Novel flexible aromatic Cu3 metal-organic π-cluster for electrocatalytic CO2 reduction reaction

Producing Cn products through electrocatalytic CO2 reduction reaction (CO2RR) is of great significance in addressing the global warming crisis. Organic-inorganic hybrid catalysts, characterized by precise and controllable active sites and metal-ligand synergistic interactions, can enhance the reaction activity and stability of Cubased catalysts. Herein, based on density functional theory (DFT), a novel flexible aromatic Cu3 metal-organic t-cluster (Cu3-t cluster) was constructed, consisting of triple-atom active centers and pentalyne ligands. During the catalytic CO2RR process, the adsorption of H can promote the activation of CO2, this converts the competing hydrogen evolution reaction (HER) into promoting CO2RR. Enhanced aromaticity of its cluster core is credited with stabilizing the coadsorption of H and CO2 (H* + CO2*), consequently lowering the reaction free energy of the CO2 activation process. Research has shown that Cu3-t cluster have high catalytic activity for electrocatalytic CO2 generation of C2H4. Considering the solvation effect, the limit potential of this reaction is -0.60 V. Furthermore, the reaction free energies suggest that the Cu3-t cluster is more inclined to yield C2H4(g) products via COCO* coupling. Moreover, the high CO coverage at the triple-atom active centers not only makes it more challenging for this cluster to adsorb H, but also reduces the energy barrier of the COCO* coupling reaction. In the entire reaction pathway of C2H4(g), there exhibits dynamic self-adaptive behavior in the bond lengths and bond angles of the three Cu atoms in the cluster core, leading to fluctuations in aromaticity. The flexibility and aromaticity changes in this structure enable the Cu3-t cluster to better stabilize intermediates. This work provides theoretical guidance for the application of metal-organic t-clusters, accelerates the screening of catalysts for CO2RR, and provides powerful theoretical guidance for the structure-activity relationships between aromaticity and catalytic activity.