CN106699665A - 一类沸石咪唑酯骨架材料及其制备方法与应用 - Google Patents

一类沸石咪唑酯骨架材料及其制备方法与应用 Download PDF

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CN106699665A
CN106699665A CN201611093585.1A CN201611093585A CN106699665A CN 106699665 A CN106699665 A CN 106699665A CN 201611093585 A CN201611093585 A CN 201611093585A CN 106699665 A CN106699665 A CN 106699665A
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zeolitic imidazolate
imidazolate framework
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石卓
于英豪
杨婉欣
游高雄
袁媛
王乐夫
李雪辉
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South China University of Technology SCUT
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
    • C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
    • C07D233/56—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
    • C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
    • C07D233/56—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms
    • C07D233/58—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring nitrogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
    • C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
    • C07D233/66—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D233/90—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
    • C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
    • C07D233/66—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D233/91—Nitro radicals
    • C07D233/92—Nitro radicals attached in position 4 or 5
    • C07D233/93—Nitro radicals attached in position 4 or 5 with hydrocarbon radicals, substituted by halogen atoms, attached to other ring members

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Abstract

本发明公开一类沸石咪唑酯骨架材料及其制备方法与应用，属于新材料技术领域。本发明选取了6种带有特异性官能团的咪唑衍生物配体，采用溶剂热方法合成介孔类沸石咪唑酯骨架材料。采用的6种配体，包括带碳碳双键的1‑乙烯基咪唑、1‑烯丙基咪唑，带酰基官能团的1‑酰基咪唑、带酰胺和氨基官能团的4‑氨基‑5‑咪唑甲酰胺，带硝基和卤素原子的2‑氯‑4‑硝基咪唑、2‑溴‑4‑硝基咪唑。本发明制备的沸石咪唑酯骨架材料，具有结晶度较高、比表面积较大、热稳定性较高等特点；本发明的沸石咪唑酯骨架材料可用于吸附化学物种、气体储藏、传感器以及催化剂等方面。

