CN107498068A - A kind of preparation method of flower-shaped nano-copper - Google Patents

A kind of preparation method of flower-shaped nano-copper Download PDF

Info

Publication number
CN107498068A
CN107498068A CN201710868958.6A CN201710868958A CN107498068A CN 107498068 A CN107498068 A CN 107498068A CN 201710868958 A CN201710868958 A CN 201710868958A CN 107498068 A CN107498068 A CN 107498068A
Authority
CN
China
Prior art keywords
solution
flower
copper
preparation
cupric salt
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201710868958.6A
Other languages
Chinese (zh)
Inventor
马海涛
尚胜艳
王云鹏
陈军
赵宁
黄明亮
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Dalian University of Technology
Original Assignee
Dalian University of Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Dalian University of Technology filed Critical Dalian University of Technology
Priority to CN201710868958.6A priority Critical patent/CN107498068A/en
Publication of CN107498068A publication Critical patent/CN107498068A/en
Pending legal-status Critical Current

Links

Classifications

    • 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
    • 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
    • B22F1/0553—Complex form nanoparticles, e.g. prism, pyramid, octahedron
    • 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
    • B22F1/07—Metallic powder characterised by particles having a nanoscale microstructure
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Nanotechnology (AREA)
  • Inorganic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • General Physics & Mathematics (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Composite Materials (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Manufacture Of Metal Powder And Suspensions Thereof (AREA)

Abstract

A preparation method of flower-shaped nano copper, belonging to the technical field of micro/nano material preparation. The method comprises the following specific steps: preparing soluble divalent copper salt solution and sodium hypophosphite solution, using a surfactant dispersing agent and a protective agent to prevent nano copper from agglomerating and oxidizing in the preparation process, preheating in a water bath at the temperature of 30-150 ℃, uniformly mixing the solution and the sodium hypophosphite solution after reaching a preset temperature, reacting for a period of time until the solution is wine red, namely generating flower-shaped nano copper particles, washing, centrifuging, and drying in a vacuum drying oven at the temperature of 50 ℃ for 4-6 hours to obtain a finished product. The invention takes the sodium hypophosphite with mild reaction as a reducing agent, avoids the potential safety hazard caused by using an over-strong reducing agent, has simple process and good repeatability, and the prepared flower-shaped nano copper material has novel structure, uniform appearance and size, good dispersibility, high purity and certain oxidation resistance, can be applied to large-scale production, and is suitable for being used as a catalyst, a conductive filler, an anti-corrosion and antibacterial material, a heat-conducting and anti-wear material and the like.

Description

一种花状纳米铜的制备方法A kind of preparation method of flower-shaped nano-copper

技术领域technical field

本发明涉及一种花状纳米铜的制备方法，属于微/纳材料制备技术领域。The invention relates to a method for preparing flower-shaped nano-copper, which belongs to the technical field of micro/nano material preparation.

背景技术Background technique

大量文献研究表明，材料的形貌和尺寸对材料的性能影响很大，尤其是当材料的尺度降到纳米时，材料的光学、热学、磁学以及其生物学等特性与常规的宏观材料相比较，均发生显著的变化。纳米技术的应用，使得功能材料的发展变得更加迅速，并带动了很多高新技术领域的快速发展，这就使纳米材料具有更广阔的应用前景。A large number of literature studies have shown that the shape and size of materials have a great influence on the performance of materials, especially when the scale of materials is reduced to nanometers, the optical, thermal, magnetic and biological properties of materials are comparable to those of conventional macroscopic materials. In comparison, significant changes occurred. The application of nanotechnology has made the development of functional materials more rapid, and led to the rapid development of many high-tech fields, which makes nanomaterials have broader application prospects.

