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...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 CO_(2).展开更多
基金supported by the National Key R&D Program of China(No.2022YFA1504500)the Strategic Priority Research Program of the Chinese Academy of Sciences(No.XDB0540000)+4 种基金the National Natural Science Foundation of China(Nos.22272185,22225205,22320102002,22127801,22161132028)the Natural Science Foundation of Hubei Province,China(No.2021CFA021)the Hubei International Scientific and Technological Cooperation Program,China(No.2022EHB021)the International Science&Technology Cooperation Base for Sustainable Catalysis and Magnetic Resonance,China(No.SH2303)the Young Top-notch Talent Cultivation Program of Hubei Province,China.
文摘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 CO_(2).
