WO2015149517A1 - Procédé de synthèse hydrothermique supercritique pour nanoparticules de métal ou d'oxyde métallique - Google Patents

Procédé de synthèse hydrothermique supercritique pour nanoparticules de métal ou d'oxyde métallique Download PDF

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Publication number
WO2015149517A1
WO2015149517A1 PCT/CN2014/090721 CN2014090721W WO2015149517A1 WO 2015149517 A1 WO2015149517 A1 WO 2015149517A1 CN 2014090721 W CN2014090721 W CN 2014090721W WO 2015149517 A1 WO2015149517 A1 WO 2015149517A1
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hydrothermal synthesis
supercritical
nano metal
metal oxide
reaction
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PCT/CN2014/090721
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English (en)
Chinese (zh)
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王树众
周璐
郭洋
钱黎黎
任萌萌
李艳辉
Original Assignee
西安交通大学
西安市万丰能源环保科技有限公司
王树众
周璐
郭洋
钱黎黎
任萌萌
李艳辉
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Application filed by 西安交通大学, 西安市万丰能源环保科技有限公司, 王树众, 周璐, 郭洋, 钱黎黎, 任萌萌, 李艳辉 filed Critical 西安交通大学
Publication of WO2015149517A1 publication Critical patent/WO2015149517A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/16—Making metallic powder or suspensions thereof using chemical processes
    • B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
    • B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/05—Metallic powder characterised by the size or surface area of the particles
    • B22F1/054—Nanosized particles
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G3/00—Compounds of copper
    • C01G3/02—Oxides; Hydroxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2999/00—Aspects linked to processes or compositions used in powder metallurgy
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids

