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Achieving efficient catalytic conversion over a heterogeneous catalyst with excellent resistance against leaching is still a grand challenge for sustainable chemical synthesis in aqueous solution. Herein, we devised a single‐atom Pt1/hydroxyapatite (HAP) catalyst via a simple hydrothermal strategy. Gratifyingly, this robust Pt1/HAP catalyst exhibits remarkable catalytic selectivity and catalyst stability for the selective oxidation of C2–C4 polyols to corresponding primary hydroxy acids. It is found that the Pt−(O−P) linkages with strong electron‐withdrawing function of PO43− (Pt1−OPO43− pair active site) not only realize the activation of the C−H bond, but also destabilize the transition state from adsorbed hydroxy acids toward the C−C cleavage, resulting in the sharply increased selectivity of hydroxy acids. Moreover, the strong PO43−‐coordination effect provides electrostatic stabilization for single‐atom Pt, ensuring the highly efficient catalysis of Pt1/HAP for over 160 hours with superior leaching resistance. [ABSTRACT FROM AUTHOR]

Achieving efficient catalytic conversion over a heterogeneous catalyst with excellent resistance against leaching is still a grand challenge for sustainable chemical synthesis in aqueous solution. Herein, we devised a single‐atom Pt1/hydroxyapatite (HAP) catalyst via a simple hydrothermal strategy. Gratifyingly, this robust Pt1/HAP catalyst exhibits remarkable catalytic selectivity and catalyst stability for the selective oxidation of C2–C4 polyols to corresponding primary hydroxy acids. It is found that the Pt−(O−P) linkages with strong electron‐withdrawing function of PO43− (Pt1−OPO43− pair active site) not only realize the activation of the C−H bond, but also destabilize the transition state from adsorbed hydroxy acids toward the C−C cleavage, resulting in the sharply increased selectivity of hydroxy acids. Moreover, the strong PO43−‐coordination effect provides electrostatic stabilization for single‐atom Pt, ensuring the highly efficient catalysis of Pt1/HAP for over 160 hours with superior leaching resistance. [ABSTRACT FROM AUTHOR]