Hydrophobicity-guided CO-CO coupling pathways in ZIF-8 modified Cu₂O for efficient CO electroreduction

The electrochemical CO reduction reaction offered a sustainable approach to convert carbon monoxide into multi-carbon products, yet controlling C-C coupling remained challenging. Herein, we designed a Z-Cu electrocatalyst by coating Cu₂O nanoparticles with ZIF-8, which enabled interfacial modulation of the electronic structure and surface wettability. Structural analyses confirmed strong Cu-Zn interactions, while electrochemical measurements revealed that Z-Cu favored C₂ products at low current densities. Both experimental and DFT calculations demonstrated that Z-Cu suppressed the hydrogenation of *CO into *COH through hydrophobic repulsion and steric hindrance, thereby inhibiting the asymmetric *CO-*COH pathway toward *OCCOH formation. Instead, Z-Cu predominantly facilitated the symmetric *CO-*CO coupling. The optimal enhanced factor of Z-Cu is 5.5 at 50 mA cm⁻². This work underscored the decisive role of hydrophobicity and interfacial electronic modulation in directing CORR pathways, providing new mechanistic insights and a generalizable design principle for advancing Cu-based catalysts toward efficient multi-carbon fuel and chemical production.