Dimetal and duplex heteroatoms co-doped graphene aerogel in electrolytic CO₂ reduction to CO in aqueous electrolyte

CO2 electrochemical reduction (CO₂ER) is a promising alternative for the conversion of CO₂ into green and value-added chemicals. Among these chemicals, CO is an important product and platform molecule of the CO₂ER, which is always used to produce various chemicals such as methanol, aldehydes, and synthesis gas (H₂/CO). Developing efficient catalytic system for the CO₂-to-CO, especially via the electrolytic chemical way is highly important. In the present work, an N and P co-doped MnZn-bimetal supported 3D graphene aerogel (GA) catalyst, denoted as MnZn/N,P-3D-GA, was prepared and used for the CO2ER to produce CO, which delivered high performance in the reaction. When the potential was -0.92 V (vs. RHE), the Faradaic efficiency of CO (FECO) reached 96.6% and the current density was 12.0 mA·cm^-2. In addition, at the potential range from -0.97 to -1.12 V (vs. RHE), the obtained FECO was all more than 90%, indicating that the catalyst has a wide electrochemical window for the reaction. Density functional theory (DFT) calculations indicated that the catalytic processes mainly involve *CO₂, *COOH, and *CO intermediates. The enhanced catalytic performance of the catalyst originated from the synergistic effect among the MnZn, N, P, and GA. The present work provides an important reference in the design and construction of catalyst with using dual-metal-loaded and dual-heteroatom-modified graphene aerogels.