WO2010045762A1

WO2010045762A1 - Device and method for preparing nanometer particles used for catalyst, nanometer catalyst product and the preparation thereof

Info

Publication number: WO2010045762A1
Application number: PCT/CN2008/072799
Authority: WO
Inventors: 李哲修; 高锡勤; 周栽镐; 李正焕; 吕运贞
Original assignee: (株)爱纳米
Priority date: 2008-10-23
Filing date: 2008-10-23
Publication date: 2010-04-29
Also published as: CN102272037A

Abstract

The device and method for preparing nanometer powder used for catalyst, nanometer catalyst and the preparation thereof. The device comprises: a vacuum chamber (410); an agitating chamber (402) located inside the vacuum chamber (410) to contain the support; vertical agitating parts located inside the agitating chamber (402) comprising a vertical rotary shaft (406) and spiral blades (405), the spiral blades (405) rotating around the vertical rotary shaft (406) to agitate the support and transport the support from the downside to the upside of the agitating chamber (402); and a depositing device (401) to deposit nanometer particles used for catalyst on the support at the upside of the agitating chamber (402) by physical depositing method. The nanometer particles deposited on the support can be made into nanometer catalyst directly.

Description

催化剂用纳米粒子制造装置、制造方法、纳米催化剂产品及其生产方法 Nanoparticle production device for catalyst, manufacturing method, nano catalyst product and production method thereof

技术领域 Technical field

本发明涉及纳米催化剂制备领域，尤其是涉及催化剂用纳米粒子制造方法及纳米催化剂应用制品。背景技术 The present invention relates to the field of nanocatalyst preparation, and more particularly to a method for producing a nanoparticle for a catalyst and a nanocatalyst application product. Background technique

催化剂是指在化学反应中不发生自身的量、质的变化只是提高化学反应速度的物质。最初发现催化剂作用的是瑞典的 J. J. Berzel ius, 1853年他把希腊语当中的表示 "放入" 的 kata与表示 "解开" 的 lusis结合在一起对此作用命名为 catalysis 对氮与氢混合气体进行加热 /加压制造氨的时候与以氧化铁为主要成分的固体接触能提高反应速度而容易合成，这是对催化剂的一个例子。科学家们对催化剂及催化作用做出了很多研究，并且通过对催化剂的功能及催化剂的作用原理的实验 /理论研究发展到了催化剂化学领域。反应物质与催化剂处于相同的相（phase) 时称之为均相催化剂，处于不同相时称之为非均相催化剂。例如，氢、氮、氨是气态而氧化铁是固态，所以属于非均相催化剂。一般催化剂是起提高反应速度的作用，这种催化剂称之为正催化剂，相反也有降低反应速度的催化剂，这种催化剂称之为负催化剂。 Catalyst refers to a substance that does not undergo its own amount in the chemical reaction, and the change in quality is only a matter of increasing the rate of chemical reaction. The catalyst was originally discovered by JJ Berzel ius of Sweden. In 1853, he combined the kata of the Greek expression "in" with the lusis which means "unwrapped". The effect was named catalyst for the mixture of nitrogen and hydrogen. When heating/pressurizing to produce ammonia, contact with a solid containing iron oxide as a main component can increase the reaction rate and be easily synthesized, which is an example of a catalyst. Scientists have done a lot of research on catalysts and catalysis, and have developed into the field of catalyst chemistry through experimental/theoretical studies on the function of catalysts and the principle of action of catalysts. When the reactants are in the same phase as the catalyst, they are called homogeneous catalysts, and when they are in different phases, they are called heterogeneous catalysts. For example, hydrogen, nitrogen, and ammonia are gaseous and iron oxide is solid, so it is a heterogeneous catalyst. Generally, the catalyst serves to increase the reaction rate. This catalyst is called a positive catalyst, and conversely, a catalyst which lowers the reaction rate. This catalyst is called a negative catalyst.

初期催化剂领域集中在化学工艺上，但近期应用于汽车尾气净化、发电厂脱窒等公害防止、燃料电池、氢等未来能源开发、烹饪用烤箱、暖炉等领域，并且需求量日益增长。在许多技术开发与应用上催化剂领域经过发展与电子学、生命工学、新材料、新能源等尖端领域一同评为核心技术要素。 The initial catalyst field is concentrated in chemical processes, but it has recently been used in the fields of automobile exhaust gas purification, power plant decontamination prevention, fuel cell, future energy development such as hydrogen, cooking ovens, and heating furnaces, and the demand is increasing. In many technologies development and application, the catalyst field has been evaluated as a core technology element along with cutting-edge fields such as electronics, biotechnology, new materials, and new energy.

在催化剂领域尤其是纳米催化剂被认定为能解决因高度产业化而引起的能源枯竭及因采用化学燃料而产生的环境污染问题的新一代技术。纳米催化剂是具有化学反应活性的纳米大小的物质，在能量转换、光催化剂、绿色化学 (Green Chemi stry)、环境、生物模仿技术、分子印刷术等领域被关注和研究。这种纳米催化剂的高效率特性很难在膨体状态下取得，而催化剂材料变成纳米大小之后就有可能。纳米催化剂使原有催化剂的活性最大化，从而使生产中所需的催化剂的量最小化，在化学反应中降低反应温度能选择性地得到生成物。因此，这种纳米催化剂的活性通过控制均一的纳米大小及制造无不纯物的纳米粒子的方法来最大化。 In the field of catalysts, in particular, nanocatalysts have been identified as a new generation of technologies that can solve the problem of depletion of energy due to high industrialization and environmental pollution caused by the use of chemical fuels. Nanocatalysts are chemically reactive nano-sized materials that have attracted attention and research in the fields of energy conversion, photocatalysis, green chemistry, environmental, biological imitation technology, and molecular printing. Such The high efficiency characteristics of the rice catalyst are difficult to obtain in the expanded state, and it is possible after the catalyst material becomes nanosized. The nanocatalyst maximizes the activity of the original catalyst, thereby minimizing the amount of catalyst required for production, and lowering the reaction temperature in the chemical reaction to selectively obtain a product. Thus, the activity of such nanocatalysts is maximized by a method that controls uniform nanometer size and produces nanoparticles without impurities.

催化剂材料的活用方法有将支持体与催化剂材料的原料以液态添加到化学溶液里使用的方法，并且还有为了选择性的控制气相反应而使用固态催化剂材料的方法。 The method of using the catalyst material is a method of adding a raw material of a support and a catalyst material to a chemical solution in a liquid state, and a method of using a solid catalyst material for selectively controlling a gas phase reaction.

将催化剂材料附着到支持体上的催化及制造方法有化学方法和物理方法。用化学方法将纳米大小的贵金属等催化剂测量附着到支持体的工艺包括附着到活性炭支持体的工艺和附着到化工陶瓷氧化物支持体的工艺。例如，将金属催化剂附着到活性炭 (Active Carbon)的纳米粒子化学制造方法有 PL (Precipitation Liquid reduction)、 PG (Precipitation Gas reduction)、 AL (Adsorption Liquid reduction)、 AG (Adsorption Gas reduction)等，相关工艺条件及工艺顺序如图 1 所示。在化工陶瓷或氧化物支持体上形成催化剂的制造方法有浸渍法 ( Impregnation) 、沸石的离子交换法 ( Ion exchange on Zeolite) 、共沉淀法 (Co-precipitation) 、沉禾只沉淀法 (Deposition & precipitation) 等。催化剂材料的化合物主要有金属盐、有机金属络合化合物（complexion compound)，金属盐中贵金属类盐例如主要有 HAuCl₄、 AuCl₃、 KAu (CN) ₂、 Au (en) ₂Cl₃、有机金属前体（Organo metallic precursor) 、 H₂PtCl₆、 Pt (N0₂) ₂ (NH₃) ₂、 PtCl₂、 RuCl₃等。还原剂主要用 LiBH₄、 NaBH₄或易混合于水的酒精类。此时使用的化工陶瓷支持体为二氧化硅 (Si lica) 、氧化铝 (Alumina) 、氧化镁 (Magnesia) 、氧化钛（Titania) 、氧化铁（Ferric oxide) 等。进行煅烧工程之前混合金属类盐、还原剂、化工陶瓷支持体。这些氧化物在水的作用下迅速转换成氢氧化物（Hydroxide) , 再次以 500-600 K进行脱水 (Dehydration) 干燥后以 1000 K 进行煅烧（Calcination) 。再将获得的材料在 500-600 K温度氢气（Hydrogen gas ) 条件下还原得贵金属。为了得到纯的贵金属催化剂，需要在水中洗涤的残留物和 C1离子后在 400- 550 K的温度氢气（Hydrogen gas )条件下再次干燥合成附着在支持体上的纳米贵金属的催化剂材料。如果采用化学方法经过如此复杂的工艺后将在活性炭或化工陶瓷等支持体上可形成催化剂用纳米粒子，在采用化学方法制造纳米粒子的过程中因为使用多种添加剂所以很难获取纯纳米粒子，很难控制纳米粒子的形状，制造工艺中生成的副产物对环境产生严重危害。 The catalytic and manufacturing methods for attaching the catalyst material to the support are chemically and physically. The process of chemically attaching a catalyst such as a nanometer-sized noble metal to a support includes a process of attaching to an activated carbon support and a process of attaching to a chemical ceramic oxide support. For example, a nanoparticle chemical manufacturing method in which a metal catalyst is attached to an activated carbon has a PL (Precipitation Liquid reduction), a PG (Precipitation Gas reduction), an AL (Adsorption Liquid reduction), an AG (Adsorption Gas reduction), and the like. The conditions and process sequence are shown in Figure 1. The manufacturing method for forming a catalyst on a chemical ceramic or an oxide support is Impregnation, Ion exchange on Zeolite, Co-precipitation, and Deposition & Precipitation) and so on. The compound of the catalyst material mainly includes a metal salt, an organic metal complex compound, and a noble metal salt of the metal salt, for example, mainly HAuCl ₄ , AuCl ₃ , KAu (CN) ₂ , Au (en) ₂ Cl ₃ , or an organic metal. Pregano metallic precursor, H ₂ PtCl ₆ , Pt (N0 ₂ ) ₂ (NH ₃ ) ₂ , PtCl ₂ , RuCl _{3 ,} and the like. The reducing agent mainly uses LiBH ₄ , NaBH ₄ or alcohol which is easily mixed with water. The chemical ceramic support used at this time is silica (Si lica), alumina (Alumina), magnesium oxide (Magnesia), titanium oxide (Titania), iron oxide (Ferric oxide) and the like. The metal salt, the reducing agent, and the chemical ceramic support are mixed before the calcination process. These oxides are rapidly converted into hydroxides by the action of water, and dehydrated again at 500-600 K. After drying, they are calcined at 1000 K (Calcination). The material obtained will be hydrogen at a temperature of 500-600 K (Hydrogen The noble metal is reduced under the condition of gas). In order to obtain a pure noble metal catalyst, it is necessary to dry the residue of the water and the C1 ion and then dry the catalyst material of the nano precious metal attached to the support again under a hydrogen gas condition of 400 to 550 K. If a chemical process is used to form a catalyst nanoparticle on a support such as activated carbon or a chemical ceramic after such a complicated process, it is difficult to obtain pure nanoparticles in the process of chemically producing the nanoparticle by using various additives. It is difficult to control the shape of the nanoparticles, and by-products generated in the manufacturing process are seriously harmful to the environment.