纳米铜作为一种铜纳米材料具有良好的导电性能、催化性能及光学性能等，纳米铜粉其颗粒极小且质地柔软，具有良好的抗磨耐磨性，也是一种良好的润滑油添加剂。纳米铜粉用于制造导电浆料，可以大幅度提高材料的导电性能，且价格低于其他贵金属（如银和钯等），在电子封装领域、微电子领域以及粉末冶金领域有着极高的应用价值。纳米铜粉尺寸小，比表面积大，表面原子配位数严重不足，且存在大量的缺陷，因而具有催化活性高、选择性好及催化效率高等特点，纳米铜粉作为催化剂，可提高反应效率，控制反应温度，优化反应途径，甚至使原本不能进行的反应成为可能，使其在催化领域的研究和应用日益深入和扩大。As a copper nanomaterial, nano-copper has good electrical conductivity, catalytic performance and optical properties, etc. Nano-copper powder has extremely small particles and soft texture, has good wear resistance and wear resistance, and is also a good lubricating oil additive. Nano-copper powder is used to make conductive paste, which can greatly improve the conductivity of the material, and the price is lower than other precious metals (such as silver and palladium, etc.), and has extremely high applications in the fields of electronic packaging, microelectronics and powder metallurgy value. Nano-copper powder is small in size, large in specific surface area, seriously insufficient in the coordination number of surface atoms, and has a large number of defects, so it has the characteristics of high catalytic activity, good selectivity and high catalytic efficiency. As a catalyst, nano-copper powder can improve the reaction efficiency. Controlling the reaction temperature, optimizing the reaction pathway, and even making the reaction that could not be carried out originally possible, makes its research and application in the field of catalysis deepen and expand day by day.

目前，已经发展出了各种方法制备形貌新颖的铜纳米结构，有纳米球、纳米棒、纳米管、纳米线、纳米片、多空立方体以及用铜纳米颗粒自组装形成的多级结构，而三维花状结构纳米铜还鲜有报导。At present, various methods have been developed to prepare copper nanostructures with novel shapes, including nanospheres, nanorods, nanotubes, nanowires, nanosheets, hollow cubes, and multi-level structures formed by self-assembly of copper nanoparticles. However, the three-dimensional flower-like structure of nano-copper is rarely reported.

发明内容Contents of the invention

本发明的目的在于提出一种花状纳米铜的制备方法。该制备方法采用水浴或者油浴加热条件，将反应物搅拌均匀混合，用液相还原法还原出花状纳米铜，实现纳米铜可控制备过程。该制备方法工艺简单，尺寸可控、纯度高且可应用于大规模生产。The purpose of the present invention is to propose a preparation method of flower-shaped nano-copper. The preparation method adopts the heating condition of a water bath or an oil bath, stirs and mixes the reactants evenly, and reduces the flower-shaped nano-copper by a liquid phase reduction method, thereby realizing a controllable preparation process of the nano-copper. The preparation method has simple process, controllable size, high purity and can be applied to large-scale production.

本发明采用的技术方案是：一种花状纳米铜的制备方法，包括以下步骤：The technical solution adopted in the present invention is: a preparation method of flower-shaped nano-copper, comprising the following steps:

步骤1、将二价铜盐溶于溶剂中配成浓度为0.05-10mol/L的二价铜盐前驱体溶液，再在二价铜盐前驱体溶液中加入表面活性剂，表面活性剂用量为所用二价铜盐质量的5－20％，制得的混合液加热到温度30-150℃备用；Step 1. Dissolve the divalent copper salt in the solvent to form a divalent copper salt precursor solution with a concentration of 0.05-10mol/L, and then add a surfactant to the divalent copper salt precursor solution. The amount of the surfactant is The mass of the divalent copper salt used is 5-20%, and the prepared mixed solution is heated to a temperature of 30-150°C for use;

步骤2、将还原剂次亚磷酸钠溶解于溶剂中，配制成0.05-10mol/L的还原剂溶液，并调整PH值，使其在2-5酸性环境，预热到温度30-150℃备用；Step 2. Dissolve the reducing agent sodium hypophosphite in the solvent, prepare a reducing agent solution of 0.05-10mol/L, and adjust the pH value to make it in an acidic environment of 2-5, preheat to a temperature of 30-150°C for later use ;

