WO2016023405A1 - 一种在氧化物陶瓷粉体表面包覆金属纳米粒子的方法 - Google Patents

一种在氧化物陶瓷粉体表面包覆金属纳米粒子的方法 Download PDF

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WO2016023405A1
WO2016023405A1 PCT/CN2015/082892 CN2015082892W WO2016023405A1 WO 2016023405 A1 WO2016023405 A1 WO 2016023405A1 CN 2015082892 W CN2015082892 W CN 2015082892W WO 2016023405 A1 WO2016023405 A1 WO 2016023405A1
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powder
metal
nanoparticles
metal organic
oxide
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PCT/CN2015/082892
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English (en)
French (fr)
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张建峰
吴玉萍
郭文敏
洪晟
李改叶
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河海大学
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Priority to SG11201700921PA priority Critical patent/SG11201700921PA/en
Priority to GB1700878.0A priority patent/GB2542321B8/en
Priority to AU2015303706A priority patent/AU2015303706B2/en
Priority to DE112015003242.8T priority patent/DE112015003242B4/de
Priority to US15/328,094 priority patent/US10112874B2/en
Publication of WO2016023405A1 publication Critical patent/WO2016023405A1/zh

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Definitions

  • the invention particularly relates to a method for coating metal nanoparticles on the surface of an oxide ceramic powder, and belongs to the field of material processing engineering.
  • a ceramic powder especially an oxide powder such as alumina (Al 2 O 3 ), zirconium oxide (ZrO 2 ), silicon oxide (SiO 2 ), or triiron tetroxide (Fe 3 O 4 )
  • oxide powder such as alumina (Al 2 O 3 ), zirconium oxide (ZrO 2 ), silicon oxide (SiO 2 ), or triiron tetroxide (Fe 3 O 4 )
  • oxide powder such as alumina (Al 2 O 3 ), zirconium oxide (ZrO 2 ), silicon oxide (SiO 2 ), or triiron tetroxide (Fe 3 O 4 )
  • oxide powder New properties such as catalytic properties, electromagnetic properties, etc., or effectively change the surface properties of the powder, such as electrochemical performance and diffusion capacity during sintering. Therefore, the development of coating technology and its application in many fields such as structural and functional ceramics have received extensive attention.
  • the preparation methods of the metal-coated ceramic powder mainly include a mechanical mixing method, a sol-gel method, an electroless plating method, and a chemical vapor deposition method.
  • the mechanical mixing method is the simplest, but powders having a large difference in density properties are often difficult to mix uniformly.
  • the sol-gel method is a method in which a raw material is dispersed in a solvent, a sol and a gel are formed by hydrolysis, and a desired nanoparticle material is obtained by drying and heat treatment.
  • Rodeghiero et al. have obtained a Ni-Al 2 O 3 powder by a sol-gel method.
  • Electroless plating coats the powder through an electrochemical process without an applied electric field. It has the advantages of simple equipment and designability of coating properties, and is a widely used method.
  • Cao Xiaoguo et al. used electroless plating to coat silver on the surface of Fe 3 O 4 powder with formaldehyde as a reducing agent in a water/ethanol medium. The test results show that the uniform and complete silver layer coated on the surface of Fe 3 O 4 powder effectively improves the bulk conductivity of Fe 3 O 4 powder. (Material Engineering, 2007, 4, pp 57-60). Mehmet Uysal et al. obtained Ni-coated Al 2 O 3 powder by electroplating.
  • the Al 2 O 3 powder first pretreated the Al 2 O 3 powder in the SnCl 2 solution to increase the surface activity of the Al 2 O 3 powder, and then used NiCl 2 as the Ni source to control the pH of the solution, the concentration of NiCl 2 and the like.
  • the parameters were such that the surface of the Al 2 O 3 powder was coated with uniformly distributed Ni nanoparticles (Ceramics International, 2013, 39, pp 5485-5493).
  • powder electroless plating has certain special characteristics. In order to achieve uniform deposition of the surface modified layer, the surface of the powder should have good catalytic activity.
  • the plating solution should have a certain stability to avoid spontaneous decomposition. Therefore, its application range is limited.
  • the chemical vapor deposition method forms a solid deposit by agglomerating a raw material gas on the surface of the particle, thereby achieving a coating effect on the powder particles.
  • Jiang Yong et al. used a chemical vapor deposition method to coat a carbon layer on the surface of a LiFePO 4 powder having a particle diameter of 200 nm (Journal of the Chinese Academy of Ceramics, 2008, 36, pp1295 to 1299).
