Gas phase reaction device for preparing transition metal oxide nanoparticles and method of using the same

Abstract

The present invention proposes a gas phase reaction device for preparing transition metal oxide nanoparticles and a method for using the same, and belongs to the field of special devices or equipment for metal powders. The gas phase reaction device includes a gas storage unit, a reaction unit and a collection unit. The gas storage unit is suitable for providing carbon monoxide and ozone; the reaction unit is configured to accommodate transition metal elements, and the reaction unit is suitable for sequentially receiving carbon monoxide and ozone, so that the transition metal elements sequentially undergo carbonylation coordination reaction and oxidation reaction in a gas phase atmosphere to obtain transition metal oxide nanoparticles, and the transition metal oxide nanoparticles are output from the reaction unit using reaction tail gas as a carrier; the collection unit is configured to filter, collect and store the transition metal oxide nanoparticles.

Description

Technical Field

[0001] The invention relates to the technical field of a special device or equipment for metal powder, and in particular to a gas phase reaction device for preparing transition metal oxide nanoparticles and a use method thereof. Background Art

[0002] Transition metal oxide nanoparticles combine the dual characteristics of transition metals and nanoparticles. Due to their unique physical and chemical properties, they show great application potential in catalysis, photocatalysis, detection, optoelectronic devices, energy storage and other fields. For example, nickel-based, cobalt-based and iron-based oxide nanomaterials have broad application prospects in magnetism, catalysis, sensing, energy storage and conversion. These materials can not only be used as microcapsule materials for controlled transport and release systems of drugs, dyes, cosmetics, etc., but also as lightweight fillers, selective catalysts or catalyst carriers, and even have extremely important value in the fields of genetic biology.

[0003] The preparation of transition metal oxide nanoparticles has become a hot topic in materials science research. In recent years, with the development of nanoscience, a variety of methods for preparing transition metal oxide nanoparticles have been explored, such as emulsion method, microemulsion method, etc. These methods have the advantages of wide application fields and controllable particle size. Through these methods, nanoparticles with good crystal form, good dispersibility and controllable size can be prepared.

[0004] Although there are many methods for preparing transition metal oxide nanoparticles, there are also some defects. For example, the sol-gel process is long and the gelation process is difficult to control; the morphology and size of the particles obtained by the precipitation method are difficult to control and may produce impurities; the hydrothermal method has high requirements for equipment and harsh reaction conditions. Since most of these preparation processes involve drying, calcination and other processes, the existing preparation process of transition metal nanoparticles has problems such as high energy consumption, complex procedures, and serious pollution, which directly affects the production efficiency and use cost of transition metal nanoparticles.

[0005] Therefore, a device and method for preparing and synthesizing transition metal oxide nanoparticles with simple design procedures, clean process and low price has great application value and promotion significance. Summary of the invention

[0006] In view of this, in order to solve at least one technical problem in the related art and other aspects, the present invention proposes a gas phase reaction device for preparing transition metal oxide nanoparticles, comprising: a gas storage unit, a reaction unit and a collection unit. The gas storage unit is suitable for providing carbon monoxide and ozone; the reaction unit is configured to accommodate transition metal elements, and the reaction unit is suitable for sequentially receiving carbon monoxide and ozone, so that the transition metal elements sequentially undergo carbonylation coordination reaction and oxidation reaction in the gas phase atmosphere to obtain transition metal oxide nanoparticles, and the transition metal oxide nanoparticles are output from the reaction unit using the reaction tail gas as a carrier; the collection unit is configured to filter, collect and store the transition metal oxide nanoparticles.

[0007] According to an embodiment of the present invention, the reaction unit includes a carbonylation subunit and an oxidation subunit. The carbonylation subunit is configured to cause carbon monoxide to undergo a carbonylation coordination reaction with a transition metal element at a temperature of 60-65°C and output a carbonylation metal gas; the oxidation subunit is configured to receive the carbonylation metal gas and ozone and undergo an oxidation reaction at a temperature of 20-45°C to generate transition metal oxide nanoparticles.

[0008] According to an embodiment of the present invention, the carbonylation subunit includes a first reaction tube and a first temperature controller. The first reaction tube is configured to contain a transition metal element inside and to have a first heating component wound around the outside; the first temperature controller is adapted to control the first heating component to adjust the temperature of the first reaction tube so that the carbon monoxide input into the first reaction tube undergoes a carbonylation coordination reaction with the transition metal element. The oxidation subunit includes a second reaction tube and a second temperature controller. The second reaction tube is wound around the outside of the second reaction tube; the second temperature controller is adapted to adjust the temperature of the second reaction tube by controlling the second heating component so that the carbonylation metal gas input into the second reaction tube undergoes an oxidation reaction with ozone, and to output transition metal oxide nanoparticles from the second reaction tube through the reaction tail gas.

