Executive Summary : | Methane, a significant greenhouse gas, is a key component of natural gas and biogas, making its direct conversion to methanol and ethylene profitable in the chemical and petrochemical industries. However, this process is challenging due to high C−H bond energy, polarization difficulties, low acidity, poor solubility, and poor selectivity due to over-oxidation. The proposal aims to develop efficient metal-based heterogeneous catalysts for this purpose, using highly electron-deficient transition-metal species within porous materials with tunable pores like metal-organic frameworks (MOFs). The negative inductive effect of MOFs and electron-withdrawing modulators will render these transition-metal species highly electron-deficient, allowing for easy C‒H activation of methane. The proposed catalysts will be synthesized and characterized, and their catalytic activity will be tested in selective methane oxidation to methanol using O₂ or H₂O₂ as the oxidant. The activity of MOF-catalysts will be optimized by tuning the electrophilicity and electronic properties of the active metal species, and selectivity in favor of methanol will be optimized by tuning the pores sizes and surface area to prevent overoxidation of methanol by adsorbing methanol or methoxy species. Other proposed systems include the node-supported W/Ta-hydride catalyst for dehydrocoupling methane to ethane and the linker-supported pincer-Ir-catalysts for dehydrogenation of ethane to ethylene. The success of this work would significantly boost the downstream business of chemical, polymer, and petrochemical industries while ensuring health, safety, and environmental stewardship. |