  • Zhang et al. used chemical vapor deposition method to use metal organic materials as raw materials. The raw materials were heated and volatilized, and Ar gas was introduced into the high temperature reaction chamber. The Ni nanoparticles were coated on the alumina surface by pyrolysis. However, at higher coating temperatures, the nanoparticles tend to agglomerate and grow, resulting in a decrease in hardness and strength after sintering of the powder (Journal of the European Ceramic Society, 2014, 34, pp 435-441).
  • An object of the present invention is to provide a method for uniformly coating metal nanoparticles on the surface of an oxide ceramic powder, and by uniformly mixing the metal organic raw material and the coated powder in advance, uniformizing the metal nanoparticles in the process of heating the reaction chamber Coating, reducing the coating temperature and improving the uniformity of dispersion.
  • the present invention adopts the following technical solution: a method for coating metal nanoparticles on the surface of an oxide ceramic, comprising the following steps:
  • the oxide ceramic powder and the metal organic raw material are compounded according to a weight ratio (1:1) to (10:1), and the mixture is ground and mixed for 1 to 3 hours to obtain a mixed powder, and the ground mixed powder is placed in a rotation. In the reactor, the rotating reactor is started to rotate;
  • step (3) Reducing the metal oxide in the step (2) to the metallic nanoparticles by introducing a reducing gas into the rotary reactor, and simultaneously cooling at a rate of 5 to 10 ° C / min, and then reducing the reduction after returning to room temperature.
  • the gas inlet valve stops the rotation of the rotary reactor, opens the instrument, removes the powder, sifts it, and collects the powder.
  • the oxide ceramic powder is any one of Al 2 O 3 , ZrO 2 , SiO 2 , MgO, and TiO 2 , and has a particle diameter of 100 nm to 100 ⁇ m and a purity of more than 95%.
  • the metal organic raw material is a stable organometallic compound formed by combining an alkyl group or an aromatic hydrocarbon group with a metal atom, and the kind thereof is selected according to the kind of the metal nanoparticle to be coated, such as when it is required to be coated on the surface of the oxidized ceramic powder.
  • the metal organic raw material is nickel (NiCp 2 ), tetrahydroxy nickel (Ni(CO) 4 ) and nickel acetate (Ni(CH 3 COO) 2 ⁇ 4H 2 O) Any one.
  • the metal organic material selected may be Cu(DPM) 2 .
  • the metal organic raw material selected is cobaltocene or hydroxycobalt.
  • the metal organic material selected is ferrocene.
  • the total mixed gas of the oxygen and argon gas introduced is 200 to 1000 Pa, wherein the partial pressure of oxygen is 50 to 200 Pa, and the temperature rising rate is 2 to 10 ° Cmin, and the rotation of the rotary reactor is performed.
  • the rate is 15 to 60 r/min.
  • the reducing gas is any one of hydrogen, carbon monoxide and methane, and the partial pressure of the reducing gas is 100 to 400 Pa.
  • the powder is sieved three times through 50 to 200 mesh.
  • the present invention provides a novel method capable of coating uniformly distributed metal nanoparticles on the surface of different oxide ceramic powders.
  • the surface of the different oxide ceramic powders is coated with a metal nanoparticle layer, thereby regulating the surface morphology and conductivity of the powder, so as to make the utilization rate of the material and the product.
  • the reliability is greatly improved, the preparation cycle is short, the energy consumption is low, the environment is friendly, the production cost is significantly reduced, and thus has a good industrial prospect.
  • the uniformity of the coating of the metal nanoparticles is improved; in addition, during the heating process, the oxidative decomposition of the metal nanoparticles is simultaneously performed, thereby reducing the reaction time at a high temperature and avoiding The coarsening and growth of metal nanoparticles.
  • Figure 1 is an X-ray diffraction pattern of Al 2 O 3 powder coated Ni nanoparticles in Example 1 : (a) before coating, (b) after coating;
  • Figure 2 is a transmission electron micrograph of the Al 2 O 3 powder coated Ni nanoparticles in Example 1;
  • Figure 3 is an X-ray diffraction pattern of ZrO 2 powder coated with Ni nanoparticles in Example 3;
  • Fig. 4 is a transmission electron micrograph of ZrO 2 powder coated Ni nanoparticles in Example 3.
  • Example 1 The surface of Al 2 O 3 powder was coated with Ni nanoparticles.