[0009] According to an embodiment of the present invention, the oxidizing subunit further comprises a capture magnetic strip installed outside the second reaction tube, and the capture magnetic strip is suitable for fixing transition oxide nanoparticles.

[0010] According to an embodiment of the present invention, the second reaction tube further includes a pressure relief outlet and a sealing rubber plug.

[0011] According to an embodiment of the present invention, the gas storage unit includes a carbon monoxide storage tank and an ozone generator.

[0012] According to an embodiment of the present invention, the gas storage unit also includes a reducing gas storage tank, which is configured to provide reducing gas to the first reaction tube before the carbonylation coordination reaction and the oxidation reaction to prevent the transition metal element from being oxidized and activate the transition metal element before the carbonylation coordination reaction and the oxidation reaction occur.

[0013] According to an embodiment of the present invention, the collecting unit comprises a collecting bottle equipped with a filter sealing cap, which is suitable for allowing the transition metal nano-oxide particles to pass through and be collected.

[0014] According to an embodiment of the present invention, the gas phase reaction device further comprises a tail gas recovery unit, comprising: an explosion-proof exhaust fan adapted to collect and prevent explosion of reaction tail gas, the reaction tail gas comprising ozone and reducing gas.

[0015] In another aspect of the present invention, a method for using the aforementioned gas phase reaction device is also proposed, comprising: first, placing a transition metal element in a first reaction tube, allowing a reducing gas storage tank to input reducing gas into the first reaction tube to activate the transition metal element, and discharging the reducing gas in the first reaction tube; then inputting carbon monoxide into the first reaction tube, causing carbon monoxide to undergo a carbonylation coordination reaction with the transition metal element to generate carbonyl metal gas, and inputting the carbonyl metal gas into a second reaction tube; then inputting ozone into the second reaction tube, causing the carbonyl metal gas and ozone to undergo an oxidation reaction to obtain transition metal oxide nanoparticles, and the transition metal oxide nanoparticles are output to a collection unit through the reaction tail gas and stored; finally, discharging the ozone in the second reaction tube.

[0016] According to an embodiment of the present invention, the device realizes an integrated process from raw gas supply, reaction process control to product collection through the close cooperation of the gas storage unit, the reaction unit and the collection unit. This design has a high degree of integration and modularization, simplifies the operation steps through the preparation environment of the gas phase reaction system, improves the preparation efficiency, and is applicable to the synthesis of nanoscale transition metal oxide particles. Through the continuous carbonylation coordination reaction and oxidation reaction, the device can prepare transition metal oxide nanoparticles with high purity, good dispersibility and uniform particle size. These characteristics make the product have a wider application prospect in the fields of catalysis and materials science. BRIEF DESCRIPTION OF THE DRAWINGS

[0017] Figure 1 is a schematic diagram of a gas phase reaction device for preparing transition metal oxide nanoparticles in an embodiment of the present invention;

[0018] Figure 2 1 is a schematic diagram of the heat-insulating outer layer of the reaction unit of the gas phase reaction device in the embodiment of the present invention;

[0019] Figure 3 1 is a schematic diagram of the principle of the thermal insulation layer of the reaction unit of the gas phase reaction device in the embodiment of the present invention;

[0020] Figure 4 is a scanning electron microscope image of the nano nickel oxide particles prepared in Example 1 of the present invention;

[0021] Figure 5 is a transmission electron microscope image of the nano nickel oxide particles prepared in Example 1 of the present invention;

[0022] Figure 6 3 is a particle size distribution diagram of the nano nickel oxide particles prepared in Example 1 of the present invention.

[0023] In the above drawings, the specific symbols have the following meanings:

[0024] 101-carbon monoxide storage tank; 102-carbon monoxide storage tank pressure reducing valve; 103-carbon monoxide flow meter; 104-first control valve; 105-ozone generator; 106-second control valve; 107-reducing gas storage tank; 108-reducing gas storage tank pressure reducing valve; 109-reducing gas flow meter; 110-third control valve;

[0025] 201-first reaction tube inlet; 202-first reaction tube; 203-first heating assembly; 204-transition metal element placement area; 205-first temperature control signal transmission line; 206-first temperature controller; 207-first reaction tube outlet; 208-absorbent cotton; 209-fourth control valve; 210-second reaction tube; 211-second heating assembly; 212-second temperature control signal transmission line; 213-second temperature controller; 214-sealing rubber plug; 215-pressure relief outlet; 216-capturing magnetic strip; 220-insulation shell; 221-insulation layer; 222-first edge fixing buckle; 223-insulation upper cover; 224-control valve adjustment port; 225-second edge fixing buckle; 226-insulation lower cover;

[0026] 301-filter sealing cover; 302-collecting bottle;

[0027] 401-fifth control valve; 402-sixth control valve; 403-explosion-proof exhaust fan;

[0028] X001-first gas path; X002-second gas path; X003-third gas path; X004-fourth gas path; X005-fifth gas path; X006-sixth gas path. DETAILED DESCRIPTION

[0029] In order to make the objectives, technical solutions and advantages of the present invention more clearly understood, the present invention is further described in detail below in conjunction with specific embodiments and with reference to the accompanying drawings.

