Supramolecules Containing Homogeneous Electron‐rich Cu Sites for Photocatalytic CO2 Reduction to C2H6

Abstract Light‐driven CO 2 reduction to multi‐carbon (C 2+ ) products is ideal but remains challenging. This paper anchors the metal active center on the electron‐rich capabilities 4‐(diphenylamine)‐thiophene carboxylic acid supramolecular receptor unit. Then a novel supramolecular catalyst that satisfies the optimal distance of C–C coupling is constructed utilizing the π‐conjugated group stacking effect. The activity of this catalyst is superior to most photocatalysts reported for the reduction of CO 2 to C 2 H 6 , with a C 2 H 6 yield of 250.9 µmol h −1 g −1 , a selectivity of 64.2%. In situ spectroscopic and theoretical calculations demonstrate that the photogenerated electrons accumulate at the adjacent metal active center, thereby effectively CO 2 activation and * CO capture. This process reduces the reaction energy barrier of C–C coupling. In addition, constructing controllable and homogeneous Cu active sites improved the selectivity of CO 2 reduction to C 2 H 6 . This study provides a new way to design photocatalysts with precisely controllable electron‐enriched metal active sits to realize photo‐driven reduction of CO 2 to C 2+ products.