  • a commercial commercial 5 g of Al 2 O 3 powder (having a particle diameter of 500 nm) and 0.5 g of Ni(CO) 4 were mixed, placed in a rotary reactor, and the reactor was rotated at a rotation rate of 45 r/min.
  • a mixed gas of oxygen and Ar was introduced, and the total pressure of the mixed gas was 1000 Pa, wherein the partial pressure of oxygen was 100 Pa.
  • the heating rate is 8 ° C / min, the temperature is raised to 450 ° C and then incubated for 45 min, Ni(CO) 4 is oxidized to nickel oxide, then the oxygen supply valve is closed, and carbon monoxide is passed to reduce the metal oxide nickel oxide to metal nanoparticles. .
  • the partial pressure of carbon monoxide was 200 Pa, the reduction reaction time was 45 min, and then the temperature was lowered, and the cooling rate was 8 ° C / min.
  • the gas valve was closed, the rotation of the instrument was stopped, and the reactor was heated.
  • the instrument was turned on, the powder was taken out, and passed through a 100 mesh sieve three times to collect the powder.
  • the collected powders were characterized, and the results are shown in Figures 1 and 2.
  • 1 is an X-ray diffraction pattern of Al 2 O 3 powder coated Ni nanoparticles, where a is before coating and b is coated, which proves that Al 2 O 3 powder is successfully coated with Ni nanoparticles.
  • . 2 is a transmission electron micrograph of the Al 2 O 3 powder coated Ni nanoparticles. As can be seen from the figure, the Ni nanoparticles are uniformly coated on the surface of the Al 2 O 3 powder.
  • Example 2 The surface of Al 2 O 3 powder was coated with Cu nanoparticles.
  • a common commercial 5 g Al 2 O 3 powder (particle size: 100 nm) and 2 g of Cu (DPM) 2 (copper dipivaloylmethanate) are mixed, placed in a rotary reactor, the inlet valve of the rotary reactor is closed, and the rotation is started. The reactor was rotated and the rotation rate was adjusted to 60 r/min. Then, a mixed gas of oxygen and argon was introduced, and the total pressure of the mixed gas was 800 Pa, wherein the partial pressure of oxygen was 50 Pa.
  • the heating rate was set to 5 ° C / min, the temperature was raised to 400 ° C and then kept for 60 min, Cu (DPM) 2 was oxidized to copper oxide, then the oxygen supply valve was closed, and methane was reduced to reduce the metal oxide CuO to metallic nanoparticles.
  • the partial pressure of methane was 100 Pa, the reduction reaction time was 60 min, and then the temperature was lowered, and the cooling rate was 5 ° C / min.
  • the carbon monoxide inlet valve and the argon inlet valve were closed, the rotation of the instrument and the heating of the reactor were stopped, the instrument was turned on, the powder was taken out, and the powder was taken through a 200-mesh sieve three times to collect the powder.
  • Example 3 The surface of the ZrO 2 powder was coated with Ni nanoparticles.
  • a commercial commercial 5 g of ZrO 2 powder (particle size: 10 ⁇ m) and 5 g of NiCp 2 (nickelocene) were mixed, placed in a rotary reactor, and the reactor was rotated at a rotation rate of 15 r/min.
  • a mixed gas of oxygen and Ar was introduced, and the total pressure of the mixed gas was 800 Pa, wherein the partial pressure of oxygen was 200 Pa.
  • the heating rate is 7 ° C / min, the temperature is raised to 450 ° C and then kept for 30 min, thereby oxidizing NiCp 2 to NiO, then closing the oxygen supply valve, and introducing hydrogen to reduce the metal oxide NiO to metallic nanoparticles.
  • FIG. 3 is the X-ray diffraction pattern of ZrO 2 powder coated Ni nanoparticles, which proves that the ZrO 2 powder is successfully coated with Ni nanoparticles.
  • Fig. 4 is a transmission electron micrograph of ZrO 2 powder coated Ni nanoparticles. It can be seen from the figure that the Ni nanoparticles are uniformly coated on the surface of the ZrO 2 powder.
  • Example 4 The surface of the TiO 2 powder was coated with Co nanoparticles.
  • a common commercial 5 g TiO 2 powder (particle size: 50 ⁇ m) and 2 g of CoCp 2 (Cobaltocene) are mixed and placed in a rotary reactor, and the reactor is placed. Rotation, the rotation rate is 60r/min. A mixed gas of oxygen and Ar was introduced, and the total pressure of the mixed gas was 200 Pa, wherein the partial pressure of oxygen was 50 Pa.