[0030] The endpoints and any values ​​of the ranges disclosed in the present invention are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of each range, the endpoint values ​​of each range and the individual point values, and the individual point values ​​can be combined with each other to obtain one or more new numerical ranges, and these numerical ranges should be regarded as specifically disclosed in the present invention.

[0031] The terms used herein are only for describing specific embodiments and are not intended to limit the present invention. The terms "comprise", "include", etc. used herein indicate the existence of the features, steps, operations and / or components, but do not exclude the existence or addition of one or more other features, steps, operations or components.

[0032] All terms (including technical and scientific terms) used herein have the meanings commonly understood by those skilled in the art unless otherwise defined. It should be noted that the terms used herein should be interpreted as having a meaning consistent with the context of this specification and should not be interpreted in an idealized or overly rigid manner.

[0033] It should be noted that, unless otherwise defined, the technical terms or scientific terms used in the present invention shall have the usual meanings understood by persons with ordinary skills in the field to which the present invention belongs. If the full text involves descriptions such as "first", "second", etc., the descriptions such as "first", "second", etc. are only used to distinguish similar objects, and cannot be understood as indicating or implying their relative importance, order of precedence, or implicitly indicating the number of technical features indicated. It should be understood that the data described by "first", "second", etc. can be interchangeable under appropriate circumstances.

[0034] To make the purpose, technical solution and advantages of the present invention more clearly understood, the present invention is further described in detail below in combination with specific embodiments and with reference to the accompanying drawings. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of them.

[0035] In the present invention, unless otherwise clearly specified and limited, the terms "installed", "connected", "connected", "fixed" and the like should be understood in a broad sense, for example, it can be a fixed connection, a detachable connection, or an integral connection; it can be a mechanical connection, an electrical connection, or can communicate with each other; it can be a direct connection, or an indirect connection through an intermediate medium, it can be the internal connection of two elements or the interaction relationship between two elements. For ordinary technicians in this field, the specific meanings of the above terms in the present invention can be understood according to specific circumstances.

[0036] In the description of the present invention, it should be understood that the terms "longitudinal", "length", "circumferential", "front", "rear", "left", "right", "top", "bottom", "inside", "outside", etc., indicating the orientation or positional relationship are based on the orientation or positional relationship shown in the accompanying drawings, and are only for the convenience of describing the present invention and simplifying the description, rather than indicating or implying that the subsystem or element referred to must have a specific orientation, be constructed and operated in a specific orientation, and therefore cannot be understood as a limitation on the present invention.

[0037] Throughout the drawings, the same elements are represented by the same or similar reference numerals. Conventional structures or configurations will be omitted when they may cause confusion in the understanding of the present invention. The shapes, sizes, and positional relationships of the components in the drawings do not reflect the actual size, proportion, and actual positional relationship. In addition, in the present invention, any reference symbol between brackets should not be constructed as a limitation to the present invention.

[0038] Similarly, in order to simplify the present invention and help understand one or more of the various disclosed aspects, in the above description of exemplary embodiments of the present invention, the various features of the present invention are sometimes grouped together into a single embodiment, figure, or description thereof. The description with reference to the terms "one embodiment", "some embodiments", "example", "specific example", or "some examples" etc. means that the specific features, structures, materials or characteristics described in conjunction with the embodiment or example are included in at least one embodiment or example of the present invention. In this specification, the schematic representation of the above terms does not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials or characteristics described may be combined in any one or more embodiments or examples in a suitable manner.

[0039] In addition, the technical solutions between the various embodiments can be combined with each other, but it must be based on the fact that ordinary technicians in the field can implement it. When the combination of technical solutions is contradictory or cannot be implemented, it should be deemed that such combination of technical solutions does not exist and is not within the scope of protection required by the present invention.

[0040] As the research on transition metal oxide nanoparticles continues to deepen, the focus of the research begins to focus on simplifying the preparation process and improving production efficiency. In the process of implementing the present invention, it is found that during the carbonylation process, the σ-π bond formed between the transition metal and carbon monoxide (CO) has a high stability, which makes the reaction highly selective and can reduce the generation of by-products. Compared with traditional preparation methods, the carbonylation and oxidation processes are relatively mild and can reduce the emission of harmful substances, which is in line with the development trend of green chemistry. Through carbonylation and oxidation treatment, a new method for preparing transition metal nanoparticles is provided, which realizes effective control of the particle size and morphology of nanoparticles.

[0041] Figure 1It is a schematic diagram of the principle of a gas phase reaction device for preparing transition metal oxide nanoparticles in an embodiment of the present invention.

