Semi-quantitative design of synergetic surficial/interfacial sites for the semi-continuous oxidation of glycerol.

ABSTRACT

Qualitatively identifying the dominant catalytic site for each step of a semi-continuous reaction and semi-quantitatively correlating such different sites to the catalytic performance is of great significance toward the integration of multiple well-optimized sites on a heterogeneous catalyst. Herein, a series of structurally defined TiOx-based catalysts were synthesized to provide a feasible approach to investigate the aforementioned issues using the semi-continuous oxidation of glycerol as a model reaction. Detailed investigations have verified the simultaneous presence of two kinds of Pt active sites 1) Negatively charged Pt bound to the oxygen vacancies of modified TiOx in the form of Ptδ--Ov-Ti3+ sites and 2) metallic Pt (Pt0 site) located away from the interface. Meanwhile, the proportion of surficial and interfacial sites varies over this series of catalysts. Combined in situ FTIR experiments revealed that the reaction network was well-tuned via a site cooperation mechanism The surficial Pt0 sites dissociatively adsorb the OH group of glycerol with a monodentate bonding geometry and the Ptδ--Ov-Ti3+ sites dissociate the C=O bond of the aldehyde group in a bidentate form. Furthermore, CO-FTIR spectroscopy confirmed a correlation between the reaction rate/product selectivity and the fraction of surficial/interfacial sites. A rational proportion of surficial and interfacial sites is key to enabling a high yield of glyceric acid. The most active catalyst with 32% surface sites and 68% interfacial sites exhibited 90.0% glycerol conversion and 68.5% GLYA selectivity. These findings provide a deeper understanding of the structure-activity relationships using qualitative identification and semi-quantitative analysis.