  • the heating rate is 10 ° C / min, the temperature is raised to 400 ° C and then incubated for 15 min, thereby converting CoCp 2 into cobalt oxide, then closing the oxygen supply valve, and introducing methane to reduce the metal oxide cobalt oxide to metallic nanoparticles.
  • the partial pressure of methane was 100 Pa, the reduction reaction time was 15 in, and then the temperature was lowered, and the cooling rate was 10 ° C / min. After dropping to room temperature, close the gas valve, stop the instrument from rotating, turn on the instrument, remove the powder, and pass through a 50 mesh sieve three times to collect the powder.
  • Example 5 The surface of the SiO 2 powder was coated with Fe nanoparticles.
  • a common commercial 5 g SiO 2 powder (particle size: 100 ⁇ m) and 1 g of FeCp 2 (ferrocene) are mixed and placed in a rotary reactor, and the reactor is placed. Rotation, the rotation rate is 60r/min.
  • a mixed gas of oxygen and Ar was introduced, and the total pressure of the mixed gas was 800 Pa, wherein the partial pressure of oxygen was 10 Pa.
  • the heating rate is 8 ° C / min
  • the final reaction temperature is 500 ° C
  • the holding time is 30 min, thereby oxidizing FeCp 2 to iron oxide, then closing the oxygen supply valve, and introducing carbon monoxide to reduce the iron oxide to metallic nanoparticles.
  • the partial pressure of carbon monoxide was 200 Pa, the reduction reaction time was 30 min, and then the temperature was lowered at a rate of 8 ° C/min. After dropping to room temperature, close the gas valve, stop the instrument from rotating, turn on the instrument, remove the powder, and pass through a 50 mesh sieve three times to collect the powder.
  • Example 6 The surface of the MgO powder was coated with Co nanoparticles.
  • MgO powder particles size: 50 ⁇ m
  • CoCp 2 Cobaltocene
  • the rotation rate is 60 r/min.
  • a mixed gas of oxygen and Ar was introduced, and the total pressure of the mixed gas was 600 Pa, wherein the partial pressure of oxygen was 150 Pa.
  • the heating rate is 6 ° C / min, the temperature is raised to 400 ° C and then kept for 20 min, so that CoCp 2 is oxidized to cobalt oxide, then the oxygen supply valve is closed, and methane is introduced to reduce the metal oxide Co 2 O 3 to metallic nanoparticles.
  • the partial pressure of methane was 100 Pa, the reduction reaction time was 15 in, and then the temperature was lowered, and the cooling rate was 10 ° C / min. After dropping to room temperature, close the gas valve, stop the instrument from rotating, turn on the instrument, remove the powder, and pass through a 50 mesh sieve three times to collect the powder.
  • Example 7 The surface of the SiO 2 powder was coated with Ni nanoparticles.
  • Ni nanoparticles coated on the surface of SiO 2 powder As an example, firstly, a common commercial 5 g SiO 2 powder (particle size: 100 ⁇ m) and 3 g of Ni(CH 3 COO) 2 ⁇ 4H 2 O are mixed and placed in a rotary reaction. In the reactor, the reactor was rotated at a rate of 50 r/min. A mixed gas of oxygen and Ar was introduced, and the total pressure of the mixed gas was 800 Pa, wherein the partial pressure of oxygen was 15 Pa.
  • the heating rate is 8 ° C / min
  • the final reaction temperature is 500 ° C
  • the holding time is 30 min, so Ni(CH 3 COO) 2 ⁇ 4H 2 O is oxidized to nickel oxide, then the oxygen supply valve is closed, and carbon monoxide is introduced to pass the nickel oxide. Reduced to metallic nanoparticles.
  • the partial pressure of carbon monoxide was 200 Pa
  • the reduction reaction time was 30 min
  • the temperature was lowered at a rate of 8 ° C/min.
  • close the gas valve stop the instrument from rotating, turn on the instrument, remove the powder, and pass through a 50 mesh sieve three times to collect the powder.

