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

• Cu-based nanostructures are highly valued in electrochemical carbon dioxide reduction (eCO 2 R) due to their ability to produce various value-added hydrocarbons and oxygenates. • Current research aims to direct eCO2R towards the formation of multi-carbon (C2+) products and to understand the complex mechanisms of carbon-carbon (C-C) coupling. • The study computationally explores the effects of doping Cu nanostructures with trace amounts of Zr atoms, finding that Zr dopants are energetically favourable and enhance charge transfer to adjacent Cu atoms. • The effect of Zr is to reduce the activation barriers for C-C coupling, promoting the formation of C1 and C2 hydrocarbons. • The interaction between Zr and oxygen weakens the C-O bond, facilitating its cleavage. The formation of C 3 products and the selectivity between hydrocarbons and oxygenates are influenced by the hydrogenation sequence on different carbon atoms. 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 (C 2+ ) 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.