采用现有化学的纳米粒子的制造方法制造附着两种以上催化剂的支持体必须同时使用能生成两种以上纳米材料的有机化合物。但是，每种金属有机化合物在分解温度和化学组成有不同特性，因此根据纳米材料能同时使用的有机化合物极少。并且由于复杂的工艺有机金属试剂或金属盐大部分很难回收、产生大量废水。采用化学纳米粒子制造方法需要进行净化这种废水或为了保管及管理的 2次设施，而且在选择支持体时根据金属盐的酸性或碱性氧化物支持体会产生水化现象，为了转换成氧化物需要热处理工艺。采用化学方法制造催化剂时支持体上残留氯离子、硝酸离子、有机金属化合物的分解物等不纯物，因此还需要进行洗涤工艺。如此可见，采用化学方法制造纳米粒子存在工艺复杂、工艺中支持体水化 (hydration)、试剂（reagent)价钱高、污染、不能制造纳米合金等多种问题，制造时采用效率低的方法使用的贵金属材料会增加进而也增加了贵金属的需求量，并且还需要使用更多的添加剂。为了解决这些问题需要采用制造效率高的物理方法来制造纳米粒子，特别是制造贵金属纳米催化剂。为了制造高纯度、高效率并亲环境的催化剂用纳米粒子，减少纳米材料使用量，应采用物理干式方法。 In the production method of the conventional chemical nanoparticles, it is necessary to simultaneously use an organic compound capable of forming two or more types of nanomaterials. However, each of the metal organic compounds has different characteristics at the decomposition temperature and chemical composition, and therefore, there are few organic compounds which can be simultaneously used depending on the nanomaterial. And because of the complicated process, organometallic reagents or metal salts are mostly difficult to recover and generate a large amount of wastewater. The use of chemical nanoparticles manufacturing methods requires purification of such wastewater or secondary facilities for storage and management, and when the support is selected, hydration occurs depending on the acidic or basic oxide support of the metal salt, in order to convert to oxide. A heat treatment process is required. When a catalyst is produced by a chemical method, impurities such as chloride ions, nitrate ions, and decomposition products of an organometallic compound remain on the support, and thus a washing process is required. It can be seen that the use of chemical methods for the production of nanoparticles has a complicated process, a hydration in the process, a high reagent cost, a pollution, and the inability to manufacture nano-alloys. Precious metal materials increase and thus increase the demand for precious metals, and more additives are needed. In order to solve these problems, it is necessary to manufacture nanoparticles using a physically efficient physical method, particularly to manufacture noble metal nanocatalysts. In order to produce high purity, high efficiency and environmentally friendly catalyst nanoparticles, and to reduce the amount of nanomaterials used, a physical dry method should be employed.

利用物理方式制造纳米催化剂的方法有机械高能粉碎法 (High Energy A method for physically producing nanocatalysts is mechanical high energy pulverization (High Energy)

Mi ll ing)、气相蒸发凝缩法（Inert Gas Condensation, IGC)、火焰烟雾剂工艺 (Flame Aerosol Process)等。目前开发的大部分物理纳米粒子制造方法在控制纳米粒子大小和产量上有限度，因此首先需要开发高效率的纳米粒子制造装置。一般物理纳米粒子制造方法是单独生产纳米材料，因此需要注意纳米粒子的收集、保管、取扱，而且为了适用于应用制品需要通过与应用制品的主要材料混合来分散纳米粒子。发明内容 Mi ll ing), Inert Gas Condensation (IGC), Flame Aerosol Process, etc. Most of the physical nanoparticle manufacturing methods currently developed have limited limitations in controlling the size and yield of nanoparticles, so it is first necessary to develop a highly efficient nanoparticle manufacturing apparatus. The general physical nanoparticle manufacturing method is to separately produce nanomaterials, so it is necessary to pay attention to the nanoparticles. The collection, storage, and handling of the granules, and in order to be suitable for the application of the article, requires dispersion of the nanoparticles by mixing with the main materials of the applied article. Summary of the invention

本发明的目的之一在于提供一种催化剂用纳米粉末制造装置，克服现有的利用化学方法制造催化剂的缺陷及现有的物理方法中对粒子大小和产量上的限制。 SUMMARY OF THE INVENTION One object of the present invention is to provide a nanopowder manufacturing apparatus for a catalyst which overcomes the drawbacks of the conventional chemical method for producing a catalyst and the limitations on particle size and yield in the existing physical methods.

相应地，本发明的另一目的在于提供一种纳米粉末制造方法。 Accordingly, another object of the present invention is to provide a method of producing a nanopowder.

本发明的另一目的在于提供一种纳米催化剂产品。 Another object of the present invention is to provide a nanocatalyst product.

本发明的另一目的在于提供一种纳米催化剂产品的生产方法。 Another object of the present invention is to provide a method of producing a nanocatalyst product.

为了实现上述目的，本发明实施例提供的催化剂用纳米粒子制造装置包括：真空槽； In order to achieve the above object, a nanoparticle production apparatus for a catalyst provided by an embodiment of the present invention includes: a vacuum chamber;

搅拌槽，位于所述真空槽内，用于容纳支持体； a stirring tank, located in the vacuum tank, for accommodating the support;

垂直搅拌部件，设置于所述搅拌槽中，包括垂直旋转轴及螺旋型搅拌翼，该螺旋型搅拌翼围绕所述垂直旋转轴的进行螺旋式旋转，以搅拌所述支持体并将搅拌槽下部的支持体输送至搅拌槽的上部；以及 a vertical agitating member, disposed in the agitation tank, comprising a vertical rotating shaft and a spiral agitating blade, the spiral agitating blade is spirally rotated around the vertical rotating shaft to stir the supporting body and lower the stirring tank The support is delivered to the upper portion of the agitation tank;

沉积装置，用于利用物理沉积方式在搅拌槽上部的支持体上沉积催化剂用纳米粒子。 A deposition apparatus for depositing catalyst nanoparticles on a support on the upper portion of the agitation tank by physical deposition.

本发明实施例的催化剂用纳米粒子制造方法包括： The method for producing a catalyst nanoparticle according to an embodiment of the present invention includes:

搅拌步骤，利用螺旋型搅拌翼进行螺旋式垂直旋转来搅拌支持体或利用水平旋转方式搅拌部件搅拌支持体； a stirring step, the spiral stirring blade is used for spiral vertical rotation to stir the support body or the horizontal stirring method is used to stir the member to stir the support body;

沉积步骤，在进行搅拌步骤的同时在真空条件下利用物理沉积方式在暴露于沉积区域的支持体上沉积催化剂用纳米粒子。 In the deposition step, the catalyst nanoparticles are deposited on the support exposed to the deposition region by physical deposition under vacuum while performing the stirring step.

本发明一实施例的纳米催化剂产品为蜂窝状，是通过对沉积有催化剂用纳米粒子的支持体进行铸型（molding) 、烧结（sintering) 处理形成。 The nanocatalyst product according to an embodiment of the present invention is in the form of a honeycomb, and is formed by a molding and a sintering treatment of a support in which nanoparticles for catalyst are deposited.

本发明另一实施例的纳米催化剂产品是通过将蜂窝状载体利用含有催化剂用纳米粒子的液体进行浸泡、喷雾、丝网印刷或涂装后进行干燥处理形成。 The nanocatalyst product according to another embodiment of the present invention is formed by subjecting a honeycomb carrier to a drying treatment by dipping, spraying, screen printing or coating a liquid containing catalyst nanoparticles.

根据本发明一实施例的纳米催化剂产品的生产方法，对沉积有催化剂用纳米粒子的支持体进行铸型、烧结处理，形成承载有纳米催化剂的蜂窝状纳米催化剂产品。根据本发明另一实施例的纳米催化剂产品的生产方法，包括： Method for producing a nanocatalyst product according to an embodiment of the present invention, for depositing nanoparticles for catalyst The support is subjected to casting and sintering to form a honeycomb nanocatalyst product carrying a nanocatalyst. A method of producing a nanocatalyst product according to another embodiment of the present invention, comprising:

将沉积有催化剂用纳米粒子的水溶性支持体进行溶解变为液体状态；利用所述液体对蜂窝状载体进行浸泡、喷雾、丝网印刷或涂装后进行干燥处理，形成承载有纳米催化剂的纳米催化剂产品。 Dissolving the water-soluble support on which the catalyst nanoparticles are deposited into a liquid state; immersing, spraying, screen printing or coating the honeycomb carrier with the liquid, followed by drying to form a nanometer carrying the nanocatalyst Catalyst product.

本发明不使用金属盐或有机化合物，因此不需要调整分解的金属盐或金属有机化合物的酸性和碱性。以本发明制造纳米粒子的装置采用真空槽直接在支持体上形成催化剂材料，因此不产生水化现象。并且为了在支持体上形成均一的催化剂材料，旋转粉体制造包括分布均匀催化剂材料的支持体。本发明工艺采用现有真空沉积方法，因此容易使多种金属或合金蒸形成气相，在支持体上均匀地形成高纯度的纳米粒子。用于物理纳米制造装置上的纳米材料沉积装置可采用如下有热蒸发 (Thermal Evaporation)、电子束沉禾只 (E-b earn Evaporation)、直流溅射（DC Sputtering) 、射频溅射（RF Sputtering) 、离子束溅射（Ion Beam Sputtering) 、分子束夕卜延 (Molecular Beam Epitaxy) 、电弧放电法 (Arc Discharge Process)、激光烧烛 (Laser Ablation) 等。 The present invention does not use a metal salt or an organic compound, and therefore it is not necessary to adjust the acidity and alkalinity of the decomposed metal salt or metal organic compound. The apparatus for producing nanoparticles according to the present invention uses a vacuum chamber to form a catalyst material directly on the support, so that no hydration occurs. And in order to form a uniform catalyst material on the support, the rotary powder produces a support comprising a uniform catalyst material. The process of the present invention employs an existing vacuum deposition method, so that it is easy to vaporize a plurality of metals or alloys into a gas phase, and uniformly form high-purity nanoparticles on the support. The nanomaterial deposition apparatus used in the physical nanofabrication apparatus may employ the following: Thermal Evaporation, Eb earn Evaporation, DC Sputtering, RF Sputtering, Ion Beam Sputtering, Molecular Beam Epitaxy, Arc Discharge Process, Laser Ablation, and the like.

