CN106967219A - 基于3,3′,5,5′‑联苯四羧酸的镉金属有机框架材料及其制备方法和应用 - Google Patents
基于3,3′,5,5′‑联苯四羧酸的镉金属有机框架材料及其制备方法和应用 Download PDFInfo
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Abstract
本发明公开了一种基于3,3′,5,5′‑联苯四羧酸的镉金属有机框架材料及其制备方法和应用。该材料的结构单元为[Cd4(BPTC)2(DMA)3(EtOH)(H2O)(NMF)]·(DMA)，其中BPTC代表失去四个羧基上H原子的3,3′,5,5′‑联苯四羧酸阴离子、DMA代表N,N‑二甲基乙酰胺、EtOH代表乙醇、NMF代表N‑甲基甲酰胺，属于正交晶系Pbcn空间群，晶胞参数a为b为c为α为90°、β为90°、γ为90°，V为该材料是以四水合硝酸镉为金属源，以3,3′,5,5′‑联苯四羧酸为配体，采用溶剂热法制备而成，其作为光催化剂用于降解有机染料亚甲基蓝、天青I、结晶紫、丁基罗丹明B、孔雀石绿、日落黄、甲基橙和丽春红等表现出显著的降解效果。
Description
技术领域
本发明属于合成金属有机骨架材料技术领域，具体涉及一种基于3,3′,5,5′-联苯四羧酸的镉金属有机框架材料，以及该材料的制备方法和在紫外光光催化降解有机染料中的应用。
背景技术
目前环境污染已经成为人类健康、生态平衡和社会经济发展所面临的重大挑战。尤其是我国工业污水、工业染料、农业污水、有毒液体排放到自然湖泊、河流等自然水体，给环境带来压力和破坏。目前工业废水排放的主要污染源来自印染业行业，并且其中的有机染料具有组成复杂、高色度、有毒、强酸强碱性等复杂特点，从而导致水质污染严重、治理难、难降解等特点。而光催化降解染料则是一种应用和研究比较普遍的处理方法，常用于各种染料废水的处理，该方法具有高效、快捷等优点，该方法是通过发生光化学反应，将水中的一些物质除去，达到净化废水的目的。
随着光催化材料的迅速发展，具有半导体性能的金属有机骨架材料(Metal-Organic Frameworks，简称MOFs)在光催化领域中得到关注。该类材料是由单一的金属原子(或金属簇)与多配位基团的有机配体组成结构规则，具有刚性多孔网的一类多孔材料。并且该类多孔MOFs材料具有可控孔道、比表面积较高、孔结构规则等特点，则可吸附特定染料分子；另外MOFs材料自身具有丰富的不饱和位点，这类金属位点是催化反应中的活性位点，且具有高度的选择。因此，基于MOFs材料在催化领域的重要作用及其广阔的发展空间，而且此类多孔金属有机骨架材料应用于光催化，其具有反应效率高，速度快，而且对多种有机污染物降解效果显著。因此，制备新型的环境友好、高效的金属有机框架材料，作为光催化剂，具有广泛基础研究价值和应用前景。
发明内容
本发明所要解决的技术问题在于提供一种基于3,3′,5,5′-联苯四羧酸的镉金属有机框架材料，并为该材料提供一种制备方法和应用。
解决上述技术问题所采用的技术方案是：该基于3,3′,5,5′-联苯四羧酸的镉金属有机框架材料的结构单元为：[Cd4(BPTC)2(DMA)3(EtOH)(H2O)(NMF)]·(DMA)，其中BPTC代表失去四个羧基上H原子的3,3′,5,5′-联苯四羧酸阴离子、DMA代表N,N-二甲基乙酰胺、EtOH代表乙醇、NMF代表N-甲基甲酰胺；该材料属于正交晶系Pbcn空间群，晶胞参数a为b为c为α为90°、β为90°、γ为90°，V为
本发明基于3,3′,5,5′-联苯四羧酸的镉金属有机框架材料的制备方法为：以N,N-二甲基乙酰胺与乙醇、去离子水体积比为5～8:1～3:1的混合液为溶剂，将四水合硝酸镉与3,3′,5,5′-联苯四羧酸按摩尔比为1:2～4，在密闭条件下110～130℃恒温静置反应4～6天，冷却至室温，过滤，洗涤，干燥，制备成基于3,3′,5,5′-联苯四羧酸的镉金属有机框架材料。