步骤3、将二价铜盐前驱体溶液和还原剂溶液边混合边在转速为200-1000r/min的转速下搅拌均匀，二价铜盐与还原剂的摩尔比为1:1-1:10，并在30-150℃水浴或者油浴条件下保温10-240min，溶液由蓝色变为酒红色产物，保持温度不变维持反应10-30min；Step 3. Mix the divalent copper salt precursor solution and the reducing agent solution while stirring evenly at a speed of 200-1000r/min, and the molar ratio of the divalent copper salt to the reducing agent is 1:1-1:10 , and keep warm for 10-240min under the condition of 30-150℃ water bath or oil bath, the solution turns from blue to wine red product, keep the temperature unchanged and keep the reaction for 10-30min;

步骤4、所述产物分别经去离子水洗涤3-5次、无水乙醇洗涤3-5次后经过离心分离，用真空干燥箱在50℃干燥4-6h，得到花状纳米铜成品。Step 4. The product is washed 3-5 times with deionized water and 3-5 times with absolute ethanol, then centrifuged and dried in a vacuum oven at 50° C. for 4-6 hours to obtain a flower-shaped nano-copper product.

所述二价铜盐选用硝酸铜、硫酸铜或醋酸铜。The divalent copper salt is selected from copper nitrate, copper sulfate or copper acetate.

所述溶剂选用去离子水、乙醇、乙二醇、苯、甲苯。Described solvent selects deionized water, ethanol, ethylene glycol, benzene, toluene for use.

所述表面活性剂选用聚乙烯吡咯烷酮、柠檬酸、十二烷基苯磺酸钠、十六烷基三甲基溴化铵、明胶或油酸。The surfactant is selected from polyvinylpyrrolidone, citric acid, sodium dodecylbenzenesulfonate, cetyltrimethylammonium bromide, gelatin or oleic acid.

所述二价铜盐溶液和还原剂溶液的混合方式是滴加或者直接混合。The method of mixing the divalent copper salt solution and the reducing agent solution is dropwise or direct mixing.

本发明专利的构思如下：本发明采用还原性能较强且安全稳定的次亚磷酸钠还原剂，并在二价铜盐前驱体溶液以及次亚磷酸钠还原剂溶液浓度较高的情况下实现Cu2+的还原过程，在还原剂充足的情况下导致在Cu2+被还原成铜单质初期有大量纳米铜晶核生成，尽管如此，但过高的二价铜盐浓度，使Cu2+浓度保持在过饱和状态，从而使铜晶核持续大量生成，故其生长过程受到抑制，同时由于纳米铜晶核粒径极小，表面能极高，极不稳定，只能通过组装在一起降低表面能，从而形成稳定三维花状结构。液相法是目前实验室和工业上制备纳米铜颗粒常用主要方法之一，具体是指将合适的可溶性金属盐溶解，通过各种途径使二价铜离子在溶液中还原形成具有一定形状和大小的颗粒，再经过后处理得到超细铜颗粒的方法，具有可精确控制化学组成，定量地掺杂以制备性能良好的复合粒子，制备的纳米颗粒表面活性高，纯度高容易控制粒子的形状和粒度，设备简单，工艺流程短以及易于工业化生产等特点。The idea of the patent of the present invention is as follows: the present invention adopts sodium hypophosphite reducing agent with strong reducing performance and is safe and stable, and realizes Cu The reduction process of 2+ leads to the generation of a large number of nano-copper crystal nuclei in the early stage when Cu 2+ is reduced to copper simple substance in the case of sufficient reducing agent. However, the excessively high concentration of divalent copper salt makes the concentration of Cu 2+ Keep in a supersaturated state, so that the copper crystal nuclei continue to be generated in large quantities, so their growth process is inhibited. At the same time, because the nano-copper crystal nuclei have extremely small particle size, high surface energy, and are extremely unstable, the surface energy can only be reduced by assembling together. able to form a stable three-dimensional flower-like structure. The liquid phase method is one of the main methods commonly used to prepare nano-copper particles in the laboratory and industry. Specifically, it refers to dissolving a suitable soluble metal salt, and reducing divalent copper ions in the solution to form a certain shape and size through various methods. The method of obtaining ultra-fine copper particles after post-processing has the advantages of precisely controlling the chemical composition and quantitatively doping to prepare composite particles with good performance. The prepared nanoparticles have high surface activity and high purity. It is easy to control the shape and shape of the particles. Granularity, simple equipment, short process flow and easy industrial production.

