The electrochemical nitrogen reduction reaction (NRR) offers a sustainable, low-energy alternative to the Haber-Bosch process for ammonia synthesis under mild conditions. Experimental studies on $\mathrm{Cu}$ clusters and stepped surfaces have indicated that high-index $\mathrm{Cu}$ facets can significantly enhance catalytic performance. However, systematic first-principles studies remain lacking on $\mathrm{Cu}$ surfaces with high-index facets. Motivated by recent breakthroughs, we conduct a comprehensive first-principles investigation of dozens of experimentally accessible $\mathrm{Cu}$ high-index surfaces. By evaluating the Gibbs free energy of the potential-determining step ($\mathrm{\Delta }{G}_{\mathrm{PDS}}^{\mathrm{NRR}}$), we identify $\mathrm{Cu}$(211), $\mathrm{Cu}$(430), and $\mathrm{Cu}$(511) as the most active. Furthermore, transition-metal doping is explored as a strategy to enhance activity, with several doped surfaces reducing $\mathrm{\Delta }{G}_{\mathrm{PDS}}^{\mathrm{NRR}}$ from 1.5 eV to around 0.3 eV. Considering competition from the hydrogen evolution reaction, $\mathrm{Co}$ and $\mathrm{Re}$-doped $\mathrm{Cu}$(430) surfaces show superior NRR selectivity. Our results offer theoretical insight into $\mathrm{Cu}$ high-index facets and propose a low-cost, efficient NRR catalyst via dopant engineering.

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• Chemical kinetics, dynamics & catalysis
• Chemical reactions
• Electrocatalysis
• Electrochemistry
• Reactions at surfaces & chemisorption
• Surfaces
• Transition metals
• Density functional calculations