A Breakthrough in Formic Acid Oxidation by a Dual‐Atomic Ir–N 4 /Pt–N 4 Catalyst via Parallel Reaction Pathways Under Over‐Boiling Point Environment

ABSTRACT Single‐atom catalysts (SACs) suffer from sluggish desorption‐charge transfer processes during complex multi‐atomic molecule oxidation (e.g., C/H/O‐containing species) due to simple active sites and tedious carbonyl/C─H bond tandem oxidation pathways. Herein, we propose a new atomically dispersed Ir–N 4 /Pt–N 4 catalyst (Ir 1 –Pt 1 NC) to construct efficient dual‐pathway reactions as directional parallel reactions, namely, Pt activates H adsorption while adjacent Ir sites specifically bind carbonyl groups (C═O) under the over‐boiling point environment. The confirmed Ir–N 4 /Pt–N 4 dual‐isolated coordination structure modulates the d‐band center to achieve greatly reduced energy barrier and form a new parallel dual‐pathway mechanism, significantly improving catalytic kinetics and boosting the charge transfer process. The molecular dynamics (MD) simulations reveal that strong hydrogen bond networks in formic acid (FA) solutions impede molecular diffusion, where over‐boiling point operation significantly weakens the hydrogen bonding of FA molecules, thus realizing a “double × double” enhancement effect. The “dual‐atomic catalyst with over‐boiling point hydrogen bond dissociation” strategy achieve an unprecedented catalytic performance, that is, a mass activity of 125.9 A mg −1 , far exceeding those of the state‐of‐the‐art single atomic catalysts (10–30 A mg −1 ) and the commercial iridium‐carbon (Ir/C) catalyst (0.1 A mg −1 ), and building a new universal “structure + environment” dual‐regulation for formic acid oxidation (FAOR) and the rapid degradation of other small organic molecules.