多孔金属卟啉框架材料的催化性能研究
详细信息 查看官网全文
- 英文论文题名：Catalytic Applications of Porous Metalloporphyrinic Frameworks
- 论文作者：杨秀丽 ; 解明华
- 英文论文作者：Xiu-Li Yang ; Ming-Hua Xie ; Collaborative Innovation Center for Ecological Building Materials and Environmental Protection Equipments ; Yancheng Institute of Technology
- 年：2016
- 作者机构：盐城工学院江苏省生态建材与环保装备协同创新中心;
- 论文关键词：金属-卟啉框架 ; 催化 ; 多孔材料
- 会议召开时间：2016-07-01
- 会议录名称：中国化学会第30届学术年会摘要集-第三十二分会： 多孔功能材料
- 语种：中文
- 分类号：O627;O643.36
- 学会代码：ZGHY
- 会议名称：中国化学会第30届学术年会-第三十二分会 ; 多孔功能材料
- 会议地点：中国辽宁大连
- 主办单位：中国化学会
- 学会名称：中国化学会
- 页数：1
- 文件大小：238k
- 原文格式：D
- 会议级别：全国
摘要
金属卟啉化合物广泛存在于自然界各种生物体内,具有高效专一的催化活性。我们设计合成了八羧基取代的镶嵌有不同金属的卟啉配体,并分别与CuII、ZnII自组装,得到三个具有新颖结构的三维多孔催化剂材料~[1,2]。其中卟啉框架材料1由镍金属卟啉和铜离子构筑,具有直径为2.1 nm的纳米笼状结构;卟啉框架材料2由锰金属卟啉和铜离子构筑,具有直径为1.5 nm的纳米管结构;卟啉框架材料3由锰金属卟啉与锌离子构筑,具有直径为2.3 nm的纳米笼结构。材料1和2对脱氢交叉偶联(CDC)反应以及材料3对烯烃环氧化反应均表现出优异于均相的催化活性。材料的开放孔道结构以及固定在孔道中裸露的金属离子是其高效催化活性的来源。通过将卟啉单元自组装,形成框架结构,有效避免了催化剂自身接触导致的失活自氧化,同时利用其开放孔道结构,提升了材料的催化活性。
We have synthesized three metalloporphyrin octacarboxylates,which were used to construct porous metalloporphyrinic frameworks containing 3D nanopore cage or nanotublar channels by reacting with Cu~(?)or Zn~(?)respectively.The topologies and catalytic activities of the frameworks are highly dependent on the species of the central metal ions and the coordination motifs of the peripheral carboxylate groups.The metalloporphyrinic frameworks showed remarkable heterogeneous catalytic activities toward the CDC reaction and olefin epoxidation,originating from the immobilization of free accessible metal ions onto the pore surfaces.In the form of frameworks,the porphyrin moieties showed enhanced catalytic activities and can be protected from suicidal self-oxidation.
We have synthesized three metalloporphyrin octacarboxylates,which were used to construct porous metalloporphyrinic frameworks containing 3D nanopore cage or nanotublar channels by reacting with Cu~(?)or Zn~(?)respectively.The topologies and catalytic activities of the frameworks are highly dependent on the species of the central metal ions and the coordination motifs of the peripheral carboxylate groups.The metalloporphyrinic frameworks showed remarkable heterogeneous catalytic activities toward the CDC reaction and olefin epoxidation,originating from the immobilization of free accessible metal ions onto the pore surfaces.In the form of frameworks,the porphyrin moieties showed enhanced catalytic activities and can be protected from suicidal self-oxidation.
引文
[1]Yang,X.-L.;Chao,Z.;He,Y.;Zhao,M.;Chen,B.;Xiang,S.;O’Keeffe,M.;Wu,C.-D.Chem.Eur.J.2014,20:1447.
[2]Yang,X.-L.;Wu,C.-D.Inorg.Chem.2014,53:4797
[2]Yang,X.-L.;Wu,C.-D.Inorg.Chem.2014,53:4797