上述制备方法中，优选以N,N-二甲基乙酰胺与乙醇、去离子水体积比为6:2:1的混合液为溶剂。
上述制备方法中，优选四水合硝酸镉与3,3′,5,5′-联苯四羧酸的摩尔比为1:2.7。
上述制备方法中，进一步优选在密闭条件下120℃恒温静置反应5天。
本发明基于3,3′,5,5′-联苯四羧酸的镉金属有机框架材料在降解有机染料中的应用，其中所述的有机染料为偶氮类、吩噻嗪类、三苯甲烷类、吡喃类染料中的任意一种，具体如亚甲基蓝、天青I、结晶紫、丁基罗丹明B、孔雀石绿、日落黄、甲基橙、丽春红等。
本发明以四水合硝酸镉为金属源，以3,3′,5,5′-联苯四羧酸为配体，在混合溶剂N,N-二甲基乙酰胺与乙醇、去离子中采用溶剂热合成法制备成基于3,3′,5,5′-联苯四羧酸的镉金属有机框架材料，该材料作为光催化剂用于降解染料亚甲基蓝(MB)和天青I(AZ)、结晶紫(CV)、丁基罗丹明B(BB)、孔雀石绿(MG)、日落黄(SY)、甲基橙(MO)和丽春红(PS)等多种有机污染物表现出显著的降解效果，反应效率高，速度快。
附图说明
图1是本发明基于3,3′,5,5′-联苯四羧酸的镉金属有机框架材料的配位结构图。
图2是配体3,3′,5,5′-联苯四羧酸的A形式配位模式图。
图3是配体3,3′,5,5′-联苯四羧酸的B形式配位模式图。
图4是本发明基于3,3′,5,5′-联苯四羧酸的镉金属有机框架材料的二维44网格图。
图5是本发明基于3,3′,5,5′-联苯四羧酸的镉金属有机框架材料的三维结构图。
图6是本发明基于3,3′,5,5′-联苯四羧酸的镉金属有机框架材料的拓扑结构图。
图7是本发明基于3,3′,5,5′-联苯四羧酸的镉金属有机框架材料的固体紫外漫反射图。
图8是本发明基于3,3′,5,5′-联苯四羧酸的镉金属有机框架材料对染料亚甲基蓝(MB)和天青I(AZ)的降解率与时间关系图。
图9是本发明基于3,3′,5,5′-联苯四羧酸的镉金属有机框架材料对染料结晶紫(CV)、丁基罗丹明B(BB)、孔雀石绿(MG)、日落黄(SY)、甲基橙(MO)和丽春红(PS)的降解率与时间关系图。
实施例1
将0.057g Cd(NO3)2·4H2O，0.025g 3,3′,5,5′-联苯四羧酸(H4BPTC)、6mL N,N-二甲基乙酰胺、2mL乙醇和1mL去离子水加入25mL烧瓶中，搅拌均匀后，密封，120℃恒温静置反应5天，然后自然冷却至室温，过滤，用蒸馏水洗涤，空气中自然干燥，制备成基于3,3′,5,5′-联苯四羧酸的镉金属有机框架材料，其结构单元为[Cd4(BPTC)2(DMA)3(ETOH)(H2O)(NMF)]·(DMA)，其中BPTC代表失去四个羧基上H原子的3,3′,5,5′-联苯四羧酸阴离子、DMA代表N,N-二甲基乙酰胺、EtOH代表乙醇、NMF代表N-甲基甲酰胺。根据镉计算该材料的产率约为54％。
所制备的基于3,3′,5,5′-联苯四羧酸的镉金属有机框架材料的配位结构如图1所示，属于正交晶系Pbcn空间群，晶胞参数a为b为c为α为90°、β为90°、γ为90°，晶胞体积V为该材料在晶体学独立单元中有4个晶体学独立的Cd2+离子、2个BPTC配体、4个DMA分子、1个配位的H2O分子和1个配位的EtOH分子。结构分析显示4个Cd2+离子均采取八面体的几何构型，其中Cd1和Cd4分别于来自3个不同的BPTC配体的6个羧基氧原子配位，而与Cd2原子配位的6个氧原子，其中3个来自3个不同的BPTC配体中羧基氧原子，另外3个氧原子则分别来自DMA分子、配位H2O分子和配位的EtOH分子中的氧原子。其中Cd-O键的键长范围为其中Cd1和Cd2、Cd3和Cd4原子分别桥连2个羧基从而形成Cd2(CO2)2二核簇结构单元，其中金属Cd1···Cd2间的键长为Cd3···Cd4间的键长为由图2和3可见，在此结构单元中配体BPTC有A(见图2)、B(见图3)两种形式的扭转角，其中A形式中两个苯环平面之间的扭转角为28.41°，其中羧基氧采取μ2-η2:η2:η2:η2的配位模式；B形式中两个苯环平面之间的扭转角仅为9.03°，并且羧基氧采取μ1-η1:η1,μ2-η2:η2的配位模式。