Unveiling the Mechanism of Glycerol Oxidation to Lactic Acid on Pt/Sn-MFI Zeolite: an In situ Solid-state NMR Study

Abstract

Heterogeneous glycerol (GLY) oxidation offers a promising route for the production of lactic acid (LA), a key monomer in biodegradable bioplastics. However, the specific reaction pathways remain poorly understood. This study presents a mechanistic investigation of GLY oxidation to LA using Pt/Sn-MFI catalysts. Characterizations via DR-UV-Vis spectroscopy, ¹¹⁹Sn NMR, and TEM reveal the formation of zeolite framework Sn and well-dispersed Pt nanoparticles in Pt/Sn-MFI. The Lewis acidity of framework Sn in MFI zeolite is confirmed through ³¹P NMR probe techniques. GLY conversion and LA selectivity correlate strongly with framework Sn concentration and the presence of Pt nanoparticles. In situ ¹³C solid-state NMR experiments, complemented by two-dimensional ¹³C correlation NMR, allow real-time monitoring of GLY conversion and identification of various mobile and rigid (surface-adsorbed) species. Results indicate that GLY preferentially transforms to LA via a dihydroxyacetone (DHA) intermediate, facilitated by the Pt-Sn synergistic effect. However, accumulation of surface-adsorbed LA on Sn sites promotes consecutive oxidation of GLY to glyceric acid, tartaric acid, and ultimately CO₂.

Keywords

Biomass conversion / In situ NMR / Glycerol oxidation / Zeolite / Reaction mechanism

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