Effect of Long-Range Spin-Exchange Interaction in CoPc-Based Two-Dimensional Bimetallic Organic Frameworks for the Electrochemical Reduction of CO<sub>2</sub> to CO
Jingwen Wang, Xiaocheng Zhou, Yu Wang, Yafei Li
Abstract
Two-dimensional metal–organic frameworks (2D MOFs) are promising candidates for the electrochemical reduction of CO 2 . However, the underlying relationship between spin and catalytic activity has yet to be fully understood. Herein, we carried out density functional theory calculations to investigate the spin–activity correlation for the electrochemical reduction of CO 2 to CO based on 2D CoPc-TMTAA frameworks (TM = Cr, Mn, Fe, Co, Ni, Cu, Zn). Our results reveal that the central Co atom is the active site for the CO 2 reduction reaction, whose spin state can be modulated by the neighboring ligand metal atoms through the long-range spin-exchange interaction. These CoPc-TMTAA frameworks exhibit superior activity for the reduction of CO 2 to CO with limiting potentials ranging from −0.13 to −0.34 V. Furthermore, our calculations show a nearly linear relationship between the catalytic activity and the spin moment variation, suggesting the electronic spin state as a good catalytic descriptor for CoPc-TMTAA framework catalysts. These findings provide important insights into the relationship between long-range spin-exchange interaction and catalytic activity, opening a new avenue for the rational design of efficient 2D bimetallic organic framework electrocatalysts.