bombarding the target surface and producing corresponding products is also called ion sputtering. Magnetron sputtering is to achieve sputtering of the target material and deposition of the thin film through ion sputtering. Compared with chemical vapor deposition (CVD), magnetron sputtering has the advantages of high sputtering rate, good uniformity of film thickness, excellent film quality, large-area deposition, and applicability to a variety of materials. Compared with other physical vapor deposition technologies, such as arc plasma plating and vacuum evaporation, it has the characteristics of strong adhesion, stable coating, and high deposition rate.

[0034] like Figure 1 and Figure 2 As shown, an embodiment of the present application proposes a preparation device for a core-shell dual-functional material, which includes a vacuum chamber, a substrate stage 1, a sample loading stage 2, and a vibration module 3.

[0035] The vacuum chamber can form a vacuum environment, and the substrate stage 1, the sample loading stage 2 and the vibration module 3 are all arranged inside the vacuum chamber. The sample loading stage 2 can be connected to the substrate stage 1 through the vibration module 3, and the sample loading stage 2 can be arranged above the vibration module 3.

[0036] The sample loading station 2 may include a stabilizing block 21 and a sample pot 22. The sample pot 22 may be connected to the top of the stabilizing block 21. The opening of the sample pot 22 may be formed in an outwardly expanding trumpet shape. The sample pot 22 is used to place the granular sputtered material 100. For ease of understanding, Figure 1 and Figure 2 It is exemplarily shown that a portion of the sputtered material 100 is significantly higher than the sample pot 22 .

[0037] A sputtering target 200 may be arranged above the sample loading table 2. A plurality of sputtering targets 200 may be provided. The spraying directions of the plurality of sputtering targets 200 may be different. The sputtering target 200 may include a first sputtering target 201 and a second sputtering target 202. The first sputtering target 201 and the second sputtering target 202 may face different directions, so that the sputtering target 200 may be sprayed onto the sputtered material 100 from different angles.

[0038] A magnetron sputtering device may be arranged in the vacuum chamber, and the magnetron sputtering device is used to sputter the sputtering target material 200 onto the sputtered material 100 in the sample loading platform 2 to form a core-shell dual-functional material.

[0039] It can be understood that the magnetron sputtering equipment is arranged in the vacuum chamber, including that part of the structure of the magnetron sputtering equipment is located in the vacuum chamber. The entire magnetron sputtering equipment can be but not necessarily arranged in the vacuum chamber, as long as the magnetron sputtering equipment can work normally.

[0040] The vacuum chamber may be connected to a vacuum pumping system, which may include a vacuum pumping device (such as a mechanical pump, a Roots pump, a molecular pump), a detection device (such as a resistance gauge, an ionization gauge, a film gauge) and a safety valve.

[0041] The magnetron sputtering equipment is located in a vacuum environment and has the following advantages.

[0042] (1) Eliminating impurities: The vacuum environment can effectively eliminate impurities in the air, such as oxygen, nitrogen and water vapor. These impurities will react with the target material 200 and the sputtered material 100, affecting the quality and performance of the sputtering. A high-purity environment can be formed by vacuuming, and the purity and stability of the coating are better.

[0043] (2) Improving sputtering efficiency: In a vacuum environment, ions move more freely and are not affected by air resistance, and can hit the target 200 at a higher speed and energy. This not only improves the sputtering efficiency, but also reduces the scattering and collision of ions, thereby improving the utilization rate of ions.

[0044] (3) Controlling coating parameters: The vacuum environment is conducive to the precise control of parameters such as air pressure, temperature and power during the coating process. By adjusting these parameters, the coating thickness, composition and structure can be precisely controlled, thereby improving the quality and performance of the coating.

[0045] The vibration module 3 may include a power unit, a return spring 31 , a vibration block 32 , a rotating shaft 33 and a bearing.

[0046] The rotating shaft 33 may be connected to a power unit, which may be a motor, and the vibration block 32 may be fixedly connected to the rotating shaft 33. The vibration block 32 may be driven by the power unit to rotate along with the rotating shaft 33. The substrate stage 1 may be provided with a bracket, and the rotating shaft 33 and / or the vibration block 32 may be rotatably connected to the bracket of the substrate stage 1 through a bearing, so that the vibration block 32 and the rotating shaft 33 may rotate relative to the substrate stage 1.

[0047] The return spring 31 may be configured to keep the stabilizing block 21 and the vibration block 32 in contact and mutually compressed state. Specifically, the stabilizing block 21 of the sample loading platform 2 may be connected to the substrate stage 1 via a plurality of (e.g., 4) return springs 31, and the return spring 31 may be a tension spring, one end of the return spring 31 being connected to the stabilizing block 21, and the other end of the return spring 31 being connected to the substrate stage 1. The tension provided by the return spring 31 may keep the stabilizing block 21 and the vibration block 32 in contact and mutually compressed state.

