Switching the Symmetry of a Trinuclear Copper Cluster Catalyst for Electroreducing CO<sub>2</sub> to an Asymmetric C<sub>2</sub> Product in an Acidic Electrolyte
Rui Wang, Long‐Zhang Dong, Jingwen Shi, Mi Zhang, Shun‐Li Li, Ya‐Qian Lan, Jiang Liu
Abstract
Achieving CO 2 electroreduction in an acidic electrolyte to obtain high-value products is a great challenge, but it has remained elusive so far due to the high requirements for catalyst stability. Herein, we designed and constructed a highly stable (acid- and alkali-resistant) and well-defined crystalline coordination compound catalyst, Inz-Cu 3, which can switch the structural symmetry by varying the distance and angle between the adjacent synergistic Cu active sites, thus achieving the selective conversion of CO 2 to a high-value C 2 product in an acidic electrolyte. At a current density of −320 mA·cm –2, it achieved up to 42.20% selectivity for the electrocatalytic reduction of CO 2 to C 2 products in an acidic electrolyte, and the highly selective catalytic conversion to C 2 products (66.79%, containing 35.27% FE C 2 H 4 and 31.52% FE C 2 H 5 OH ) can also be achieved in a conventional alkaline electrolyte. Moreover, the density functional theory (DFT) calculation and control experiments revealed that the adjacent asymmetric Cu active sites with close distance can stabilize *CHOHCH 3 intermediates, thus improving the selectivity of the asymmetric C 2 product. This work demonstrates a strategy for the structural design of asymmetric crystalline coordination catalysts and enables the achievement of electroreduction conversion of CO 2 to high-value-added C 2 products in an acidic electrolyte.