本发明采用多种旋转方式旋转支持体，并在支持体上形成纳米大小的催化剂物质，为了提高支持体与纳米催化剂粒子之间的黏着力，通过热处理工艺能制造出更有耐久性的催化剂材料。用本发明制造的催化剂用纳米粒子的大小及含量可通过控制沉积速度、沉积能量、沉积时间、支持体大小、支持体形状、支持体搅拌速度、支持体的温度、真空度等等参数来进行调整。附图说明 The invention rotates the support body by a plurality of rotation modes, and forms a nanometer-sized catalyst substance on the support body. In order to improve the adhesion between the support body and the nano catalyst particles, a more durable catalyst material can be manufactured by the heat treatment process. . The size and content of the nanoparticles for the catalyst produced by the present invention can be controlled by controlling the deposition rate, deposition energy, deposition time, support size, support shape, support stirring speed, support temperature, vacuum degree and the like. Adjustment. DRAWINGS

此处所说明的附图用来提供对本发明的进一步理解，构成本申请的一部分，并不构成对本发明的限定。在附图中： The drawings described herein are provided to provide a further understanding of the invention, and are not intended to limit the invention. In the drawing:

图 1是利用化学方法制造活性炭的催化剂纳米粒子的制造工艺的示意图；图 2是采用本发明的纳米粒子制造的工艺概念图； 1 is a schematic view showing a manufacturing process of a catalyst nanoparticle using a chemical method for producing activated carbon; FIG. 2 is a conceptual view of a process for manufacturing a nanoparticle using the present invention;

图 3是水平转轴方式纳米粒子制造装备；图 4是装有中心垂直移送方式搅拌部件的纳米粒子制造装备； Figure 3 is a horizontal shaft-axis nanoparticle manufacturing equipment; Figure 4 is a nanoparticle manufacturing equipment equipped with a central vertical transfer type stirring member;

图 5是装有内壁垂直移送方式搅拌部件的纳米粒子制造装备； Figure 5 is a nanoparticle manufacturing equipment equipped with an inner wall vertical transfer type stirring member;

图 6是采用本发明制造纳米粒子后应用形态的例子； Figure 6 is an illustration of an application form after the production of nanoparticles by the present invention;

图 7是采用本发明制造纳米粒子后涂装纳米粒子的方法。具体实施方式 Fig. 7 is a view showing a method of coating nanoparticles after manufacturing nanoparticles using the present invention. detailed description

为使本发明的目的、技术方案和优点更加清楚，下面结合附图对本发明的具体实施例进行详细说明。在此，本发明的示意性实施例及其说明用于解释本发明，但并不作为对本发明的限定。 In order to make the objects, technical solutions and advantages of the present invention more comprehensible, the specific embodiments of the present invention will be described in detail below. The illustrative embodiments of the present invention and the description thereof are intended to be illustrative of the invention, but are not intended to limit the invention.

本发明与原有湿式化学的催化剂用纳米粒子制造方法不同，本发明的催化剂用纳米粒子制造装置和方法是采用亲环境的干式物理气相沉积方式在真空容器内旋转支持体，将催化剂材料直接沉积在支持体上面形成的纳米大小的催化剂粒子。 The present invention is different from the original wet chemical catalyst nanoparticle production method. The catalyst nanoparticle production apparatus and method of the present invention uses an environmentally friendly dry physical vapor deposition method to rotate the support in a vacuum vessel, and the catalyst material is directly Nanosized catalyst particles formed on the support are deposited.

用物理方式在活性炭或化工陶瓷等支持体上制造纳米催化剂的方法在很多专利及非专利文献 [1-12]上公开并已有详细的说明。已公开专利文献及非专利文献所揭示的方法存在沉积率低、纳米粒子的分布广、支持体搅拌不均匀、施加于支持体的负荷过大、装备的耐久性低等问题。特别是制造批量生产用纳米粒子时制造装备存在非效率性沉积、支持体的不均匀搅拌、装备的耐久性低、搅拌构造物的过负荷、支持体之间负荷引起的支持体过度粉碎等问题。因此现有的支持体搅拌方式的纳米粒子制造装置的设计为主要用于实验或少量生产，因此不适合用于产业批量生产。 The method of physically producing a nanocatalyst on a support such as activated carbon or a chemical ceramic is disclosed in many patents and non-patent documents [1-12] and has been described in detail. The methods disclosed in the published patent documents and non-patent documents have problems such as low deposition rate, wide distribution of nanoparticles, uneven stirring of the support, excessive load applied to the support, and low durability of the equipment. In particular, when manufacturing nano-particles for mass production, there are inefficient deposition of the manufacturing equipment, uneven stirring of the support, low durability of the equipment, overload of the agitating structure, excessive pulverization of the support due to load between the supports, and the like. . Therefore, the existing nanoparticle manufacturing apparatus supporting the stirring method is mainly designed for experiments or small-scale production, and thus is not suitable for industrial mass production.

本发明采用的是在旋转支持体时沉积催化剂材料使适量纳米材料附着于支持体的技术。在进行物理气相沉积时，一般在沉积的初期阶段在基板上形成核，但是如果进行连续的持续沉积，初期形成的核继续接受气相状态的金属原子而成长，最终形成薄膜。如果采用不连续的沉积方式，即控制初期阶段形成的核经过一段非沉积时间，该非沉积时间内不接受气相原子，这样核就变得稳定，不能继续成长而只能维持核的形态。如此控制纳米材料的不连续沉积，能阻止核的过度成长或变成薄膜，进而能制造所需大小的纳米粒子。图 2表示了用本发明制造纳米粒子的制造工艺概念图。如图 2所示，沉积源 201设置于支持体 203的上方，在初期阶段支持体短暂地暴露在被沉积的蒸汽中，而后在搅拌作用 (图 2中标记 204标识支持体搅拌动作）下离开沉积区域，使核成长形成纳米粒子 102 并抑制核过度生长。在支持体上形成纳米粒子后反复进行持续搅拌沉积纳米粒子的阶段，持续地在支持体上形成核制造出纳米粒子。上述可知，本发明制造纳米粒子的原理是不连续的沉积方法，通过控制纳米材料在支持体上的沉积时间与非沉积时间在支持体上制造出均匀大小而稳定的纳米粉末。利用控制适当的沉积时间防止纳米粒子过度的成长，能使纳米粒子在非沉积时间内处于稳定状态后即使重新暴露在沉积区域也不再成长，而是在支持体上形成另外的核。稳定的纳米粒子在支持体表面形成后想得到高含量纳米粒子时可在已形成的纳米粒子上又形成新的纳米粒子并再次稳定化。本发明实施例中所述物理气相沉积方式例如可为如下物理沉积方式中的任意一种：直流溅射、射频溅射、离子束溅射、微波沉积、磁控溅射、热蒸发、电子束蒸发、激光烧蚀、离子镀、电弧放电沉积及分子束外延，但并不限于此。 The present invention employs a technique of depositing a catalyst material to attach a suitable amount of nanomaterial to a support while rotating the support. In the physical vapor deposition, a core is generally formed on the substrate in the initial stage of deposition, but if continuous continuous deposition is performed, the initially formed core continues to receive metal atoms in the gas phase to grow, and finally a thin film is formed. If a discontinuous deposition method is used, that is, the core formed in the initial stage of control is subjected to a non-deposition time, the gas phase atoms are not accepted during the non-deposition time, so that the core becomes stable and cannot continue to grow and can only maintain the morphology of the core. Such control of the discontinuous deposition of the nanomaterial can prevent the nuclear from overgrowth or become a thin film, thereby producing nanoparticles of a desired size. Figure 2 shows the use of this A conceptual diagram of a manufacturing process for inventing and manufacturing nanoparticles. As shown in Fig. 2, a deposition source 201 is disposed above the support 203, and the support is temporarily exposed to the deposited vapor in an initial stage, and then left under agitation (label 204 identifies support agitating action in Fig. 2). The deposition area causes the nucleus to grow into nanoparticles 102 and inhibit nuclear overgrowth. After the nanoparticles are formed on the support, the stage of continuously stirring and depositing the nanoparticles is repeated, and the core is continuously formed on the support to produce the nanoparticles. As can be seen from the above, the principle of the present invention for producing nanoparticles is a discontinuous deposition method for producing a uniform size and stable nanopowder on the support by controlling the deposition time and non-deposition time of the nanomaterial on the support. By controlling the appropriate deposition time to prevent excessive growth of the nanoparticles, the nanoparticles can be stabilized after being re-exposed to the deposition area after being in a stable state in the non-deposition time, and an additional core is formed on the support. When the stable nanoparticles are formed on the surface of the support and want to obtain high-content nanoparticles, new nanoparticles can be formed on the formed nanoparticles and stabilized again. The physical vapor deposition method in the embodiment of the present invention may be, for example, any one of the following physical deposition methods: DC sputtering, RF sputtering, ion beam sputtering, microwave deposition, magnetron sputtering, thermal evaporation, electron beam Evaporation, laser ablation, ion plating, arc discharge deposition, and molecular beam epitaxy, but are not limited thereto.