[0042] The present invention provides a gas phase reaction device for preparing transition metal oxide nanoparticles, such as Figure 1 As shown, the gas phase reaction device includes: a gas storage unit, a reaction unit and a collection unit. The gas storage unit is suitable for providing carbon monoxide and ozone; the reaction unit is configured to accommodate transition metal elements, and the reaction unit is suitable for sequentially receiving carbon monoxide and ozone, so that the transition metal elements sequentially undergo carbonylation coordination reaction and oxidation reaction in the gas phase atmosphere to obtain transition metal oxide nanoparticles, and the transition metal oxide nanoparticles are output from the reaction unit using the reaction tail gas as a carrier; the collection unit is configured to filter, collect and store the transition metal oxide nanoparticles.

[0043] According to an embodiment of the present invention, the device realizes an integrated process from raw gas supply, reaction process control to product collection through the close cooperation of the gas storage unit, the reaction unit and the collection unit. This design has a high degree of integration and modularization, simplifies the operation steps through the preparation environment of the gas phase reaction system, improves the preparation efficiency, and is applicable to the synthesis of nanoscale transition metal oxide particles. Through the continuous carbonylation coordination reaction and oxidation reaction, the device can prepare transition metal oxide nanoparticles with high purity, good dispersibility and uniform particle size. These characteristics make the product have a wider application prospect in the fields of catalysis and materials science.

[0044] Specifically, the gas storage unit can accurately control the input sequence and flow rate of carbon monoxide and ozone; the reaction unit flexibly controls the reaction process and heating conditions, thereby ensuring that the transition metal element undergoes carbonylation coordination reaction and oxidation reaction in the gas phase atmosphere in sequence; the collection unit adopts a filtering collection method, which can effectively intercept transition metal oxide nanoparticles, and use the remaining gas as a carrier to output the reaction unit, avoiding product loss and pollution. This design improves the collection efficiency and purity of the product. At the same time, the design of the gas storage unit and the reaction unit takes into account the safe storage of gas and the safety during the reaction process, avoiding the leakage of toxic gases and the occurrence of accidents. The device reduces the emission of harmful substances during the preparation process, meets the requirements of green chemistry and sustainable development, and achieves energy conservation and rational use of resources by accurately controlling reaction conditions and efficiently collecting products.

[0045] In some specific embodiments, the device is suitable for preparing oxide nanoparticles of various transition metals, such as nickel oxide, iron oxide, cobalt oxide, etc., by simply adjusting the heating conditions in the reaction unit and the starting transition metal element. Taking transition metal nickel as an example, the reaction process is as follows (1).

[0046] Formula (1).

[0047] Specifically, this flexibility makes the device have a wide range of application potentials in the preparation of different types of transition metal oxide nanoparticles; on the other hand, it can accurately find the gas phase concentration level that improves the efficiency of continuous synthesis in actual tests, thereby improving the efficiency of synthesis operations. The design of the device is easy to expand and upgrade to meet the needs of larger-scale preparation. By increasing the number or capacity of gas storage units, reaction units, and collection units, the scale of production can be easily expanded.

[0048] In some specific embodiments, the reaction tail gas includes the carrier gas in the carbonylation coordination reaction, the carbon dioxide gas produced in the oxidation reaction, and the oxygen. Specifically, the carrier gas in the carbonylation coordination reaction is the excess carbon monoxide introduced into the carbonylation coordination reaction. After the carbonylation coordination reaction is completed, the excess carbon monoxide carries the carbonylation metal gas into the next reaction.

[0049] According to an embodiment of the present invention, the gas storage unit includes a carbon monoxide storage tank 101 and an ozone generator 105 .

[0050] In some specific embodiments, the carbon monoxide storage tank 101 is suitable for storing and providing carbon monoxide, and the carbon monoxide storage tank 101 is connected to the first reaction tube 202 through a first gas circuit X001, and the first gas circuit X001 is provided with a first control valve 104 to control the opening and closing of the first gas circuit X001; the ozone generator 105 is suitable for preparing and providing ozone, and the ozone generator 105 is connected to the second reaction tube 210 through a second gas circuit X002, and the second gas circuit X002 is provided with a second control valve 106 to control the opening and closing of the second gas circuit X002.

[0051] In some specific embodiments, the carbon monoxide storage tank 101 is provided with a carbon monoxide storage tank pressure reducing valve 102 and a carbon monoxide flow meter 103 for outputting carbon monoxide and recording the output flow rate.

[0052] According to an embodiment of the present invention, the gas storage unit also includes a reducing gas storage tank 107, which is configured to provide reducing gas to the first reaction tube 202 before the carbonylation coordination reaction and the oxidation reaction to prevent the transition metal element from being oxidized and activate the transition metal element before the carbonylation coordination reaction and the oxidation reaction occur.

[0053] In some specific embodiments, the reducing gas storage tank 107 is configured to be in communication with the first reaction tube 202 via a third gas path X003 , and the third gas path X003 is provided with a third control valve 110 to control the opening and closing of the third gas path X003 .