如图4所示，每一个二核Cd2(CO2)2簇连接四个配体BPTC，另外每个配体BPTC连接四个二核Cd2(CO2)2簇，在ac-平面扩展成两种孔道结构的44网格；进一步沿b-轴方向通过配体BPTC形成具有的一维孔道A，同时4个一维孔道A通过共用四个二核Cd2(CO2)2簇和四个配体BPTC而形成具有的B孔道，进而扩展成具有A、B两种孔道类型的三维金属有机框架(见图5)。为了进一步简化其结构图，将二核Cd2(CO2)2簇为4-连接节点，BPTC为4-连接节点，进一步拓展成具有4,4-连接的拓扑结构(见图6)。
所制备产物的元素分析：理论值H,3.90；C,40.56；N,4.38；实验值H,3.95；C,40.87；N,4.56。
由图7可见，固体紫外漫反射测定其带隙值为3.43eV，说明其具有较好的半导体性能，并具有潜在的紫外光光催化的性能。
实施例2
实施例1制备的基于3,3′,5,5′-联苯四羧酸的镉金属有机框架材料在降解有机染料中的应用
发明人采用实施例1制备的基于3,3′,5,5′-联苯四羧酸的镉金属有机框架材料分别降解亚甲基蓝(MB)、天青I(AZ)、结晶紫(CV)、丁基罗丹明B(BB)、孔雀石绿(MG)、日落黄(SY)、甲基橙(MO)、丽春红(PS)，结果如图8和9所示。
由图8、图9可见，本发明基于3,3′,5,5′-联苯四羧酸的镉金属有机框架材料对亚甲基蓝(MB)具有超快的降解速率，在15min即可降解89.3％；天青I(AZ)则在60min降解51.1％；在420min，对结晶紫(CV)降解97.1％、丁基罗丹明B(BB)降解90.7％、孔雀石绿(MG)降解87.8％；在600min，对日落黄(SY)降解率为52.5％、甲基橙(MO)降解率为43.6％、丽春红(PS)降解率为40.0％。
Claims (7)
1.一种基于3,3′,5,5′-联苯四羧酸的镉金属有机框架材料，其特征在于该材料的结构单元为：[Cd4(BPTC)2(DMA)3(EtOH)(H2O)(NMF)]·(DMA)，其中BPTC代表失去四个羧基上H原子的3,3′,5,5′-联苯四羧酸阴离子、DMA代表N,N-二甲基乙酰胺、EtOH代表乙醇、NMF代表N-甲基甲酰胺；该材料属于正交晶系Pbcn空间群，晶胞参数a为b为c为α为90°、β为90°、γ为90°，V为
2.一种权利要求1所述的基于3,3′,5,5′-联苯四羧酸的镉金属有机框架材料的制备方法，其特征在于：以N,N-二甲基乙酰胺与乙醇、去离子水体积比为5～8:1～3:1的混合液为溶剂，将四水合硝酸镉与3,3′,5,5′-联苯四羧酸按摩尔比为1:2～4，在密闭条件下110～130℃恒温静置反应4～6天，冷却至室温，过滤，洗涤，干燥，制备成基于3,3′,5,5′-联苯四羧酸的镉金属有机框架材料。
3.根据权利要求2所述的基于3,3′,5,5′-联苯四羧酸的镉金属有机框架材料的制备方法，其特征在于：以N,N-二甲基乙酰胺与乙醇、去离子水体积比为6:2:1的混合液为溶剂。
4.根据权利要求2所述的基于3,3′,5,5′-联苯四羧酸的镉金属有机框架材料的制备方法，其特征在于：所述的四水合硝酸镉与3,3′,5,5′-联苯四羧酸的摩尔比为1:2.7。
5.根据权利要求2所述的基于3,3′,5,5′-联苯四羧酸的镉金属有机框架材料的制备方法，其特征在于：在密闭条件下120℃恒温静置反应5天。
6.权利要求1所述的基于3,3′,5,5′-联苯四羧酸的镉金属有机框架材料在降解有机染料中的应用，其中所述的有机染料为偶氮类、吩噻嗪类、三苯甲烷类、吡喃类染料中的任意一种。
7.根据权利要求6所述的基于3,3′,5,5′-联苯四羧酸的镉金属有机框架材料在降解有机染料中的应用，其特征在于：所述的有机染料为亚甲基蓝、天青I、结晶紫、丁基罗丹明B、孔雀石绿、日落黄、甲基橙、丽春红中的任意一种。
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