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 Cu 2 O 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 C 2 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. Hydrophobic ZIF-8 modification on Cu 2 O regulates interfacial electron transfer and suppresses *CO → *COH conversion, promoting symmetric *CO-*CO coupling for enhanced C 2 selectivity in CO electroreduction. • A wet-chemical in-situ growth strategy was developed to construct ZIF-8/Cu 2 O. • Stronger linearly bound *CO adsorption was observed on the Z-Cu interfaces. • Hydrophobic interfaces of Z-Cu suppressed asymmetric *CO-*COH coupling during CORR. • Experiments and simulations revealed Z-Cu favored symmetric *CO-*CO coupling. • Z-Cu highly enhanced CO-to-C 2 transformation at lower current density.