Intrinsic Activity Identification of Noble Metal Single‐Sites for Electrocatalytic Chlorine Evolution

Single-atom catalysts with maximal atom-utilization have emerged as promising alternatives for chlorine evolution reaction (CER) toward valuable Cl₂ production. However, understanding their intrinsic CER activity has so far been plagued due to the lack of well-defined atomic structure controlling. Herein, we prepare and identify a series of atomically dispersed noble metals (e.g., Pt, Ir, Ru) in nitrogen-doped nanocarbons (M₁-N-C) with an identical M-N₄ moiety, which allows objective activity evaluation. Electrochemical experiments, operando Raman spectroscopy, and quasi-in situ electron paramagnetic resonance spectroscopy analyses collectively reveal that all the three M₁-N-C proceed the CER via a direct Cl-mediated Vomer-Heyrovský mechanism with reactivity following the trend of Pt₁-N-C>Ir₁-N-C>Ru₁-N-C. Density functional theory (DFT) calculations reveal that this activity trend is governed by the binding strength of Cl*-Cl intermediate (ΔG_Cl*-Cl) on M-N₄ sites (Pt<Ir<Ru) featuring distinct d-band centers, providing a reliable thermodynamic descriptor for rational design of single metal sites toward Cl₂ electrosynthesis.