CN106040307B - 一步水热法合成Fe3O4(PAA)@C-Au核壳结构微球的制备方法 - Google Patents
一步水热法合成Fe3O4(PAA)@C-Au核壳结构微球的制备方法 Download PDFInfo
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
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- B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
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Abstract
本发明提供一种一步水热法合成Fe3O4(PAA)@C‑Au核壳结构微球的制备方法,属于纳米复合材料领域。1)制备单分散、粒径均一的聚丙烯酸(PAA)修饰的Fe3O4磁性微球。2)通过一步水热法将多孔碳层和具有高催化活性的贵金属纳米粒子负载在磁性微球表面,得到负载型贵金属纳米复合催化材料。该方法通过在磁性功能微球上一步负载具有高催化活性的贵金属纳米催化材料,多孔碳层为底物分子的传输和产物的运输提供了通道,促进了催化活性中心与底物分子的碰撞几率;纳米贵金属粒子的稳定固载有效解决了贵金属纳米催化剂使用过程中易流失、易团聚等问题;该方法制备的纳米复合催化材料具有高催化效率和强循环稳定性。用本发明提供的方法反应工艺简单、流程短、无污染、能耗少,适合工业化生产。
Description
技术领域
本发明属于纳米复合材料领域,特别涉及一种一步水热法合成 Fe3O4(PAA)@C-Au核壳结构微球的制备方法。
背景技术
贵金属纳米粒子如金(Au)、银(Ag)、铂(Pt)、钯(Pd)等由于高比表面积、原子尺寸效应、等离子体共振效应以及优良的底物吸附能力而被广泛应用于 C-C键和C-H键耦合反应、加氢反应、氧化还原反应等催化反应中。然而,贵金属纳米粒子很容易团聚,且在反应结束后难以回收利用,大大地限制了其发展。利用贵金属纳米催化剂载体如分子筛、聚合物、活性炭及金属氧化物等固载贵金属纳米粒子,有利于贵金属纳米粒子的高效稳定固载,因此将贵金属纳米粒子固载化,开发一种温和条件下易制备的负载型贵金属催化材料成为催化领域的研究热点。
从相关研究领域申报的专利中,可知将贵金属金纳米粒子与具有固载能力的载体复合,得到负载型贵金属纳米催化剂,是目前得到高效可回收利用的贵金属复合纳米粒子的主要方式之一。CN101108423提供了一种Fe3O4/Au磁性复合纳米粒子的制备方法,运用超声化学法将金离子还原到氨基或巯基功能化的磁性纳米粒子上。CN101145425提高了一种Fe3O4-Au磁性沉积薄膜的制备方法,运用湿化学法将金离子持续不断还原到氨基或巯基功能化的磁性纳米粒子上。 CN103223178A提供了一种叶酸修饰的多功能靶向造影剂磁性氧化铁/金纳米颗粒的制备方法,通过将纳米金颗粒包裹在修饰了靶向分子叶酸的树状大分子内部,然后在Fe3O4纳米颗粒表面形成高分子多层膜,进行壳层交联,得到复合纳米颗粒Fe3O4/Au-FA。现有的专利中均未有对一步水热法合成Fe3O4(PAA)@C-Au核壳结构微球的报道。
因此,选择一种具有高效负载能力的贵金属纳米催化剂载体,稳定固载贵金属纳米粒子,在保持贵金属纳米粒子高效催化活性的同时解决其使用过程中易流失、易团聚等问题,仍然是本领域的一个技术难题。
发明内容
本发明的目的在于提供一种一步水热法合成Fe3O4(PAA)@C-Au核壳结构微球的制备方法,通过贵金属纳米粒子的稳定固载,有效解决了贵金属纳米催化剂使用过程中易流失、易团聚等问题。
本发明的技术方案是:贵金属纳米粒子由于高比表面积、原子尺寸效应、等离子体共振效应以及优良的底物吸附能力,成为目前最受关注的纳米催化材料,但其易团聚、难以回收利用的问题限制了其广泛应用。本发明通过在 Fe3O4(PAA)@C微球表面负载贵金属金纳米粒子,得到Fe3O4(PAA)@C-Au核壳结构微球,在不影响金纳米粒子催化活性的同时,有效解决其使用过程中易流失、易团聚等问题。
具体制备步骤为:
1、单分散磁性四氧化三铁微球的制备:在50~80℃油浴条件下,将三氯化铁和聚丙烯酸(PAA)分散在乙二醇中,然后加入无水乙酸钠并强烈搅拌0.5~3h,混合均匀后,将得到的土黄色前躯体溶液转移至密闭容器中,将温度控制在100℃~300℃反应6~24h,经过磁性分离、醇洗、水洗,烘干,得到直径在200~500nm 的磁性四氧化三铁微球。其中,三氯化铁、聚丙烯酸、乙二醇、无水乙酸钠的质量比为:1:(0.01~0.02):(30~50):(6~10);