图 3是利用水平旋转轴的纳米粒子制造装置的例子，可以将能用作催化剂的金属、金属合金、金属氧化物或金属氮化物等作为沉积源材料，在含碳物质（如活性碳）、氧化物或氮化物等支持体上沉积催化剂用纳米粒子。为了增加装置的容量可使用多个搅拌轴进行搅拌，但由于强制不自然地搅拌支持体，支持体会有过度粉碎的倾向。图 2所示的装置采用物理方式制备催化剂用纳米粒子，有效克服了现有化学的制造催化剂用纳米粒子的方法的缺陷。但采用水平旋转轴时也具有一些不足：采用水平旋转轴搅拌方式的纳米粒子制造装置会产生搅拌槽 302中的支持体 303偏向一边、堆积在一侧的现象，由于支持体过度堆积在特定区域，因此很难均匀地搅拌支持体。支持体在微米大小时随搅拌翼 305旋转时会出现支持体以块状存在的现象，搅拌轻的支持体时还会出现严重的飞散现象。并且搅拌支持体材料时由于旋转翼 305露在外面，因此纳米粒子会沉积在旋转翼上。如此，纳米粒子沉积在不必要的地方会降低纳米粒子的沉积效率，进而变成非效率性工程。在采用水平旋转方式时，用单一旋转轴构造进行纳米粒子批量生产的装备有限度，因此为了制造批量生产装备可以并列使用几个单一旋转轴。如果几个旋转轴向同一方向旋转会使支持体向一侧堆积，因此要随机转换旋转方向 304。搅拌轴的随机旋转会引起支持体材料之间的摩擦，由于瞬间转变旋转方向而引起的支持体无分别移动、不均匀的支持体搅拌、支持体材料的飞散或脱离、装备的耐久型降低等问题。旋转方向急速变化时搅拌构造物对支持体材料施加力量会导致支持体的粉碎或向外脱离等现象。并且这种纳米粒子制造装置在随机搅拌时产生热量，因此很难用不耐热支持体。支持体粉碎形成的粒子会产生粉尘，真空槽 306中从搅拌槽 302脱离出来的支持体通过真空排气管进入到真空泵里会污染真空泵。旋转方向急速变化时旋转部位受到强烈的外力使有关搅拌的构造物容易受损从而降低装备的耐久性。由于这种原因缩短维持 / 保修期间产生额外费用降低制品的生产性。在纳米粒子的大小、含量、分布等控制面上看支持体的搅拌不均匀很难制造大小均匀的纳米粒子反而形成多种大小的纳米粒子降低制品的质量。 3 is an example of a nanoparticle manufacturing apparatus using a horizontal rotating shaft, and a metal, a metal alloy, a metal oxide, or a metal nitride which can be used as a catalyst can be used as a deposition source material in a carbonaceous substance (such as activated carbon), Nanoparticles for catalyst deposition on supports such as oxides or nitrides. In order to increase the capacity of the apparatus, a plurality of stirring shafts can be used for stirring, but since the support is unnaturally stirred, the support tends to be excessively pulverized. The apparatus shown in Fig. 2 physically prepares the nanoparticles for the catalyst, effectively overcoming the drawbacks of the conventional chemical method for producing nanoparticles for the catalyst. However, there are some disadvantages when using a horizontal rotating shaft: The nanoparticle manufacturing apparatus using the horizontal rotating shaft stirring method causes the support body 303 in the stirring tank 302 to be sideways and stacked on one side, because the support is excessively stacked in a specific area. Therefore, it is difficult to uniformly stir the support. When the support body rotates with the stirring blade 305 at a micron size, a phenomenon in which the support body exists in a block form occurs, and a severe scattering phenomenon occurs when the light support is stirred. And when the support material is stirred, since the rotary wing 305 is exposed, the nanoparticles are deposited on the rotary wing. In this way, the deposition of nanoparticles in unnecessary places will reduce the deposition efficiency of the nanoparticles, and then change Incompetent engineering. In the horizontal rotation mode, the equipment for mass production of nanoparticles by a single rotating shaft configuration is limited, so that several single rotating shafts can be used in parallel for manufacturing mass production equipment. If several rotation axes are rotated in the same direction, the support body is stacked to one side, so the rotation direction 304 is randomly converted. The random rotation of the agitator shaft causes friction between the support materials, the support body does not move separately due to the instantaneous change of the rotation direction, the uneven support body agitation, the scattering or detachment of the support material, the durability of the equipment, etc. problem. When the direction of rotation changes rapidly, the agitating structure exerts a force on the support material, which may cause pulverization or outward detachment of the support. Moreover, such a nanoparticle producing apparatus generates heat when randomly stirred, so that it is difficult to use a heat-resistant support. The particles formed by the support pulverization generate dust, and the support body detached from the agitation tank 302 in the vacuum chamber 306 enters the vacuum pump through the vacuum exhaust pipe to contaminate the vacuum pump. When the direction of rotation changes rapidly, a strong external force is applied to the rotating portion to cause the structure to be agitated to be easily damaged, thereby reducing the durability of the equipment. For this reason, the additional cost incurred during the maintenance/warranty period is reduced to reduce the productivity of the product. It is difficult to produce nanoparticles of uniform size on the control surface of the size, content, distribution, etc. of nanoparticles, and it is difficult to produce nanoparticles of various sizes to form nano-particles of various sizes to reduce the quality of the product.

对此，本发明优选采用比水平旋转方式先进的垂直旋转方式旋转支持体的纳米粒子制造装置，如图 4和图 5所示。本发明提供的利用垂直旋转轴的纳米粒子制造装置分为中心垂直移送和内壁垂直移送两种方式。图 4是利用垂直螺旋型搅拌部件（垂直螺旋形暗轮）把支持体从搅拌槽中心部的下部移送到上部的方式进行搅拌的例子，即采用中心垂直移送的粒子。图 4所示的催化剂用纳米粒子制造装置包括：搅拌槽 402、搅拌部件、支持板 409、一个以上的上部旋转翼（散播机） 407、一个以上的下部旋转翼 408、沉积装置 401、真空槽 410 及真空泵（未示出）。其中： In this regard, the present invention preferably employs a nanoparticle manufacturing apparatus that rotates the support in a vertical rotation mode that is more advanced than the horizontal rotation mode, as shown in Figs. 4 and 5. The nanoparticle manufacturing device using the vertical rotation axis provided by the present invention is divided into two modes: a central vertical transfer and an inner wall vertical transfer. Fig. 4 shows an example in which the support is transferred from the lower portion of the center portion of the stirring tank to the upper portion by means of a vertical spiral type stirring member (vertical spiral dark wheel), that is, particles which are transferred vertically in the center. The catalyst nanoparticle manufacturing apparatus shown in FIG. 4 includes: a stirring tank 402, a stirring member, a support plate 409, one or more upper rotary blades (scatterers) 407, one or more lower rotary blades 408, a deposition device 401, and a vacuum chamber. 410 and vacuum pump (not shown). among them:

所述搅拌部件设置于所述搅拌槽 402中，该螺旋型搅拌部件包括垂直旋转轴 406 (由旋转电机 411驱动）及固定于该垂直旋转轴上的螺旋型搅拌翼（暗轮） 405，该螺旋型搅拌翼 405在垂直旋转轴的带动下进行螺旋式旋转，搅拌支持体并将搅拌槽下部的支持体输送至搅拌槽的上部；所述支持板 409环绕在所述螺旋型搅拌部件的上部，以支持输送至搅拌槽的上部的支持体，为了有助于支持体在支持板上的滑动，该支持板为中间高、外周低的锥台形，该支持板与搅拌槽的内壁之间存在间隙，以利于支持板上的支持体在移动至支持板边缘时能够滑落到搅拌槽中（图 4中标记 404表示支持体移动方向）。为了控制支持体暴露时间，所述支持板上还可设置有多个孔，使支持体从支持板上快速下落，孔的数量和孔径的大小都可以进行变化。 The agitating member is disposed in the agitating tank 402. The spiral agitating member includes a vertical rotating shaft 406 (driven by the rotating electric machine 411) and a spiral agitating wing (dark wheel) 405 fixed to the vertical rotating shaft. The spiral stirring blade 405 is spirally rotated by the vertical rotating shaft, and the supporting body is stirred and the support body at the lower part of the stirring tank is sent to the upper portion of the stirring tank; The support plate 409 surrounds the upper portion of the spiral agitating member to support the support body that is transported to the upper portion of the agitation tank. In order to facilitate the sliding of the support body on the support plate, the support plate is intermediate high and low at the outer periphery. In the shape of a truncated cone, there is a gap between the support plate and the inner wall of the agitation tank, so that the support on the support plate can slide down into the agitation tank when moving to the edge of the support plate (mark 404 in FIG. 4 indicates the direction of movement of the support) . In order to control the exposure time of the support, the support plate may be provided with a plurality of holes, so that the support body can quickly fall from the support plate, and the number of holes and the size of the aperture can be changed.

所述一个或一个以上的上部旋转翼 407位于支持板上并固定于所述垂直旋转轴 406，用于搅拌所述支持板上的支持体。 The one or more upper rotor blades 407 are located on a support plate and are secured to the vertical rotation shaft 406 for agitating the support on the support plate.

所述一个以上下部旋转翼 408固定于所述垂直旋转轴 406下方，以均匀搅拌下部的支持体。 The one or more lower rotary blades 408 are fixed below the vertical rotation shaft 406 to uniformly agitate the lower support.

所述真空槽 410容纳沉积装置的沉积源 401及搅拌槽 402，利用真空泵可控制真空槽 410内的真空状态。真空槽内真空度可根据需要控制在 5 X 10— ¹托至 1 X 10—⁶ 托，但并不限于此。真空度的高低可影响纳米粒子的形成大小。为了去除支持体所含水分、气体或挥发性物质，可在所述搅拌槽外部设置加热装置，以对搅拌槽内的支持体进行加热处理。而在真空槽内使用有挥发性支持体的情况下，可在所述搅拌槽外部设置冷却装置，以对搅拌槽内的支持体进行冷却。也可同时设置有加热及冷却装置，以根据需要决定是否开启所述加热或冷却装置。 The vacuum chamber 410 accommodates a deposition source 401 of the deposition apparatus and a stirring tank 402, and the vacuum state in the vacuum chamber 410 can be controlled by a vacuum pump. The vacuum in the vacuum chamber can be controlled from 5 X 10 - ¹ Torr to 1 X 10 - ⁶ Torr as needed, but is not limited thereto. The degree of vacuum can affect the size of the nanoparticles. In order to remove moisture, gas or volatile substances in the support, a heating device may be provided outside the agitation tank to heat the support in the agitation tank. When a volatile support is used in the vacuum chamber, a cooling device may be provided outside the agitation tank to cool the support in the agitation tank. It is also possible to provide heating and cooling means at the same time to decide whether to open the heating or cooling device as needed.

图 4所示的装置还可设有表面处理部件，用于在沉积前、沉积过程中或沉积后对支持体表面进行离子束或等离子体轰击处理。 The apparatus shown in Figure 4 can also be provided with surface treatment components for ion beam or plasma bombardment treatment of the support surface prior to deposition, during deposition, or after deposition.