[0048] The vibration block 32 may be columnar, and the circumference of the vibration block 32 is used to contact the stabilizing block 21. The circumference of the vibration block 32 may have protrusions, so that when the vibration block 32 rotates, the protrusions of the vibration block 32 can slap or knock the stabilizing block 21. When the vibration block 32 rotates to different positions, the sample loading platform 2 can have different heights. When the vibration block 32 rotates, the protrusions of the vibration block 32 can push the sample loading platform 2 to move upward, and the reset spring 31 can limit the displacement of the sample loading platform 2 moving upward. Then, when the protrusion of the vibration block 32 leaves the stabilizing block 21, the sample loading platform 2 can move downward and reset under the action of the reset spring 31. The sample loading platform 2 is continuously slapped by the vibration block 32, which can exert an impact force on the particles in the sample pot 22, causing the particles to bounce and roll continuously.

[0049] Optionally, the cross section of the vibration block 32 may be a polygon. Furthermore, the number of sides of the polygonal cross section of the vibration block 32 may be 3 to 10.

[0050] Furthermore, the cross section of the vibration block 32 may be a square, the side length of the square may be 3 to 8 cm, and the vibration block 32 may be a cube. The rotation axis 33 may be connected to the center of the side of the vibration block 32. It can be understood that the vibration amplitude of the sample loading platform 2 is half of the difference between the side length and the diagonal of the vibration block 32. For example, the vibration amplitude of the sample loading platform 2 in the up and down direction may be 0.6 cm to 1.7 cm.

[0051] The vibration module 3 can make the particles of the sputtered material 100 tumble violently in the loading platform. When the sputtering target 200 is ionized and ejected, the particles of the sputtered material 100 can be evenly coated with a coating layer of the sputtering target 200, thereby forming a core-shell dual-functional material. In the chemical utilization process, the core-shell dual-functional material has a more significant catalytic reaction ability due to its spatial confinement.

[0052] The embodiments of the present application provide a method for preparing a core-shell dual-functional material.

[0053] S1: The granular sputtered material 100 is loaded on the sample loading platform 2 and repeatedly impacts the bottom of the sample loading platform 2, so that the sample loading platform 2 can vibrate in the up and down directions, and the sputtered material 100 in the sample loading platform 2 continuously bounces and rolls.

[0054] S2: The vacuum chamber is evacuated, and the sputtering target 200 is bombarded with high-energy particles, so that the atoms on the surface of the sputtering target 200 obtain the energy of the incident particles and are excited to be emitted from the surface of the sputtering target 200 and deposited on the surface of the sputtered material 100. A coating layer of the sputtering target 200 is evenly plated on the surface of the granular sputtered material 100.

[0055] The core-shell bifunctional material obtained in this way has a significant coating structure and spatial confinement effect, and can adapt to the existing tandem catalytic reaction system.

[0056] Optionally, the particle size (diameter) of the sputtered material 100 may be 250 to 450 micrometers. Such a particle size allows the core-shell dual-functional material manufactured by the present application to be directly used for chemical catalysis.

[0057] Optionally, the rotation speed of the rotating shaft 33 may be 20 to 50 revolutions per minute (RPM).

[0058] Optionally, the vibration block 32 may tap or knock the sample loading platform 2 at a frequency of 80 to 200 times per minute, so that the sputtered material 100 can be rolled violently, but will not be shaken out of the sample loading platform 2.

[0059] The device for bombarding the sputtering target with high-energy particles is a magnetron sputtering device, the sputtering power of the magnetron sputtering device is 250 to 300 watts, and the sputtering time is 30 to 120 minutes. In this way, the ignition can be successful and the ionized sputtering target 200 can be released, and the sputtering target 200 can be uniformly deposited on the surface of the sputtered material 100 to form a coating structure.

[0060] Optionally, the sputtered material 100 may be a mixture of calcium and aluminum, and the sputtering target 200 may be a metal, for example, the sputtering target 200 may be iron.

[0061] The plating opening can be called the valve opening. The pressure of the vacuum chamber and the deposition pressure can be controlled together by the size of the valve opening and the argon gas flow rate.

[0062] The deposition rate plays a key role in the growth of catalyst metals on the surface of core-shell materials. Specifically, the deposition rate determines the energy of the particles, and the energy of the particles determines the crystal phase, chemical composition, etc. of the atoms deposited on the surface of the material, which will ultimately affect the distribution morphology, defect formation, and crystal structure of the metal.

[0063] In the present application, the deposition rate can be 2 to 3.2 angstroms / second, and the argon gas flow rate can be 10 to 60 standard cubic centimeters per minute (sccm). Table 1 lists three groups of optional preparation parameters for preparing Ca-Fe (the inner core is a mixture of calcium and aluminum, and the surface is iron) core-shell dual-functional materials.

[0064] Table 1

[0065]

[0066] It should be understood that at least some aspects or features of the above-mentioned implementation modes, embodiments or examples may be appropriately combined.

