CN104722274B - 一种磁性mof‑5纳米复合吸附剂的制备及应用 - Google Patents
一种磁性mof‑5纳米复合吸附剂的制备及应用 Download PDFInfo
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Abstract
本发明公开了一种磁性MOF‑5纳米复合吸附剂的制备及应用。本发明基于微波辅助合成技术,在金属有机框架结构形成的开始阶段即将表面经PVP修饰的磁性Fe3O4纳米颗粒加入MOF‑5合成溶液中,利用磁性纳米颗粒表面修饰的高分子PVP中羰基与金属有机骨架结构中的锌离子之间的配位作用,从而有效地将磁性纳米颗粒与金属有机骨架复合,在很短的时间里原位合成出具有超顺磁性的金属有机骨架纳米复合物。采用微波辅助技术,反应温度比水热法制备该材料的温度低很多,并且大大缩短了反应时间,很大程度上节约了能源。本发明制备的磁性MOF‑5纳米复合吸附剂适用于环境样品及食品等基质中痕量弱极性及非极性有机物污染物的富集、分离与分析。
Description
技术领域
本发明属于无机有机纳米复合材料制备技术及现代分离分析技术领域,特别涉及一种磁性金属有机骨架纳米复合吸附剂的微波辅助一锅法快速制备及其应用。
技术背景
利用溶剂热法制备的超顺磁性的油相Fe3O4纳米颗粒因粒径较小、化学稳定性好、大小均一、并且在实验过程中操作简单、省时快速以及具有较强的磁性等特点,其在分析化学领域受到很多的关注(Yingxin Ma,Sheng Huang,Leyu Wang,Multifunctionalinorganic–organic hybrid nanospheres for rapid and selective luminescencedetection of TNT in mixed nitroaromatics via magnetic separation,Talanta,2013,116,535-540)。
金属有机骨架材料(MOFs)是通过金属离子或者金属簇与有机配体之间相互作用,组装形成多孔的微米或者纳米材料,由于具有比表面积高、化学稳定性或物理稳定性好、孔径大小的可调以及内外孔道的基团的可修饰等优异性能在储气,载药,化学传感、催化以及富集分离检测等领域得到很多的研究及应用(ValentinValtchevand LubomiraTosheva,Porous Nanosized Particles:Preparation,Properties,andApplications,Chem.Rev.,2013,113,6734-6760)。
结合MOFs的超高吸附能力及Fe3O4纳米粒子的磁分离功能,有效地将超顺磁性的磁性纳米粒子和金属有机骨架材料结合起来,制备稳定高效的的复合吸附剂,从而有效地增强环境中有毒有害物质的萃取以及使操作更加简便,在分析化学领域受到广泛关注。
微波辅助合成技术是指在微波作用下,利用其快速加热、均质与选择性等特点应用于现代有机合成中的技术。
发明内容
本发明的目的是提供一种基于配位键作用的磁性金属有机骨架纳米复合吸附剂的微波辅助一锅法快速制备及其应用于环境样品及食品等基质中多种有害有机物(如多农药残留)的快速富集、分离及检测,构建高灵敏度、高效、方便的痕量有机物的分析检测方法。
