Synergistic Effects of Amine Functional Groups and Enriched‐Atomic‐Iron Sites in Carbon Dots for Industrial‐Current–Density CO2 Electroreduction

Abstract Metal phthalocyanine molecules with Me‐N 4 centers have shown promise in electrocatalytic CO 2 reduction (eCO 2 R) for CO generation. However, iron phthalocyanine (FePc) is an exception, exhibiting negligible eCO 2 R activity due to a higher CO 2 to * COOH conversion barrier and stronger * CO binding energy. Here, amine functional groups onto atomic‐Fe‐rich carbon dots (Af‐Fe‐CDs) are introduced via a one‐step solvothermal molecule fusion approach. Af‐Fe‐CDs feature well‐defined Fe‐N 4 active sites and an impressive Fe loading (up to 8.5 wt%). The synergistic effect between Fe‐N 4 active centers and electron‐donating amine functional groups in Af‐Fe‐CDs yielded outstanding CO 2 ‐to‐CO conversion performance. At industrial‐relevant current densities exceeding 400 mA cm −2 in a flow cell, Af‐Fe‐CDs achieved >92% selectivity, surpassing state‐of‐the‐art CO 2 ‐to‐CO electrocatalysts. The in situ electrochemical FTIR characterization combined with theoretical calculations elucidated that Fe‐N 4 integration with amine functional groups in Af‐Fe‐CDs significantly reduced energy barriers for * COOH intermediate formation and * CO desorption, enhancing eCO 2 R efficiency. The proposed synergistic effect offers a promising avenue for high‐efficiency catalysts with elevated atomic‐metal loadings.