Selective reductive conversion of CO to CH-bridged compounds by using a Fe-functionalized graphene oxide-based catalyst.

Anthropogenic climate change drastically affects our planet, with CO 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 CO 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 CO 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 CO into a formaldehyde oxidation level, thus opening the door for interesting molecular structures using CO 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 CO.