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.

中文翻译：

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在无碱培养基中，通过 PtM3 衍生的双金属催化剂将甘油氧化为甘油酸的一般描述符


由于缺乏机制驱动的方法，探索用于多元醇选择性氧化的高效 Pt 基催化剂仍然是一个挑战。在这里，通过密度泛函理论 （DFT） 线性同步传递和二次同步传递 （LST/QST） 辅助基于描述符的微动力学建模，系统研究了低 Pt 含量 PdM3 对甘油氧化为甘油酸 （GLYA） 的影响。结果显示，PdM3 表面诱导 O2 和 H2O 解离形成极化 PdM3-OH* 表面，参与甘油和含氧中间体的后续吸附和活化。此外，O 和 H 在 PdM3 上的结合能可以标记为描述催化选择性和活性的描述符。在此基础上，EO 描述的强电子重构效应（-4.5 至 -3.0 eV）和 EH 描述的适当脱氢能力（-3.5 至 -2.5 eV）有助于提高甘油选择性氧化为 GLYA 的催化性能。本研究可能为高效 Pt 基多元醇氧化催化剂的合理设计提供见解。