WO2015149517A1 - Supercritical hydrothermal synthesis method for metal or metal oxide nanoparticles - Google Patents

Supercritical hydrothermal synthesis method for metal or metal oxide nanoparticles Download PDF

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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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French (fr)
Chinese (zh)
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王树众
周璐
郭洋
钱黎黎
任萌萌
李艳辉
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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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Publication of WO2015149517A1 publication Critical patent/WO2015149517A1/en

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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

A supercritical hydrothermal synthesis method for metal or metal oxide nanoparticles comprises the following steps: fully mixing a soluble metal salt solution with an alkaline solution or with a mixture of an alkaline solution, a reducing agent solution and an organic ligand to serve as a reaction precursor of supercritical hydrothermal synthesis; using a high-pressure pump to separately pressurize and pump the reaction precursor and preheated supercritical water into a mixer, heating up by direct mixing, and then performing a supercritical hydrothermal synthesis reaction; and after reaction for a period of time, cooling, centrifuging and drying the obtained product, so as to obtain metal or metal oxide nanoparticles. The metal or metal oxide nanoparticles prepared by using the method have the advantages of small particle size, good dispersibility, and high purity.

Description

纳米金属或纳米金属氧化物颗粒的超临界水热合成方法Supercritical hydrothermal synthesis method of nano metal or nano metal oxide particles 技术领域Technical field
本发明涉及一种纳米颗粒的制备方法，特别是涉及一种纳米金属或纳米金属氧化物颗粒的超临界水热合成方法。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.
背景技术Background technique
纳米金属或纳米金属氧化物颗粒是重要的工业产品，与普通的金属或金属氧化物粉体相比，具有更优越的性能，如大的比表面积、界面效应、量子效应和量子隧道效应等，赋予了其不同于传统材料的各种独特性能以及特异的电学、热学、磁学、光学及力学性能，广泛应用于各个领域，如用作催化剂，具有粒径小、比表面大、颗粒表面的活性中心数目多等特点，催化效率高、选择性强；在传感器方面，用作传感器的包覆膜，能大大提高传感器的选择性和灵敏度；在电池行业，有望用于高性能化学电池的负极材料；用于玻璃、陶瓷的着色剂、尾气净化材料、触点材料等。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. In the sensor aspect, 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.
传统的纳米颗粒制备方法分为物理法和化学法两大类。物理法包括机械研磨法和物理气相沉积法，其缺点是工艺设备复杂，产量低，大规模生产难度较大。微乳液法和喷雾热解法等一般都要经过高温热处理，导致颗粒易发生团聚，出现颗粒异常生长现象。而常规的水热法反应周期较长，通常需要数个小时，甚至数天反应时间，难免颗粒生长较大的问题。化学电解法制备纳米金属颗粒是一种比较成熟且工业生产方法，但是得到的金属粉末通常需要再经过球磨、分筛等工艺才最终得到超细金属颗粒，并且电解废液中含有大量的金属离子，任意排放会造成资源浪费和环境的污染，从而制约了该方法的大规模应用。液相还原法是近年来较为活跃的纳米颗粒制备方法，但该方法通常需采用大量的有机溶剂或剧毒的添加剂成分， 在生产中造成严重污染，使得其应用受到很大限制。因此，探索以水为反应介质的绿色、高效的纳米颗粒制备技术具有重要意义。Traditional 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. However, 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. Any discharge will cause waste of resources and environmental pollution, which restricts the large-scale application of the method. 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.
超临界水(Supercritical water，简称SCW)是指温度和压力均高于其临界点(T＝374.15℃，P＝22.12MPa)的特殊状态的水。超临界水兼具液态和气态水的性质，该状态下的水中只有少量的氢键存在，介电常数近似于有机溶剂，具有高的扩散系数和低的粘度。超临界水热合成反应是指在密闭的高压反应器中，以超临界水作为反应介质，使金属盐在水热介质中发生水解、脱水反应，进而成核、生长、最终形成具有一定粒度和结晶形态的纳米晶粒的反应。在超临界水中，还原性有机物或氢气等无极性气体可与超临界水混溶形成均相反应体系，实现金属氧化物高效还原，生成高纯度的金属纳米颗粒。由于反应介质为超临界水，反应过程在密闭的高压容器中进行，因而在反应过程中不会引入其它污染物，被认为是一种绿色环保的纳米制备技术。Supercritical water (SCW) refers to water in a special state where both temperature and pressure are higher than its critical point (T=374.15 °C, P=22.12 MPa). Supercritical water combines the properties of liquid and gaseous water. In this state, only a small amount of hydrogen bonds exist in the water. The dielectric constant is similar to that of an organic solvent, and has a high diffusion coefficient and a low viscosity. 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. In supercritical water, 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.