[0054] In some specific embodiments, the reducing gas storage tank 107 is provided with a reducing gas storage tank pressure reducing valve 108 and a reducing gas flow meter 109 for outputting the reducing gas and recording the output flow.

[0055] In some specific embodiments, the reducing gas may be hydrogen, which is used to achieve complete reduction activation of the transition metal element surface inert layer. Specifically, the transition metal element activation temperature may be 400-450°C.

[0056] According to an embodiment of the present invention, the reaction unit includes a carbonylation subunit and an oxidation subunit. The carbonylation subunit is configured to cause carbon monoxide to undergo a carbonylation coordination reaction with a transition metal element at a temperature of 60-65°C and output a carbonylation metal gas; the oxidation subunit is configured to receive the carbonylation metal gas and ozone and undergo an oxidation reaction at a temperature of 20-45°C to generate transition metal oxide nanoparticles.

[0057] In some specific embodiments, the carbonylation subunit and the oxidation subunit are connected via a fourth gas line X004, and a fourth control valve 209 is provided on the fourth gas line X004 to control opening and closing.

[0058] According to an embodiment of the present invention, the carbonylation subunit includes a first reaction tube 202 and a first temperature controller 206. The first reaction tube 202 is configured to contain a transition metal element in a transition metal element placement area 204, and to be wrapped with a first heating component 203 on the outside; the first temperature controller 206 is adapted to control the first heating component 203 to adjust the temperature of the first reaction tube 202, so that the carbon monoxide input into the first reaction tube 202 undergoes a carbonylation coordination reaction with the transition metal element. The oxidation subunit includes a second reaction tube 210 and a second temperature controller 213. The second reaction tube 210 is wrapped with a second heating component 211 on the outside; the second temperature controller 213 is adapted to adjust the temperature of the second reaction tube 210 by controlling the second heating component 211, so that the carbonylation metal gas input into the second reaction tube 210 undergoes an oxidation reaction with ozone, and the transition metal oxide nanoparticles are output from the second reaction tube 210 through the remaining ozone.

[0059] In some specific embodiments, the first temperature controller 206 is connected to and regulates the first heating component 203 via the first temperature control signal transmission line 205 ; the second temperature controller 213 is connected to and regulates the second heating component 211 via the second temperature control signal transmission line 212 .

[0060] In some specific embodiments, the first reaction tube inlet 201 is configured as a three-way interface, so that the first reaction tube inlet 201 is respectively connected to the carbon monoxide storage tank 101 and the reducing gas storage tank 107. The first reaction tube outlet 207 is configured as a three-way interface, so that the first reaction tube outlet 207 is respectively connected to the fourth gas path X004 and the sixth gas path X006.

[0061] In some specific embodiments, the first reaction tube outlet 207 is further provided with absorbent cotton 208 to prevent the transition metal element from being carried away from the first reaction tube 202 by the airflow.

[0062] Figure 2 is a schematic diagram of the heat-insulating outer layer of the reaction unit of the gas phase reaction device in the embodiment of the present invention, Figure 3 It is a principle schematic diagram of the thermal insulation layer of the reaction unit of the gas phase reaction device in the embodiment of the present invention.

[0063] According to an embodiment of the present invention, a "Z-shaped" heat-insulating outer layer is provided outside the reaction unit to ensure a stable reaction temperature. Figure 2 As shown, in the longitudinal section, the insulation outer layer includes an insulation shell 220 and an insulation layer 221. The insulation shell 220 is fixed by a plurality of first edge fixing buckles 222. The insulation outer layer can be made of metal material, and the insulation layer 221 can be made of rock wool. Figure 2 In the embodiment, there are 8 first edge fixing buckles 222; Figure 3 As shown, the insulation layer 221 includes an insulation upper cover 223, a control valve regulating port 224 and an insulation lower cover 226. The first reaction tube 202 and the second reaction tube 210 are arranged in the storage cavity of the insulation layer 221. The control valve regulating port is suitable for fixing and exposing the fourth control valve 209 and connecting the first reaction tube 202 and the second reaction tube 210. The insulation upper cover 223 and the insulation lower cover 226 are fixed by a plurality of second edge fixing buckles 225. Figure 3 In the embodiment, there are eight second edge fixing buckles 225 .

[0064] According to an embodiment of the present invention, the oxidizing subunit further includes a capture magnetic strip 216 installed outside the second reaction tube 210 , and the capture magnetic strip 216 is suitable for fixing transition oxide nanoparticles.

[0065] According to an embodiment of the present invention, the second reaction tube 210 further includes a pressure relief outlet 215 and a sealing rubber plug 214 .

