Efficient molecular oxygen activation is crucial for catalytic oxidation reaction, but highly depends on the construction of active sites. In this study, we demonstrate that dual adjacent Fe atoms anchored on MnO2 can assemble into a diatomic site, also called as MnO2-hosted Fe dimer, which activates molecular oxygen to form an active intermediate species Fe(O = O)Fe for highly efficient CO oxidation. These adjacent single-atom Fe sites exhibit a stronger O2 activation performance than the conventional surface oxygen vacancy activation sites. This work sheds light on molecular oxygen activation mechanisms of transition metal oxides and provides an efficient pathway to activate molecular oxygen by constructing new active sites through single atom technology.

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Regulating the distribution of reactive oxygen species generated from H2O2 activation is the prerequisite to ensuring the efficient and safe use of H2O2 in the chemistry and life science fields. Herein, we demonstrate that constructing a dual Cu−Fe site through the self‐assembly of single‐atomic‐layered Cu5 nanoclusters onto a FeS2 surface achieves selective H2O2 activation with high efficiency. Unlike its unitary Cu or Fe counterpart, the dual Cu−Fe sites residing at the perimeter zone of the Cu5/FeS2 interface facilitate H2O2 adsorption and barrierless decomposition into ⋅OH via forming a bridging Cu‐O‐O‐Fe complex. The robust in situ formation of ⋅OH governed by this atomic‐layered catalyst enables the effective oxidation of several refractory toxic pollutants across a broad pH range, including alachlor, sulfadimidine, p‐nitrobenzoic acid, p‐chlorophenol, p‐chloronitrobenzene. This work highlights the concept of building a dual catalytic site in manipulating selective H2O2 activation on the surface molecular level towards efficient environmental control and beyond.