发明内容Summary of the invention
本发明的目的是提供一种纳米金属或纳米金属氧化物颗粒的超临界水热合成方法，该方法制备的纳米金属或纳米金属氧化物物颗粒具有粒径小、分散性良好、纯度高等优点。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.
为达到上述目的，本发明采用以下技术方案予以实现：In order to achieve the above object, the present invention is implemented by the following technical solutions:
纳米金属或纳米金属氧化物颗粒的超临界水热合成方法，包括如下步骤：A method for supercritical hydrothermal synthesis of nano metal or nano metal oxide particles, comprising the following steps:
1)采用纯水溶解可溶性金属盐，得到可溶性金属盐溶液；1) dissolving the soluble metal salt in pure water to obtain a soluble metal salt solution;
2)分别将得到的可溶性金属盐溶液与碱液或碱液、还原剂和有机配体的混合物加压至超临界压力，并在常温下将两者进行预混合，得到用于超临界水热合成反应的反应前驱物；2) respectively pressurizing the obtained soluble metal salt solution with a mixture of an alkali solution or an alkali solution, a reducing agent and an organic ligand to a supercritical pressure, and premixing the two at room temperature to obtain a supercritical water heat. a reaction precursor for the synthesis reaction;
3)将步骤2)得到的反应前驱物与经过预热的超临界水直接混合，加热至超临界状态，并进入超临界水热合成反应器中进行超临界水热合成反应，待反应完成后，对反应产物进行冷却、降压和收集，得到反应产物样品； 3) 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. Cooling, depressurizing and collecting the reaction product to obtain a sample of the reaction product;
4)将所得的反应产物样品进行离心分离，洗涤，干燥，即可得到纳米金属或纳米金属氧化物颗粒产物。4) The obtained reaction product sample is subjected to centrifugation, washing, and drying to obtain a nano metal or nano metal oxide particle product.
本发明进一步改进在于：可溶性金属盐为硫酸盐、硝酸盐或氯化盐。A further improvement of the invention resides in that the soluble metal salt is a sulfate, nitrate or chloride salt.
本发明进一步改进在于：在配制可溶性金属盐溶液时，对其进行预热以提高可溶性金属盐的溶解度。A further improvement of the invention consists in preheating the soluble metal salt solution to increase the solubility of the soluble metal salt.
本发明进一步改进在于：碱液或碱液、还原剂和有机配体的混合物的添加量应使反应前驱物呈中性。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.
本发明进一步改进在于：还原剂为氢气或甲酸，其用于对高价态的金属离子进行还原。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.
本发明进一步改进在于：有机配体的分子中含有极性官能团的羧基或胺基，同时其在超临界水中具有热稳定性。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.
本发明进一步改进在于：有机配体为乙二胺四乙酸。The invention is further improved in that the organic ligand is ethylenediaminetetraacetic acid.
本发明进一步改进在于：超临界水热合成反应器为间歇式超临界水热合成反应釜或连续式超临界水热合成反应釜。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.
本发明进一步改进在于：步骤4)中，经纯水和无水乙醇洗涤后，在60℃下再进行真空干燥。Further improvement of the present invention is that in step 4), after washing with pure water and absolute ethanol, vacuum drying is further carried out at 60 °C.
与现有技术相比，本发明的优点是：The advantages of the present invention over the prior art are:
本发明制备的纳米金属或纳米金属氧化物颗粒具有粒径小、分散性好和纯度高等特点，得到的纳米金属或纳米金属氧化物可用于高效催化剂、染色剂的添加剂或电极材料等。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.
附图说明DRAWINGS
图1为本发明纳米金属或纳米金属氧化物颗粒的超临界水热合成方法的流程框图。1 is a flow chart of a method for supercritical hydrothermal synthesis of nano metal or nano metal oxide particles of the present invention.
