CN107151834A - 一种磁性Fe3O4纳米纤维材料、制备方法及其在类过氧化物酶催化反应中的应用 - Google Patents
一种磁性Fe3O4纳米纤维材料、制备方法及其在类过氧化物酶催化反应中的应用 Download PDFInfo
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Abstract
一种磁性Fe3O4纳米纤维材料、制备方法及其在类过氧化物酶催化反应中的应用,属于特定形貌磁性金属氧化物纳米材料制备技术领域。本发明利用静电纺丝技术、空气氛围高温煅烧、以及聚合物辅助惰性气氛热还原三个步骤,制备了磁性Fe3O4纳米纤维材料。所得到的Fe3O4材料整体形貌为纤维状,纤维直径为100~200nm。该方法简单易行、重复性好。本发明制备的Fe3O4纳米纤维材料具有优异的催化性能,能够用作类过氧化物酶催化剂,其催化活性远远高于传统方法制备的Fe3O4纳米粒子。
Description
技术领域
本发明属于金属氧化物纳米纤维材料可控制备技术领域,具体涉及一种磁性Fe3O4纳米纤维材料、制备方法及其在类过氧化物酶催化反应中的应用。
背景技术
自从碳纳米管被发现以来,一维纳米结构材料逐渐引起了人们的广泛关注。过去几十年中,不仅一维碳纳米结构材料被广泛研究,金属、金属氧化物、金属硫化物以及功能聚合物等一维纳米结构材料也引起了人们的特殊兴趣,尤其是金属氧化物的一维纳米结构材料。由于其特殊的电子传输性质、丰富的晶体结构以及活跃的氧化还原特性,从而具有优异的光、电以及磁学性质。目前,各种金属氧化物一维纳米材料包括纳米线、纳米棒、纳米带、纳米管等都被大量报道。金属氧化物一维纳米结构材料在传感器、纳米光电器件、催化、生物医学、环境以及能源存储和转换等领域都具有重要应用。
在各种金属氧化物一维纳米结构材料中,Fe3O4是比较重要的一类具有超顺磁性的金属氧化物材料。在过去的报道中,各种结构的Fe3O4纳米材料得到了广泛的研究,其中Fe3O4纳米粒子由于制备方法的多样性被关注的最多。Fe3O4纳米粒子可以在水相中合成,但是其粒径分布不是很均匀。利用油相制备的 Fe3O4纳米粒子尺寸均一,而且直径可以有效控制,而且通过配体交换的方法也可以使其较好的分散在水相中,因此这种方法受到了极大的关注。另外,利用水热合成技术也可以实现非常均匀的Fe3O4纳米球的可控制备。虽然各种结构的 Fe3O4纳米材料被广泛研究,但是对于一维Fe3O4纳米纤维材料的制备还是一个比较难的课题。本发明采用了一种新的制备方法,先利用静电纺丝技术结合空气煅烧制备Fe2O3纳米纤维,然后利用聚合物辅助惰性气氛热还原的方法可控的制备Fe3O4纳米纤维。这种方法制备的Fe3O4纳米纤维形貌均匀,在类酶催化反应中具有较高的催化性能,其催化活性远远高于传统方法合成的Fe3O4纳米粒子。
发明内容
本发明的目的是提供一种磁性Fe3O4纳米纤维材料、制备方法及其在类过氧化物酶催化反应中的应用。
我们采用静电纺丝技术结合空气氛围煅烧,然后在聚合物辅助惰性气氛中加热还原制备磁性Fe3O4纳米纤维材料。所得到的Fe3O4材料整体形貌为纤维状,纤维直径为100~200nm。该方法简单易行、重复性好。本发明制备的Fe3O4纳米纤维材料用作类过氧化物酶催化剂具有优异的催化性能,其催化活性远远高于传统方法制备的Fe3O4纳米粒子。
