In Situ Exsolved CuZn Alloy Electrocatalysts for CO₂ Conversion to Tunable Syngas Production

Abstract Alloying is considered as a promising method for syngas (H 2 and CO mixture gas) generation. However, it is challenging to elucidate the relationship between the ratios of syngas and alloy components for CO 2 reduction reaction. Herein, through tuning the Cu/Zn ratio on CuZn alloy, the H 2 /CO ratios in CuZn‐2 (Cu/Zn = 0.77) can be tuned in a noticeable range between 0.8 and 5.8 at −0.88 to −1.28 V versus RHE, and a durable stability of 12 h. The CuZn‐2 displays better performance and enhanced dynamics than other samples. Electrochemical impedance spectroscopies and Tafel results reveal that CuZn‐2 behaves kinetically optimized performance. Density functional theory calculations results reveal that CuZn alloy exhibits middle desorption intensity of *H for HER compared with pure Zn and Cu. CuZn alloy effectively decreases the energy barrier of CO 2 molecules activated to *COOH relative to Zn, and also the alloy renders it easier for *CO desorb to generate CO for Cu. In situ Fourier transform infrared spectroscopies also observe a significant intensity of *CO on CuZn‐2. This work demonstrates that alloying Cu and Zn can create active sites, in which Cu acts as an auxiliary active site further facilitating *CO generation.