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Abstract

一种在氧化物陶瓷粉体表面均匀包覆无碳杂质的金属纳米粒子的方法，包括将金属有机原料和氧化物陶瓷粉末研磨混合后放入旋转反应室中，然后在旋转加热的条件通入氧化性气体将金属有机原料氧化为金属氧化物，最后通入还原性气体，将金属氧化物还原为金属态纳米粒子，实现了金属态纳米粒子的均匀包覆，避免高温下长时间包覆反应所导致的纳米粒子粗化和长大的问题。本发明方法简单，制备周期短，制备出的金属纳米粒子分散均匀，作为催化材料、导电陶瓷等在多个领域具有广阔的应用前景。

Description

一种在氧化物陶瓷粉体表面包覆金属纳米粒子的方法 技术领域
本发明具体涉及一种在氧化物陶瓷粉体表面包覆金属纳米粒子的方法，属于材料加工工程领域。
背景技术
在陶瓷粉体，特别是氧化铝(Al2O3)、氧化锆(ZrO2)、氧化硅(SiO2)、四氧化三铁(Fe3O4)等氧化物粉体表面包覆一层一种或几种异相金属纳米粒子，可以同时具备金属包覆壳和陶瓷核的性能，降低粉体团聚效应及各物相(特别是金属和陶瓷)之间的偏聚，赋予氧化物粉体新的性能，如催化性能、电磁性能等，或者有效改变粉体的表面性能，如电化学性能和烧结过程中的扩散能力。因此包覆技术的开发及在结构与功能陶瓷等多领域的应用受到了广泛关注。
目前金属包覆陶瓷型粉体的制备方法主要有机械混合法、溶胶凝胶法、化学镀法和化学气相沉积法等。其中机械混合法最为简单，但对密度性质差别较大的粉体通常难以混合均匀。溶胶凝胶法是将原料分散在溶剂中，通过水解形成溶胶及凝胶，经过干燥和热处理获得所需纳米粒子材料的方法。Rodeghiero等人就曾采用溶胶凝胶法在获得了Ni-Al2O3粉体。他们将溶胶凝胶处理后的粉体在H2气氛中热处理1小时，将Ni盐还原为Ni，后将粉体在1350～1400℃的温度条件下热压烧结2～4小时，获得了致密的Al2O3-Ni复合材料(Materials Science and Engineering A,1995,195,pp151～161)。虽然与固相反应相比，溶胶凝胶法中的化学反应更容易进行，且合成温度较低，但后续的高温热处理(煅烧晶化及还原得到金属相)往往温度较高，易引起粉体团聚及金属相的微烧结。
化学镀通过无外加电场的电化学过程对粉体进行包覆，具有设备简单、镀层性能可设计等优点，是应用较为广泛的一种方法。曹晓国等人采用化学镀法，以甲醛为还原剂，在水/乙醇介质中将银包覆在Fe3O4粉体表面。测试结果表明，在Fe3O4粉体表面包覆的均匀、完整的银层有效提高了Fe3O4粉体的体剂电导率。(材料工程，2007，4，pp57～60)。Mehmet Uysal等人采用电镀法获得了Ni包覆的Al2O3粉体。他们首先是在SnCl2溶液中对Al2O3粉体进行预处理以提高Al2O3粉体的表面活性，然后以NiCl2为Ni源，通过控制溶液的PH值，NiCl2浓度等工艺参数，在Al2O3粉体表面包覆了均匀分布的Ni纳米粒子(Ceramics  International，2013，39，pp5485-5493)。但粉体化学镀具有一定的特殊性。要实现表面改性层的均匀沉积，粉体表面应具有良好的催化活性，对于陶瓷等不具有表面催化活性的粉体，应进行必要的预处理使之活化；同时，为使粉体能在镀液中均匀分散，镀液应具有一定的稳定性以免自发分解。因此，其应用范围受到一定的限制。
化学气相沉积法通过原料气体在颗粒表面聚集反应而形成固态沉积物，从而达到对粉体颗粒的包覆效果。蒋永等采用化学气相沉积法在粒径为200nm的LiFePO4粉体表面包覆了碳层(硅酸盐学报，2008，36，pp1295～1299)。Zhang等人采用化学气相沉积法，以金属有机物为原料，先将原料加热挥发，以Ar气带入到高温反应室中，通过高温分解在氧化铝表面包覆了Ni纳米粒子。但在较高的包覆温度下，纳米粒子容易团聚和长大，从而导致粉体烧结后的硬度和强度降低(Journal of the European Ceramic Society,2014,34,pp435-441)。