[0067] It is understood that in the present application, when the number of parts or components is not particularly limited, the number may be one or more, and the multiple here means two or more. For the case where the number of parts or components shown in the drawings and / or described in the specification is a specific number such as two, three, four, etc., the specific number is usually exemplary and not restrictive, and it can be understood as multiple, that is, two or more, but this does not mean that the present application excludes the case of one.

[0068] In the present application, unless otherwise clearly stated or limited, the terms such as "install", "assemble", "assemble", "connect", "connect", "couple", "link", "abut", "connect", "interconnect", "intercommunication", "conduction", "fixation", "fastening" and the like should be understood in a broad sense, for example, they can be direct or indirect. For example, regarding connection, it can be a fixed connection, a detachable connection, or an integral one; it can be a mechanical connection or an electrical connection; it can be a direct connection, or it can be indirectly connected through an intermediate medium, it can be the internal connection of two elements or the interaction relationship between two elements, unless otherwise clearly stated or limited. For example, regarding connectivity / conduction, it can be direct connectivity / conduction, or it can be indirect connectivity / conduction via an intermediate medium. For those of ordinary skill in the art, the specific meanings of the above terms in the present application can be understood according to the specific circumstances.

[0069] In the present application, unless otherwise clearly stated or limited, a component disposed on / installed on / located on / accommodated on / placed in, within, inside, etc. another component may be any of the following two situations: a part or most of the one component is located in the other component; and the one component is completely accommodated in the other component.

[0070] Although the present application is described in detail using the above-mentioned embodiments, it is obvious to those skilled in the art that the present application is not limited to the embodiments described in this specification. The present application can be modified and implemented as a modified embodiment without departing from the subject matter and scope of the present application as determined by the claims. Therefore, the description in this specification is for the purpose of illustration and does not have any restrictive meaning for the present application.

Claims

1. A preparation device for a core-shell dual-functional material, characterized in that: include: A vibration module (3), the vibration module (3) comprising a power unit, a return spring (31), and a vibration block (32), the power unit being connected to the vibration block (32) so as to drive the vibration block (32) to rotate, A sample loading platform (2), wherein the sample loading platform (2) is arranged above the vibration block (32), and the return spring (31) is arranged to keep the sample loading platform (2) and the vibration block (32) in a state of contact and mutual compression, The vibrating block (32) has a convex surface, so that when the vibrating block (32) rotates, the convex surface of the vibrating block (32) can slap or knock the sample loading platform (2), and the sample loading platform (2) can vibrate in the up and down directions, so that the material in the sample loading platform (2) can bounce and roll.

2. The preparation device of core-shell dual-functional material according to claim 1, characterized in that: The cross section of the vibration block (32) is polygonal.

3. The preparation device of core-shell dual-functional material according to claim 1, characterized in that: The cross section of the vibration block (32) is square.

4. The preparation device of core-shell dual-functional material according to claim 1, characterized in that: The vibration amplitude of the sample loading platform (2) in the up and down direction is 0.6 cm to 1.7 cm.

5. The preparation device of core-shell dual-functional material according to claim 1, characterized in that: The preparation device further comprises a vacuum chamber, which is capable of forming a vacuum environment, and the sample loading platform (2) and the vibration module (3) are both arranged inside the vacuum chamber.

6. The preparation device of core-shell dual-functional material according to claim 5, characterized in that: It also includes a magnetron sputtering device located in the vacuum chamber, and the magnetron sputtering device is used to sputter a sputtering target material (200) onto a sputtered material (100) in the sample loading platform (2) to form a core-shell dual-functional material.

7. A method for preparing a core-shell dual-functional material, characterized in that: The preparation method uses the preparation device according to any one of claims 1 to 6, and the preparation method comprises: S1: a granular sputtered material (100) is loaded on the sample loading platform (2), and the sputtered material (100) in the sample loading platform (2) is repeatedly impacted on the bottom of the sample loading platform (2) so as to continuously roll; S2: The sputtering target (200) is bombarded with high-energy particles, so that atoms on the surface of the sputtering target (200) obtain the energy of the incident particles and are excited to be emitted from the surface of the sputtering target (200) and toward the sputtered material (100), and the sputtering target (200) is deposited on the surface of the sputtered material (100) to form a coating layer.

8. The method for preparing a core-shell dual-functional material according to claim 7, characterized in that: The sputtered material (100) is a mixture of calcium and aluminum, and the sputtering target (200) is a metal.

9. The method for preparing a core-shell dual-functional material according to claim 7, characterized in that: The particle size of the sputtered material (100) is 250 to 450 micrometers; and / or The sputtered material (100) is impacted at a frequency of 80 to 200 times per minute.

10. The method for preparing a core-shell dual-functional material according to claim 7, characterized in that: The device for bombarding the sputtering target (200) with high-energy particles is a magnetron sputtering spraying device, the spraying power of the magnetron sputtering spraying device is 250 to 300 watts, and the spraying time is 30 to 120 minutes.

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