Description

一类沸石咪唑酯骨架材料及其制备方法与应用
技术领域
本发明属于新材料技术领域，具体涉及一类沸石咪唑酯骨架材料及其制备方法与应用。
背景技术
金属有机骨架材料(Metal Organic Frameworks，简称MOFs)的出现，使多孔材料的组成由无机多孔材料延伸到无机有机多孔材料，并因而具有新的物理化学性能。MOFs可供选择的金属离子种类繁多且金属离子价态和配位丰富，可通过选择不同的有机配体或者对有机配体进行官能团修饰来控制孔结构和尺
寸，因而在气体吸附分离方面显示了应用价值。但是，MOFs由于其配位价态较高，热稳定性和化学稳定性都不及无机沸石，在水中的稳定性也较差，使其实际应用受到了限制。
沸石咪唑酯骨架材料(Zeolitic Imdazolate Framework，简称ZIFs)，是一类新的具有沸石拓扑结构的金属有机骨架材料。ZIFs由Zn2+、Co2+、Cu2+等过渡态金属离子与咪唑或咪唑衍生物配位形成的新型多孔晶体材料，结构与无机沸石相似，其骨架可以看作是金属离子(用M表示)取代无机沸石中的硅或铝，咪唑和咪唑衍生物(用IM表示)取代无机沸石中的氧桥(式1)，形成的具有和沸石具有相同键角(145°)的多孔性材料，具有类似于无机沸石高的化学与热稳定性、良好的耐水、耐溶剂、耐酸碱性。同时，还可以通过对咪唑配体上2、4、5位的碳原子嫁接不同结构的官能团，改变配体和金属原子之间的相互作用以及配体自身之间的空间位阻效应，可以制备出不同结构的ZIFs材料，拥有类似于MOFs高孔隙率、大比表面积、低密度、以及孔道可调性等特性。集无机沸石和MOFs优点于一身的ZIFs，在催化剂、磁性材料、润滑剂、药物输送、化学气体传感器、石油化工中链烃烯烃的分离、气体吸附分离及储存等方面有着广泛的用途。
式1咪唑沸石分子筛与无机沸石的结构对比
目前，使用新配体合成的ZIFs材料依旧较少，而且这些ZIFs的性能及应用有待进一步的发现，这也是本发明试图解决的问题。
发明内容
为了克服现有技术的缺点与不足，本发明的首要目的在于提供一类沸石咪唑酯骨架材料的制备方法。具体而言，本发明选取了6种文献中未见报道的带有特异性官能团的咪唑衍生物配体，采用溶剂热方法合成沸石咪唑酯骨架材料。
本发明的另一目的在于提供通过上述制备方法制备得到的沸石咪唑酯骨架材料。该骨架材料结晶度较高、比表面积较大、热稳定与化学稳定性较好。
本发明的再一目的在于上述沸石咪唑酯骨架材料的应用。
本发明的目的通过下述技术方案实现：
一类沸石咪唑酯骨架材料的制备方法，该材料采用溶剂热方法合成，并包括以下步骤：
(1)将金属盐与咪唑衍生物配体，加入至N,N-二甲基甲酰胺(DMF)中，混合后搅拌均匀，得到混合液；
(2)把步骤(1)得到的混合溶液转移至聚四氟乙烯内衬不锈钢反应釜中，反应；
(3)将反应釜自然冷却至室温，离心所得的反应液，沉淀经分离后加入N,N-二甲基甲酰胺进行超声洗涤，干燥，即得到沸石咪唑酯骨架材料。
所述的金属盐为六水合硝酸锌(Zn(NO3)2·6H2O)、七水合硫酸锌(ZnSO4·7H2O)、二水合醋酸锌(Zn(OAc)2·2H2O)和氯化锌(ZnCl2)中的一种。
所述的咪唑衍生物配体为1-乙烯基咪唑、1-烯丙基咪唑、1-乙酰咪唑、4-氨基-5-咪唑甲酰胺、2-氯-4-硝基咪唑和2-溴-4-硝基咪唑中的一种，结构式如下：
所述的金属盐与咪唑衍生物配体的摩尔配比为1:2～1:4，DMF的用量为40～100mL；
所述的反应的条件为120～160℃反应20～30h；
所述的干燥的条件为110～130℃干燥16～32h。
一种介孔类沸石咪唑酯骨架材料，通过上述制备方法制备得到。
所述的沸石咪唑酯骨架材料可用于吸附化学物种、气体储藏、传感器以及催化剂等方面。
现有沸石咪唑酯骨架材料相比，本发明具有如下的优点及效果：
(1)在制备过程中，本发明采用了6种全新的有机配体，包括带碳碳双键的1-乙烯基咪唑、1-烯丙基咪唑，带酰基官能团的1-酰基咪唑、带酰胺和氨基官能团的4-氨基-5-咪唑甲酰胺，带硝基和卤素原子的2-氯-4-硝基咪唑、2-溴-4-硝基咪唑。
(2)本发明制备的沸石咪唑酯骨架材料，具有结晶度较高、比表面积较大、热稳定性较高等特点；本发明的沸石咪唑酯骨架材料可用于吸附化学物种、气体储藏、传感器以及催化剂等方面。
附图说明
图1是实施例3制得的含1-乙酰咪唑的ZIFs的XRD谱图。
图2是实施例3制得的含1-乙酰咪唑的ZIFs的红外谱图。
图3是实施例3制得的含1-乙酰咪唑的ZIFs在空气中的TG曲线。
具体实施方式
下面结合实施例及附图对本发明作进一步详细的描述，但本发明的实施方式不限于此。
实施例1
以1-乙烯基咪唑为配体的类ZIFs材料的合成
称取0.657g(3mmol)Zn(OAc)2·2H2O溶于40mL DMF中，再加入0.846g(9mmol)1-乙烯基咪唑；搅拌均匀后转入聚四氟乙烯内衬不锈钢反应釜，在恒温鼓风干燥箱中140℃下反应30h；用DMF超声洗涤5min，循环洗涤3次后，离心分离，所得沉淀在120℃下烘干24h，即可得到目标材料。
实施例2
以1-烯丙基咪唑为配体的类ZIFs材料的合成
称取0.891g(3mmol)Zn(NO3)2·6H2O溶于60mL DMF中，再加入0.972g(9mmol)1-烯丙基咪唑；搅拌均匀后转入聚四氟乙烯内衬不锈钢反应釜，在恒温鼓风干燥箱中120℃下反应24h；用DMF超声洗涤5min，循环洗涤3次后，离心分离，所得沉淀在110℃下烘干32h，即可得到目标材料。
实施例3
以1-乙酰咪唑为配体的类ZIFs材料的合成
称取0.861g(3mmol)ZnSO4·7H2O溶于80mL DMF中，再加入0.660g(6mmol)1-乙酰咪唑；搅拌均匀后转入聚四氟乙烯内衬不锈钢反应釜，在恒温鼓风干燥箱中160℃下反应24h；用DMF超声洗涤5min，循环洗涤3次后，离心分离，所得沉淀在130℃下烘干16h，即可得到目标材料。
本实施例制得的含1-乙酰咪唑的ZIFs的XRD谱图分析，如图1所示。从图中可以看出，所合成的含1-乙酰咪唑配体的ZIFs新材料具有很高的结晶度(110晶面的衍射峰强度达到10318)，说明在该条件下得到了该物质规整的晶体结构。
本实施例制得的含1-乙酰咪唑的ZIFs的红外谱图分析，如图2所示。从图中可以看出，1680cm-1归属于酰基上C＝O的伸缩振动峰，3120cm-1归属于咪唑环上N-H的伸缩振动峰，1490cm-1归属于咪唑环上C-H面内弯曲振动峰，1094cm-1归属于咪唑环上C-C伸缩振动峰。说明所合成ZIFs新材料的红外谱图中，含有1-乙酰咪唑配体上的特征官能团，该配体成功用于ZIFs材料的合成。
本实施例制得的含1-乙酰咪唑的ZIFs在空气中的TG曲线，如图3所示。从图中可以看出，在空气气氛下，该ZIFs新材料的热稳定温度达到490℃，热稳定性较高。
实施例4
以4-氨基-5-咪唑甲酰胺为配体的类ZIFs材料的合成
称取0.414g(3mmol)ZnCl2溶于100mL DMF中，再加入1.512g(12mmol)4-氨基-5-咪唑甲酰胺；搅拌均匀后转入聚四氟乙烯内衬不锈钢反应釜，在恒温鼓风干燥箱中160℃下反应20h；用DMF超声洗涤5min，循环洗涤3次后，离心分离，所得沉淀在120℃下烘干24h，即可得到目标材料。
实施例5
以2-氯-4-硝基咪唑为配体的类ZIFs材料的合成
称取0.891g(3mmol)Zn(NO3)2·6H2O溶于90mL DMF中，再加入1.332g(9mmol)2-氯-4-硝基咪唑；搅拌均匀后转入聚四氟乙烯内衬不锈钢反应釜，在恒温鼓风干燥箱中120℃下反应30h；用DMF超声洗涤5min，循环洗涤3次后，离心分离，所得沉淀在120℃下烘干20h，即可得到目标材料。
实施例6
以2-溴-4-硝基咪唑为配体的类ZIFs材料的合成
称取0.891g(3mmol)Zn(NO3)2·6H2O溶于60mL DMF中，再加入1.498g(7.8mmol)2-溴-4-硝基咪唑；搅拌均匀后转入聚四氟乙烯内衬不锈钢反应釜，在恒温鼓风干燥箱中140℃下反应24h；用DMF超声洗涤5min，循环洗涤3次后，离心分离，所得沉淀在130℃下烘干20h，即可得到目标材料。
实施例1～2、4～6获得的目标材料的XRD谱图、红外谱图、TG曲线均能获得与图1～3类似的结果，在此就不一一赘述。
上述实施例为本发明较佳的实施方式，但本发明的实施方式并不受上述实施例的限制，其他的任何未背离本发明的精神实质与原理下所作的改变、修饰、替代、组合、简化，均应为等效的置换方式，都包含在本发明的保护范围之内。