利用图 4所示的装置制造附着催化剂用金属纳米粒子时，沉积源的材料可选择金，银，铂，铑，铹，钯，钌，锇，铼 Re，铱 Ir中的任一种金属材料，或者选择这些金属材料中的两种以上金属材料组成的合金，如果要沉积催化剂用金属氧化物或金属氮化物纳米粒子，可以直接选择金属氧化物或金属氮化物靶材作为沉积源，也可以在支持体表面沉积金属纳米粒子的同时将氧气或氮气供给到支持体表面来制造出金属氧化物或金属氮化物催化剂纳米粒子。支持体可以为含碳物质（如活性碳）、氧化物或氮化物（如 Mg0， Ce0₂， A1₂0₃， Y₂0₃， Ti0₂，氧化钒 (Vanadium Oxide)， CrN, FeN等)，所述支持体可以是粉末 (powder)、弹丸（pellet )或片状（chip)等形状。通过调节沉积率（D印 osition Rate) 、沉积时间、沉积时间与非沉积时间的比率（与支持板的倾斜度、支持板上孔的多少与大小等有关）、搅拌速度、蒸发源的温度、支持体的温度、真空度、暴露在沉积区域下的全部支持体表面积与该全部支持体体积的比等等条件来控制纳米粒子的大小和含量。例如，可控制制造出的催化剂纳米材料在支持体上的平均厚度为在 0.1埃〜 1000埃，该厚度范围仅为举例，并非用于限定本发明。 When the metal nanoparticles for attaching catalysts are produced by using the apparatus shown in FIG. 4, the material of the deposition source may be any one of gold, silver, platinum, rhodium, ruthenium, palladium, iridium, osmium, iridium, iridium. , or an alloy composed of two or more metal materials of these metal materials, if a metal oxide or metal nitride nanoparticle for catalyst is to be deposited, a metal oxide or a metal nitride target may be directly selected as a deposition source, or Metal oxide or metal nitride catalyst nanoparticles are produced by supplying oxygen or nitrogen to the surface of the support while depositing metal nanoparticles on the surface of the support. The support may be a carbonaceous material (such as activated carbon), an oxide or a nitride (such as Mg0, Ce0 ₂ , A1 ₂ 0 ₃ , Y ₂ 0 ₃ , Ti0 ₂ , Vanadium Oxide, CrN, FeN, etc., the support may be in the form of a powder, a pellet or a chip. By adjusting the ratio of deposition rate, deposition time, deposition time to non-deposition time (related to the inclination of the support plate, the number and size of the holes on the support plate), the stirring speed, the temperature of the evaporation source, The size and content of the nanoparticles are controlled by conditions such as the temperature of the support, the degree of vacuum, the ratio of the total surface area of the support exposed to the deposition area to the volume of the total support, and the like. For example, the average thickness of the fabricated catalyst nanomaterial on the support can be controlled to be from 0.1 angstroms to 1000 angstroms. This thickness range is by way of example only and is not intended to limit the invention.

图 4 中，移送到上部的支持体在上部支持体支持板的上面在散播机的作用下散播到内壁，从支持板的内壁移动到下部。中心垂直移送搅拌方式相比水平轴旋转方式有对机械和支持体的负载少，因此能减少支持体之间的摩擦力，减少搅拌时微小粉末的飞散现象等优点。但是在上部不容易均匀地散播支持体，并且为了均匀地搅拌移送到上部的支持体必须设置支持板、散播机和暗轮 405等复杂构造。支持体经过支持体的时候被散播机散播产生支持体的飞散现象会污染沉积装置。从支持板内壁移动到下部的粉末做自由落体运动会产生粉尘的飞散现象。 In Fig. 4, the support transferred to the upper portion is spread on the upper wall of the upper support support plate by the spreader, and moves from the inner wall of the support plate to the lower portion. The center vertical transfer agitation method has less load on the machine and the support than the horizontal axis rotation mode, so that the friction between the support bodies can be reduced, and the scattering phenomenon of the fine powder during the agitation can be reduced. However, it is not easy to uniformly spread the support at the upper portion, and a complicated structure such as a support plate, a spreader, and a dark wheel 405 must be provided in order to uniformly agitate the support to the upper portion. When the support passes through the support, it is scattered by the spreader to produce a scattering phenomenon of the support, which may contaminate the deposition device. The free-falling movement of the powder moving from the inner wall of the support plate to the lower portion produces dust scattering.

图 5是关于利用垂直旋转轴的另一种形态的纳米粒子制造装置采用内壁垂直移送方式的例子。采用内壁垂直移送方式的纳米粒子制造装置是比中心垂直移送方式更先进的装置，而且没有支持板、散播机、螺旋形暗轮，所以在构造上更加简单。 Fig. 5 is a view showing an example in which the nanoparticle manufacturing apparatus of another embodiment using the vertical rotation axis adopts an inner wall vertical transfer method. The nanoparticle manufacturing apparatus adopting the vertical wall inner transfer method is a more advanced device than the center vertical transfer method, and has no support plate, a spreader, and a spiral dark wheel, so that the structure is simpler.

如图 5所示的催化剂用纳米粒子制造装置包括：真空槽 506、搅拌槽 502、螺旋型搅拌部件、沉积装置及真空泵（未示出）。 The catalyst manufacturing apparatus for a catalyst shown in Fig. 5 includes a vacuum chamber 506, a stirring tank 502, a screw type stirring member, a deposition device, and a vacuum pump (not shown).

所述搅拌槽 502位于所述真空槽 506内，用于容纳支持体 503； The agitation tank 502 is located in the vacuum chamber 506 for accommodating the support 503;

所述螺旋型搅拌部件设置于所述搅拌槽 502中，包括垂直旋转轴 507 (由旋转电机 508驱动）及螺旋型搅拌翼 505，该螺旋型搅拌翼在所述垂直旋转轴的带动下进行螺旋式旋转，搅拌所述支持体 503并将搅拌槽下部的支持体 503输送至搅拌槽的上部。螺旋型搅拌翼的外侧靠近所述搅拌槽的内壁，并且螺旋型搅拌翼与垂直旋转轴之间存在间隙并经由至少一连接体 509相连接，使所述搅拌槽上部的支持体能够通过所述间隙移动至搅拌槽的下部。所述沉积装置用于利用物理沉积方式在搅拌槽上部的支持体 503上沉积纳米粒子，该沉积装置的沉积源 501位于真空槽内支持体的上方。 The spiral agitating member is disposed in the agitation tank 502, and includes a vertical rotating shaft 507 (driven by a rotating electric machine 508) and a spiral agitating wing 505. The spiral agitating blade is spiraled by the vertical rotating shaft. Rotating, the support body 503 is stirred and the support body 503 at the lower portion of the agitation tank is conveyed to the upper portion of the agitation tank. The outer side of the spiral agitating blade is adjacent to the inner wall of the agitation tank, and a gap exists between the spiral agitating blade and the vertical rotating shaft and is connected via at least one connecting body 509, so that the support of the upper portion of the agitation tank can pass the The gap moves to the lower portion of the agitation tank. The deposition apparatus is for depositing nanoparticles on the support 503 on the upper portion of the agitation tank by physical deposition, and the deposition source 501 of the deposition apparatus is located above the support in the vacuum chamber.

图 5所示的催化剂用纳米粒子制造装置也可同时设置有加热及冷却装置，以根据需要决定是否开启所述加热或冷却装置。 The catalyst nanoparticle producing apparatus shown in Fig. 5 may be provided with heating and cooling means at the same time to determine whether or not to turn on the heating or cooling device as needed.

图 5所示的装置还可以包括表面处理部件，用于在沉积前、沉积过程中或沉积后对支持体表面进行离子束或等离子体轰击处理。 The apparatus shown in Fig. 5 may further include a surface treatment member for performing ion beam or plasma bombardment treatment on the surface of the support before, during, or after deposition.

利用图 5所示的装置制造附着在支持体上的催化剂用金属纳米粒子时，沉积源的材料可选择金，银，铂，铑，铹，钯，钌，锇，铼 Re，铱 Ir中的任一种金属材料，或者选择这些金属材料中的两种以上金属材料组成的合金，如果要沉积催化剂用金属氧化物或金属氮化物纳米粒子，可以直接选择金属氧化物或金属氮化物靶材作为沉积源，也可以在支持体表面沉积金属纳米粒子的同时将氧气或氮气供给到支持体表面来制造出金属氧化物或金属氮化物催化剂纳米粒子。支持体可以为含碳物质（如活性碳）、氧化物或氮化物，所述支持体可以是粉末 (powder) 、弹丸（pellet )或片状（chip)等形状。通过控制搅拌 /沉积阶段的沉积率、沉积时间、搅拌部件的搅拌速率、蒸发源的温度、支持体的温度、真空度、暴露在沉积区域下的全部支持体表面积与该全部支持体体积的比等，可以有效调整纳米粒子的大小及含量。例如，可控制制造出的催化剂纳米材料在支持体上的平均厚度为在 0.1埃 -1000埃，该厚度范围仅为举例，并非用于限定本发明。 When the metal nanoparticles for catalyst attached to the support are fabricated by using the apparatus shown in FIG. 5, the material of the deposition source may be selected from the group consisting of gold, silver, platinum, rhodium, ruthenium, palladium, iridium, osmium, iridium, iridium. Any metal material, or an alloy composed of two or more metal materials selected from these metal materials. If a metal oxide or metal nitride nanoparticle for catalyst is to be deposited, a metal oxide or metal nitride target can be directly selected as the metal oxide or metal nitride target. The deposition source can also be used to produce metal oxide or metal nitride catalyst nanoparticles by supplying oxygen or nitrogen to the surface of the support while depositing metal nanoparticles on the surface of the support. The support may be a carbonaceous material (e.g., activated carbon), an oxide or a nitride, and the support may be in the form of a powder, a pellet, or a chip. By controlling the deposition rate in the stirring/deposition stage, the deposition time, the stirring rate of the stirring member, the temperature of the evaporation source, the temperature of the support, the degree of vacuum, the total surface area of the support exposed to the deposition area, and the ratio of the total support volume Etc., the size and content of the nanoparticles can be effectively adjusted. For example, the catalyst nanomaterials can be controlled to have an average thickness on the support of from 0.1 angstroms to 1000 angstroms, which is merely exemplary and is not intended to limit the invention.