本发明的有益效果是：采用简便的化学还原法制备出花状纳米铜，与现有技术相比有以下优点：The beneficial effects of the present invention are: the flower-shaped nano-copper is prepared by a simple and convenient chemical reduction method, which has the following advantages compared with the prior art:

（1）工艺流程简便易行，反应条件温和，反应时间短，在较低温度下便可合成具有复杂形貌的花状纳米铜。(1) The process is simple and easy, the reaction conditions are mild, and the reaction time is short. Flower-like nano-copper with complex morphology can be synthesized at a relatively low temperature.

（2）设备简单，不需要复杂精密的大型仪器设备，降低生产投资成本以及操作费用。(2) The equipment is simple and does not require complex and sophisticated large-scale instruments and equipment, reducing production investment costs and operating costs.

（3）产品性能优异，从SEM图片可以看出制备出的纳米铜形貌为三维花状结构，粒径均匀，从TEM可以看出花状纳米铜是有很多5-10nm的小颗粒组装而成的，故三维花状结构具有更大的表面活性以及表面粗糙度。从XRD可以看出，仅有铜的衍射峰，没有氧化铜的衍射峰出现，表面制出的花状纳米铜纯度高结晶度好，且就有一定抗氧化能力。(3) The product has excellent performance. It can be seen from the SEM pictures that the prepared nano-copper has a three-dimensional flower-like structure and uniform particle size. It can be seen from the TEM that the flower-shaped nano-copper is assembled with many small particles of 5-10nm. Therefore, the three-dimensional flower-like structure has greater surface activity and surface roughness. It can be seen from XRD that there are only diffraction peaks of copper, and no diffraction peaks of copper oxide appear. The flower-shaped nano-copper produced on the surface has high purity and good crystallinity, and has a certain oxidation resistance.

附图说明Description of drawings

图1是花状纳米铜的XRD谱图。Figure 1 is the XRD spectrum of flower-like nano-copper.

图2是花状纳米铜的SEM扫描电镜图。Fig. 2 is a SEM scanning electron micrograph of flower-like nano-copper.

图3是花状纳米铜的TEM透射电镜图。Fig. 3 is a TEM transmission electron microscope image of the flower-like nano-copper.

具体实施方式detailed description

下面结合实施例对本发明进行详细说明，实施例仅是本发明的优选实施方式，不是对本发明的限定。The present invention will be described in detail below in conjunction with examples, which are only preferred implementations of the present invention, and are not limitations of the present invention.

实施例1Example 1

（1） 现将CuSO4·5H2O配成摩尔浓度为0.1mol/L二价铜盐溶液，再在二价铜盐中加入表面活性剂，表面活性剂用量为所用二价铜盐质量的5%，并将制得的混合液加热到60℃备用。(1) Now make CuSO 4 5H 2 O into a divalent copper salt solution with a molar concentration of 0.1mol/L, and then add a surfactant to the divalent copper salt. The amount of the surfactant is the mass of the divalent copper salt used 5%, and the prepared mixture was heated to 60°C for later use.

（2） 将还原剂次亚磷酸钠溶解于去离子水中，配制成0.1mol/L的溶液，并调整PH值，使其在2-4酸性环境，预热到一定温度备用。(2) Dissolve the reducing agent sodium hypophosphite in deionized water to prepare a 0.1mol/L solution, and adjust the pH value to make it in an acidic environment of 2-4, preheat to a certain temperature for later use.