发明内容
本发明的目的在于提供一种在氧化物陶瓷粉体表面均匀包覆金属纳米粒子的方法，通过事先将金属有机原料和包覆粉体混合，在反应室加热的过程中实现金属纳米粒子的均匀包覆，降低包覆温度，提高分散的均匀性。
为实现上述技术目的，本发明采取如下技术方案：一种在氧化物陶瓷表面包覆金属纳米粒子的方法，包括如下步骤：
(1)将氧化物陶瓷粉体与金属有机原料按照重量比(1:1)～(10:1)进行配料，研磨混合1～3h得到混合粉体，将研磨后的混合粉体放置于旋转式反应器中，启动旋转反应器使其旋转；
(2)向旋转反应器内通入氧气和氩气的混合气体，以5～10℃/min的速率升温至400～500℃后，保温0.5～2h，使金属有机原料氧化为金属氧化物，然后关闭氧气和氩气的气体进气阀门；
(3)向旋转式反应器中通入还原性气体将步骤(2)中的金属氧化物还原为金属态纳米粒子，同时以5～10℃/min的速率降温，降至室温后，关闭还原性气体的进气阀门，停止旋转式反应器的旋转，打开仪器，取出粉体，过筛，收集粉体。
其中，所述的氧化物陶瓷粉体为Al2O3、ZrO2、SiO2、MgO和TiO2中的任意一种，粒径为100nm～100μm，纯度大于95％。
所述金属有机原料原料为烷基或者芳香基的烃基与金属原子结合形成的稳定有机金属化合物，其种类根据需要包覆的金属纳米粒子的种类进行选择，如当需要在氧化陶瓷粉体表面包覆镍纳米粒子时，所述的金属有机原料原料为二茂镍(NiCp2)、四羟基镍(Ni(CO)4)和醋酸镍(Ni(CH3COO)2·4H2O)中的任意一种。
当需要在氧化陶瓷粉体表面包覆铜纳米粒子时，选用的金属有机原料可以为Cu(DPM)2。
当需要在氧化陶瓷粉体表面包覆钴纳米粒子时，选用的金属有机原料为二茂钴或羟基钴。
当需要在氧化陶瓷粉体表面包覆铁纳米粒子时，选用的金属有机原料为二茂铁。
具体地，步骤(2)中，通入的氧气和氩气的混合气体总压力为200～1000Pa，其中氧气的分压为50～200Pa，升温速度为2～10℃min，旋转反应器的旋转速率为15～60r/min。
步骤(3)中，所述的还原性气体为氢气、一氧化碳和甲烷中的任意一种，所述还原性气体的分压为100～400Pa。
优选地，步骤(3)中，所述的粉体过50～200目筛三次。
有益效果：本发明提供了一种能够在不同氧化物陶瓷粉体表面包覆均匀分布的金属纳米粒子的新方法。通过控制工艺条件和选择合适的金属有机原料，在不同氧化物陶瓷粉体表面包覆金属纳米粒子层，从而对粉体的表面形貌、导电性等进行调控，使材料的利用率、产品的可靠性得到大大提高，制备周期短、能耗低、环境友好，生产成本显著降低，从而具有良好的产业前景。通过将氧化物陶瓷粉体与金属有机原料预先混合，提高了金属纳米粒子包覆的均匀性；另外在加热过程中，同时进行金属纳米粒子的氧化分解，降低了在高温下反应时间，避免了金属纳米粒子的粗化和长大。
附图说明
图1实施例1中Al2O3粉体包覆Ni纳米粒子的X射线衍射图谱：(a)包覆前，(b)包覆后；
图2实施例1中Al2O3粉体包覆Ni纳米粒子的透射电镜照片；
图3实施例3中ZrO2粉体包覆Ni纳米粒子后的X射线衍射图谱；
图4实施例3中ZrO2粉体包覆Ni纳米粒子的透射电镜照片。
具体实施方式
以下为本发明的优选实施方式，仅用于解释本发明，而非用于限制本发明，且由该说明所作出的改进都属于本发明所附权利要求所保护的范围。
实施例1 Al2O3粉体表面包覆Ni纳米粒子。