本发明的技术方案为:首先采用硫酸亚铁铵为原料制备具有超顺磁性、大小均一的Fe3O4纳米颗粒;在Fe3O4纳米颗粒表面修饰一层高分子聚乙烯吡咯烷酮;然后加入对苯二甲酸溶液中,并与可溶锌盐的N,N-二甲基甲酰胺溶液混合均匀,利用Fe3O4纳米颗粒表面聚乙烯吡咯烷酮结构中的羰基与金属有机骨架中锌离子的配位作用,采用微波辅助一锅法快速制备得到具有磁性的金属有机骨架纳米复合物。
本发明所述的磁性MOF-5纳米复合吸附剂的制备方法,其具体制备步骤为:
(1)Fe3O4纳米颗粒的制备:配制浓度为0.1-10mol·L-1的氢氧化钠水溶液1-20mL,依次加入1-20mL的乙醇和1-20mL的油酸,然后再加入1-20mL浓度为0.01-1mol·L-1的硫酸亚铁铵水溶液,室温下,搅拌10-30min,将搅拌均匀的混合溶液转入高压反应釜中,100-300℃条件下结晶1-30h,自然冷却至室温,用环己烷和乙醇洗涤后,分散于0.1-10mL氯仿中,即为超顺磁性的、大小均一的Fe3O4纳米颗粒分散液;
(2)聚乙烯吡咯烷酮修饰的磁性Fe3O4的制备:向1-50mL浓度为0.0035-0.025mmol·L-1的聚乙烯吡咯烷酮氯仿溶液中加入0.01-1mL步骤(1)得到的Fe3O4纳米颗粒分散液,室温下搅拌1-48h;然后用正己烷和氯仿洗涤,最终沉淀分散于0.5-20mL甲醇溶液中,即为聚乙烯吡咯烷酮修饰的磁性Fe3O4分散液;
(3)磁性MOF-5纳米复合吸附剂的制备:在搅拌条件下,将0.1-10mL步骤(2)得到的聚乙烯吡咯烷酮修饰的磁性Fe3O4分散液滴加到1-50mL浓度为0.01-0.1mol·L-1的对苯二甲酸的N,N-二甲基甲酰胺溶液中;混合均匀后,再滴加1-50mL浓度为0.1-2mol·L-1的可溶锌盐的N,N-二甲基甲酰胺溶液;搅匀后,转移到微波反应器中,50-100℃下,反应10-40min,冷却至室温,用甲醇和N,N-二甲基甲酰胺洗涤,最终在30-150℃下烘箱中干燥1-24h,即得磁性MOF-5纳米复合吸附剂。
所述的可溶锌盐为硝酸锌或乙酸锌。
上述制备得到的磁性MOF-5纳米复合吸附剂在环境样品中农药的富集、分离与分析方面的应用。
本发明基于微波辅助合成技术,在金属有机框架结构形成的开始阶段即将表面经PVP修饰的磁性Fe3O4纳米颗粒加入MOF-5合成溶液中,利用磁性纳米颗粒表面修饰的高分子PVP中羰基与金属有机骨架结构中的锌离子之间的配位作用,从而有效地将磁性纳米颗粒与金属有机骨架复合,在很短的时间里原位合成出具有超顺磁性的金属有机骨架纳米复合物。采用微波辅助技术,反应温度比水热法制备该材料的温度低很多,并且大大缩短了反应时间,很大程度上节约了能源。由于磁性纳米粒子表面和MOF-5之间的配位及疏水作用共同存在,从而大大提高了复合吸附剂的结构稳定性,结合MOF-5的超高吸附能力及Fe3O4纳米粒子的磁分离功能,使复合吸附剂具有较好的化学和物理稳定性,在固相萃取过程中可以快速分离,并保证在高萃取效率下多次循环使用,减少了固相萃取的成本。本发明制备的磁性MOF-5纳米复合吸附剂适用于环境样品及食品等基质中痕量弱极性及非极性有机物污染物的富集、分离与分析,将其作为固相萃取吸附剂可实现磁固相萃取(MSPE),与高效液相色谱联用,可以同时检测水中多种农药残留,具有高效,高灵敏度的特点;此外,该磁性MOF-5纳米复合吸附剂还可应用于磁性靶向载药,负载贵金属催化剂用于催化以及回收等应用领域。
附图说明
图1为实施例1制备的磁性MOF-5纳米复合吸附剂的XRD图;
图2为实施例1制备的磁性MOF-5纳米复合吸附剂的透射电镜形貌;
图3为实施例1制备的磁性MOF-5纳米复合吸附剂的扫描电镜形貌;