[0066] According to an embodiment of the present invention, the pressure relief outlet 215 can, on the one hand, open the sealing plug 214 by releasing pressure, and on the other hand, can also play a role of pressure relief protection when the gas path of the gas phase reaction device is blocked; the sealing plug 214 can be opened to collect the transition metal oxide nanoparticles collected by the capture magnetic strip 216 in the second reaction tube 210.

[0067] According to an embodiment of the present invention, the collection unit comprises a collection bottle 302 equipped with a filter sealing cover 301, which is suitable for allowing the transition metal nano-oxide particles to pass through and be collected.

[0068] In some specific embodiments, the second reaction tube 210 and the collecting bottle 302 are connected via a spherical collecting tube, wherein a plurality of spherical collecting tubes and collecting bottles 302 may be provided.

[0069] In some specific embodiments, the collecting bottle 302 is a light-proof brown bottle.

[0070] According to an embodiment of the present invention, the gas phase reaction device further comprises a tail gas recovery unit, including: an explosion-proof exhaust fan 403, adapted to collect and prevent explosion of reaction tail gas, the reaction tail gas comprising ozone and reducing gas.

[0071] In some specific embodiments, the collection unit and the explosion-proof exhaust fan 403 are connected through the fifth gas line X005, the fifth gas line X005 is provided with a fifth control valve 401 to control the opening and closing of the fifth gas line X005, and the fifth gas line X005 is suitable for discharging ozone; the first reaction tube 202 and the explosion-proof exhaust fan 403 are connected through the sixth gas line X006, the sixth gas line X006 is provided with a sixth control valve 402 to control the opening and closing of the sixth gas line X006, and the sixth gas line X006 is suitable for discharging reducing gas.

[0072] According to an embodiment of the present invention, the gas phase reaction device proposed in the present invention further includes a control unit to control the opening and closing and state of each structure. Specifically, the first control valve 104, the second control valve 106, the third control valve 110, the fourth control valve 209, the fifth control valve 401, the sixth control valve 402, the first temperature controller 206, and the second temperature controller 213 are respectively connected to the control unit.

[0073] In some specific embodiments, the gas path and various connecting devices in the gas phase reaction device may be made of Teflon material and / or other stable colloid hoses.

[0074] Specifically, the connection depth between adjacent Teflon three-way interfaces and Teflon tubes is 1-1.5 cm, the connection depth between the Teflon three-way interfaces and each reaction tube of the reaction unit is 0.5-1.3 cm, and the inner diameter of the colloid hose is 1-2 mm smaller than the inner diameter of the Teflon tube connected thereto.

[0075] In another aspect of the present invention, a method for using the aforementioned gas phase reaction device is also proposed, comprising: first, placing a transition metal element in a transition metal element placement area 204 in a first reaction tube 202, allowing a reducing gas storage tank to input reducing gas into the first reaction tube 202 to activate the transition metal element, and discharge the reducing gas in the first reaction tube 202; then inputting carbon monoxide into the first reaction tube 202, so that carbon monoxide and the transition metal element undergo a carbonylation coordination reaction to generate carbonyl metal gas, and inputting the carbonyl metal gas into the second reaction tube 210; then inputting ozone into the second reaction tube 210, so that the carbonyl metal gas and ozone undergo an oxidation reaction to obtain transition metal oxide nanoparticles, and the transition metal oxide nanoparticles are output to a collection unit through the remaining ozone and stored; finally, opening the fifth control valve 401 to discharge the ozone in the second reaction tube 210.

[0076] According to an embodiment of the present invention, by first inputting a reducing gas (such as hydrogen, etc.) into the first reaction tube 202, the transition metal element can be effectively activated and its reactivity can be improved. This step lays a good foundation for the subsequent carbon monoxide carbonylation coordination reaction, which helps to improve the overall reaction efficiency and product quality. The method clearly stipulates the input sequence and timing of reducing gas, carbon monoxide and ozone, ensuring that the carbonylation coordination reaction and oxidation reaction can be carried out in sequence and in an orderly manner. This precise reaction step control helps to obtain high-quality, uniform-size transition metal oxide nanoparticles. During the reaction process, the emission of harmful substances is reduced by precisely controlling the reaction conditions and the collection method of the product. At the same time, the method also uses the remaining ozone as a carrier to output the transition metal oxide nanoparticles, avoiding additional energy consumption and environmental pollution.

[0077] According to the embodiments of the present invention, the product efficiency of the gas phase reaction device proposed by the present invention can be 100%, and it has the beneficial effects of efficient preparation and reaction control, improved product quality and collection efficiency, safety and environmental protection, flexibility and scalability in the preparation of transition metal oxide nanoparticles. These advantages make the device have broad application prospects and important research value in the fields of catalysis, material science, biomedicine, etc.

[0078] In some specific embodiments, the gas phase reaction device proposed in the present invention can achieve 100% conversion of transition metal elements. Since the present invention prepares transition metal oxide nanoparticles through a gas phase reaction system, the obtained transition metal oxide nanoparticles have high purity and small particle size of about 5-35nm, and the particles are evenly dispersed.

