Competitive Coordination Constructed Heteronuclear Pt ₁ ‐Fe ₁ Dual Single‐Atom Sites for Selective Oxidation of Allylic Alcohol

Abstract Dual single‐atom catalysts (DSACs) have attracted considerable attention owing to their exceptional atom efficiency and synergistic catalytic effects. Nevertheless, establishing precise synthetic methodologies for DSACs and exploring its application in complex reaction systems still present significant challenges. Here, we have fabricated a hydroxyapatite (HAP)‐supported heteronuclear Pt 1 ‐Fe 1 dual single‐atom catalyst (Pt 1 ‐Fe 1 /HAP) via a competitive coordination strategy for selective oxidation of allylic alcohols. Through a thermodynamically driven competitive coordination process, heteronuclear Pt 1 ‐Fe 1 with distinct charge densities is co‐anchored within adjacent periodic Ca 2+ vacancies of HAP lattice via PO 4 3− bridges, achieving a controlled atomic separation of ∼2.7 Å for electronic synergy. Unexpectedly, orbital hybridization between heteronuclear Pt 1 ‐Fe 1 induces a spin‐state transition of Fe from low‐spin to medium‐spin, facilitating activation of O 2 and following cascade oxidation of allylic alcohol. Benefiting from the modification of spin state, Pt 1 ‐Fe 1 /HAP exhibits ultrahigh aldehyde selectivity (92%) and a high turnover frequency (12 090.8 h −1 ) in oxidation of various allylic alcohol substrates, 20‐fold higher than that of Pt 1 /HAP single‐atom catalyst (543.8 h −1 ). This work establishes the thermodynamically driven competitive coordination strategy as a universal approach for constructing high‐performance heteronuclear dual‐atom catalysts with precisely engineered electronic synergy in demanding industrial processes.