Interstitial Atomic Bi Charge‐Alternating Processor Boosts Twofold Molecular Oxygen Activation Enabling Rapid Catalytic Oxidation Reactions at Room Temperature

Abstract Molecular O 2 activation on metallic oxide‐based catalysts surfaces is pivotal for catalytic oxidation reactions but highly depends on the O 2 activation pathways or mechanisms. Thus, comprehensively understanding the mechanism of efficient O 2 activation is conducive to extending the fundamental principles for O 2 activation theories and designing novel catalysts for catalytic oxidation reactions. In this study, it is declared that the interstitial atomic Bi (IA Bi) anchored in the lattice interstice of MnO 2 (Bi/MnO 2 ) is capable of triggering an alternative twofold O 2 activation boosting the catalytic oxidation reactions at room temperature. Explicitly, the IA Bi facilely induces the local lattice distortion reconstructing the local charge landscape, thus weakening the O 2 dissociation energy barrier by elongating the OO bond length. And, the charge‐alternating process engineered by the IA Bi drives the alternative twofold O 2 activation of the adjacent lattice oxygen and adsorbs dangling oxygen assisted by the consecutive O 2 replenishment. Conclusively, this study not only declares the role of IA Bi in driving the charge‐alternating process during the twofold O 2 activation but also extends the fundamental principles toward O 2 activation mechanisms for catalytic oxidation reactions via atomic makeup engineering.