图 5中垂直旋转方式与图 4是同样的，但是中心垂直移送方式的支持体移送旋转翼在搅拌槽的中央，内壁垂直移送方式的支持体移送旋转翼在搅拌槽的内壁。下部的支持体从搅拌槽倾斜的内壁移送到上部，移送到上部的支持体再移送到搅拌槽的中心部位（图 5中标记 504表示支持体的移动方向），从而形成支持体的循环。比起垂直移送方式没有支持体强制性散播机器，没有从内壁自由降落下来的路径因此没有飞散现象，能进行支持体高效率的搅拌和纳米粒子均匀的沉积。图 5所示的纳米粒子制造装置不仅构造简单，减少了机械负载，减少了支持体之间的摩擦现象，防止飞散现象，还增加了沉积效率，保证了微小粉末的均匀搅拌等优点。 The vertical rotation mode in Fig. 5 is the same as that of Fig. 4, but the support body of the center vertical transfer type conveys the rotary wing in the center of the agitation tank, and the support body of the inner wall vertical transfer type transfers the rotary wing to the inner wall of the agitation tank. The lower support body is transferred from the inclined inner wall of the agitation tank to the upper portion, and is transferred to the upper support body and then transferred to the center portion of the agitation tank (mark 504 in Fig. 5 indicates the moving direction of the support), thereby forming a circulation of the support. Compared with the vertical transfer mode, there is no support for the forced spreading machine, and there is no free path from the inner wall, so there is no scattering phenomenon, and the support can be efficiently stirred and the nanoparticles can be uniformly deposited. The nanoparticle manufacturing apparatus shown in FIG. 5 is not only simple in construction, but also reduces mechanical load. The friction phenomenon between the support bodies is reduced, the scattering phenomenon is prevented, the deposition efficiency is increased, and the uniform stirring of the fine powder is ensured.

利用图 4或图 5所示的装置，载采用两个以上不同贵金属材料的沉积源或者采用贵金属合金的沉积源时可以同时沉积生成两种以上材料的催化剂纳米粒子。 Using the apparatus shown in Fig. 4 or Fig. 5, catalyst nanoparticles of two or more materials can be simultaneously deposited by using a deposition source of two or more different noble metal materials or a deposition source using a noble metal alloy.

利用本发明图 3、图 4或图 5所示的催化剂用纳米粒子制造装置，催化剂用纳米粒子的制造过程包括：纳米材料及支持体材料的选定、纳米材料的安装及支持体材料的装入阶段、真空排气阶段、纳米粒子制造阶段（搅拌 /沉积）、破坏真空阶段、取出沉积有纳米粒子的支持体阶段。为了制造催化剂用纳米粒子首先选定适合于应用领域的纳米材料靶材（沉积源材料，如金属材料、金属氧化物材料或金属氮化物材料）和支持体材料（如活性炭、氧化物或氮化物），把纳米材料靶材安装在沉积源之后把支持体材料装入搅拌槽内。真空排气阶段是在大气压状态下先利用低真空泵进行第 1 次真空排气，达到适当真空度后利用高真空泵进行第 2 次真空排气。在真空排气时为了有效的排出支持体含有的气体或支持体之间存在的空气，可同时利用搅拌部件搅拌真空槽中的支持体。真空排气结束后利用物理方式对沉积源进行在支持体上形成纳米粒子的沉积过程。在纳米粒子沉积过程中利用搅拌部件搅拌支持体，从沉积源供给来的纳米材料在支持体上形成纳米大小粒子。如果要制造催化剂用的金属氧化物或金属氮化物纳米粒子，一种方法是直接利用金属氧化物或金属氮化物靶材以物理方法在支持体表面进行沉积，在支持体表面形成金属氧化物或金属氮化物纳米粒子；另一种方法是利用金属或金属合金靶材，在支持体表面进行物理沉积的同时将氧气或氮气供给到支持体表面，同样可以在支持体表面形成金属氧化物或金属氮化物纳米粒子。在沉积 /搅拌阶段沉积于支持体上的材料暴露在沉积区域时成长为粒子，一定大小的纳米粒子在支持体的搅拌下从沉积区域的表面随支持体移动到搅拌槽的下部。移动到搅拌槽内的纳米粒子在重新暴露在沉积区域之前处于稳定状态，形成一定大小的纳米粒子。如果纳米粒子在稳定之前暴露在沉积区域里，很可能会使纳米粒子继续成长形成非常大的纳米粒子。调整沉积时间和非沉积时间可以调整支持体上形成的纳米粒子的大小。通过搅拌 /沉积过程中的沉积率、沉积时间、搅拌速度、沉积能量（包括沉积源的温度等）、支持体的温度、真空度、暴露在沉积区域下的支持体表面积对比整个支持体体积的比等可以控制纳米粒子的大小及含量。例如，可控制制造出的纳米粉末的平均大小在 lnm-500nm范围之内，控制沉积在支持体上面的银纳米粉末的含量在 lppm-20， OOOppm范围之内。纳米粒子制造工程结束后破坏真空从真空槽中取出附着纳米粉末的支持体。本发明的制造纳米粒子的方法的又一个优点是可以从最终应用制品构成材料中选取作为支持体的材料，进而简单化了工艺，没有添加物因此既环保又能最大发挥纳米粉末的固有特性。 By using the catalyst nanoparticle manufacturing apparatus shown in FIG. 3, FIG. 4 or FIG. 5 of the present invention, the manufacturing process of the catalyst nanoparticles includes: selection of nano materials and support materials, mounting of nano materials, and loading of support materials. In the stage, the vacuum exhaust stage, the nanoparticle manufacturing stage (stirring/deposition), the vacuum destruction stage, and the removal of the support stage in which the nanoparticles are deposited. In order to manufacture catalyst nanoparticles, first select nanomaterial targets (deposited source materials such as metal materials, metal oxide materials or metal nitride materials) and support materials (such as activated carbon, oxide or nitride) suitable for the application field. After installing the nanomaterial target on the deposition source, the support material is placed in the agitation tank. In the vacuum exhaust stage, the first vacuum evacuation is performed by a low vacuum pump under atmospheric pressure, and after the appropriate degree of vacuum, the second vacuum is exhausted by the high vacuum pump. In order to efficiently discharge the gas contained in the support or the air existing between the supports during vacuum evacuation, the support in the vacuum chamber may be stirred by the stirring member at the same time. After the end of the vacuum evacuation, the deposition source is physically deposited on the support to form nanoparticles. The support is stirred by the stirring member during the deposition of the nanoparticles, and the nanomaterial supplied from the deposition source forms nanosized particles on the support. If a metal oxide or metal nitride nanoparticle for a catalyst is to be produced, one method is to physically deposit a metal oxide or a metal nitride target on the surface of the support, forming a metal oxide on the surface of the support or Metal nitride nanoparticles; another method is to use metal or metal alloy targets to supply oxygen or nitrogen to the surface of the support while physically depositing on the surface of the support. It is also possible to form metal oxides or metals on the surface of the support. Nitride nanoparticles. The material deposited on the support during the deposition/stirring phase grows into particles when exposed to the deposition area, and the nanoparticles of a certain size move from the surface of the deposition area to the lower portion of the agitation tank from the surface of the deposition area under the agitation of the support. The nanoparticles moved into the agitation tank are in a stable state before re-exposure to the deposition zone to form nanoparticles of a certain size. If the nanoparticles are exposed to the deposition area before stabilization, it is likely that the nanoparticles will continue to grow to form very large nanoparticles. Adjustment sink The accumulated time and non-deposition time can adjust the size of the nanoparticles formed on the support. The deposition rate, deposition time, agitation speed, deposition energy (including the temperature of the deposition source, etc.) during the stirring/deposition process, the temperature of the support, the degree of vacuum, and the surface area of the support exposed to the deposition area are compared with the entire support volume. The ratio can control the size and content of the nanoparticles. For example, the average size of the manufactured nanopowder can be controlled to be in the range of 1 nm to 500 nm, and the content of the silver nanopowder deposited on the support is controlled to be in the range of 1 ppm to 20, OOO ppm. After the completion of the nanoparticle manufacturing process, the vacuum is broken and the support to which the nanopowder is attached is taken out from the vacuum chamber. Still another advantage of the method for producing nanoparticles of the present invention is that a material as a support can be selected from the final applied product constituent materials, thereby simplifying the process, and without additives, it is environmentally friendly and can maximize the intrinsic properties of the nanopowder.

贵金属催化剂用纳米材料属于高价纳米材料，因此为了用最少量贵金属效率性地产生催化剂效果，使催化剂用纳米材料在要进行分解的流体或气体的流动中以最大表面存在是非常重要的。为了产生效率性的催化剂效果，应尽可能形成小的纳米粒子，极大化纳米粒子的表面积。利用本发明制造的扶着有纳米材料的支持体材料可以直接应用作催化剂用材料或制作成溶液状态后浸泡扶着有催化剂用纳米材料的支持体，来制造催化剂用制品。 Nanomaterials for noble metal catalysts are high-priced nanomaterials, so in order to efficiently produce a catalyst effect with a minimum amount of precious metal, it is very important that the catalyst is present at a maximum surface in the flow of a fluid or gas to be decomposed. In order to produce an efficient catalyst effect, small nanoparticles should be formed as much as possible to maximize the surface area of the nanoparticles. The support material having the nanomaterials produced by the present invention can be directly used as a catalyst material or in a solution state, and then immersed in a support for supporting a catalyst nanomaterial to produce a catalyst product.

