Highly Selective Electrocatalytic Reduction of CO₂ into Methane on Cu–Bi Nanoalloys

Methane (CH₄), the main component of natural gas, is one of the most valuable products facilitating energy storage via electricity conversion. However, the poor selectivity and high overpotential for CH₄ formation with metallic Cu catalysts prevent realistic applications. Introducing a second element to tune the electronic state of Cu has been widely used as an effective method to improve catalytic performance, but achieving high selectivity and activity toward CH₄ remains challenging. Here, we successfully synthesized Cu–Bi NPs, which exhibit a CH₄ Faradaic efficiency (FE) as high as 70.6% at −1.2 V versus reversible hydrogen electrode (RHE). The FE of Cu–Bi NPs has increased by approximately 25-fold compared with that of Cu NPs. DFT calculations showed that alloying Cu with Bi significantly decreases the formation energy of *COH formation, the rate-determining step, which explains the improved performance. Further analysis showed that Cu that has been partially oxidized because of electron withdrawal by Bi is the most possible active site