[0079] In some specific embodiments, the collection bottle of the collection unit can be replaced with a filtering shaping mold or a coating cavity, and pure-phase solid transition metal oxide materials or coatings in the form of sheets, strips or blocks can be directly synthesized, thereby achieving the agglomeration and shaping of synthetic transition metal oxide nanoparticles or the coating of substrate materials in one step, and the obtained target material or coating has fine particle size and uniform properties.

[0080] It should be noted that the described embodiments are only some embodiments of the present invention, rather than all embodiments. Based on the embodiments of the present invention, other embodiments obtained by ordinary technicians in this field without creative work are all within the scope of protection of the present invention.

[0081] With the popularization of renewable energy and the development of clean energy technology, the demand for nickel oxide in energy storage devices, including lithium-ion batteries, nickel-metal hydride batteries and supercapacitors, continues to increase. As a positive electrode material, nickel oxide has good electrochemical properties and cycle stability, which can improve the performance and cycle life of energy storage devices. In the chemical industry, nickel oxide plays a key role as a catalyst, for example, in hydrogenation reactions, methane reforming and water gas conversion. The excellent hydrogen adsorption and release properties of nickel oxide make it one of the candidates for hydrogen storage materials, which can realize the adsorption, storage and release of hydrogen, and improve the efficiency and recyclability of hydrogen storage systems. In addition, nickel oxide can also be composited with other hydrogen storage materials to form high-performance composite hydrogen storage materials, which can improve the hydrogen adsorption capacity and hydrogen storage density. Catalytic decomposition of hydrogen and reaction kinetics are two other important aspects of nickel oxide in the field of hydrogen storage, which are of key significance to the design and optimization of hydrogen storage systems.

[0082] Nickel oxide is a wide bandgap P-type semiconductor oxide with excellent thermal sensitivity, photoelectricity, gas sensitivity and catalytic activity in its nanostructure. Currently, it is mainly prepared by nickel salt calcination decomposition method, nickel carbonate method, solid phase oxidation / calcination method and other methods.

[0083] Example 1

[0084] Specifically, in this embodiment, taking the synthesis of nickel oxide nanoparticles as an example, the method for using the aforementioned gas phase reaction device includes the following steps S1 to S5.

[0085] Step S1: Gas pre-production: According to the needs of the synthesis operation, the reducing gas is set to hydrogen, and the concentrations of the reducing gas, carbon monoxide and ozone are set.

[0086] Step S2: Equipment prefabrication: Assemble the gas phase reaction device, place nickel powder and absorbent cotton 208 in the first reaction tube 202, use nitrogen gas flow to displace the residual air in the reaction unit before the formal start, and check the air tightness of the gas phase reaction device.

[0087] Step S3: metal activation. Open the reducing gas storage tank 107, adjust the reducing gas flowmeter 109 to an appropriate flow rate, open the third control valve 110 on the third gas path X003 and the sixth control valve 402 on the sixth gas path X006, so that the reducing gas hydrogen fills the first reaction tube 202; open the first temperature controller 206, control the first reaction tube 202 to reach the reduction occurrence temperature of the inert nickel oxide layer on the surface of the nickel powder, and maintain the temperature until the inert layer on the surface of the nickel powder is completely reduced and activated; cool the first reaction tube 202 to room temperature, close the reducing gas storage tank 107, and complete the reduction and activation of the inert layer on the surface of the nickel powder.

[0088] Step S4: product synthesis. According to the operation requirements, the carbon monoxide storage tank pressure reducing valve 102 is opened, the carbon monoxide flowmeter 103 is adjusted to an appropriate flow rate, the sixth control valve 402 is closed, the first control valve 104 on the first gas path X001, the fourth control valve 209 on the fourth gas path X004 and the fifth control valve 401 on the fifth gas path X005 are opened, and the carbon monoxide displaces the residual reducing gas in the gas phase reaction device; the first temperature controller 206 and the second temperature controller 213 are opened, and the optimal reaction temperature of the carbonyl nickel gas and the optimal temperature of the carbonyl nickel ozone oxidation are adjusted respectively. After the temperature in the first reaction tube 202 and the second reaction tube 210 is stable, the ozone generator 105 and the second control valve 106 on the second gas path X002 are opened, and a high concentration ozone gas flow is introduced, and the black particles formed in the second reaction tube 210 are collected in the product collection bottle 302, that is, the gas phase reaction system preparation of nano nickel oxide (NiO) is completed.

[0089] Step S5: Reset the equipment. Close the first temperature controller 206 and the second temperature controller 213, and after the temperature in the first reaction tube 202 and the second reaction tube 210 drops to room temperature, close the first control valve 104 and the second control valve 106, stop introducing carbon monoxide and ozone, remove the collection bottle 302 and seal it for storage, and finally close the fourth control valve 209 and the fifth control valve 401, clean the residual waste in the first reaction tube 202 and the second reaction tube 210, and clean the gas phase reaction device to complete the reset, and return to step S1 to prepare for the next round of experiments.

