Effective electrochemical reduction of carbon dioxide to formate under mild conditions helps mitigate the energy crisis but requires the use of high-performance catalysts. The addition of a third metal to the binary metal catalyst may further promote the electrochemical reduction of carbon dioxide to formate. Herein, we provided a co-electrodeposition method to grow CuSnBi catalysts on pretreated copper foam and discussed the effects of both pH value and molar ratio of metal ions (Cu²⁺, Sn²⁺, and Bi³⁺) in the electrodeposition solution on the electrocatalytic performance of CO₂ to HCOO⁻. When the pH value of the electrodeposition solution was 8.5 and the molar ratio of Cu²⁺, Sn²⁺, and Bi³⁺ was 1:1:1, the electrode showed the highest FE_HCOO⁻ of 91.79% and the formate partial current density of 36.6 mA·cm⁻² at −1.12 V_RHE. Furthermore, the electrode kept stable for 20 h at −1.12 V_RHE, and FE_HCOO⁻ was always beyond 85% during the electrolysis process, which is excellent compared to the previously reported ternary metal catalytic electrodes. This work highlights the vital impact of changes (pH value and molar ratio of metal ions) in electrodeposition liquid on catalytic electrodes and their catalytic performance, and refreshing the electrolyte is essential to maintain the activity and selectivity during the electrochemical reduction of CO₂ to HCOO⁻.

The efficient electrochemical reduction of carbon dioxide to formate under mild conditions is a promising approach to mitigate the energy crisis, but requires the use of high-performance catalysts. The selectivity and activity of catalysts can be enhanced through multi-metal doping, further advancing the electrochemical reduction of CO₂ to formate. This study demonstrates a co-electrodeposition strategy for synthesizing SnBi electrocatalysts on pretreated copper foam substrates, systematically evaluating how the Sn²⁺/Bi³⁺ molar ratio in the electrodeposition solution and the applied current density affect the catalytic performance for CO₂-to-formate conversion. Optimal performance was achieved with a molar ratio of Sn²⁺ to Bi³⁺ of 1:0.5 and a deposition current density of 3 mA cm⁻², resulting in a formate Faradaic efficiency (FE_formate) of 97.80% at −1.12 V (vs. RHE) and a formate current density of 26.9 mA·cm⁻². Furthermore, the Sn₁Bi_0.50-3 mA·cm⁻² electrode demonstrated stable operation at the specified potential for 9 h, maintaining a FE_formate above 90%. Compared to previously reported metal catalysts, the SnBi catalytic electrode exhibits superior performance for the electrochemical reduction of CO₂ to HCOOH. The study highlights the significant impact of the metal ion molar ratio and deposition current density in the electrodeposition process on the characteristics and catalytic performance of the electrode.