首先将普通商用5g Al2O3粉体(粒径为500nm)和0.5g Ni(CO)4混合后，放入旋转反应器中，将反应器旋转，旋转速率为45r/min。通入氧气和Ar的混合气体，混合气体的总压力为1000Pa，其中氧气的分压为100Pa。升温速率为8℃/min，升温至温度为450℃后保温45min，使Ni(CO)4氧化为氧化镍，然后关闭氧气供应阀门，通入一氧化碳将金属氧化物氧化镍还原为金属态纳米粒子。一氧化碳的分压为200Pa，还原反应时间为45min，然后开始降温，降温速率为8℃/min。降至室温后，关闭气体阀门，停止仪器旋转和反应器的加热，打开仪器，取出粉体，过100目筛三次，收集粉体。对收集的粉体进行表征，结果如图1和图2所示。其中，图1为Al2O3粉体包覆Ni纳米粒子的X射线衍射图谱，a为包覆前，b为包覆后，证明了Al2O3粉体成功包覆上了Ni纳米粒子。图2为Al2O3粉体包覆Ni纳米粒子的透射电镜照片，从图中可以看出，Ni纳米粒子均匀地包覆在Al2O3粉体表面。
实施例2 Al2O3粉体表面包覆Cu纳米粒子。
首先将普通商用5g Al2O3粉体(粒径为100nm)和2g Cu(DPM)2(copper dipivaloylmethanate)混合后，放入旋转反应器中，关闭旋转反应器的入料口阀门，启动旋转反应器旋转，旋转速率调节为60r/min。然后通入氧气和氩气的混合气体，混合气体的总压力为800Pa，其中氧气的分压为50Pa。升温速率设置为5℃/min，升温至400℃后保温60min，使Cu(DPM)2氧化为氧化铜，然后关闭氧气供应阀门，通入甲烷将金属氧化物CuO还原为金属态纳米粒子。甲烷的分压为100Pa，还原反应时间为60min，然后开始降温，降温速率为5℃/min。降至室温后，关闭一氧化碳进气阀门和氩气进气阀门，停止仪器旋转和反应器的加热，打开仪器，取出粉体，过200目筛三次，收集粉体。
实施例3 ZrO2粉体表面包覆Ni纳米粒子。
首先将普通商用5g ZrO2粉体(粒径为10μm)和5g NiCp2(nickelocene)混合 后，放入旋转反应器中，将反应器旋转，旋转速率为15r/min。通入氧气和Ar的混合气体，混合气体的总压力为800Pa，其中氧气的分压为200Pa。升温速率为7℃/min，升温至温度为450℃后保温30min，从而将NiCp2氧化为NiO，然后关闭氧气供应阀门，通入氢气将金属氧化物NiO还原为金属态纳米粒子。氢气的分压为400Pa，还原反应时间为30min，然后开始降温，降温速率为7℃/min。降至室温后，关闭气体阀门，停止仪器旋转和反应器的加热，打开仪器，取出粉体，过100目筛三次，收集粉体。对收集的粉体进行表征，结果如图3和图4所示。其中，图3为ZrO2粉体包覆Ni纳米粒子的X射线衍射图谱，证明了ZrO2粉体成功包覆上了Ni纳米粒子。图4为ZrO2粉体包覆Ni纳米粒子的透射电镜照片，从图中可以看出，Ni纳米粒子均匀地包覆在ZrO2粉体表面。
实施例4 TiO2粉体表面包覆Co纳米粒子。
以在TiO2粉体表面包覆Co纳米粒子为例，首先将普通商用5g TiO2粉体(粒径为50μm)和2g CoCp2(Cobaltocene)混合后，放入旋转反应器中，将反应器旋转，旋转速率为60r/min。通入氧气和Ar的混合气体，混合气体的总压力为200Pa，其中氧气的分压为50Pa。升温速率为10℃/min，升温至温度为400℃后保温15min，从而将CoCp2转化为氧化钴，然后关闭氧气供应阀门，通入甲烷将金属氧化物氧化钴还原为金属态纳米粒子。甲烷的分压为100Pa，还原反应时间为15in，然后开始降温，降温速率为10℃/min。降至室温后，关闭气体阀门，停止仪器旋转，打开仪器，取出粉体，过50目筛三次，收集粉体。
实施例5 SiO2粉体表面包覆Fe纳米粒子。
以在SiO2粉体表面包覆Fe纳米粒子为例，首先将普通商用5g SiO2粉体(粒径为100μm)和1g FeCp2(ferrocene)混合后，放入旋转反应器中，将反应器旋转，旋转速率为60r/min。通入氧气和Ar的混合气体，混合气体的总压力为800Pa，其中氧气的分压为10Pa。升温速率为8℃/min，最终反应温度为500℃，保温时间为30min，从而将FeCp2氧化为氧化铁，然后关闭氧气供应阀门，通入一氧化碳将氧化铁还原为金属态纳米粒子。一氧化碳的分压为200Pa，还原反应时间为30min，然后以8℃/min的速率降温。降至室温后，关闭气体阀门，停止仪器旋转，打开仪器，取出粉体，过50目筛三次，收集粉体。