本发明所述的一种磁性Fe3O4纳米纤维材料的制备方法,其包括如下步骤:
A.通过静电纺丝及空气煅烧制备Fe2O3纳米纤维:首先,将0.4~1.5g硝酸铁和0.4~1.5g聚乙烯基吡咯烷酮(PVP)溶于2~10mL N,N-二甲基甲酰胺 (DMF)和2~10mL异丙醇的混合溶液中;室温下磁力搅拌,得到均一的纺丝前驱体溶液;然后利用静电纺丝装置在纺丝距离10~25cm、纺丝电压10~30kV 的条件下纺丝,制备得到PVP/硝酸铁纳米纤维,再在空气中300~800℃下煅烧 2~6h,得到粉红色的Fe2O3纳米纤维;
B.聚合物辅助惰性气氛热还原的方法制备Fe3O4纳米纤维:将步骤A得到的 Fe2O3纳米纤维放置在管式炉内的石英坩埚中,在距离其2~10cm处放置另外一个装有20~100mg聚合物的石英坩埚;然后在氩气或者氮气气氛中300~700℃下煅烧2~6h,得到Fe3O4纳米纤维,产物呈黑色粉末状并带有磁性;
步骤B中放置在石英坩埚中的聚合物为聚乙烯基吡咯烷酮、聚丙烯腈、聚苯乙烯、聚甲基丙烯酸甲酯、聚乙烯醇、聚丙烯、聚乙烯、聚氯乙烯、聚丙烯酸、聚碳酸酯、环氧树脂、酚醛树脂、聚醋酸乙烯酯、聚酰胺、聚酰亚胺、聚醚醚酮、聚醚砜、聚苯胺、聚吡咯、聚噻吩等。
本发明所述的Fe3O4纳米纤维材料可以作为一种类过氧化物酶催化剂,对常见的酶底物进行催化氧化。具体是将本发明制备的Fe3O4纳米纤维材料超声分散在水中作为催化剂(分散液浓度为1.0~5.0mg/mL);然后配置不同pH的醋酸- 醋酸钠水溶液(pH=2~6)作为反应溶液;取上述醋酸-醋酸钠溶液1~5mL,在其中依次加入10~50μL、5~30mM酶底物的二甲基亚砜溶液(酶底物为3,3',5,5'- 四甲基联苯胺、邻苯二胺或2,2联氮双(三乙基苯并噻唑啉-6-磺酸)和10~50μL、质量分数30%的过氧化氢水溶液,最后加入10~50μL上述Fe3O4纳米纤维材料催化剂的水分散液,实现对酶底物的催化氧化反应。实验结果表明,Fe3O4纳米纤维材料对酶底物的催化活性远远高于传统方法所合成的Fe3O4纳米粒子。
本方法得到的Fe3O4纳米纤维材料类过氧化物酶催化剂,具有制备方法简单、活性高的优点,对促进类过氧化物酶催化剂的发展和商业化进程将具有十分重要的意义。
附图说明
图1:实施例4制备的Fe3O4纳米纤维材料的扫描电镜照片;
图2:实施例4制备的Fe3O4纳米纤维材料的透射电镜照片;
图3:实施例4制备的Fe3O4纳米纤维材料的拉曼光谱;
图4:实施例4制备的Fe3O4纳米纤维材料的X射线衍射谱图;
图5:实施例4制备的Fe3O4纳米纤维材料对3,3',5,5'-四甲基联苯胺(TMB) 的催化氧化反应谱图。
如图1所示,实施例4所制得的Fe3O4纳米纤维材料的扫描电镜照片,可以看到复合材料整体为纤维形貌,纤维直径大约为100~200nm,纤维表面粗糙。
如图2所示,实施例4所制得的Fe3O4纳米纤维材料的透射电镜照片,从图中可以看出纤维是由许多纳米粒子非常紧密的堆积所组成的,纤维表面具有孔洞结构。
如图3所示,实施例4所制得的Fe3O4纳米纤维材料的拉曼光谱,660.5cm-1处的特征峰对应于Fe3O4的A1g特征峰。
