CN102974285B - 一种具有多级孔结构、粒径均一可调的磁性微球的制法 - Google Patents
一种具有多级孔结构、粒径均一可调的磁性微球的制法 Download PDFInfo
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Abstract
本发明公开了一种具有多级孔结构、粒径均一可调的磁性微球的制备方法，此方法为：采用一种含铁的离子液体作为原料，加入加热时产生气体的碱源，以乙二醇作为溶剂，搅拌均匀后加入到密闭反应容器中于180℃~300℃下反应3小时~24小时得到具有多级孔结构、粒径均一的磁性微球，其组成为MFe2O4（M=Fe、Co、Ni、Mn和Zn）。调节反应条件，所得磁性纳米微球的粒径可以在23～600纳米范围内进行调节，其饱和磁化率高（73~89emu/g），比表面积为55~74m2/g，三级孔的孔径分布范围分别为2~3nm、7~12nm、7~70nm。
Description
技术领域：
本发明属于纳米材料制备技术，具体涉及一种具有多级孔结构、粒径均一可调的磁性微球的制备方法。
背景技术：
室温离子液体是由特定阳离子和阴离子构成的在室温或近于室温下呈液态的物质，它具有非挥发性、低熔点、宽液程、强的静电场、宽的电化学窗口、良好的导电与导热性、高热容、高稳定性、选择性溶解力与可设计性。这些特点促使对离子液体的研究和使用从最初的化学化工领域，迅速拓展到包括功能材料、能源、资源环境、生命科学在内的众多领域。
在纳米材料合成领域中，离子液体可以替代常规的有机溶剂，使得反应可以在常压下进行，并避免对环境造成污染；离子液体具有很强的自组装能力，它能够通过氢键形成超分子结构，作为模板或者辅助模板存在；另外，由于离子液体具有较低的表面能，可以起到提高成核速率和稳定纳米颗粒的作用。相对于在水相中合成纳米颗粒，若以离子液体为模板，既能阻止纳米颗粒团聚，反应后又能用简单的方法将离子液体除去。
目前，人们使用离子液体中合成了众多类型的纳米材料，包括金属(金、银、钯等)、非金属（硒、碲等）、二氧化硅、有机氧化硅、金属氧化物、金属硫属化合物、金属盐等[参见：Ma, Z.; Yu, J.; Dai, S.: Preparation of inorganic materials using ionic liquids. Advanced materials 2010, 22, 261-285.]。朱英杰等[参见：Cao, S.-W.; Zhu, Y.-J.: Iron oxide hollow spheres: Microwave-hydrothermal ionic liquid preparation, formation mechanism, crystal phase and morphology control and properties. Acta Materialia 2009, 57, 2154-2165.]使用微波辅助离子液体法先制备了α-FeOOH空心球，然后以其为模板，加入硫酸亚铁盐共沉淀法制备了Fe3O4空心球。Zhou等[参见：Zhou, S.; Ma, Z.; Baker, G. A.; Rondinone, A. J.; Zhu, Q.; Luo, H.; Wu, Z.; Dai, S.: Self-Assembly of Metal Oxide Nanoparticles into Hierarchically Patterned Porous Architectures Using Ionic Liquid/Oil Emulsions. Langmuir 2009, 25, 7229-7233.]在离子液体与烯烃混合溶剂组成的乳液中合成了具有约300纳米或者微米级别孔径的Fe3O4泡沫。