Achieving efficient catalytic conversion over heterogeneous catalyst with excellent resistance against leaching is still a grand challenge for sustainable chemical synthesis in aqueous solution. Herein, we devised a leaching free atomically dispersed Pt1/hydroxyapatite (HAP) catalyst with unique switchable structure via a simple and green in-situ anchoring strategy. Gratifyingly, this robust Pt1/HAP catalyst exhibits remarkable catalytic selectivity and catalyst stability for the selective

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... tion of C2-C4 bio-polyols (e.g., ethylene glycol, propanediol, glycerol and butanediol) to corresponding primary hydroxy acids. X-ray absorption spectroscopy, in-situ Fourier Transform infrared spectroscopy, density functional theory calculation and kinetics study elucidated that the switchable Pt-(O-P) linkages with strong electronic-withdrawing function of PO43− (Pt1-OPO43− active site) not only realize the activation of 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, originating from the enhanced interaction between positively charged Pt1 and negatively charged OPO43−, provides electrostatic stabilization for the atomically dispersed Pt, ensuring the highly efficient catalysis of Pt1/HAP for over 160 hours without metal leaching. This finding opens up new opportunities for efficient upgrading of bio-polyols over atomically dispersed catalysts.