General descriptors for glycerol oxidation to glyceric acid over <scp>PtM₃</scp>‐derived bimetallic catalysts in base‐free medium

Abstract Exploring efficient Pt‐based catalysts for the selective oxidation of polyol is still a challenge due to the lack of a mechanism‐driven approach. Here, low‐Pt content PdM 3 were systematically investigated for glycerol oxidation to glyceric acid (GLYA) by density functional theory (DFT) linear synchronous transit and quadratic synchronous transit (LST/QST) assisted descriptor‐based micro‐kinetic modeling. Results revealed that the PdM 3 surface induces the dissociation of O 2 and H 2 O to form a polarized PdM 3 ‐OH* surface, participating in the subsequent adsorption and activation of glycerol and oxygen‐containing intermediates. Moreover, the binding energy of O and H on the PdM 3 could be labeled as descriptors describing catalytic selectivity and activity. On this basis, a strong electron reconstruction effect described by E O (−4.5 to −3.0 eV) and appropriate dehydrogenation ability described by E H (−3.5 to −2.5 eV) contribute to the improvement of catalytic performance for the selective oxidation of glycerol to GLYA. This study may give insights into the rational design of high‐efficient Pt‐based catalysts for polyol oxidation.