Hu等[参见：Hu, H.; Yang, H.; Huang, P.; Cui, D.; Peng, Y.; Zhang, J.; Lu, F.; Lian, J.; Shi, D.: Unique role of ionic liquid in microwave-assisted synthesis of monodisperse magnetite nanoparticles. Chemical Communications 2010, 46, 3866-3868.]在1, 2-十六二醇和二苯醚中加入少量油酸和[BMIM][BF4]，以Fe(acac)3作为铁源合成了粒径为6nm的单分散的Fe3O4纳米颗粒。Oliveira等[参见：Oliveira, F. C. C.; Effenberger, F. B.; Sousa, M. H.; Jardim, R. F.; Kiyohara, P. K.; Dupont, J.; Rubim, J. C.; Rossi, L. M.: Ionic liquids as recycling solvents for the synthesis of magnetic nanoparticles. Physical Chemistry Chemical Physics 2011, 13, 13558-13564.]以[BMIM][PF6]或者[BMIM][NTf2]离子液体作为溶剂，以Fe(acac)3/M(acac)3(M=Co、Fe、Mn或Ni)作为原料，加入油胺作为还原剂和稳定剂合成了粒径为8纳米~15纳米的MFe2O4(M=Co、Fe、Mn或Ni)纳米颗粒。Zhang等[参见：Zhang, Y.; Liu, D.; Wang, X.; Song, S.; Zhang, H.: Synthesis of Ferrite Nanocrystals Stabilized by Ionic-Liquid Molecules through a Thermal Decomposition Route. Chemistry--A European Journal 2011, 17, 920-924.]以末端带羧基和离子液体基团的PEG作为结构引导剂和稳定剂，以Fe(acac)3/M(acac)2(M=Co、Fe、Zn或Ni)为原料合成了粒径为8~11纳米的MxFe3-xO4(M=Co、Fe、Zn或Ni，0<x<1)纳米晶。Yin等[参见：Yin, S.; Luo, Z.; Xia, J.; Li, H.: Microwave-assisted synthesis of Fe3O4 nanorods and nanowires in an ionic liquid. Journal of Physics and Chemistry of Solids 2010, 71, 1785-1788.]在[BMIM][BF4]离子液体存在的情况下用微波辅助共沉淀法合成了Fe3O4纳米棒和纳米线。Li等[参见：Li, X.; Liu, D.; Song, S.; Wang, X.; Ge, X.; Zhang, H.: Rhombic dodecahedral Fe3O4: ionic liquid-modulated and microwave-assisted synthesis and their magnetic properties. CrystEngComm 2011, 13, 6017-6020.]在[C12Py][ClO4]离子液体存在的情况下以硫酸亚铁铵为原料,加入苯酚和六次甲基四胺, 微波辅助加热合成了Fe3O4十二面纳米颗粒。