2、核壳结构Fe3O4(PAA)@C-Au微球的制备:将磁性四氧化三铁微球、葡萄糖、去离子水、氯金酸、添加剂按一定比例超声混合均匀,然后转移至密闭容器中,将温度控制在120℃~250℃反应2~10h,得到核壳结构Fe3O4(PAA)@C-Au微球。其中,磁性四氧化三铁微球、葡萄糖、去离子水、氯金酸、添加剂的质量比为:1:(50~90):(500~1000):(0.2~0.5):(0.2~2)。
所述的添加剂包括十六烷基三甲基溴化铵(CTAB)、柠檬酸钠中的一种或几种。
本发明的优点在于:1)通过一步水热法将多孔碳层和具有高催化活性的贵金属纳米粒子负载在磁性微球表面,得到负载型贵金属纳米复合催化材料;2) 用本发明提供的方法将具有高催化活性的贵金属纳米催化材料稳定固载在多孔碳层孔道结构中,多孔碳层为底物分子的传输和产物的运输提供了通道,促进了催化活性中心与底物分子的碰撞几率;且有效解决了贵金属纳米催化剂使用过程中易流失、易团聚等问题;3)用本发明提供的方法反应工艺简单、条件温和、流程短,适合工业化生产。
附图说明
图1为本发明制备得到的Fe3O4(PAA)@C-Au核壳结构微球透镜照片。
图2a为无添加剂时制备得到的Fe3O4(PAA)@C-Au核壳结构微球透镜照片;
图2b为以CTAB为添加剂制备得到的Fe3O4(PAA)@C-Au核壳结构微球透镜照片;
图2c为以柠檬酸钠为添加剂制备得到的Fe3O4(PAA)@C-Au核壳结构微球透镜照片;
图2d为以CTAB和柠檬酸钠为添加剂制备得到的Fe3O4(PAA)@C-Au核壳结构微球透镜照片。
具体实施方式
下面结合具体的实施方式对本发明的技术方案做进一步说明。
实施案例1
在60℃油浴条件下,将三氯化铁和聚丙烯酸分散在乙二醇中,然后加入无水乙酸钠并强烈搅拌2h,混合均匀后,将得到的土黄色前躯体溶液转移至密闭容器中,将温度控制在200℃反应8h,经过磁性分离、醇洗、水洗,烘干,得到直径在260nm的磁性四氧化三铁微球。其中,三氯化铁、聚丙烯酸、乙二醇、无水乙酸钠的质量比为:1:0.02:42:8;
将磁性四氧化三铁微球、葡萄糖、去离子水、氯金酸按一定比例超声混合均匀,然后转移至至密闭容器中,将温度控制在180℃反应6h,得到核壳结构Fe3O4(PAA)@C-Au微球。其中,磁性四氧化三铁微球、葡萄糖、去离子水、氯金酸的质量比为:1:70:800:0.4,得到形貌如图2a的Fe3O4(PAA)@C-Au核壳结构微球。
实施案例2
在60℃油浴条件下,将三氯化铁和聚丙烯酸分散在乙二醇中,然后加入无水乙酸钠并强烈搅拌2h,混合均匀后,将得到的土黄色前躯体溶液转移至密闭容器中,将温度控制在200℃反应8h,经过磁性分离、醇洗、水洗,烘干,得到直径在260nm的磁性四氧化三铁微球。其中,三氯化铁、聚丙烯酸、乙二醇、无水乙酸钠的质量比为:1:0.02:42:8;
将磁性四氧化三铁微球、葡萄糖、去离子水、氯金酸、CTAB按一定比例超声混合均匀,然后转移至至密闭容器中,将温度控制在180℃反应6h,得到核壳结构Fe3O4(PAA)@C-Au微球。其中,磁性四氧化三铁微球、葡萄糖、去离子水、氯金酸、CTAB的质量比为:1:70:800:0.4:0.3,得到形貌如图2b的 Fe3O4(PAA)@C-Au核壳结构微球。
实施案例3
在60℃油浴条件下,将三氯化铁和聚丙烯酸分散在乙二醇中,然后加入无水乙酸钠并强烈搅拌2h,混合均匀后,将得到的土黄色前躯体溶液转移至密闭容器中,将温度控制在200℃反应8h,经过磁性分离、醇洗、水洗,烘干,得到直径在260nm的磁性四氧化三铁微球。其中,三氯化铁、聚丙烯酸、乙二醇、无水乙酸钠的质量比为:1:0.02:42:8;
将四氧化三铁微球、葡萄糖、去离子水、氯金酸、柠檬酸钠按一定比例超声混合均匀,然后转移磁性至至密闭容器中,将温度控制在180℃反应6h,得到核壳结构Fe3O4(PAA)@C-Au微球。其中,磁性四氧化三铁微球、葡萄糖、去离子水、氯金酸、柠檬酸钠的质量比为:1:70:800:0.4:1.2,得到形貌如图2c 的Fe3O4(PAA)@C-Au核壳结构微球。
实施案例4
在60℃油浴条件下,将三氯化铁和聚丙烯酸分散在乙二醇中,然后加入无水乙酸钠并强烈搅拌2h,混合均匀后,将得到的土黄色前躯体溶液转移至密闭容器中,将温度控制在200℃反应8h,经过磁性分离、醇洗、水洗,烘干,得到直径在260nm的磁性四氧化三铁微球。其中,三氯化铁、聚丙烯酸、乙二醇、无水乙酸钠的质量比为:1:0.02:42:8;
