In-situ Formed Surface Complexes Promoting NIR-Light-Driven Carbonylation of Diamine with CO on Ultrathin Co2CO3(OH)2 Nanosheets

Tailoring the surficial chemical environment of two-dimensional materials by organic modification is an effective way to optimize their catalytic behaviors. Herein, we present a dynamic coordination approach to improve the photocatalytic performance of ultrathin Co2CO3(OH)2 nanosheets (u-CoCH) in NIR light (λ > 780 nm) driven carbonylation reaction by using the reacting substrates (diamines) as the ligands. The coordination of diamines with surface Co2+ ions form a binuclear complex at the crystallographic planes of u-CoCH. The as-formed complexes can reduce the energy barrier of carbonylation reaction by weaking the N-H bond of the substrate on u-CoCH, and afford enhanced light response as well as the prolonged photogenerated electron lifetime. Together with the successful synthesis of a series of important structural motifs in pharmaceuticals and bioactive agents, the promoted photosynthesis reaction mode via in-situ formed surface complexes offers a model toward full-spectrum-solar-energy conversion in the field of chemical synthesis. [Display omitted] •Diamines act as substrate and ligand to tailor the surficial chemical environment of CoCO3(OH)2 nanosheets.•The surface adjacent Co2+ ions binding to diamine molecules form a binuclear complex.•The complexes enhanced light absorption ability and reduced the energy barrier of carbonylation by weaking the N-H bonds.•A protocol for accessing cyclic ureas through NIR light driven carbonylation of diamine with CO over CoCO3(OH)2.