图2是本发明实施案例1中所得纳米氧化铜产品的TEM图。2 is a TEM image of the nano-copper oxide product obtained in Example 1 of the present invention.
图3是本发明实施例1中所得纳米氧化铜产品的XRD图。 3 is an XRD chart of a nano-copper oxide product obtained in Example 1 of the present invention.
图4是本发明实施例2中所得纳米铜产品的TEM图。4 is a TEM image of the nano copper product obtained in Example 2 of the present invention.
图5是本发明实施例2中所得纳米铜产品的XRD图。Fig. 5 is an XRD chart of the nano copper product obtained in Example 2 of the present invention.
具体实施方式detailed description
下面结合附图和具体实施例对本发明做进一步详细说明。The present invention will be further described in detail below with reference to the accompanying drawings and specific embodiments.
参见图1，本发明纳米金属或纳米金属氧化物颗粒的超临界水热合成方法，包括如下步骤：Referring to FIG. 1, a method for supercritical hydrothermal synthesis of nano metal or nano metal oxide particles of the present invention comprises the following steps:
1)采用纯水溶解可溶性金属盐，得到可溶性金属盐溶液，在配制可溶性金属盐溶液时，可对其进行预热以提高可溶性金属盐的溶解度。1) Dissolving the soluble metal salt with pure water to obtain a soluble metal salt solution, which can be preheated to improve the solubility of the soluble metal salt when the soluble metal salt solution is prepared.
2)分别将得到的可溶性金属盐溶液与碱液或碱液、还原剂和有机配体的混合物加压至超临界压力，并在常温下将两者进行预混合，得到用于超临界水热合成反应的反应前驱物；其中，碱液或碱液、还原剂和有机配体的混合物的添加量应使反应前驱物呈中性，还原剂可以为氢气或甲酸，其用于对高价态的金属离子进行还原，有机配体的分子中含有极性官能团的羧基或胺基，同时其在超临界水中具有热稳定性，比如乙二胺四乙酸。2) respectively pressurizing the obtained soluble metal salt solution with a mixture of an alkali solution or an alkali solution, a reducing agent and an organic ligand to a supercritical pressure, and premixing the two at room temperature to obtain a supercritical water heat. a reaction precursor for the synthesis reaction; wherein the mixture of the alkali solution or the alkali solution, the reducing agent and the organic ligand is added in such a manner that the reaction precursor is neutral, and the reducing agent may be hydrogen or formic acid, which is used for the high valence state. The metal ion is reduced, and the molecule of the organic ligand contains a carboxyl group or an amine group of a polar functional group, and it has thermal stability in supercritical water, such as ethylenediaminetetraacetic acid.
3)将步骤2)得到的反应前驱物与经过预热的超临界水直接混合，加热至超临界状态，并进入超临界水热合成反应器中进行超临界水热合成反应，待反应完成后，对反应产物进行冷却、降压和收集，得到反应产物样品；其中，超临界水热合成反应器为间歇式超临界水热合成反应釜或连续式超临界水热合成反应釜。3) 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.
4)将所得的反应产物样品进行离心分离，经纯水和无水乙醇洗涤后，在60℃下再进行真空干燥，即可得到纳米金属或纳米金属氧化物颗粒产物。4) The obtained 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.
其中，上述可溶性金属盐为硫酸盐、硝酸盐或氯化盐。Wherein the soluble metal salt is a sulfate, a nitrate or a chloride salt.
实施例1： Example 1:
本实施例以采用硫酸铜超临界水热合成制备纳米氧化铜为例，对本发明方法进行说明，包括以下步骤：In this embodiment, 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:
1)将CuSO4·5H2O晶体(Cu(NO3)2晶体或CuCl2晶体)溶解于纯水中，得到0.5mol/L的硫酸铜(硝酸铜或氯化铜)溶液；1) dissolving CuSO 4 ·5H 2 O crystal (Cu(NO 3 ) 2 crystal or CuCl 2 crystal) in pure water to obtain 0.5 mol/L copper sulfate (copper nitrate or copper chloride) solution;
2)采用NaOH溶液调节硫酸铜(硝酸铜或氯化铜)溶液的pH值至接近中性，将获得的混合物作为超临界水热合成反应的反应前驱物；2) adjusting the pH of the copper sulfate (copper nitrate or copper chloride) solution to near neutral using a NaOH solution, and using the obtained mixture as a reaction precursor of the supercritical hydrothermal synthesis reaction;
3)采用高压泵分别将步骤2)生成的反应前驱物与预热至超临界温度的纯水直接混合进入超临界水热合成反应器，反应时间一段时间后(通常小于1min)，收集经冷却、降压的反应产物，采用离心分离机分离纳米氧化铜产物，再经过纯水和无水乙醇反复洗涤、在60℃下再进行真空干燥后，即可得到纳米氧化铜产物。3) 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.