如图4所示,实施例4所制得的Fe3O4纳米纤维材料的X射线衍射谱图,可以看到本发明制备的Fe3O4纳米纤维材料在30.1、35.4、37.1、43.1、53.4、 56.9、62.5、73.9°出现了Fe3O4的(220)、(311)、(222)、(400)、(422)、(511)、 (440)、(533)面的特征峰,证明了所制备的Fe3O4纳米纤维属于单斜晶系。
如图5所示,为利用紫外吸收光谱检测实施例4所制得的Fe3O4纳米纤维材料对TMB的催化氧化过程的谱图。从图中可以看出,在TMB溶液中加入过氧化氢和催化剂后,在紫外可见吸收谱图中651nm处逐渐出现了氧化TMB的特征峰。该吸收峰对应于TMB氧化过程中形成的电荷转移复合物和TMB阳离子的特征吸收峰。相比较,在无催化剂或者不加入过氧化氢和TMB底物的条件下都没有TMB氧化过程的发生,说明了Fe3O4纳米纤维材料具有类过氧化物酶催化活性。并且该材料的类过氧化物酶催化活性优于商业Fe3O4纳米颗粒。
具体实施方式
静电纺丝法结合空气氛围煅烧制备Fe2O3纳米纤维
实施例1:
将0.9g硝酸铁和0.9g聚乙烯基吡咯烷酮(PVP)溶于6mL DMF和6mL 异丙醇的混合溶液中。室温下磁力搅拌,得到均一的纺丝前驱体溶液。然后利用静电纺丝装置在纺丝距离20cm、纺丝电压18kV的条件下纺丝,制备PVP/硝酸铁纳米纤维。再在空气中450℃煅烧3h,得到粉红色的Fe2O3纳米纤维。该条件下得到的Fe2O3形貌为纤维状,得到的产物质量大约为50mg。
实施例2:
将0.9g硝酸铁和0.4g聚乙烯基吡咯烷酮(PVP)溶于6mL DMF和6mL 异丙醇的混合溶液中。室温下磁力搅拌,得到均一的纺丝前驱体溶液。然后利用静电纺丝装置在纺丝距离20cm、纺丝电压18kV的条件下纺丝,制备PVP/硝酸铁纳米纤维。再在空气中450℃煅烧3h,得到粉红色的Fe2O3纳米纤维。相对于实施例1,该条件下得到的Fe2O3纳米纤维形貌除了大部分为纤维状,还有少量粒子状产物,得到的产物质量大约为50mg。
实施例3:
将0.9g硝酸铁和1.5g聚乙烯基吡咯烷酮(PVP)溶于6mL DMF和6mL 异丙醇的混合溶液中。室温下磁力搅拌,得到均一的纺丝前驱体溶液。然后利用静电纺丝装置在纺丝距离20cm、纺丝电压18kV的条件下纺丝,制备PVP/硝酸铁纳米纤维。再在空气中450℃煅烧3h,得到粉红色的Fe2O3纳米纤维。该条件下得到的Fe2O3纳米纤维形貌均为纤维状,但相对于实施例1其直径较粗,得到的产物质量大约为50mg。
聚合物辅助惰性气氛热还原的方法制备Fe3O4纳米纤维
实施例4:
将实施例1得到的10mg Fe2O3纳米纤维放置在管式炉中的石英坩埚中,在距离其5cm处放置另外一个装有聚乙烯基吡咯烷酮(50mg)的石英坩埚。然后在氩气气氛中500℃下煅烧4h,得到Fe3O4纳米纤维,产物呈黑色粉末状并带有磁性,得到的产物质量大约为9mg,纤维直径为100~200nm。
实施例5:
将实施例1得到的10mg Fe2O3纳米纤维放置在管式炉中的石英坩埚中,在距离其5cm处放置另外一个装有聚丙烯腈(50mg)的石英坩埚。然后在氩气气氛中500℃下煅烧4h,得到Fe3O4纳米纤维,产物呈黑色粉末状并带有磁性,得到的产物质量大约为9mg,纤维直径为100~200nm。