（3） 分别取相同体积的二价铜盐前驱体溶液和还原剂溶液，边混合边在转速为600r/min的转速下搅拌均匀，120min左右，溶液由蓝色变为酒红色，说明溶液中有纳米铜生成，并在60℃保温维持反应50min；(3) Take the same volume of divalent copper salt precursor solution and reducing agent solution respectively, and stir evenly at a speed of 600r/min while mixing. After about 120min, the solution changes from blue to wine red, indicating that the solution is Nano-copper is generated, and the reaction is maintained at 60°C for 50 minutes;

（4） 将以上步骤所得产物分别经去离子水洗涤3-5次、无水乙醇洗涤3-5次后经过离心分离，用真空干燥箱在50℃干燥4-6h，即可得到花状纳米铜成品。(4) Wash the product obtained in the above steps for 3-5 times with deionized water and 3-5 times with absolute ethanol, then centrifuge and dry in a vacuum oven at 50°C for 4-6 hours to obtain flower-shaped nano Finished copper.

实施例2Example 2

（1）现将CuSO4·5H2O配成摩尔浓度为0.2mol/L二价铜盐溶液，再在二价铜盐中加入表面活性剂，表面活性剂用量为所用二价铜盐质量的10%，并将制得的混合液加热到一定温度60℃备用。(1) Now make CuSO 4 5H 2 O into a divalent copper salt solution with a molar concentration of 0.2mol/L, and then add a surfactant to the divalent copper salt. The amount of the surfactant is the mass of the divalent copper salt used 10%, and the prepared mixture was heated to a certain temperature of 60°C for later use.

（2）将还原剂次亚磷酸钠溶解于去离子水中，配制成0.2mol/L的溶液，并调整PH值，使其在2-4酸性环境，预热到一定温度备用。(2) Dissolve the reducing agent sodium hypophosphite in deionized water to prepare a 0.2mol/L solution, and adjust the pH value to make it in an acidic environment of 2-4, preheat to a certain temperature for later use.

（5） 二价铜盐前驱体溶液和还原剂溶液体积比为1:2，边混合边在转速为600r/min的转速下搅拌均匀，并在60℃水浴或者油浴条件下保温60min左右，溶液由蓝色变为酒红色，说明溶液中有纳米铜生成，并在60℃保温维持反应50min；(5) The volume ratio of the divalent copper salt precursor solution and the reducing agent solution is 1:2, stir evenly at a speed of 600r/min while mixing, and keep warm for about 60min in a water bath or oil bath at 60°C. The solution turns from blue to wine red, indicating that nano-copper is formed in the solution, and the reaction is maintained at 60°C for 50 minutes;

（3）将以上步骤所得的产物分别经去离子水洗涤3-5次、无水乙醇洗涤3-5次后经过离心分离，用真空干燥箱在50℃干燥4-6h，即可得到花状纳米铜。(3) Wash the product obtained in the above steps for 3-5 times with deionized water and 3-5 times with absolute ethanol, then centrifuge and dry at 50°C for 4-6 hours in a vacuum oven to obtain a flower-like nano copper.

实施例3Example 3

（1）现将CuSO4·5H2O配成摩尔浓度为0.3mol/L二价铜盐溶液，再在二价铜盐中加入表面活性剂，表面活性剂用量为所用二价铜盐质量的15%，并将制得的混合液加热到一定温度80℃备用。(1) Now make CuSO 4 5H 2 O into a divalent copper salt solution with a molar concentration of 0.3mol/L, and then add a surfactant to the divalent copper salt. The amount of the surfactant is the mass of the divalent copper salt used 15%, and the prepared mixture was heated to a certain temperature of 80°C for later use.

（2）将还原剂次亚磷酸钠溶解于去离子水中，配制成0.3mol/L的溶液，并调整PH值，使其在2-4酸性环境，预热到一定温度备用。(2) Dissolve the reducing agent sodium hypophosphite in deionized water to prepare a 0.3mol/L solution, and adjust the pH value to make it in an acidic environment of 2-4, and preheat it to a certain temperature for later use.