经检测，得到的纳米氧化铜产物的粒度为20～100nm，产物粒径通常随反应物浓度增大而增大，并随NaOH添加量增大而减小。After testing, 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.
参见图2和图3，图2是本发明实施案例1中所得纳米氧化铜产品的TEM图；图3是本发明实施例1中所得纳米氧化铜产品的XRD图。从图2和图3可以看出，采用超临界水热合成技术制备的纳米氧化铜颗粒呈均匀的椭球形结构；从XRD分析图谱可以看出，产物完全由氧化铜组成，不存在其它杂质成分。2 and FIG. 3, FIG. 2 is a TEM image of the nano-copper oxide product obtained in Embodiment 1 of the present invention; and 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. .
实施例2：Example 2:
本实施例以采用可溶性铜盐超临界水热合成制备纳米铜为例，对本发明方法进行说明，包括以下步骤：In this embodiment, 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:
1)将CuSO4·5H2O晶体(Cu(NO3)2晶体或CuCl2晶体)溶解于纯水中，得到0.5mol/L的硫酸铜(硝酸铜或氯化铜)溶液；1) dissolving CuSO 4 ·5H 2 O crystal (Cu(NO 3 ) 2 crystal or CuCl 2 crystal) in pure water to obtain 0.5 mol/L copper sulfate (copper nitrate or copper chloride) solution;
2)将获得的硫酸铜(硝酸铜或氯化铜)溶液与NaOH溶液、甲酸溶液和乙二胺四乙酸的混合物进行充分混合，作为超临界水热合成反应的反应前驱物； 2) thoroughly mixing the obtained copper sulfate (copper nitrate or copper chloride) solution with a mixture of NaOH solution, formic acid solution and ethylenediaminetetraacetic acid as a reaction precursor of the supercritical hydrothermal synthesis reaction;
3)采用高压泵分别将步骤2)生成的反应前驱物与预热至超临界温度的纯水直接混合后，进入超临界水热合成反应器，反应时间一段时间后，收集经冷却、降压的反应产物，采用离心分离机分离纳米铜产物，再经过纯水和无水乙醇反复洗涤、在60℃下再进行真空干燥后，即可得到纳米铜产物。3) 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.
经检测，得到的纳米铜产物的粒度为15～80nm，产物粒径通常随反应物浓度增大而增大，随NaOH添加量增大而减小；所得产物为高纯度的纳米铜颗粒，不含氧化铜或氧化亚铜杂质。After testing, 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.
参见图4和图5，图4是本发明实施例2中所得纳米铜产品的TEM图；图5是本发明实施例2中所得纳米铜产品的XRD图。从图4和图5可以看出，采用超临界水热合成技术制备的纳米铜颗粒粒径分布均匀，颗粒分散性良好。从XRD分析图谱可以看出，产物完全有氧化铜组成，不存在其它杂质成分；从XRD分析图谱可以看出，产品由纯的纳米铜组成、纯度极高。 4 and FIG. 5, FIG. 4 is a TEM image of the nano copper product obtained in Example 2 of the present invention; and 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.