Definitions

  • the invention relates to a method for preparing nano particles, in particular to a method for supercritical hydrothermal synthesis of nano metal or nano metal oxide particles.
  • Nano-metal or nano-metal oxide particles are important industrial products with superior properties compared to common metal or metal oxide powders, such as large specific surface area, interfacial effects, quantum effects and quantum tunneling effects. It imparts its unique properties different from traditional materials as well as its specific electrical, thermal, magnetic, optical and mechanical properties. It is widely used in various fields, such as catalysts, with small particle size, large specific surface and particle surface. The characteristics of the number of active centers are high, and the catalytic efficiency is high and the selectivity is strong.
  • the coating film used as the sensor can greatly improve the selectivity and sensitivity of the sensor; in the battery industry, it is expected to be used for the negative electrode of high performance chemical battery. Materials; colorants for glass, ceramics, exhaust gas purification materials, contact materials, etc.
  • Nanoparticle preparation methods are divided into physical and chemical methods.
  • Physical methods include mechanical grinding and physical vapor deposition.
  • the disadvantages are complex process equipment, low yield, and large scale production.
  • Microemulsion method and spray pyrolysis method generally have to be subjected to high temperature heat treatment, which causes the particles to agglomerate and abnormal particle growth.
  • the conventional hydrothermal reaction cycle is long, and it usually takes several hours or even several days of reaction time, which inevitably causes a problem of large particle growth.
  • the preparation of nano metal particles by chemical electrolysis is a relatively mature and industrial production method, but the obtained metal powder usually needs to be subjected to ball milling, sieving and the like to finally obtain ultrafine metal particles, and the electrolytic waste liquid contains a large amount of metal ions.
  • the liquid phase reduction method is a relatively active preparation method of nanoparticles in recent years, but the method generally requires a large amount of organic solvent or highly toxic additive component. It causes serious pollution in production, which limits its application. Therefore, it is of great significance to explore green and efficient nanoparticle preparation technology using water as the reaction medium.
  • the supercritical hydrothermal synthesis reaction refers to the use of supercritical water as a reaction medium in a closed high-pressure reactor to cause hydrolysis and dehydration of the metal salt in the hydrothermal medium, thereby nucleating, growing, and finally forming a certain particle size and The reaction of nanocrystalline grains in crystalline form.
  • a non-polar gas such as a reducing organic substance or hydrogen can be mixed with supercritical water to form a homogeneous reaction system, thereby achieving high-efficiency reduction of the metal oxide and generating high-purity metal nanoparticles. Since the reaction medium is supercritical water, the reaction process is carried out in a closed high-pressure vessel, so that no other pollutants are introduced during the reaction, which is considered to be a green nano-preparation technology.
  • the object of the present invention is to provide a supercritical hydrothermal synthesis method of nano metal or nano metal oxide particles, and the nano metal or nano metal oxide particles prepared by the method have the advantages of small particle size, good dispersibility and high purity.
  • a method for supercritical hydrothermal synthesis of nano metal or nano metal oxide particles comprising the following steps:
  • reaction precursor obtained in the step 2) is directly mixed with the preheated supercritical water, heated to a supercritical state, and entered into a supercritical hydrothermal synthesis reactor for supercritical hydrothermal synthesis reaction, after the reaction is completed. Cooling, depressurizing and collecting the reaction product to obtain a sample of the reaction product;
  • reaction product sample is subjected to centrifugation, washing, and drying to obtain a nano metal or nano metal oxide particle product.
  • a further improvement of the invention resides in that the soluble metal salt is a sulfate, nitrate or chloride salt.
  • a further improvement of the invention consists in preheating the soluble metal salt solution to increase the solubility of the soluble metal salt.
  • the invention is further improved in that the mixture of lye or lye, reducing agent and organic ligand is added in an amount such that the reaction precursor is neutral.
  • a further improvement of the invention resides in that the reducing agent is hydrogen or formic acid which is used to reduce metal ions in the high valence state.
  • the present invention is further improved in that the molecule of the organic ligand contains a carboxyl group or an amine group of a polar functional group while being thermally stable in supercritical water.
  • the invention is further improved in that the organic ligand is ethylenediaminetetraacetic acid.
  • the invention is further improved in that the supercritical hydrothermal synthesis reactor is a batch type supercritical hydrothermal synthesis reactor or a continuous supercritical hydrothermal synthesis reactor.
  • step 4 after washing with pure water and absolute ethanol, vacuum drying is further carried out at 60 °C.
  • the nano metal or nano metal oxide particles prepared by the invention have the characteristics of small particle size, good dispersibility and high purity, and the obtained nano metal or nano metal oxide can be used for high-efficiency catalysts, additives for dyes or electrode materials.
  • FIG. 1 is a flow chart of a method for supercritical hydrothermal synthesis of nano metal or nano metal oxide particles of the present invention.
  • Example 2 is a TEM image of the nano-copper oxide product obtained in Example 1 of the present invention.
  • Example 3 is an XRD chart of a nano-copper oxide product obtained in Example 1 of the present invention.
  • Example 4 is a TEM image of the nano copper product obtained in Example 2 of the present invention.
  • Fig. 5 is an XRD chart of the nano copper product obtained in Example 2 of the present invention.
  • a method for supercritical hydrothermal synthesis of nano metal or nano metal oxide particles of the present invention comprises the following steps:
  • the reaction precursor obtained in the step 2) is directly mixed with the preheated supercritical water, heated to a supercritical state, and entered into a supercritical hydrothermal synthesis reactor for supercritical hydrothermal synthesis reaction, after the reaction is completed.
  • the reaction product is cooled, depressurized and collected to obtain a sample of the reaction product; wherein the supercritical hydrothermal synthesis reactor is a batch supercritical hydrothermal synthesis reactor or a continuous supercritical hydrothermal synthesis reactor.
  • reaction product sample is subjected to centrifugal separation, washed with pure water and anhydrous ethanol, and then vacuum dried at 60 ° C to obtain a nano metal or nano metal oxide particle product.
  • the soluble metal salt is a sulfate, a nitrate or a chloride salt.
  • the method for preparing the nanometer copper oxide by using copper sulfate supercritical hydrothermal synthesis is described as an example, and the method comprises the following steps:
  • the high-pressure pump separately mixes the reaction precursor generated in step 2) with the pure water preheated to the supercritical temperature into the supercritical hydrothermal synthesis reactor. After a certain period of reaction (usually less than 1 min), the collection is cooled.
  • the depressurized reaction product is obtained by separating the nano copper oxide product by a centrifugal separator, repeatedly washing with pure water and absolute ethanol, and vacuum drying at 60 ° C to obtain a nano copper oxide product.
  • the obtained nano-copper oxide product has a particle size of 20-100 nm, and the particle size of the product generally increases as the concentration of the reactant increases, and decreases as the amount of NaOH added increases.
  • FIG. 2 is a TEM image of the nano-copper oxide product obtained in Embodiment 1 of the present invention
  • FIG. 3 is an XRD pattern of the nano-copper oxide product obtained in Example 1 of the present invention. It can be seen from Fig. 2 and Fig. 3 that the nano-copper oxide particles prepared by the supercritical hydrothermal synthesis technique have a uniform ellipsoidal structure; it can be seen from the XRD analysis that the product is completely composed of copper oxide, and there are no other impurity components. .
  • the method of the present invention is described by taking the preparation of nano copper by supercritical hydrothermal synthesis of soluble copper salt as an example, and the following steps are included:
  • the high-pressure pump separately mixes the reaction precursor formed in step 2) with the pure water preheated to the supercritical temperature, and then enters the supercritical hydrothermal synthesis reactor. After a reaction time, the collection is cooled and reduced.
  • the reaction product is obtained by separating the nano copper product by a centrifugal separator, repeatedly washing with pure water and absolute ethanol, and vacuum drying at 60 ° C to obtain a nano copper product.
  • the obtained nano copper product has a particle size of 15 to 80 nm, and the particle size of the product generally increases with the increase of the reactant concentration, and decreases with the increase of the NaOH addition amount; the obtained product is a high purity nano copper particle, Contains copper oxide or cuprous oxide impurities.
  • FIG. 4 is a TEM image of the nano copper product obtained in Example 2 of the present invention
  • FIG. 5 is an XRD pattern of the nano copper product obtained in Example 2 of the present invention. It can be seen from Fig. 4 and Fig. 5 that the nano copper particles prepared by the supercritical hydrothermal synthesis technology have uniform particle size distribution and good particle dispersibility. It can be seen from the XRD analysis chart that the product is completely composed of copper oxide and there are no other impurity components. It can be seen from the XRD analysis that the product is composed of pure nano copper and has a very high purity.

