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Rational screening of efficient supported metal catalysts is still a great challenge due to the complicated reaction mechanism for selective polyol oxidation. Exemplifying glycerol oxidation to glyceric acid as a model reaction, we perform a DFT assisted descriptor based microkinetic modeling to reveal the underlying mechanism. It is found that the addition/formation of OH− could polarize the metal surface (M‐OH*) to regulate the d‐band center of Pt accompanied by the electron transfer from OH− to metal atoms, thus promoting the adsorption of glycerol. Moreover, the linear chemisorption energy and transition state energy scaling relations are well established on the formation energies of adsorbed C and O. Activity map obtained from descriptor based microkinetic analysis demonstrates that Pt and Ir metals exhibit the highest catalytic activity. Meanwhile, further analysis of the desorption energy and CC bond cleavage activation energy of glyceric acid product shows that Au and Pt metals display the optimal glyceric acid selectivity. Satisfactorily, these results from microkinetic analysis are in good agreement with the comparative experimental results. The insights revealed here may open a new avenue for rational design of transition metal catalysts in the bio‐polyol oxidation system. [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]