Copper cluster regulated by N, B atoms for enhanced CO2 electroreduction to formate

Electrochemical CO 2 conversion into formate by intermittent renewable electricity, presents a captivating prospect for both the storage of renewable electrical energy and the utilization of emitted CO 2 . Typically, Cu-based catalysts in CO 2 reduction reactions favor the production of CO and other by-products. However, we have shifted this selectivity by incorporating B, N co-doped carbon (BNC) in the fabrication of Cu clusters. These Cu clusters are regulated with B, N atoms in a porous carbon matrix (Cu/BN-C), and Zn 2+ ions were added to achieve Cu clusters with the diameter size of ∼1.0 nm. The obtained Cu/BN-C possesses a significantly improved catalytic performance in CO 2 reduction to formate with a Faradaic efficiency (FE) of up to 70 % and partial current density (j formate ) surpassing 20.8 mA cm −2 at −1.0 V vs RHE. The high FE and j formate are maintained over a 12-hour. The overall catalytic performance of Cu/BN-C outperforms those of the other investigated catalysts. Based on the density functional theory (DFT) calculation, the exceptional catalytic behavior is attributed to the synergistic effect between Cu clusters and N, B atoms by modulating the electronic structure and enhancing the charge transfer properties, which promoted a preferential adsorption of HCOO* over COOH*, favoring formate formation.