（6） 分别取相同体积的二价铜盐前驱体溶液和还原剂溶液，边混合边在转速为500r/min的转速下搅拌均匀，并在水浴或者油浴条件下保持一定温度80℃不变，20min左右，溶液由蓝色变为酒红色，说明溶液中有纳米铜生成，并在60℃保温维持反应50min；(6) Take the same volume of divalent copper salt precursor solution and reducing agent solution, stir evenly at a speed of 500r/min while mixing, and keep a certain temperature of 80°C under the condition of water bath or oil bath , about 20 minutes, the solution changed from blue to wine red, indicating that nano-copper was formed in the solution, and the reaction was maintained at 60°C for 50 minutes;

（3）将以上步骤所得产物分别经去离子水洗涤3-5次、无水乙醇洗涤3-5次后经过离心分离，用真空干燥箱在50℃干燥4-6h，即可得到花状纳米铜。(3) Wash the product obtained in the above steps for 3-5 times with deionized water and 3-5 times with absolute ethanol, then centrifuge and dry in a vacuum oven at 50°C for 4-6 hours to obtain flower-shaped nano copper.

实施例4Example 4

（1）现将CuSO4·5H2O配成摩尔浓度为0.4mol/L二价铜盐溶液，再在二价铜盐中加入表面活性剂，表面活性剂用量为所用二价铜盐质量的20%，并将制得的混合液加热到一定温度90℃备用。(1) Now make CuSO 4 5H 2 O into a divalent copper salt solution with a molar concentration of 0.4mol/L, and then add a surfactant to the divalent copper salt. The amount of the surfactant is the mass of the divalent copper salt used 20%, and the prepared mixture was heated to a certain temperature of 90°C for later use.

（2）将还原剂次亚磷酸钠溶解于去离子水中，配制成0.4mol/L的溶液，并调整PH值，使其在2-4酸性环境，预热到一定温度备用。(2) Dissolve the reducing agent sodium hypophosphite in deionized water to prepare a 0.4mol/L solution, and adjust the pH value to make it in an acidic environment of 2-4, preheat to a certain temperature for later use.

（7） 分别取相同体积的二价铜盐前驱体溶液和还原剂溶液，边混合边在转速为400r/min的转速下搅拌均匀，并在水浴或者油浴条件下保持一定温度90℃不变，10min左右，溶液由蓝色变为酒红色，说明溶液中有纳米铜生成，并在60℃保温维持反应50min；(7) Take the same volume of divalent copper salt precursor solution and reducing agent solution, stir evenly at a speed of 400r/min while mixing, and keep a certain temperature of 90°C under the condition of water bath or oil bath , about 10 minutes, the solution changed from blue to wine red, indicating that nano-copper was formed in the solution, and the reaction was maintained at 60°C for 50 minutes;

（3）将以上步骤所得产物分别经去离子水洗涤3-5次、无水乙醇洗涤3-5次后经过离心分离，用真空干燥箱在50℃干燥4-6h，即可得到花状纳米铜。(3) Wash the product obtained in the above steps for 3-5 times with deionized water and 3-5 times with absolute ethanol, then centrifuge and dry in a vacuum oven at 50°C for 4-6 hours to obtain flower-shaped nano copper.

Claims (5)

1. a kind of preparation method of flower-like nanometer copper, it is characterized in that：Comprise the following steps：
Step 1, cupric salt is dissolved in the cupric salt precursor solution for being made into that concentration is 0.05-10mol/L in solvent, then Surfactant is added in cupric salt precursor solution, dosage of surfactant is the 5-20% of cupric salt quality used, It is standby that obtained mixed liquor is heated to 30-150 DEG C of temperature；
Step 2, reducing agent sodium hypophosphite is dissolved in solvent, is configured to 0.05-10mol/L reductant solution, and adjust Whole pH value, make it that it is standby to be preheating to 30-150 DEG C of temperature in 2-5 sour environments；
Step 3, the rotating speed by cupric salt precursor solution and reductant solution in mixing in rotating speed for 200-1000r/min Under stir, the mol ratio of cupric salt and reducing agent is 1:1-1:10, and under the conditions of 30-150 DEG C of water-bath or oil bath 10-240min is incubated, generates nanometer copper product in the solution, solution is changed into claret from blueness, is incubated 10-30min；
Step 4, the product are used respectively after deionized water washing 3-5 times, absolute ethyl alcohol wash 3-5 times by centrifuging Vacuum drying chamber obtains flower-like nanometer copper finished product in 50 DEG C of dry 4-6h.
2. a kind of preparation method of flower-like nanometer copper according to claim 1, it is characterized in that：The cupric salt selects nitre Sour copper, copper sulphate or copper acetate.
3. a kind of preparation method of flower-like nanometer copper according to claim 1, it is characterized in that：The solvent selects deionization Water, ethanol, ethylene glycol, benzene, toluene.
4. a kind of preparation method of flower-like nanometer copper according to claim 1, it is characterized in that：The surfactant is selected Polyvinylpyrrolidone, citric acid, neopelex, cetyl trimethylammonium bromide, gelatin or oleic acid.
5. a kind of preparation method of flower-like nanometer copper according to claim 1, it is characterized in that：The cupric salt solution and The hybrid mode of reductant solution is to be added dropwise or directly mix.
CN201710868958.6A 2017-09-22 2017-09-22 A kind of preparation method of flower-shaped nano-copper Pending CN107498068A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201710868958.6A CN107498068A (en) 2017-09-22 2017-09-22 A kind of preparation method of flower-shaped nano-copper

