Executive Summary : | Photocatalytic conversion of CO₂ into carbonaceous chemical fuels and building blocks is a promising strategy for addressing the fossil energy crisis and reducing CO₂ emissions. Current technologies mainly focus on gas adsorption and storage due to CO₂'s inert nature. Metalated Porous-Organic-Polymers (M-POPs) have the potential to bridge the gap between MOFs and POPs, providing structural stability. This has led to an increasing research interest in visible-light assisted CO₂ photoreduction, addressing challenges in solar-fuel production society. This proposed project aims to develop a new family of homometallic Cu-metalated polyimine networks (Cu₃-pyz-POPs) and heterometallic dinuclear polyimine networks (CuI-ZnII-pyz-POP) with extensive π-conjugations. These visible-light active donor-acceptor composed metalated POPs have the potential to assist photo conversion of CO₂ to C₂H₄ with higher selectivity and faster kinetics. The photoreduction of CO₂ using these POPs will be carried out in a two-necked quartz photoreactor under irradiation using a 300 W xenon light equipped with a 390 nm filter. The project also explores the catalyst structure-activity relationship using synchrotron-based X-ray absorption spectroscopy (XAFS), identifying the local atomic structural environment of M-POPs and active surface species generated during CO2 hydrogenation. This innovative approach in designing light-harvesting umbrellas like POP-based photosensitizers (PS) will improve durability and enhance visible-light absorption responsibility to longer wavelengths. This project proposal will demonstrate the potential of POPs as next-generation photocatalysts for C2H4 production and provide unprecedented insight into the mechanistic origins for light-driven CO₂ reduction. |