Abstract

L'invention se rapporte à un procédé de synthèse hydrothermique supercritique pour nanoparticules de métal ou d'oxyde métallique qui comprend les étapes suivantes consistant à : mélanger complètement une solution de sel de métal soluble avec une solution alcaline ou avec un mélange d'une solution alcaline, d'une solution d'agent de réduction et d'un ligand organique pour servir de précurseur de réaction de synthèse hydrothermique supercritique ; utiliser une pompe à haute pression pour mettre sous pression séparément et pomper le précurseur de réaction et l'eau supercritique préalablement chauffée dans un mélangeur, chauffer par mélange direct, puis réaliser une réaction de synthèse hydrothermique supercritique ; et après la réaction pendant un laps de temps donné, refroidir, centrifuger et sécher le produit obtenu de manière à obtenir des nanoparticules de métal ou d'oxyde métallique. Les nanoparticules de métal ou d'oxyde métallique préparées au moyen du procédé présentent comme avantages une faible granulométrie, une bonne dispersabilitéet une grande pureté.
PCT/CN2014/090721 2014-04-02 2014-11-10 Procédé de synthèse hydrothermique supercritique pour nanoparticules de métal ou d'oxyde métallique WO2015149517A1 (fr)

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CN201410131897.1A CN103934468B (zh) 2014-04-02 2014-04-02 纳米金属或纳米金属氧化物颗粒的超临界水热合成方法
CN201410131897.1 2014-04-02

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GB2560235A (en) * 2017-01-06 2018-09-05 Aegis Eng Ltd Nanoscale coating for enhanced fabrics
CN112276107A (zh) * 2019-07-25 2021-01-29 上海沪正实业有限公司 纳米铜粒子及其在制备纳米铜织物后整理剂中的用途
CN112499662A (zh) * 2020-11-13 2021-03-16 安徽清水湖新材料技术有限公司 一种氧化铜纳米材料及其制备方法
CN113772752A (zh) * 2021-08-04 2021-12-10 中国科学院广州地球化学研究所 一种PdO2不规则锥型纳米颗粒材料的制备方法
WO2022067210A1 (fr) * 2020-09-25 2022-03-31 Woodholdings Environmental. Inc. Procédé d'amélioration de la résistance au feu d'un matériau cellulosique
CN115676871A (zh) * 2022-11-04 2023-02-03 安徽铜冠产业技术研究院有限责任公司 一种纳米氧化铜粉体的制备工艺
CN115784293A (zh) * 2022-11-18 2023-03-14 中国计量大学 一种超临界水热法制备稀土硫化铈的方法
CN116275085A (zh) * 2023-05-11 2023-06-23 哈尔滨工业大学(深圳)(哈尔滨工业大学深圳科技创新研究院) 纳米银、石墨烯复合材料及其制备方法

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CN112276107A (zh) * 2019-07-25 2021-01-29 上海沪正实业有限公司 纳米铜粒子及其在制备纳米铜织物后整理剂中的用途
WO2022067210A1 (fr) * 2020-09-25 2022-03-31 Woodholdings Environmental. Inc. Procédé d'amélioration de la résistance au feu d'un matériau cellulosique
CN112499662A (zh) * 2020-11-13 2021-03-16 安徽清水湖新材料技术有限公司 一种氧化铜纳米材料及其制备方法
CN113772752A (zh) * 2021-08-04 2021-12-10 中国科学院广州地球化学研究所 一种PdO2不规则锥型纳米颗粒材料的制备方法
CN115676871A (zh) * 2022-11-04 2023-02-03 安徽铜冠产业技术研究院有限责任公司 一种纳米氧化铜粉体的制备工艺
CN115676871B (zh) * 2022-11-04 2023-12-05 安徽铜冠产业技术研究院有限责任公司 一种纳米氧化铜粉体的制备工艺
CN115784293A (zh) * 2022-11-18 2023-03-14 中国计量大学 一种超临界水热法制备稀土硫化铈的方法
CN116275085A (zh) * 2023-05-11 2023-06-23 哈尔滨工业大学(深圳)(哈尔滨工业大学深圳科技创新研究院) 纳米银、石墨烯复合材料及其制备方法

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