Nanoporous Intermetallic Cu₃ Sn/Cu Hybrid Electrodes as Efficient Electrocatalysts for Carbon Dioxide Reduction

Designing highly selective and cost-effective electrocatalysts toward electrochemical carbon dioxide (CO₂ ) reduction is crucial for desirable transformation of greenhouse gas into fuels or high-value chemical products. Here, the authors report intermetallic Cu₃ Sn that is in situ formed and seamlessly integrated on self-supported bimodal nanoporous Cu skeleton (Cu₃ Sn/Cu) via a spontaneous alloying of Sn and Cu as robust electrocatalyst for selective electroreduction of CO₂ to CO. By virtue of Sn atoms strengthening CO adsorption on Cu atoms, the intermetallic Cu₃ Sn has an intrinsic activity of ≈10.58 μA cm^-2 , more than 80-fold higher than that of monometallic Cu. By virtue of hierarchical bicontinuous nanoporous Cu architecture facilitating electron transfer and CO₂ and proton mass transport and offering high specific surface areas for full use of electroactive Cu₃ Sn sites, the nanoporous Cu₃ Sn/Cu hybrid electrodes produce CO at a low overpotential of 0.09 V, and exhibit high partial current density of ≈15 mA cm^-2 _geo at overpotential of 0.59 V, along with excellent stability and selectivity of 91.5% Faradaic efficiency. The outstanding electrochemical performance make them attractive alternatives to precious Au- and Ag-based electrocatalysts for building low-cost CO₂ electrolyzers to selectively produce CO.