O‐Bridged Co‐Cu Dual‐Atom Catalyst Synergistically Triggers Interfacial Proton‐Coupled Electron Transfer: A New Approach to Sustainable Decontamination

Abstract Heteroatom‐bridged dual‐atom catalysts (DACs), featuring more flexible active sites and intermetallic interaction, provide an opportunity for sustainable environmental remediation. Herein, an innovative oxygen‐bridged Co‐Cu DAC supported on nano‐alumina (CoOCu‐DAC) is fabricated using a straightforward two‐step process. The as‐prepared catalyst significantly enhances both decontamination kinetics and peroxymonosulfate (PMS) utilization efficiency by 1–3 orders of magnitude toward monoethanolamine (MEA, pK_a = 9.5) compared to Co single‐atom catalyst (Co‐SAC) and bulk metal catalysts, and largely outperforms previously reported systems. In‐situ ATR‐FTIR and theoretical investigations reveal that the secondary introduction of Cu plays multiple important roles: it activates lattice oxygen to trigger key proton transfer (PT) of MEAH⁺ via nucleophilic attack at the interface and subsequently favors deprotonated MEA as an efficient electron donor to accelerate electron transfer (ET) by enhancing orbital overlaps for the co‐activation of O₂ and PMS. Such a stepwise proton‐coupled electron transfer (PCET)‐enhanced catalytic pathway mediated by CoOCu‐DAC is fundamentally different from common route identified in Co‐SAC‐involved Fenton‐like system. The established binary QSAR further substantiates the universality of PCET‐enhanced strategy toward versatile nitrogen‐containing organic compounds. This study offers a new perspective for sustainable water decontamination and other related areas of catalysis based on rationalized design of multifunctional catalysts at atomic level.