Platform Development for Characterization of Iron Catalysts Encapsulated in Metal-Organic Framework UiO-66

Abstract

Host-guest chemistry provides a unique platform for catalysis by combining the specificity of homogeneous catalysts with the stability and recyclability of heterogeneous catalysts. Metal-Organic Frameworks (MOFs), such as UiO-66 are ideal hosts for host-guest catalysis. The vast porous network UiO-66 forms is chemically and thermally stable and the individual cages that make up the crystals can be modified by simple organic syntheses. The method developed in our group provides a mild, synthetically simple route for non-covalent organometallic guest encapsulation that decouples host synthesis from guest encapsulation. In this study, the so-called aperture opening encapsulation method is tested using an unstable class of iron-based carbon dioxide hydrogenation catalysts. The study results in launching an extensive investigation into the driving force behind aperture opening encapsulation with the goal of increasing guest loadings. Various methods to achieve this goal are explored including synthesizing novel UiO-66 linkers and taking advantage of factors such as columbic force. In conclusion, the information gained from a bigger picture examination of aperture opening encapsulation directly leads to guest loadings high enough to utilize useful characterization techniques. Accordingly, a standard protocol for characterization of iron catalysts encapsulated in UiO-66 is developed.