文献类型：期刊文献

英文题名：Structural Dependency in Base-Free Glycerol Oxidation over Ordered PtSb Intermetallics for Selective Dihydroxyacetone Production

作者：Fang, Junyan[1];Chen, Wenyao[1];Cao, Yueqiang[1];Zhang, Jing[1];Duan, Xuezhi[1];Qian, Gang[1];Zhou, Xinggui[1]

机构：[1]East China Univ Sci & Technol, State Key Lab Chem Engn & Low Carbon Technol, 130 Meilong Rd, Shanghai 200237, Peoples R China

年份：2025

外文期刊名：CATALYSIS SURVEYS FROM ASIA

收录：;EI(收录号：20255019686018);WOS:【SCI-EXPANDED(收录号:WOS:001631431100001)】；

基金：This work was financially supported by the Natural Science Foundation of China (22178101).

语种：英文

外文关键词：Glycerol oxidation; Intermetallic compound; PtSb; Dihydroxyacetone; Density functional theory

摘要：Achieving high selectivity toward dihydroxyacetone (DHA) in the base-free oxidation of glycerol is difficult, as it requires preferential activation of the intrinsically less reactive secondary hydroxyl group. To address this, well-defined ordered intermetallic compounds (IMCs) with distinct phases were constructed. Two PtSb IMCs, Pt1Sb1/CNT and Pt1Sb2/CNT, were synthesized via an impregnation-reduction method using carbon nanotubes (CNT) as supports. The Pt1Sb1/CNT catalyst demonstrated superior activity (79.9% conversion) and DHA selectivity (61.1%) compared to Pt1Sb2/CNT (70.1%, 55.8%), alongside enhanced durability. More importantly, Pt1Sb1/CNT delivers a markedly higher intrinsic activity, with a turnover frequency (TOF) of 299 h-1, over twice that of Pt1Sb2/CNT (144 h-1). This performance superiority is attributed to its finer nanoparticle size, more electron-deficient Pt surfaces, and robust structural integrity. Density functional theory (DFT) calculations unveiled that the C-H bond cleavage is the rate-determining step and identified a strikingly lower energy barrier for secondary C-H activation on the Pt1Sb1(100) surface (0.68 eV) than on Pt1Sb2(210) (0.95 eV), which conclusively explains the phase-dependent selectivity. This work underscores the critical role of intermetallic phase selection in designing high-performance catalysts for biomass valorization via precise geometric and electronic engineering.