Confined CO in a sandwich structure promotes C-C coupling in electrocatalytic CO₂ reduction

Microenvironment regulation near the catalyst surface plays a critical role in heterogeneous electrocatalytic reactions. The local concentration of reactants and intermediates significantly affects the reaction kinetics and product selectivity. Herein, we propose an innovative strategy of utilizing the spatial confinement effect in a sandwich-structured C/Cu/C assembly to regulate kinetic mass transport during the electrocatalytic CO₂ reduction reaction. The sandwich C/Cu/C assembly catalyst was successfully prepared using a simple bidirectional freezing and freeze-drying method. The sandwich structure changes the free diffusion pathway of the CO intermediate within the sandwich interlayer and helps confine CO with locally increased CO concentration near the catalyst surface, which in turn promotes C-C coupling and thus improves the reaction activity and doubles the C₂ product selectivity compared to its disordered mixture counterpart. This kinetics regulation in the sandwich structure may provide a new insight into the catalyst design and inspire the understanding of the structure-performance relationship in electrocatalysis.