实施例6:
将实施例1得到的10mg Fe2O3纳米纤维放置在管式炉中的石英坩埚中,在距离其5cm处放置另外一个装有聚苯乙烯(50mg)的石英坩埚。然后在氩气气氛中500℃下煅烧4h,得到Fe3O4纳米纤维,产物呈黑色粉末状并带有磁性,得到的产物质量大约为9mg,纤维直径为100~200nm。
Fe3O4纳米纤维材料的类过氧化物酶催化性质
实施例9:
将实施例4中得到的产物超声分散到水中配置成浓度为3mg/mL的含有 Fe3O4纳米纤维材料的水分散液。在3mL醋酸-醋酸钠水溶液(pH=4)中加入 20μL、15mM TMB的二甲基亚砜溶液,然后加入20μL过氧化氢水溶液(质量分数30%),最后加入20μL上述Fe3O4纳米纤维材料的水分散液,利用紫外可见吸收光谱检测其类酶催化反应活性。
Claims (6)
1.一种磁性Fe3O4纳米纤维材料的制备方法,其步骤如下:
A.将0.4~1.5g硝酸铁和0.4~1.5g聚乙烯基吡咯烷酮溶于2~10mL N,N-二甲基甲酰胺和2~10mL异丙醇的混合溶液中;室温下磁力搅拌,得到均一的纺丝前驱体溶液;然后利用静电纺丝装置在纺丝距离10~25cm、纺丝电压10~30kV的条件下纺丝,制备得到PVP/硝酸铁纳米纤维,再在空气中300~800℃下煅烧2~6h,得到粉红色的Fe2O3纳米纤维;
B.将步骤A得到的Fe2O3纳米纤维放置在管式炉内的石英坩埚中,在距离其2~10cm处放置另外一个装有20~100mg聚合物的石英坩埚;然后在氩气或者氮气气氛中300~700℃下煅烧2~6h,得到Fe3O4纳米纤维,产物呈黑色粉末状并带有磁性。
2.如权利要求1所述的一种磁性Fe3O4纳米纤维材料的制备方法,其特征在于:步骤B所述的聚合物为聚乙烯基吡咯烷酮、聚丙烯腈、聚苯乙烯、聚甲基丙烯酸甲酯、聚乙烯醇、聚丙烯、聚乙烯、聚氯乙烯、聚丙烯酸、聚碳酸酯、环氧树脂、酚醛树脂、聚醋酸乙烯酯、聚酰胺、聚酰亚胺、聚醚醚酮、聚醚砜、聚苯胺、聚吡咯或聚噻吩。
3.一种磁性Fe3O4纳米纤维材料,其特征在于:是由权利要求1或2所述的方法制备得到。
4.权利要求3所述的一种磁性Fe3O4纳米纤维材料在类过氧化物酶催化反应中的应用。
5.如权利要求4所述的一种磁性Fe3O4纳米纤维材料在类过氧化物酶催化反应中的应用,其特征在于:是将Fe3O4纳米纤维材料超声分散在水中作为催化剂,分散液浓度为1.0~5.0mg/mL;然后配置pH=2~6的醋酸-醋酸钠水溶液作为反应溶液;取上述醋酸-醋酸钠溶液1~5mL,在其中依次加入10~50μL、5~30mM酶底物的二甲基亚砜溶液和10~50μL、质量分数30%的过氧化氢水溶液,最后加入10~50μL的Fe3O4纳米纤维材料的水分散液,实现对酶底物的催化氧化反应。
6.如权利要求5所述的一种磁性Fe3O4纳米纤维材料在类过氧化物酶催化反应中的应用,其特征在于:酶底物为3,3',5,5'-四甲基联苯胺、邻苯二胺或2,2联氮双(三乙基苯并噻唑啉-6-磺酸。
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