The selective and efficient production of methane (CH4) through the CO2 reduction reaction (CO2RR) has been a significant challenge due to high energy requirements and various reaction pathways. This study introduces a novel Zn-based polyoxometalate (ZnPOM) photocatalyst, which, when paired with an Ir-based photosensitizer (TIr3), selectively produces CH4 rather than the more common CO. The combination of ZnPOM and TIr3 enhances the photocatalytic CO2RR by enabling rapid electron transfer due to strong molecular interactions. Additionally, the hybridization of molecular orbitals between ZnPOM and *CO intermediates facilitates efficient electron transfer, promoting CH4 production. This innovative approach offers new insights into designing CO2RR catalysts beyond traditional Cu-based materials.-Scientific Journal cover design by scapiens

https://pubs.rsc.org/en/content/articlelanding/2021/nh/d0nh00657b#!divAbstract