为了使利用上述方法形成的纳米大小的催化剂粒子能牢牢地附着在支持体上，在真空沉积前、沉积途中或沉积后可对支持体进行加热来增加催化剂材料与支持体之间的结合力。在真空沉积前用离子束或等离子体进行表面改性 In order to enable the nanosized catalyst particles formed by the above method to be firmly attached to the support, the support may be heated before, during or after deposition to increase the bonding force between the catalyst material and the support. . Surface modification with ion beam or plasma before vacuum deposition

( Surface Modification) 处理是增加纳米材料与支持体之间结合力的另一种方法。利用离子束工艺或等离子体工艺可以在支持体表面形成极性作用基或亲水性表面。纳米粒子在化学构造发生变化的支持体表面上能更均匀地分布形成相对比较小的纳米粒子。本发明在经表面处理的支持体上制造纳米粒子能确保纳米粒子与支持体之间强烈的结合力，并且调整纳米粒子沉积条件能获得所需大小和含量的纳米粒子。将附着纳米粒子的支持体直接应用于催化剂领域时增大处于表面的纳米粒子的表面积是非常重要的，因此通过调整沉积能量、沉积时间、搅拌条件等形成适量纳米粒子是非常重要的。用本发明制造的制品是固体状态，因此制造纳米粒子后可以加工成各种形态。如图 6所示，能应用于粉末、溶液、纤维、胶带形、立体形等多种形态。用本发明制造纳米粉末时如果采用可使用在应用制品上的支持体，附着在支持体上的纳米粉末可以直接应用到制品上，并且可以与多种形态的液状或固体原料混合应用到制品上，例如，使用水溶性材料作为支持体时将制造的附着在支持体上的纳米粒子变成液状后可以通过浸泡（Dipping) 、喷雾（Spray) 、丝网印刷（Screen Printing) 或涂布（Painting) 等方式将纳米粒子制作到各种制品上；使用弹丸（pellet ) 或芯片（ chip)形状的材料作为支持体时通过后加工可以制作成纤维状或三维立体状应用到多种制品上。 ( Surface Modification) Treatment is another way to increase the bonding between nanomaterials and supports. A polar or hydrophilic surface can be formed on the surface of the support by an ion beam process or a plasma process. The nanoparticles are more uniformly distributed on the surface of the support whose chemical structure changes to form relatively small nanoparticles. The fabrication of nanoparticles on the surface treated support of the present invention ensures a strong binding force between the nanoparticles and the support, and the nanoparticle deposition conditions are adjusted to obtain nanoparticles of the desired size and content. It is very important to increase the surface area of the nanoparticles on the surface when the support to which the nanoparticles are attached is directly applied to the catalyst field, so it is very important to form an appropriate amount of nanoparticles by adjusting deposition energy, deposition time, stirring conditions, and the like. The article produced by the present invention is in a solid state, and thus can be processed into various forms after the production of nanoparticles. As shown in Fig. 6, it can be applied to various forms such as powder, solution, fiber, tape shape, and three-dimensional shape. When the nanopowder is manufactured by the present invention, if a support which can be used on an applied article is used, the nanopowder attached to the support can be directly applied to the article, and can be applied to the article by mixing with various forms of liquid or solid raw materials. For example, when a water-soluble material is used as a support, the manufactured nanoparticles attached to the support can be made into a liquid, and then can be dipped, sprayed, screened, or coated (Painting). The nanoparticle is prepared into various products by a method such as a pellet or a chip shape, and can be fabricated into a fiber or a three-dimensional shape by post-processing to a plurality of articles.

图 7所示的是利用本发明制造的纳米粒子应用到汽车用催化剂工艺的例子。首先介绍为了将贵金属纳米粒子附着于使用在汽车用催化剂支持体上的两种代表性的方法。一种是把直接用于汽车用催化剂的支持体粉末 (A1₂0₃)作为支持体，把贵金属 (Pt， Rh， Pd等)作为催化剂用纳米材料的靶材经过本发明的纳米粉末制造方法 /装置将催化剂用纳米粒子（如 Pt， Rh, Pd等贵金属纳米粒子）形成于支持体 (A1₂0₃)上，利用这些附着于支持体上的纳米材料通过铸型 (molding)、烧结 (sintering)等工艺可制造蜂窝形状构造物的贵金属催化剂。在铸造过程中可以用添加结合材 (binder)的方法提高支持体之间的结合力。另一种方法是通过本发明的纳米粒子制造方法 /装置在水溶性支持体（如有机粉末）上形成贵金属纳米粒子，放入液体变成溶液状态后将使用于汽车用催化剂的蜂窝状载体浸泡于该溶液中（或者利用该溶液进行喷雾、丝网印刷或涂布），再进行干燥热处理后，制造出汽车用贵金属催化剂，此时蜂窝状载体可以为前述的造蜂窝形状构造物的贵金属催化剂，也可以普通的不具有催化作用的蜂窝状载体。利用多种形态的原材料（固体原材料或液态原材料)可以制造汽车用催化剂，因此不仅能用于汽车用催化剂领域还可以用于其他多种催化剂工艺。本发明的优点是可以根据所需应用领域选定多种支持体，给一种制品增加功能时根据功能可选择具有特定机械、电、磁、光学等特性的纳米材料或支持体材料。本工艺中不存在支持体与纳米材料之间的特别的制约条件因此容易选择支持体和纳米材料，并且组合方式多样。利用本发明工艺能克服以往化学方法很难体现的支持体与支持体之间的选定，并且容易获取具有特殊功能的多种纳米制品。 Figure 7 shows an example of the application of the nanoparticles produced by the present invention to a catalyst process for automobiles. First, two representative methods for attaching noble metal nanoparticles to a catalyst support for automobiles will be described. One is a support powder directly used for a catalyst for automobiles (A1 ₂ 0 ₃ ) as a support, and a noble metal (Pt, Rh, Pd, etc.) is used as a target for a nanomaterial for a catalyst, and the nano powder is produced by the present invention. / Apparatus The catalyst is formed on a support (A1 ₂ 0 ₃ ) by using nanoparticles (such as Pt, Rh, Pd, etc.), and the nanomaterials attached to the support are used for molding and sintering ( Processes such as sintering) can produce noble metal catalysts for honeycomb shaped structures. The bonding force between the supports can be increased by adding a binder during the casting process. Another method is to form a noble metal nanoparticle on a water-soluble support (such as an organic powder) by the nanoparticle production method/device of the present invention, and put it into a liquid state to be in a solution state, and then soak the honeycomb carrier used for the automobile catalyst. In the solution (or spray, screen printing or coating with the solution), and then drying and heat treatment, a noble metal catalyst for automobiles is produced, and the honeycomb carrier may be a noble metal catalyst for forming the honeycomb structure described above. It is also possible to use a conventional honeycomb carrier which does not have a catalytic action. Automobile catalysts can be produced by using various forms of raw materials (solid raw materials or liquid raw materials), and therefore can be used not only in the field of automotive catalysts but also in various other catalyst processes. An advantage of the present invention is that a plurality of supports can be selected depending on the desired field of application, and a nanomaterial or support material having specific mechanical, electrical, magnetic, optical, etc. characteristics can be selected depending on the function when adding an function to an article. Not in this process There are special constraints between the support and the nanomaterial, so it is easy to select the support and the nanomaterial, and the combination is diverse. The process of the present invention can overcome the selection between the support and the support which are difficult to be embodied by the conventional chemical methods, and it is easy to obtain a plurality of nano-products having special functions.

以上所述的具体实施例，对本发明的目的、技术方案和有益效果进行了进一步详细说明，所应理解的是，以上所述仅为本发明的具体实施例而已，并不用于限定本发明的保护范围，凡在本发明的精神和原则之内，所做的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。 The above described specific embodiments of the present invention are further described in detail, and are intended to be illustrative of the embodiments of the present invention. The scope of the protection, any modifications, equivalents, improvements, etc., made within the spirit and scope of the invention are intended to be included within the scope of the invention.

【参考文献】【references】

[1] 公开号为 GB1537839的英国专利申请。 [1] British Patent Application Publication No. GB1537839.

[2] High dispersion platinum catalyst by RF sputtering, J. Catal. 83 (1983), p. 477. [2] High dispersion platinum catalyst by RF sputtering, J. Catal. 83 (1983), p. 477.

[3] High-dispersion d.c. sputtered platinum-titania powder catalyst active in ethane hydrogenolysis, [3] High-dispersion d.c. sputtered platinum-titania powder catalyst active in ethane hydrogenolysis,

J. Phys. Chem. 93 (1989), p. 1510. J. Phys. Chem. 93 (1989), p. 1510.

[4] Nanoparticles of gold on γ-Α1203 produced by dc magnetron sputtering, J. Catal. 231 (2005), p.151. [4] Nanoparticles of gold on γ-Α1203 produced by dc magnetron sputtering, J. Catal. 231 (2005), p.151.

[5] Gold catalysts prepared by coprecipitation for low-temperature oxidation of hydrogen and of carbon monoxide, J. Catal. 115 (1989), p. 301. [5] Gold catalysts prepared by coprecipitation for low-temperature oxidation of hydrogen and of carbon monoxide, J. Catal. 115 (1989), p. 301.

[6] A technique for sputter coating of ceramic reinforcement particles, Surf. Coat. Technol. 91 (1997), p. 64. [6] A technique for sputter coating of ceramic reinforcement particles, Surf. Coat. Technol. 91 (1997), p. 64.

[7] Catalysis by Gold, Catal. Rev.-Sci. Eng. 41 (1999), p. 319. [7] Catalysis by Gold, Catal. Rev.-Sci. Eng. 41 (1999), p. 319.

[8] Gold: a relatively new catalyst, Catal. Today 72 (2002), p. 5. [8] Gold: a relatively new catalyst, Catal. Today 72 (2002), p. 5.

[9] Surface treatment of aluminum oxide and tungsten carbide powders by ion beam sputter deposition, Surf. Coat. Technol. 163-164 (2003), p. 281. [9] Surface treatment of aluminum oxide and tungsten carbide powders by ion beam sputter deposition, Surf. Coat. Technol. 163-164 (2003), p. 281.

[10] Gold as a Novel Catalyst in the 21st Century: Preparation, Working Mechanisms and Applications, Gold Bull. 37 (2004), p. 27 [10] Gold as a Novel Catalyst in the 21st Century: Preparation, Working Mechanisms and Applications, Gold Bull. 37 (2004), p. 27

[11] Oxidation of CO on Gold Supported Catalysts Prepared by Laser Vaporization: Direct Evidence of Support Contribution, J. Am. Chem. Soc. 126 (2004), p. 1199. [11] Oxidation of CO on Gold Supported Catalysts Prepared by Laser Vaporization: Direct Evidence of Support Contribution, J. Am. Chem. Soc. 126 (2004), p. 1199.

[12] 韩国专利申请 No.KR1005862700000。 [12] Korean Patent Application No. KR1005862700000.

Claims

权利要求 Rights request

1. 一种催化剂用纳米粉末制造装置，其特征在于，该装置包括：真空槽； A nano powder manufacturing apparatus for a catalyst, characterized in that the apparatus comprises: a vacuum tank;

2. 根据权利要求 1所述的装置，其特征在于： 2. Apparatus according to claim 1 wherein:

所述支持体为粉末状、弹丸状或片状。 The support is in the form of a powder, a pellet or a sheet.

3. 根据权利要求 1或 2所述的装置，其特征在于： 3. Apparatus according to claim 1 or 2, characterized in that:

所述支持体为活性炭、氧化物或氮化物。 The support is activated carbon, oxide or nitride.

4. 根据权利要求 1所述的装置，其特征在于： 4. Apparatus according to claim 1 wherein:

所述螺旋型搅拌翼与所述垂直旋转轴之间存在间隙并经由至少一连接体相连接，使所述搅拌槽上部的支持体能够通过所述间隙移动至搅拌槽的下部。 A gap exists between the spiral agitating blade and the vertical rotating shaft and is connected via at least one connecting body, so that the support of the upper portion of the agitation tank can be moved to the lower portion of the agitation tank through the gap.