图4为实施例1制备的磁性MOF-5纳米复合吸附剂在样品溶液中磁分离前后的对比照片;
图5为实施例1制备的磁性MOF-5纳米复合吸附剂富集分离3种农药的色谱图;
图6为实施例2制备的磁性MOF-5纳米复合吸附剂分离5种农药的色谱图,其中(A)为自来水的液相色谱图,(B)为利用磁性MOF-5纳米复合吸附剂富集分离添加了5种农药的自来水样色谱图。
具体实施方式
实施例1
(1)超顺磁性Fe3O4纳米颗粒的制备
称取0.196g的Fe(NH4)2(SO4)2·6H2O溶解于10mL去离子水中配成硫酸亚铁胺的水溶液;称取1g氢氧化钠溶解于10mL去离子水中配成氢氧化钠的水溶液,再依次加入10mL乙醇和10mL油酸,混合均匀;然后,将上述配制的硫酸亚铁铵溶液加到氢氧化钠混合溶液中,室温下,搅拌10min,将搅拌均匀的混合溶液转入高压反应釜中,180℃条件下结晶10h,自然冷却至室温,用环己烷和乙醇洗涤2次,最终分散于1mL氯仿中,即为超顺磁性的,大小均一的Fe3O4纳米颗粒分散液;
(2)聚乙烯吡咯烷酮修饰的磁性Fe3O4的制备
称取100mg聚乙烯吡咯烷酮(PVP,K30)溶解于10mL氯仿溶液中,量取步骤(1)的Fe3O4氯仿溶液130μL,滴加到上述的聚乙烯吡咯烷酮氯仿溶液中,室温下,搅拌24h,然后,用正己烷和氯仿洗涤3次,最终分散于4mL甲醇溶液,即得聚乙烯吡咯烷酮修饰的磁性Fe3O4分散液;
(3)磁性MOF-5纳米复合吸附剂的制备
称取101.3mg对苯二甲酸,溶解于8mL氮,氮二甲基甲酰胺溶液;称取339.8mg乙酸锌,溶解于10mL氮,氮二甲基甲酰胺溶液;量取0.8mL聚乙烯吡咯烷酮修饰的磁性Fe3O4分散液,搅拌条件下,滴加到上述的对苯二甲酸的氮,氮二甲基甲酰胺溶液中,然后将乙酸锌的氮,氮二甲基甲酰胺溶液滴加到上述的聚乙烯吡咯烷酮修饰的磁性Fe3O4与对苯二甲酸的混合溶液中,搅拌均匀后,转移到微波反应器中,95℃下反应20min,冷却至室温,用甲醇和氮,氮二甲基甲酰胺洗涤3次,最终在60℃下烘箱中干燥4h,即得磁性MOF-5纳米复合吸附剂。
(4)磁固相萃取(MSPE)与液相色谱(HPLC)联用分离检测水中多种农药
称取10mg的上述磁性MOF-5纳米复合吸附剂,在超声条件下,分散于10mL添加农药的水样中,3种农药(溴虫腈,茚虫威,蝇毒磷)添加水平均为10μg/mL,机械振荡30min,在外加磁铁的作用下进行磁分离,采用有机溶剂洗脱出磁性MOF-5纳米复合吸附剂中吸附的农药,在35℃下,用氮吹仪浓缩并定容至0.1mL,采用高效液相色谱进行检测,色谱方法采用的是乙腈和水的混合溶剂进行梯度洗脱。
实施例2
(1)超顺磁性Fe3O4纳米颗粒的制备
称取0.196g的Fe(NH4)2(SO4)2·6H2O溶解于10mL去离子水中配成硫酸亚铁胺的水溶液;称取1g氢氧化钠溶解于10mL去离子水中配成氢氧化钠的水溶液,再依次加入10mL乙醇和10mL油酸,混合均匀;然后,将上述配制的硫酸亚铁铵溶液加到氢氧化钠混合溶液中,室温下,搅拌30min,将搅拌均匀的混合溶液转入高压反应釜中,180℃条件下结晶10h,自然冷却至室温,用环己烷和乙醇洗涤2次,最终分散于1mL氯仿中,即得超顺磁性的,大小均一的Fe3O4纳米颗粒分散液;
(2)聚乙烯吡咯烷酮修饰的磁性Fe3O4的制备
称取100mg聚乙烯吡咯烷酮(PVP,K30)溶解于10mL氯仿溶液中,量取上述的Fe3O4氯仿分散液130μL,滴加到上述的聚乙烯吡咯烷酮氯仿溶液中,室温下,搅拌24h;然后,用正己烷和氯仿洗涤3次,最终分散于4mL甲醇溶液,即得聚乙烯吡咯烷酮修饰的磁性Fe3O4分散液;
