Tailoring local structures of atomically dispersed copper sites for highly selective CO₂ electroreduction

Abstract Atomically‐dispersed copper sites coordinated with nitrogen‐doped carbon (Cu–N–C) can provide novel possibilities to enable highly selective and active electrochemical CO 2 reduction reactions. However, the construction of optimal local electronic structures for nitrogen‐coordinated Cu (Cu–N 4 ) on remains challenging. Here, we synthesized Cu–N–C catalysts atomically‐dispersed edge‐hosted Cu–N C 8 located in a micropore between two graphitic sheets via facile method control concentration metal precursor. Edge‐hosted outperformed previously reported M–N–C ‐to‐CO conversion, achieving maximum Faradaic efficiency (FE 96%, current density –8.97 mA cm –2 at –0.8 V versus reversible hydrogen electrode (RHE), over FE 90% from –0.6 –1.0 RHE. Computational studies revealed that layer causes d ‐orbital energy level atom shift upward, which return decreases occupancy antibonding states *COOH binding. This research suggests new insights into tailoring locally structure electrocatalyst atomic scale achieve electrocatalytic