关于具有多级孔结构的磁性纳米微球，目前已有报导的合成方法非常复杂。Kido等[参见：Kido, Y.; Nakanishi, K.; Miyasaka, A.; Kanamori, K.: Synthesis of Monolithic Hierarchically Porous Iron-Based Xerogels from Iron(III) Salts via an Epoxide-Mediated Sol–Gel Process. Chemistry of Materials 2012, 24, 2071-2077.]采用溶胶凝胶法合成了一种同时具有微米级大孔和介孔的Fe3O4/Fe/Fe3C多孔复合材料。这种方法首先将FeCl3和聚丙烯酰胺溶解到水和甘油的混合溶剂中，然后加入环氧丙烷作为交联剂形成凝胶，进一步处理成气溶胶后高温碳化得到磁性复合材料。但是用离子液体来合成具有多级孔结构、粒径均一可调的磁性纳米微球的方法尚未见文献报道。
发明内容：
本发明公开了一种以含铁离子液体为原料合成具有多级孔结构、粒径均一且可调的磁性纳米微球的方法。本合成方法制备工艺简单，产率高。
本发明的技术方案如下：
一种具有多级孔结构、粒径均一可调的磁性微球的制法，它包括下列步骤：
1. 含铁离子液体的配制：
所述的含铁的离子液体的阳离子为以下所述阳离子中的一种或多种，阴离子为以下所述阴离子中的一种或多种，并加入可溶性铁(III)盐或者可溶性铁(III)盐和可溶性二价盐的混合物，特别地，当阴离子为含铁的Fe(III)Cl4 -时，可以不加入可溶性铁(III)盐和可溶性二价盐，或只加入可溶性二价盐；
所述的阳离子为1, 3-二烷基咪唑离子 [R1R2IM]+、1, 2, 3-三烷基咪唑离子 [R1R2R3IM]+、N-烷基吡啶离子[RPy]+、N1, N2-二烷基吡唑离子[R1R2Pz]+、N-烷基噻唑离子[RTz]+、N1, N2-二烷基哌啶离子[R1R2Pp]+、N1, N2-二烷基吡咯烷离子[R1R2P]+、四烷基季铵离子[NR1R2R3R4]+、四烷基季鏻离子[PR1R2R3R4]+ 或三烷基锍离子[SR1R2R3]+；
所述的阴离子为Fe(III)Cl4 -、M(II)Cl4 2-(M=Fe, Co, Ni, Mn, Zn)、Cl-、Br-、BF4 -、PF6 -、CH3COO-、CF3COO-、C3F7COO-、CF3SO3 -、C4F9SO3 -、(CF3SO2)2N-、 (C2F5SO2)2N-、(CF3SO2)3C-、SbF6 -、AsF6 -、CB11H12 -、[BR1R2R3R4]-、[N(CN)2]-、NO3 -、NO2 -中的一种；
所述的可溶性铁(III)盐包括氯化铁，溴化铁，硝酸铁，硫酸铁，醋酸铁等；
所述的可溶性二价盐包括亚铁、钴、镍、锰或锌等的硝酸盐，硫酸盐，醋酸盐，氯化物或溴化物等；
2. 在搅拌的情况下，将含铁的离子液体溶解于乙二醇中形成0.01mol/L~0.2mol/L溶液，然后加入浓度为0.5mol/L~2mol/L的碱溶液，碱溶液的用量为含铁的离子液体中铁(III)的摩尔数的2~50倍，继续搅拌直至均匀，所述的碱溶液为加热时可以产生气体碱溶液，包括氨水、水合肼，羟胺，尿素，六次亚甲基四胺等的水溶液；
3. 将上述所配制的溶液转移到密闭容器中（如内衬聚四氟乙烯的钢制高压釜），然后将密闭容器转移到加热器里加热到180℃~300℃范围内的某一温度，保持温度反应3小时~24小时，反应结束后自然冷却；
4. 通过磁性分离、离心或者过滤等手段将上述反应得到的固体产物分离，并用水和乙醇多次反复洗涤，最后置于40℃~80℃的真空干燥箱中干燥，即得到目标产品磁性微球。
上述的磁性微球的制法，步骤2可以通过调节所述的碱溶液的加入量调节磁性微球的粒径，增加加入的碱溶液的浓度或体积，可以减小粒径，在碱溶液的浓度为0.5mol/L~2mol/L、用量为铁(III)的摩尔数的2~50倍的条件下，粒径可调范围为600nm~23nm。
