Laser‐Synthesized Co‐Doped CuO Electrocatalyst: Unveiling Boosted Methanol Oxidation Kinetics for Enhanced Hydrogen Production Efficiency by In Situ/Operando Raman and Theoretical Analyses

The present study details the strategic development of Co-doped CuO nanostructures via sophisticated and expedited pulsed laser ablation in liquids (PLAL) technique. Subsequently, these structures are employed as potent electrocatalysts for the anodic methanol oxidation reaction (MOR), offering an alternative to the sluggish oxygen evolution reaction (OER). Electrochemical assessments indicate that the Co-CuO catalyst exhibits exceptional MOR activity, requiring a reduced potential of 1.42 V at 10 mA cm^-2 compared to that of pure CuO catalyst (1.57 V at 10 mA cm^-2). Impressively, the Co-CuO catalyst achieved a nearly 180 mV potential reduction in MOR compared to its OER performance (1.60 V at 10 mA cm^-2). Furthermore, when pairing Co-CuO(+)ǀǀPt/C(-) in methanol electrolysis, the cell voltage required is only 1.51 V at 10 mA cm^-2, maintaining remarkable stability over 12 h. This represents a substantial voltage reduction of ≈160 mV relative to conventional water electrolysis (1.67 V at 10 mA cm^-2). Additionally, both in situ/operando Raman spectroscopy studies and theoretical calculations have confirmed that Co-doping plays a crucial role in enhancing the activity of the Co-CuO catalyst. This research introduces a novel synthetic approach for fabricating high-efficiency electrocatalysts for large-scale hydrogen production while co-synthesizing value-added formic acid.