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

Abstract

AbstractMetal phthalocyanine molecules with Me‐N4 centers have shown promise in electrocatalytic CO2 reduction (eCO2R) for CO generation. However, iron phthalocyanine (FePc) is an exception, exhibiting negligible eCO2R activity due to a higher CO2 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‐N4 active sites and an impressive Fe loading (up to 8.5 wt%). The synergistic effect between Fe‐N4 active centers and electron‐donating amine functional groups in Af‐Fe‐CDs yielded outstanding CO2‐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 CO2‐to‐CO electrocatalysts. The in situ electrochemical FTIR characterization combined with theoretical calculations elucidated that Fe‐N4 integration with amine functional groups in Af‐Fe‐CDs significantly reduced energy barriers for *COOH intermediate formation and *CO desorption, enhancing eCO2R efficiency. The proposed synergistic effect offers a promising avenue for high‐efficiency catalysts with elevated atomic‐metal loadings.