This PhD thesis explores the application of Metal-organic frameworks (MOFs) in heterogeneous catalysis, with a specific focus on their use in CO2 valorization reactions. The thesis is divided into three main parts.

The first part introduces a novel method for controlling the phase composition of MOF-derived solids by incorporating water during pyrolysis, steam pyrolysis. Basolite F300 and In@ZIF-67 are used as MOF precursors in this study. The resulting solids are then evaluated for their performance in carbon dioxide hydrogenation reactions. A thorough investigation and comparison are conducted between samples prepared with and without the water addition. Ultimately, the study demonstrates the apparent difference in catalytic performance between pyrolyzed and steam-pyrolyzed samples.

The second part of the thesis addresses the limitations associated with using MOF-based materials in catalysis. MOF-74 is examined as a promising platform for obtaining a bimetallic Ni-Co catalyst for dry reforming of methane (DRM). This approach allows for the synthesis of bimetallic systems with a high metal content that is uniformly distributed within a graphitic carbon shell. The bimetallic Ni-Co@CMOF-74 catalyst exhibits superior catalytic performance compared to monometallic materials. This enhanced performance is attributed to the synergistic effects of Ni and Co, which lead to a significantly slower formation of coke during the reaction.

The final part of the thesis investigates the use of MOF-derived Ni@CMOF-74 catalysts in the photothermal conversion of CO2 to CH4. The study delves into the underlying factors responsible for differences in catalytic performance resulting from pyrolysis at different temperatures. Furthermore, the recyclability of the catalyst is explored under batch conditions, and its performance is tested in a continuous flow reactor. As a proof of concept, an outdoor experiment is conducted utilizing ambient solar irradiation as the primary energy source.