Hierarchical CuO Nanorods via Cyclic Voltammetry Treatment: Freestanding Electrodes for Selective CO₂-to-Formate...

Electrochemical CO₂ reduction reaction (CO₂RR) represents a promising pathway for carbon neutralization. Here, we report hierarchical CuO nanorod arrays synthesized via cyclic voltammetry (CV) treatment as freestanding electrodes for selective CO₂RR. The CV activation process generates ultrathin nanosheets on CuO nanorods, creating abundant interfaces that facilitate formate production. Optimized CV-2000-CuO achieves 42% Faradaic efficiency (FE) for formate at -1.4 V vs. RHE while suppressing hydrogen evolution reaction (HER). Comprehensive characterization reveals that CV treatment promotes partial surface reduction to metallic Cu and generates high-density grain boundaries during CO₂RR operation. These structural features enhance CO₂RR activity and stability compared to pristine CuO (P-CuO). This work demonstrates a novel electrode engineering strategy combining freestanding architecture with electrochemical activation for efficient CO₂-to-formate conversion.