[0090] The morphology of the nano nickel oxide particles prepared in Example 1 was characterized.

[0091] Figure 4 is a scanning electron microscope image of the nano nickel oxide particles prepared in Example 1 of the present invention, Figure 5 is a transmission electron microscope image of the nano nickel oxide particles prepared in Example 1 of the present invention, Figure 6 3 is a particle size distribution diagram of the nano nickel oxide particles prepared in Example 1 of the present invention.

[0092] like Figure 4-Figure 6As shown, the transition metal oxide nanoparticles prepared by the gas phase reaction device proposed by the present invention are spherical particles with a small particle size (5-35nm) and can maintain relatively uniform dispersion.

[0093] The specific embodiments described above further illustrate the objectives, technical solutions and beneficial effects of the present invention in detail. It should be understood that the above description is only a specific embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present invention should be included in the scope of protection of the present invention.

Claims

1. A gas phase reaction device for preparing transition metal oxide nanoparticles, characterized in that: The gas phase reaction device comprises: a gas storage unit suitable for providing carbon monoxide and ozone; A reaction unit is configured to contain a transition metal element, the reaction unit is adapted to sequentially receive the carbon monoxide and the ozone, so that the transition metal element sequentially undergoes a carbonylation coordination reaction and an oxidation reaction in a gas phase atmosphere to obtain transition metal oxide nanoparticles, and the transition metal oxide nanoparticles are output from the reaction unit using the reaction tail gas as a carrier; A collection unit, configured to filter, collect and preserve the transition metal oxide nanoparticles; The reaction unit comprises: The carbonylation subunit is configured to cause the carbon monoxide to undergo a carbonylation coordination reaction with a transition metal element at a temperature of 60-65° C., and output a carbonylation metal gas; an oxidation subunit configured to receive the carbonyl metal gas and the ozone and to perform an oxidation reaction at a temperature of 20-45° C. to generate transition metal oxide nanoparticles; The carbonylation subunit comprises: The first reaction tube is configured to contain a transition metal element inside and to have a first heating component wrapped around the outside; a first temperature controller, adapted to control the first heating assembly to adjust the temperature of the first reaction tube, so that the carbon monoxide input into the first reaction tube undergoes the carbonylation coordination reaction with the transition metal element; The oxidation subunit comprises: A second reaction tube, with a second heating assembly wrapped around the outside; a second temperature controller, adapted to adjust the temperature of the second reaction tube by controlling the second heating assembly, so that the carbonylation metal gas and the ozone input into the second reaction tube undergo the oxidation reaction, and the transition metal oxide nanoparticles are output from the second reaction tube through the reaction tail gas; The gas storage unit includes a reducing gas storage tank configured to provide reducing gas to the first reaction tube before the carbonylation coordination reaction and the oxidation reaction to prevent the transition metal element from being oxidized and activate the transition metal element before the carbonylation coordination reaction and the oxidation reaction occur.

2. The gas phase reaction device according to claim 1, characterized in that: The oxidizing subunit further comprises a capture magnetic strip installed outside the second reaction tube, and the capture magnetic strip is suitable for fixing the transition metal oxide nanoparticles.

3. The gas phase reaction device according to claim 1, characterized in that: The second reaction tube also includes a pressure relief outlet and a sealing rubber plug.

4. The gas phase reaction device according to claim 1, characterized in that: The gas storage unit includes a carbon monoxide storage tank and an ozone generator.

5. The gas phase reaction device according to claim 1, characterized in that: The collection unit comprises a collection bottle equipped with a filter sealing cap, which is suitable for allowing the transition metal oxide nanoparticles to pass through and be collected.

6. The gas phase reaction device according to claim 1, characterized in that: The gas phase reaction device further comprises a tail gas recovery unit, comprising: an explosion-proof exhaust fan, adapted to collect and prevent the reaction tail gas from exploding, the reaction tail gas comprising the ozone and the reducing gas.

7. A method for using the gas phase reaction device according to any one of claims 1 to 6, characterized in that: The method of use includes: Placing a transition metal element in a first reaction tube, allowing a reducing gas storage tank to input reducing gas into the first reaction tube to activate the transition metal element, and exhausting the reducing gas in the first reaction tube; Inputting carbon monoxide into the first reaction tube so that the carbon monoxide undergoes a carbonylation coordination reaction with the transition metal element to generate carbonyl metal gas, and inputting the carbonyl metal gas into the second reaction tube; Inputting ozone into the second reaction tube, so that the carbonylation metal gas and the ozone undergo an oxidation reaction to obtain transition metal oxide nanoparticles, and the transition metal oxide nanoparticles are output to a collection unit through reaction tail gas and stored; The reaction tail gas in the second reaction tube is discharged.

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