Claims (9)

  1. 纳米金属或纳米金属氧化物颗粒的超临界水热合成方法，其特征在于，包括如下步骤：A method for supercritical hydrothermal synthesis of nano metal or nano metal oxide particles, comprising the steps of:
    1)采用纯水溶解可溶性金属盐，得到可溶性金属盐溶液；1) dissolving the soluble metal salt in pure water to obtain a soluble metal salt solution;
    2)分别将得到的可溶性金属盐溶液与碱液或碱液、还原剂和有机配体的混合物加压至超临界压力，并在常温下将两者进行预混合，得到用于超临界水热合成反应的反应前驱物；2) respectively pressurizing the obtained soluble metal salt solution with a mixture of an alkali solution or an alkali solution, a reducing agent and an organic ligand to a supercritical pressure, and premixing the two at room temperature to obtain a supercritical water heat. a reaction precursor for the synthesis reaction;
    3)将步骤2)得到的反应前驱物与经过预热的超临界水直接混合，加热至超临界状态，并进入超临界水热合成反应器中进行超临界水热合成反应，待反应完成后，对反应产物进行冷却、降压和收集，得到反应产物样品；3) 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. Cooling, depressurizing and collecting the reaction product to obtain a sample of the reaction product;
    4)将所得的反应产物样品进行离心分离，洗涤，干燥，即可得到纳米金属或纳米金属氧化物颗粒产物。4) The obtained reaction product sample is subjected to centrifugation, washing, and drying to obtain a nano metal or nano metal oxide particle product.
  2. 根据权利要求1所述的纳米金属或纳米金属氧化物颗粒的超临界水热合成方法，其特征在于：可溶性金属盐为硫酸盐、硝酸盐或氯化盐。The method for supercritical hydrothermal synthesis of nano metal or nano metal oxide particles according to claim 1, wherein the soluble metal salt is a sulfate, a nitrate or a chloride salt.
  3. 根据权利要求1所述的纳米金属或纳米金属氧化物颗粒的超临界水热合成方法，其特征在于：在配制可溶性金属盐溶液时，对其进行预热以提高可溶性金属盐的溶解度。The method for supercritical hydrothermal synthesis of nano metal or nano metal oxide particles according to claim 1, wherein when the soluble metal salt solution is prepared, it is preheated to increase the solubility of the soluble metal salt.
  4. 根据权利要求1所述的纳米金属或纳米金属氧化物颗粒的超临界水热合成方法，其特征在于：碱液或碱液、还原剂和有机配体的混合物的添加量应使反应前驱物呈中性。The method for supercritical hydrothermal synthesis of nano metal or nano metal oxide particles according to claim 1, wherein the mixture of the alkali solution or the alkali solution, the reducing agent and the organic ligand is added in such an amount that the reaction precursor is present. neutral.
  5. 根据权利要求1或4所述的纳米金属或纳米金属氧化物颗粒的超临界水热合成方法，其特征在于：还原剂为氢气或甲酸，其用于对高价态的金属离子进行还原。The supercritical hydrothermal synthesis method of nano metal or nano metal oxide particles according to claim 1 or 4, wherein the reducing agent is hydrogen or formic acid, which is used for reducing metal ions in a high valence state.
  6. 根据权利要求1或4所述的纳米金属或纳米金属氧化物颗粒的超临界水热合成方法，其特征在于：有机配体的分子中含有极性官能团的羧基或胺基，同时其在超临界水中具有热稳定性。The method for supercritical hydrothermal synthesis of nano metal or nano metal oxide particles according to claim 1 or 4, wherein the molecular group of the organic ligand contains a carboxyl group or an amine group of a polar functional group, and at the same time, it is supercritical The water is thermally stable.
  7. 根据权利要求6所述的纳米金属或纳米金属氧化物颗粒的超临界水热合成方法，其特征在于：有机配体为乙二胺四乙酸。 The method of supercritical hydrothermal synthesis of nano metal or nano metal oxide particles according to claim 6, wherein the organic ligand is ethylenediaminetetraacetic acid.
  8. 根据权利要求1所述的纳米金属或纳米金属氧化物颗粒的超临界水热合成方法，其特征在于：超临界水热合成反应器为间歇式超临界水热合成反应釜或连续式超临界水热合成反应釜。The method for supercritical hydrothermal synthesis of nano metal or nano metal oxide particles according to claim 1, wherein the supercritical hydrothermal synthesis reactor is a batch type supercritical hydrothermal synthesis reactor or continuous supercritical water. Thermal synthesis reactor.
  9. 根据权利要求1所述的纳米金属或纳米金属氧化物颗粒的超临界水热合成方法，其特征在于：步骤4)中，经纯水和无水乙醇洗涤后，在60℃下再进行真空干燥。 The method for supercritical hydrothermal synthesis of nano metal or nano metal oxide particles according to claim 1, wherein in step 4), after washing with pure water and absolute ethanol, vacuum drying is performed at 60 ° C. .
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