Dynamic Metal–Support Interaction-Activated Sub-Nanometer Pt Clusters on FeOx Supports for Aqueous Phase Reforming and Hydrogenolysis of Glycerol

The dynamic metal–support interaction (DMSI) plays a significant role in charge transfer, active site reconfiguration, and interface reconstruction between metals and oxide supports under redox conditions. However, developing an equilibrium between oxidation and reduction properties, greatly influenced by dynamic interactions, proves to be a considerable challenge when coupling a reforming reaction with a hydrogenation reaction. Herein, we engineered the DMSI effect between sub-nanometer Pt clusters and FeOx supports for the aqueous phase reforming and hydrogenolysis of glycerol. Additionally, regulating surface reconstructions and cyclic transformations of active sites (Ptδ−–Ov–Fe2+ ↔ Ptδ+–O–Fe3+) is effective in balancing the redox reaction process. In this study, a 2.5Pt/FeOx catalyst exhibits superior catalytic performance in terms of glycerol conversion (94.7%), liquid-phase conversion (46.3%), 1,2-propanediol (1,2-PDO) liquid-phase selectivity (78.4%), and 1,2-PDO yield (36.3%) during hydrogenolysis of glycerol with in situ-generated H2. Finally, a possible reaction pathway is proposed for the coupling reaction over the cyclic reconstruction of active sites on the Pt/FeOx catalyst.