本发明制备的磁性纳米微球的组成为MFe2O4（M=Fe、Co、Ni、Mn和Zn），其粒径可调范围为23～600纳米，其饱和磁化率为73~89emu/g，比表面积为55~74m2/g。此磁性纳米微球同时具有三级不同孔径的孔，平均孔径分布范围分别为2~3nm、7~12nm、7~70nm。如图2和图3a所示，第一级孔分布在纳米微球的表面，其平均孔径分布为7~70nm；如图3b所示，第二级孔分布在纳米微球的内部，其平均孔径分布为7~12nm；如图3c所示，第三级孔分布在纳米微球的内部，位于纳米晶核之间，其平均孔径分布为2~3nm。特别地，当纳米微球的粒径小于100nm时，第一级孔与第二级孔具有相近的孔径分布。
本发明所制备的具有多级孔结构的磁性材料因其独特的孔结构和优异的磁性能，有望应用于生物医学、传感器、锂离子电池、药物储存与缓释、催化、环境污害的吸附去除以及雷达波吸波材料等。
附图说明
图1. 具有多级孔结构的磁性纳米微球的粉末X射线衍射图。
图2. 具有多级孔结构的磁性纳米微球的扫描电镜图。
图3. 具有多级孔结构的磁性纳米微球的透射电镜图，其中：图3a、图3b和图3c是不同放大倍数图。
图4. 具有多级孔结构的磁性纳米微球的饱和磁化率。
具体实施方式：
实施例1：将1mmol的1-甲基-3-丁基咪唑离子的[FeCl4]-盐（ [C4C1IM][FeCl4]）加入到35mL乙二醇中，磁力搅拌得到均匀溶液，加入1mL 25wt%氨水, 继续搅拌30min, 将溶液转入50mL内衬聚四氟乙烯的高压釜中。然后将高压釜放入烘箱中，加热到200℃，反应12h。取出高压釜后，待其自然冷却到室温，用磁铁分离所得溶液中的固体沉淀，并用少量水和少量乙醇洗涤3次，在40℃~80℃真空烘箱中干燥。所制备的磁性微球平均粒径为300纳米，其饱和磁化率为89emu/g，比表面积为70m2/g，多级孔的平均孔径分别为2nm、10nm、60nm。其形貌和测试数据如图1~图4所示。
实施例2：将0.5mmol的氯化（1-乙基-2-甲基-3-丁基咪唑 ）（[C2C1C4IM]Cl）、0.4mmolFeCl3和0.1mmolFeCl2加入到35mL乙二醇中，磁力搅拌得到均匀溶液，加入0.5mL 50wt%水合肼溶液, 继续搅拌30min, 将溶液转入50mL内衬聚四氟乙烯的高压釜中。然后将高压釜放入烘箱中，加热到260℃，反应3h。取出高压釜后，待其自然冷却到室温，用磁铁分离所得溶液中的固体沉淀，并用少量水和少量乙醇洗涤3次，在40℃~80℃真空烘箱中干燥。所制备的磁性微球平均粒径为600纳米，其饱和磁化率为89emu/g，比表面积为74m2/g，多级孔的平均孔径分别为3nm、12nm、70nm。
实施例3：将2.5mmol的N-丁基吡啶离子的[AsF6]-盐（[C4Py][AsF6]、2.5mmold的N1-己基-N2-甲基哌啶离子的氟硼酸盐（[C6C1Pp]BF4）、5mmol的Fe(NO3)3和1mmol 的Ni(NO3)2加入到30mL乙二醇中，磁力搅拌得到均匀溶液，加入5mL 40wt%尿素溶液, 继续搅拌30min, 将溶液转入50mL内衬聚四氟乙烯的高压釜中。然后将高压釜放入烘箱中，加热到300℃，反应24h。取出高压釜后，待其自然冷却到室温，用磁铁分离所得溶液中的固体沉淀，并用少量水和少量乙醇洗涤3次，在40℃~80℃真空烘箱中干燥。所制备的磁性微球平均粒径为23纳米，其饱和磁化率为73emu/g，比表面积为55m2/g，多级孔的平均孔径分别为2nm、7nm、7nm。
实施例4：将0.5mmol的N1-己基-N2-甲基吡咯烷离子的七氟丁酸盐 （[C6C1P][C3F7COO]）、1mmol的N1-丁基-N2-甲基吡唑乙酸盐（[C4C1Pz][CH3COO]）、1mmol的N-丁基噻唑（[C4Tz][CF3SO3]）、1.5mmol 的Fe(CH3COO)3和0.5mol的 Mn(CH3COO)2加入到35mL乙二醇中，磁力搅拌得到均匀溶液，加入1mL 50wt%六次甲基四胺溶液, 继续搅拌30min, 将溶液转入50mL内衬聚四氟乙烯的高压釜中。然后将高压釜放入烘箱中，加热到180℃，反应18h。取出高压釜后，待其自然冷却到室温，用磁铁分离所得溶液中的固体沉淀，并用少量水和少量乙醇洗涤3次，在40℃~80℃真空烘箱中干燥。所制备的磁性微球平均粒径为250纳米，其饱和磁化率为81emu/g，比表面积为64m2/g，多级孔的平均孔径分别为2nm、10nm、54nm。
