Sun, Yujia (2018-12). Construction of Highly Stable Metal-Organic Frameworks with Multiple Functionalities. Doctoral Dissertation. Thesis uri icon

abstract

  • Metal-organic frameworks (MOFs) are a class of newly emerged crystalline porous materials consisting of metal ions or clusters and organic linkers. Through judicious choice of inorganic joints and organic struts, the structure, porosity and functionality of MOFs can be tuned. However, the lack of high stability of most of the reported MOFs as well as limited methods to introduce multiple functionalities into the framework hinders the exploration of MOFs towards a wide variety of potential applications. The main goal of this research is to develop synthetic strategies to construct MOFs with high stability and multiple functionalities. Firstly, a brief introduction of MOFs was provided, focusing on strategies to increase their stability and introduce functionalities. Secondly, a facile one-pot synthetic strategy was developed to introduce porphyrin into highly stable UiO-66 homogeneously. The crystal structure, morphology, and ultrahigh chemical stability of UiO-66 were well maintained in the functionalized MOFs. In addition, the amount of integrated porphyrin can be gradually tuned. Thirdly, a general in situ secondary ligand incorporation (ISLI) strategy was investigated to synthesize multivariate UiO series of MOFs. Both experimental and computational studies were carried out to understand the chemistry behind this strategy. Fourthly, ISLI strategy was further applied in highly stable Zr-MOFs constructed from multitopic ligands to incorporate multiple functionalities. Fifthly, a porphyrin and pyrene-based mixed-ligand MOF with high stability and novel topology was synthesized. This MOF provides an ideal platform for further functionalization and exploration of new structures. In summary, different strategies were investigated to construct highly stable MOFs with the incorporation of multiple functionalities. These studies provide useful tools to explore stable MOFs with desired multifunctionality for potential applications.
  • Metal-organic frameworks (MOFs) are a class of newly emerged crystalline porous materials consisting of metal ions or clusters and organic linkers. Through judicious choice of inorganic joints and organic struts, the structure, porosity and functionality of MOFs can be tuned. However, the lack of high stability of most of the reported MOFs as well as limited methods to introduce multiple functionalities into the framework hinders the exploration of MOFs towards a wide variety of potential applications. The main goal of this research is to develop synthetic strategies to construct MOFs with high stability and multiple functionalities.

    Firstly, a brief introduction of MOFs was provided, focusing on strategies to increase their stability and introduce functionalities.

    Secondly, a facile one-pot synthetic strategy was developed to introduce porphyrin into highly stable UiO-66 homogeneously. The crystal structure, morphology, and ultrahigh chemical stability of UiO-66 were well maintained in the functionalized MOFs. In addition, the amount of integrated porphyrin can be gradually tuned.

    Thirdly, a general in situ secondary ligand incorporation (ISLI) strategy was investigated to synthesize multivariate UiO series of MOFs. Both experimental and computational studies were carried out to understand the chemistry behind this strategy.

    Fourthly, ISLI strategy was further applied in highly stable Zr-MOFs constructed from multitopic ligands to incorporate multiple functionalities.

    Fifthly, a porphyrin and pyrene-based mixed-ligand MOF with high stability and novel topology was synthesized. This MOF provides an ideal platform for further functionalization and exploration of new structures.

    In summary, different strategies were investigated to construct highly stable MOFs with the incorporation of multiple functionalities. These studies provide useful tools to explore stable MOFs with desired multifunctionality for potential applications.

publication date

  • December 2018