将磁性四氧化三铁微球、葡萄糖、去离子水、氯金酸、CTAB、柠檬酸钠按一定比例超声混合均匀,然后转移至至密闭容器中,将温度控制在180℃反应6h,得到核壳结构Fe3O4(PAA)@C-Au微球。其中,磁性四氧化三铁微球、葡萄糖、去离子水、氯金酸、CTAB、柠檬酸钠的质量比为:1:70:800:0.4:0.3:1.2,得到形貌如图2d的Fe3O4(PAA)@C-Au核壳结构微球。
以上所述仅是本发明优选实施方式,应当指出,对于本技术领域的普通技术员来说,在不脱离本发明技术原理的前提下,还可以做出若干改进和变型,这些改进和变型也应该视为本发明的保护范围。
Claims (1)
1.一种一步水热法合成Fe3O4(PAA)@C‐Au核壳结构微球的制备方法;其特征在于具体制备步骤如下:
(1)单分散四氧化三铁磁性微球的制备:在50~80℃油浴条件下,将三氯化铁和聚丙烯酸分散在乙二醇中,然后加入无水乙酸钠并强烈搅拌0.5~3h,混合均匀后,将得到的土黄色前躯体溶液转移至密闭容器中,将温度控制在100℃~300℃反应6~24h,经过磁性分离、醇洗、水洗,烘干,得到直径在200~500nm的磁性四氧化三铁微球;其中,三氯化铁、聚丙烯酸、乙二醇、无水乙酸钠的质量比为:1:(0.01~0.02):(30~50):(6~10);
(2)核壳结构Fe3O4(PAA)@C‐Au微球的制备:将磁性四氧化三铁微球、葡萄糖、去离子水、氯金酸、添加剂按一定比例超声混合均匀,然后转移至密闭容器中,将温度控制在120℃~250℃反应2~10h,得到核壳结构Fe3O4(PAA)@C‐Au微球;
步骤(2)中,磁性四氧化三铁微球、葡萄糖、去离子水、氯金酸、添加剂的质量比为:1:(50~90):(500~1000):(0.2~0.5):(0.2~2);
所述的添加剂为十六烷基三甲基溴化铵、柠檬酸钠中的一种或几种。
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CN101728044A (zh) * | 2009-12-15 | 2010-06-09 | 陕西北美基因股份有限公司 | 一种金磁微粒的制备方法 |
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Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
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CN101728044A (zh) * | 2009-12-15 | 2010-06-09 | 陕西北美基因股份有限公司 | 一种金磁微粒的制备方法 |
Non-Patent Citations (3)
Title |
---|
Ag@C Core/Shell Structured Nanoparticles: Controlled Synthesis, Characterization, and Assembly;Xiaoming Sun, et al;《LANGMUIR》;20050514;第21卷(第13期);第6019-6024页 * |
Constructing Carbon-Coated Fe3O4 Microspheres as Antiacid and Magnetic Support for Palladium Nanoparticles for Catalytic Applications;Lirong Kong, et al;《ACS APPLIED MATERIALS & INTERFACES》;20101214;第3卷(第1期);第35-42页 * |
Facile Hydrogen-Bond-Assisted Polymerization and Immobilization Method to Synthesize Hierarchical Fe3O4@Poly(4-vinylpyridine-codivinylbenzene)@Au Nanostructures and Their Catalytic Applications;Wanchun Guo, et al;《CHEMISTRY-AN ASIAN JOURNAL》;20130405;第8卷(第6期);第1160-1167页 * |
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