CO2 chemical transformations using metal-organic frameworks

During the last decades, intensive efforts have been applied to tackle the enormous emissions of CO2 into atmosphere. These efforts include not only developing efficient carbon capture techniques, but also the introduction of new ways to transform the captured CO2 into the valuable products. In this context, numerous catalytic systems have been developed for the reduction of CO2. Typically, homogeneous systems provide better selectivity, due to more precise control of the chemical properties of the catalytic moiety, and require milder reaction conditions, compared to the currently employed heterogeneous catalysts. However, the majority of industrial chemical processes deploy heterogeneous catalytic systems, as their comparative stability and facile separation of the products from the catalyst facilitates scale-up and continuous production. Therefore, the crucial vector of successful transfer of the newest achievements in chemical catalysis lies in merging the advantages provided by homogeneous catalysts with the benefits of heterogeneous systems. Metal-organic frameworks (MOFs) are crystalline materials formed by the self-assembly of metal ions or clusters with organic ligands and possess unique merits, such as extremely high surface area, uniform and tunable porous structure, wide opportunities for rational design. Amalgamation of the newly developed concepts, such as FLP chemistry, showing promising results in activation of CO2, as well as recent advances in conventional catalysis with MOFs should allow the advantages of MOFs as materials with directed assembly to converge with the versatile needs of a catalytic material an improve the potential for application of them both in industry and chemical synthesis. This thesis describes the implementation of the FLP concept into MOFs. A proof of a concept, demonstrating feasibility and potential applicability of this approach for CO2 fixation is followed by the development and evaluation of a recyclable and water tolerant heterogeneous MOF catalyst for FLP-mediated reduction of CO2. Additionally, MOF-based catalysts, employing incorporated functionalities and supported metal nanoparticles, were accessed for CO2 conversion.