Zirconium-doped ultrathin copper nanowires for C1 and C2+ products in electrochemical CO2 reduction reaction

Cu-based nanostructures have garnered significant attention in the field of electrochemical carbon dioxide reduction (eCO(2)R), due to their significant activity and ability to produce a variety of value-added hydrocarbons and oxygenates. Current research efforts focus on steering eCO(2)R towards the formation of multi-carbon (C2+) products and elucidating the complex mechanisms of C-C coupling. One promising approach involves transition metals into Cu nanostructures. This study computationally investigates the impact of trace Zr atom doping on Cu nanostructures, specifically at the interfaces of (100) and (110) surfaces of ultrathin Cu nanowires. Our findings reveal that Zr dopants are energetically favourable and facilitate charge transfer to adjacent Cu atoms, thereby reducing the activation barriers for C-C coupling and enhancing the formation of C-1 and C-2 hydrocarbons. Additionally, the Zr-O interaction weakens the C-O bond, promoting C-O bond cleavage. The formation of C-3 products, and the selectivity between hydrocarbons and oxygenates, are influenced by the hydrogenation sequence on different carbon atoms.