Claims (7)

1.一类沸石咪唑酯骨架材料的制备方法，其特征在于采用溶剂热方法合成，并包括以下步骤：
(1)将金属盐与咪唑衍生物配体，加入至DMF中，混合后搅拌均匀，得到混合液；
(2)把步骤(1)得到的混合溶液转移至聚四氟乙烯内衬不锈钢反应釜中，反应；
(3)将反应釜自然冷却至室温，离心所得的反应液，沉淀经分离后加入N,N-二甲基甲酰胺进行超声洗涤，干燥，即得到沸石咪唑酯骨架材料；
所述的咪唑衍生物配体为1-乙烯基咪唑、1-烯丙基咪唑、1-乙酰咪唑、4-氨基-5-咪唑甲酰胺、2-氯-4-硝基咪唑和2-溴-4-硝基咪唑中的一种。
2.根据权利要求1所述的介孔类沸石咪唑酯骨架材料的制备方法，其特征在于：
所述的金属盐为六水合硝酸锌、七水合硫酸锌、二水合醋酸锌和氯化锌中的一种。
3.根据权利要求1所述的介孔类沸石咪唑酯骨架材料的制备方法，其特征在于：
所述的金属盐与咪唑衍生物配体的摩尔配比为1:2～1:4，DMF的用量为40～100mL。
4.根据权利要求1所述的介孔类沸石咪唑酯骨架材料的制备方法，其特征在于：
所述的反应的条件为120～160℃反应20～30h。
5.根据权利要求1所述的介孔类沸石咪唑酯骨架材料的制备方法，其特征在于：
所述的干燥的条件为110～130℃干燥16～32h。
6.一类沸石咪唑酯骨架材料，其特征在于通过权利要求1～5任一项所述的制备方法制备得到。
7.权利要求6所述的沸石咪唑酯骨架材料在吸附化学物种、气体储藏、传感器以及催化剂中的应用。
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