5. 根据权利要求 1所述的装置，其特征在于： 5. Apparatus according to claim 1 wherein:

所述螺旋型搅拌翼的外侧靠近所述搅拌槽的内壁。 The outer side of the spiral agitating blade is adjacent to the inner wall of the agitation tank.

6. 根据权利要求 1所述的装置，其特征在于，该装置还包括： The device according to claim 1, wherein the device further comprises:

支持板，环绕在所述螺旋型搅拌部件的上部，以支持输送至搅拌槽的上部的支持体，该支持板为中间高、外周低的锥台形，并与搅拌槽的内壁之间存在间隙。 A support plate is disposed around the upper portion of the spiral agitating member to support a support body that is conveyed to an upper portion of the agitation vessel. The support plate has a frustum shape with a middle height and a low outer circumference, and a gap exists between the support plate and the inner wall of the agitation tank.

7. 根据权利要求 6所述的装置，其特征在于，该装置还包括： 7. The device according to claim 6, wherein the device further comprises:

一个以上的上部旋转翼，位于所述支持板上并固定于所述垂直旋转轴，用以搅拌所述支持板上的支持体。 More than one upper rotary wing is located on the support plate and is fixed to the vertical rotary shaft for agitating the support on the support plate.

8. 根据权利要求 1所述的装置，其特征在于，该装置还包括：一个以上的下部旋转翼，位于所述搅拌槽的下方并固定于所述垂直旋转轴，用以搅拌所述搅拌槽中的支持体。 The device according to claim 1, wherein the device further comprises: More than one lower rotary wing is located below the agitation tank and fixed to the vertical rotation shaft for agitating the support in the agitation tank.

9. 根据权利要求 1所述的装置，其特征在于： 9. Apparatus according to claim 1 wherein:

所述物理沉积方式为如下方式中的任意一种：直流溅射、射频溅射、离子束溅射、微波沉积、磁控溅射、热蒸发、电子束蒸发、激光烧蚀、离子镀、电弧放电沉积及分子束外延。 The physical deposition mode is any one of the following modes: DC sputtering, RF sputtering, ion beam sputtering, microwave deposition, magnetron sputtering, thermal evaporation, electron beam evaporation, laser ablation, ion plating, arc Discharge deposition and molecular beam epitaxy.

10. 根据权利要求 1所述的装置，其特征在于： 10. Apparatus according to claim 1 wherein:

在沉积装置沉积纳米粒子的过程中，所述真空槽的真空度为 5 X 10— ¹ 托〜 1 X 10—⁶ 托。 In the process of depositing nanoparticles by the deposition device, the vacuum chamber has a vacuum of 5 X 10 - ¹ Torr to 1 X 10 - ⁶ Torr.

11. 根据权利要求 1所述的装置，其特征在于： 11. Apparatus according to claim 1 wherein:

沉积的催化剂用纳米粒子为：金，银，铂，铑，铹，钯，钌，锇，铼 Re，铱 Ir中的至少一种材料组成的纳米粒子。 The deposited catalyst nanoparticles are: nanoparticles composed of at least one of gold, silver, platinum, rhodium, ruthenium, palladium, rhodium, iridium, iridium Re, 铱 Ir.

12. 根据权利要求 1所述的装置，其特征在于： 12. Apparatus according to claim 1 wherein:

沉积的催化剂用纳米粒子为：金属氧化物或金属氮化物纳米粒子。 The deposited catalyst nanoparticles are: metal oxide or metal nitride nanoparticles.

13. 根据权利要求 1所述的装置，其特征在于，该装置还包括： 13. The device according to claim 1, wherein the device further comprises:

加热部件，用于在沉积前、沉积过程中或沉积后对支持体进行加热处理。 A heating element for heat-treating the support before, during, or after deposition.

14. 根据权利要求 1所述的装置，其特征在于，该装置还包括： The device according to claim 1, wherein the device further comprises:

表面处理部件，用于在沉积前、沉积过程中或沉积后对支持体表面进行离子束或等离子体轰击处理。 A surface treatment component for performing ion beam or plasma bombardment treatment on the surface of the support before, during, or after deposition.

15. 根据权利要求 1所述的装置，其特征在于：以另一种搅拌部件代替权利要求 1中的搅拌部件； 15. The apparatus according to claim 1, wherein: the agitating member of claim 1 is replaced with another agitating member;

所述另一种搅拌部件利用水平旋转轴搅拌支持体，该水平旋转轴上连接有一个以上的搅拌翼。 The other agitating member agitates the support body with a horizontal rotating shaft to which one or more agitating blades are coupled.

16. 一种催化剂用纳米粒子制造方法，其特征在于，该方法包括：搅拌步骤，利用螺旋型搅拌翼进行螺旋式垂直旋转来搅拌支持体或利用水平旋转方式搅拌部件搅拌支持体；沉积步骤，在进行搅拌步骤的同时在真空条件下利用物理沉积方式在暴露于沉积区域的支持体上沉积催化剂用纳米粒子。 A method for producing a nanoparticle for a catalyst, comprising: a stirring step of stirring a support by spiral-type vertical rotation using a spiral agitating blade or agitating a support by a horizontally rotating stirring member; In the deposition step, the catalyst nanoparticles are deposited on the support exposed to the deposition region by physical deposition under vacuum while performing the stirring step.

17. 根据权利要求 16所述的方法，其特征在于： 17. The method of claim 16 wherein:

所述催化剂用纳米粒子为：金，银，铂，铑，铹，钯，钌，锇，铼 Re，铱 Ir 中的至少一种材料组成的纳米粒子。 The catalyst nanoparticles are nanoparticles composed of at least one of gold, silver, platinum, rhodium, ruthenium, palladium, rhodium, iridium, iridium Re, 铱 Ir.

18. 根据权利要求 16所述的方法，其特征在于： 18. The method of claim 16 wherein:

19. 根据权利要求 16所述的方法，其特征在于，该方法还包括： The method according to claim 16, wherein the method further comprises:

对所述支持体进行表面改性处理。 The support is subjected to surface modification treatment.

20. 根据权利要求 16所述的方法，其特征在于，该方法还包括： The method according to claim 16, wherein the method further comprises:

所述表面改性处理包括：离子束或等离子体轰击处理。 The surface modification treatment includes: ion beam or plasma bombardment treatment.

21. 根据权利要求 16所述的方法，其特征在于： 21. The method of claim 16 wherein:

22. 根据权利要求 21所述的方法，其特征在于： 22. The method of claim 21, wherein:

23. 根据权利要求 16所述的方法，其特征在于： 23. The method of claim 16 wherein:

24. 根据权利要求 16所述的方法，其特征在于： 24. The method of claim 16 wherein:

所述真空条件是指 5 X 10— ¹托〜 1 X 10—⁶托的真空度。 The vacuum condition means a degree of vacuum of 5 X 10 - ¹ Torr to 1 X 10 - ⁶ Torr.

25. 根据权利要求 16所述的方法，其特征在于： 25. The method of claim 16 wherein:

所述纳米粒子在支持体上形成的厚度为 0. 1埃〜 1000埃。 The thickness of the nanoparticles formed on the support is 0.1 angstroms to 1000 angstroms.

26. 一种纳米催化剂产品，其特征在于： 26. A nanocatalyst product characterized by:

该产品为蜂窝状，是通过对沉积有催化剂用纳米粒子的支持体进行铸型、烧结处理形成，所述沉积有催化剂用纳米粒子的支持体是利用权利要求 1所述的装置或权利要求 16所述的方法制造获得。 The product is formed in a honeycomb shape by casting and sintering a support for depositing catalyst nanoparticles, and the support for depositing nanoparticles for a catalyst is the same as described in claim 1. The device or the method of claim 16 is produced.

27. 一种纳米催化剂产品，其特征在于： 27. A nanocatalyst product characterized by:

该产品是通过将蜂窝状载体利用含有催化剂用纳米粒子的液体进行浸泡、喷雾、丝网印刷或涂装后进行干燥处理形成，所述催化剂用纳米粒子是利用权利要求 1所述的装置或权利要求 16所述的方法制造获得。 The product is formed by immersing, spraying, screen printing or coating a honeycomb carrier with a liquid containing catalyst nanoparticles, and the catalyst nanoparticles are obtained by using the apparatus or the right according to claim 1. The method described in claim 16 is made.

28. 根据权利要求 27所述的产品，其特征在于： 28. The product of claim 27, wherein:

所述蜂窝状载体为通过对另行沉积有催化剂用纳米粒子的支持体进行铸型、烧结处理形成。 The honeycomb carrier is formed by casting and sintering a support in which nanoparticles for catalyst are separately deposited.

29. 一种纳米催化剂产品的生产方法，其特征在于，该方法包括：对沉积有催化剂用纳米粒子的支持体进行铸型、烧结处理，形成承载有纳米催化剂的蜂窝状纳米催化剂产品；其中所述沉积有催化剂用纳米粒子的支持体是利用权利要求 1所述的装置或权利要求 16所述的方法制造获得。 A method for producing a nanocatalyst product, the method comprising: casting and sintering a support on which a catalyst nanoparticle is deposited to form a honeycomb nanocatalyst product carrying a nanocatalyst; The support in which the nanoparticles for catalyst are deposited is obtained by the apparatus according to claim 1 or the method of claim 16.

30. 根据权利要求 29所述的方法，其特征在于： 30. The method of claim 29, wherein:

在所述铸型过程中，对沉积在支持体上的纳米粒子之间添加粘合剂。 In the casting process, a binder is added between the nanoparticles deposited on the support.

31. 一种纳米催化剂产品的生产方法，其特征在于： 31. A method of producing a nanocatalyst product, characterized by:

将沉积有催化剂用纳米粒子的水溶性支持体进行溶解变为液体状态，其中所述沉积有催化剂用纳米粒子的水溶性支持体是利用权利要求 1所述的装置或权利要求 16所述的方法制造获得； The water-soluble support on which the catalyst nanoparticles are deposited is dissolved into a liquid state, wherein the water-soluble support on which the catalyst nanoparticles are deposited is the apparatus according to claim 1 or the method according to claim 16 Manufactured;

利用所述液体对蜂窝状载体进行浸泡、喷雾、丝网印刷或涂装后进行干燥处理，形成承载有纳米催化剂的纳米催化剂产品。 The honeycomb carrier is immersed, sprayed, screen printed or coated with the liquid and then dried to form a nanocatalyst product carrying the nanocatalyst.

32. 根据权利要求 31所述的方法，其特征在于： 32. The method of claim 31, wherein: