Selective reductive conversion of CO₂ to CH₂-bridged compounds by using a Fe-functionalized graphene oxide-based...

Anthropogenic climate change drastically affects our planet, with CO₂ being the most critical gaseous driver. Despite the existing carbon dioxide capture and transformation, there is much need for innovative carbon dioxide hydrogenation catalysts with excellent selectivity. Here, we present a fast, effective, and sustainable route for coupling diverse alcohols, amines and amides with CO₂ via heterogenization of a natural metal-based homogeneous catalyst through decorating on functionalized graphene oxide (GO). Combined synthetic, experimental, and theoretical studies unravel mechanistic routes to convergent 4‑electron reduction of CO₂ under mild conditions. We successfully replace the toxic and expensive ruthenium species with inexpensive, ubiquitously available and recyclable iron. This iron-based functionalized graphene oxide (denoted as Fe@GO-EDA, where EDA represents ethylenediamine) functions as an efficient catalyst for the selective conversion of CO₂ into a formaldehyde oxidation level, thus opening the door for interesting molecular structures using CO₂ as a C1 source. Overall, this work describes an intriguing heterogeneous platform for the selective synthesis of valuable methylene-bridged compounds via 4‑electron reduction of CO₂.