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201710868958.6A CN107498068A (en) 2017-09-22 2017-09-22 A kind of preparation method of flower-shaped nano-copper

Publications (1)

Publication Number Publication Date
CN107498068A true CN107498068A (en) 2017-12-22

Family

ID=60698380

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201710868958.6A Pending CN107498068A (en) 2017-09-22 2017-09-22 A kind of preparation method of flower-shaped nano-copper

Country Status (1)

Country Link
CN (1) CN107498068A (en)

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108277458A (en) * 2018-04-25 2018-07-13 河南科技大学 A method of preparing free state flower-shape copper particle without template
CN109822108A (en) * 2018-11-27 2019-05-31 西安航天化学动力有限公司 A kind of nano copper particle preparation method of the surface with bayonet fittings
CN110026550A (en) * 2018-11-07 2019-07-19 扬州工业职业技术学院 A kind of nano zero-valence copper and preparation method and application
CN113000855A (en) * 2021-03-23 2021-06-22 中国科学技术大学先进技术研究院 Preparation method of micro-nano copper powder
CN113084186A (en) * 2021-03-30 2021-07-09 武汉大学 Flower-shaped copper particle and preparation method thereof
CN114535863A (en) * 2022-03-25 2022-05-27 重庆平创半导体研究院有限责任公司 Self-sintered nano-copper soldering paste, preparation method and use method thereof
CN114892300A (en) * 2022-06-02 2022-08-12 浙江理工大学 Preparation method of antibacterial antiviral thermal fiber
CN115028187A (en) * 2022-08-02 2022-09-09 沈阳工业大学 Chemical preparation method of copper oxide nanoparticles

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06212241A (en) * 1991-06-19 1994-08-02 Nippon Steel Corp Method for vacuum-refining molten steel by using large diameter immersion tube
CN1709617A (en) * 2004-06-18 2005-12-21 中国科学院兰州化学物理研究所 Preparation method of nano copper particles
CN102198513A (en) * 2011-05-27 2011-09-28 中南大学 Method for preparing nano copper particle
CN102601381A (en) * 2012-03-11 2012-07-25 郭雨 Copper nano powder and preparation method of copper nano powder
CN105598466A (en) * 2016-01-18 2016-05-25 大连理工大学 A kind of synthesis method of fluorescent copper nanocluster

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06212241A (en) * 1991-06-19 1994-08-02 Nippon Steel Corp Method for vacuum-refining molten steel by using large diameter immersion tube
CN1709617A (en) * 2004-06-18 2005-12-21 中国科学院兰州化学物理研究所 Preparation method of nano copper particles
CN102198513A (en) * 2011-05-27 2011-09-28 中南大学 Method for preparing nano copper particle
CN102601381A (en) * 2012-03-11 2012-07-25 郭雨 Copper nano powder and preparation method of copper nano powder
CN105598466A (en) * 2016-01-18 2016-05-25 大连理工大学 A kind of synthesis method of fluorescent copper nanocluster