实施例5：将1mmol的四丁基季铵离子的（[NC4C4C4C4][N(CN)2]）、0.5mmol的四丙基季鏻离子的（[P C3C3C3C3][(CF3SO2)3C]）、0.5mmol [SC3C3C3][CB11H12]、0.5mmol Fe2(SO4)3和0.5mol CoCl2加入到35mL乙二醇中，磁力搅拌得到均匀溶液，加入2mL 50wt%羟胺溶液, 继续搅拌30min, 将溶液转入50mL内衬聚四氟乙烯的高压釜中。然后将高压釜放入烘箱中，加热到220℃，反应10h。取出高压釜后，待其自然冷却到室温，用磁铁分离所得溶液中的固体沉淀，并用少量水和少量乙醇洗涤3次，在40℃~80℃真空烘箱中干燥。所制备的磁性微球平均粒径为100纳米，其饱和磁化率为79emu/g，比表面积为60m2/g，多级孔的平均孔径分别为2nm、8nm、10nm。
Claims (2)
1.一种具有多级孔结构、粒径均一可调的磁性微球的制法，其特征是它包括下列步骤：
1)含铁离子液体的配制：
所述的含铁的离子液体的阳离子为以下所述阳离子中的一种或多种，阴离子为以下所述阴离子中的一种或多种，并加入可溶性三价铁盐或者可溶性三价铁盐和可溶性二价盐的混合物，特别地，当阴离子为含铁的FeCl4 -时，可以不加入可溶性三价铁盐和可溶性二价盐，或只加入可溶性二价盐；
所述的阳离子为1,3-二烷基咪唑离子[R1R2IM]+、1,2,3-三烷基咪唑离子[R1R2R3IM]+、N-烷基吡啶离子[RPy]+、N1,N2-二烷基吡唑离子[R1R2Pz]+、N-烷基噻唑离子[RTz]+、N1,N2-二烷基哌啶离子[R1R2Pp]+、N1,N2-二烷基吡咯烷离子[R1R2P]+、四烷基季铵离子[NR1R2R3R4]+、四烷基季鏻离子[PR1R2R3R4]+或三烷基锍离子[SR1R2R3]+；
所述的阴离子为FeCl4 -、MCl4 2-、Cl-、Br-、BF4 -、PF6 -、CH3COO-、CF3COO-、C3F7COO-、CF3SO3 -、C4F9SO3 -、(CF3SO2)2N-、(C2F5SO2)2N-、(CF3SO2)3C-、SbF6 -、AsF6 -、CB11H12 -、[BR1R2R3R4]-、[N(CN)2]-、NO3 -、NO2 -中的一种，其中M＝Fe,Co,Ni,Mn或Zn；
所述的可溶性三价铁盐包括氯化铁、溴化铁、硝酸铁、硫酸铁或醋酸铁；
所述的可溶性二价盐包括亚铁、钴、镍、锰或锌的硝酸盐，硫酸盐，醋酸盐，氯化物或溴化物；
2)在搅拌的情况下，将含铁的离子液体溶解于乙二醇中形成0.01mol/L～0.2mol/L溶液，然后加入浓度为0.5mol/L～2mol/L的碱溶液，碱溶液的用量为含铁的离子液体中三价铁的摩尔数的2～50倍，继续搅拌直至均匀，所述的碱溶液为加热时能产生气体的碱溶液，包括氨水、水合肼，羟胺，尿素，六次亚甲基四胺的水溶液；
3)将上述所配制的溶液转移到密闭容器中，然后将密闭容器转移到加热器里加热到180℃～300℃范围内的某一温度，保持温度反应3小时～24小时，反应结束后自然冷却；
4)通过磁性分离、离心或者过滤将上述反应得到的固体产物分离，并用水和乙醇多次反复洗涤，最后置于40℃～80℃的真空干燥箱中干燥，即得到目标产品磁性微球。
2.根据权利要求1所述的磁性微球的制法，其特征是：步骤2中，通过调节所述的碱溶液的加入量调节磁性微球的粒径，增加加入的碱溶液的浓度或体积，则粒径减小，在碱溶液的浓度为0.5mol/L～2mol/L、用量为三价铁的摩尔数的2～50倍的条件下，粒径可调范围为600nm～23nm。
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