实施例6 MgO粉体表面包覆Co纳米粒子。
以在MgO粉体表面包覆Co纳米粒子为例，首先将普通商用6g MgO粉体 (粒径为50μm)和2g CoCp2(Cobaltocene)混合后，放入旋转反应器中，将反应器旋转，旋转速率为60r/min。通入氧气和Ar的混合气体，混合气体的总压力为600Pa，其中氧气的分压为150Pa。升温速率为6℃/min，升温至温度为400℃后保温20min，从而CoCp2被氧化为氧化钴，然后关闭氧气供应阀门，通入甲烷将金属氧化物Co2O3还原为金属态纳米粒子。甲烷的分压为100Pa，还原反应时间为15in，然后开始降温，降温速率为10℃/min。降至室温后，关闭气体阀门，停止仪器旋转，打开仪器，取出粉体，过50目筛三次，收集粉体。
实施例7 SiO2粉体表面包覆Ni纳米粒子。
以在SiO2粉体表面包覆Ni纳米粒子为例，首先将普通商用5g SiO2粉体(粒径为100μm)和3g Ni(CH3COO)2·4H2O混合后，放入旋转反应器中，将反应器旋转，旋转速率为50r/min。通入氧气和Ar的混合气体，混合气体的总压力为800Pa，其中氧气的分压为15Pa。升温速率为8℃/min，最终反应温度为500℃，保温时间为30min，从而Ni(CH3COO)2·4H2O被氧化为氧化镍，然后关闭氧气供应阀门，通入一氧化碳将氧化镍还原为金属态纳米粒子。一氧化碳的分压为200Pa，还原反应时间为30min，然后以8℃/min的速率降温。降至室温后，关闭气体阀门，停止仪器旋转，打开仪器，取出粉体，过50目筛三次，收集粉体。

Claims (9)

  1. 一种在氧化物陶瓷表面包覆金属纳米粒子的方法，其特征在于，包括如下步骤：
    (1)将氧化物陶瓷粉体与金属有机原料按照重量比(1:1)～(10:1)进行配料，研磨混合1～3h得到混合粉体，将研磨后的混合粉体放置于旋转式反应器中，启动旋转反应器使其旋转，其中，所述的金属有机原料为烷基或者芳香基的烃基与金属原子结合形成的稳定有机金属化合物；
    (2)向旋转反应器内通入氧气和氩气的混合气体，以5～10℃/min的速率升温至400～500℃后，保温0.5～2h，使金属有机原料氧化为金属氧化物，然后关闭氧气和氩气的气体进气阀门；
    (3)向旋转式反应器中通入还原性气体将步骤(2)中的金属氧化物还原为金属态纳米粒子，同时以5～10℃/min的速率降温，降至室温后，关闭还原性气体的进气阀门，停止旋转式反应器的旋转，打开仪器，取出粉体，过筛，收集粉体。
  2. 根据权利要求1所述的方法，其特征在于，所述的氧化物陶瓷粉体为Al2O3、ZrO2、SiO2、MgO和TiO2中的任意一种，粒径为100nm～100μm，纯度大于95％。
  3. 根据权利要求1所述的方法，其特征在于，所述的金属有机原料为二茂镍、四羟基镍和醋酸镍中的任意一种。
  4. 根据权利要求1所述的方法，其特征在于，所述的金属有机原料为Cu(DPM)2。
  5. 根据权利要求1所述的方法，其特征在于，所述的金属有机原料为二茂钴或羟基钴。
  6. 根据权利要求1所述的方法，其特征在于，所述的金属有机原料为二茂铁。
  7. 根据权利要求1所述的方法，其特征在于，步骤(2)中，通入的氧气和氩气的混合气体总压力为200～1000Pa，其中氧气的分压为50～200Pa，旋转反应器的旋转速率为15～60r/min。
  8. 根据权利要求1所述的方法，其特征在于，步骤(3)中，所述的还原性气体为氢气、一氧化碳和甲烷中的任意一种，所述还原性气体的分压为100～400Pa。
  9. 根据权利要求1所述的方法，其特征在于，步骤(3)中，所述的粉体过50～200目筛三次。
PCT/CN2015/082892 2014-08-11 2015-06-30 一种在氧化物陶瓷粉体表面包覆金属纳米粒子的方法 WO2016023405A1 (zh)

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