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108277458B (en) * 2018-04-25 2020-01-07 河南科技大学 A method for preparing free-form flower-shaped copper particles without template
CN108277458A (en) * 2018-04-25 2018-07-13 河南科技大学 A method of preparing free state flower-shape copper particle without template
CN110026550A (en) * 2018-11-07 2019-07-19 扬州工业职业技术学院 A kind of nano zero-valence copper and preparation method and application
CN109822108A (en) * 2018-11-27 2019-05-31 西安航天化学动力有限公司 A kind of nano copper particle preparation method of the surface with bayonet fittings
CN113000855B (en) * 2021-03-23 2024-04-19 中国科学技术大学先进技术研究院 Preparation method of micro-nano copper powder
CN113000855A (en) * 2021-03-23 2021-06-22 中国科学技术大学先进技术研究院 Preparation method of micro-nano copper powder
CN113084186A (en) * 2021-03-30 2021-07-09 武汉大学 Flower-shaped copper particle and preparation method thereof
CN114535863A (en) * 2022-03-25 2022-05-27 重庆平创半导体研究院有限责任公司 Self-sintered nano-copper soldering paste, preparation method and use method thereof
CN114535863B (en) * 2022-03-25 2024-01-16 重庆平创半导体研究院有限责任公司 Self-sintered nano copper soldering paste, preparation method and use method thereof
CN114892300A (en) * 2022-06-02 2022-08-12 浙江理工大学 Preparation method of antibacterial antiviral thermal fiber
CN114892300B (en) * 2022-06-02 2024-05-28 浙江理工大学 Preparation method of antibacterial antiviral thermal fiber
CN115028187A (en) * 2022-08-02 2022-09-09 沈阳工业大学 Chemical preparation method of copper oxide nanoparticles
CN115028187B (en) * 2022-08-02 2024-04-19 沈阳工业大学 A chemical preparation method of copper oxide nanoparticles

Similar Documents

Publication Publication Date Title
CN107498068A (en) A kind of preparation method of flower-shaped nano-copper
JP2022116130A (en) Method for manufacturing silver-coated copper nanowire having core-shell structure by using chemical reduction method
CN104985190B (en) Synthetic method of flower-like silver microparticles
CN102756131B (en) Preparation method for micro-order platy silver powder
CN101693297A (en) Preparation method of copper nanoparticles with different particle diameters
CN106077695B (en) A kind of preparation method of high-copper tungsten copper nano composite powder
CN104646683A (en) Spherical silver powder with controllable granularity and preparation method thereof
CN113600829B (en) Macro preparation method of ultra-small size nano-copper powder
CN101716685A (en) Method for preparing spherical superfine silver powder by using chemical reduction method
CN110899722B (en) A kind of thin single-plate silver powder synthesized by chemical method and preparation method thereof
CN108840313B (en) A kind of preparation method of multi-level spherical nickel diselenide
CN103352132A (en) Copper-nickel nanowire and preparation method thereof
CN108620601A (en) A method of it is nanocrystalline to prepare sheet Cu under room temperature
CN102557106A (en) Preparation method of cuprous oxide hollow nanometer cubes
CN102389949A (en) Method for preparing sea urchin-shaped nanometer copper particles
CN102838172A (en) Method for preparing nanometer alpha-Fe2O3 material
CN108723379A (en) A kind of preparation method of multi-principal elements alloy nano-powder
CN103691965A (en) Preparation method for copper/silver heterojunction nano-particles
CN103273075A (en) HPAA nano-iron particle dispersing method
CN114105107B (en) Highly monodisperse MoSe with different morphologies 2 Method for preparing nano material
CN105290419B (en) Herring-bone form nuclear shell structure nano monel powder and preparation method thereof
CN108161024A (en) A kind of preparation method of the micro-nano metallic copper of threadiness
CN113814408B (en) Preparation and component regulation and control method of CuPd alloy nanocrystalline
CN110681872A (en) A kind of preparation method of copper/silver corn-like structure nanoparticles
CN110125433A (en) A method of preparing copper nanoparticle at room temperature

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
WD01 Invention patent application deemed withdrawn after publication

Application publication date: 20171222

WD01 Invention patent application deemed withdrawn after publication