(3)磁性MOF-5纳米复合吸附剂的制备
称取101.3mg对苯二甲酸,溶解于8mL氮,氮二甲基甲酰胺溶液;称取339.8mg乙酸锌,溶解于10mL氮,氮二甲基甲酰胺溶液;量取0.8mL聚乙烯吡咯烷酮修饰的磁性Fe3O4分散液,搅拌条件下,滴加到上述的对苯二甲酸的氮,氮二甲基甲酰胺溶液中,然后将乙酸锌的氮,氮二甲基甲酰胺溶液滴加到上述的聚乙烯吡咯烷酮修饰的磁性Fe3O4与对苯二甲酸的混合溶液中,搅拌均匀后,转移到微波反应器中,95℃下反应20min,冷却至室温,用甲醇和氮,氮二甲基甲酰胺洗涤3次,最终在60℃下烘箱中干燥4h,即得磁性MOF-5纳米复合吸附剂。
(4)磁固相萃取(MSPE)与液相色谱(HPLC)联用分离检测水中多种农药
称取10mg的上述磁性MOF-5纳米复合吸附剂,在超声条件下,分散于10mL添加农药的水样中,5种农药(莎蜱磷,丁硫克百威,溴虫腈,茚虫威,蝇毒磷)添加水平均为10μg/mL,机械振荡30min,在外加磁铁的作用下进行磁分离,采用有机溶剂洗脱出磁性MOF-5纳米复合吸附剂中吸附的农药,在35℃下,采用氮吹仪浓缩并定容至0.1mL,采用高效液相色谱进行检测,色谱方法采用的是乙腈和水的混合溶剂进行梯度洗脱。
以上两实施例以水样中痕量多农药残留为例,对本发明的应用进行描述,但并不以此限定本发明的保护范围。
Claims (3)
1.一种磁性MOF-5纳米复合吸附剂的制备方法,其特征在于,其具体制备步骤为:
(1)Fe3O4纳米颗粒的制备:配制浓度为0.1-10 mol·L-1的氢氧化钠水溶液1-20mL,依次加入1 - 20 mL的乙醇和1 - 20 mL的油酸,然后再加入1-20mL浓度为0.01-1 mol·L-1的硫酸亚铁铵水溶液,室温下,搅拌10-30 min,将搅拌均匀的混合溶液转入高压反应釜中,100-300 ℃条件下结晶1-30 h,自然冷却至室温,用环己烷和乙醇洗涤后,分散于0.1-10mL氯仿中,即为超顺磁性的、大小均一的Fe3O4纳米颗粒分散液;
(2)聚乙烯吡咯烷酮修饰的磁性Fe3O4的制备:向1-50mL浓度为0.0035-0.025 mmol·L-1的聚乙烯吡咯烷酮氯仿溶液中加入0.01-1mL步骤(1)得到的Fe3O4纳米颗粒分散液,室温下搅拌1-48 h;然后用正己烷和氯仿洗涤,最终沉淀分散于0.5-20mL甲醇溶液中,即为聚乙烯吡咯烷酮修饰的磁性Fe3O4分散液;
(3)磁性MOF-5纳米复合吸附剂的制备:在搅拌条件下,将0.1-10mL步骤(2)得到的聚乙烯吡咯烷酮修饰的磁性Fe3O4分散液滴加到1-50mL浓度为0.01- 0.1 mol·L-1的对苯二甲酸的N,N-二甲基甲酰胺溶液中;混合均匀后,再滴加1-50mL浓度为0.1-2 mol·L-1的可溶锌盐的N,N-二甲基甲酰胺溶液;搅匀后,转移到微波反应器中,50-100 ℃下,反应10-40 min,冷却至室温,用甲醇和N,N-二甲基甲酰胺洗涤,最终在30-150 ℃下烘箱中干燥1-24 h,即得磁性MOF-5纳米复合吸附剂。
2.根据权利要求1所述的制备方法,其特征在于,所述的可溶锌盐为硝酸锌或乙酸锌。
3.根据权利要求1所述的方法制备得到的磁性MOF-5纳米复合吸附剂在环境样品中农药的富集、分离与分析方面的应用。
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