General descriptors for glycerol oxidation to glyceric acid over PtM3‐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 PdM3 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 PdM3 surface induces the dissociation of O2 and H2O to form a polarized PdM3‐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 PdM3 could be labeled as descriptors describing catalytic selectivity and activity. On this basis, a strong electron reconstruction effect described by EO (−4.5 to −3.0 eV) and appropriate dehydrogenation ability described by EH (−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.