Selective ethane oxidation with O2 in the presence of CO offers a one-step route to ethanol, yet achieving high selectivity with long-term durability remains challenging because CO-assisted systems often undergo CO-induced sintering, which disrupts the cationic/metallic surface ensembles required for sustained activity. Here, platinum–titanium (Pt–Ti) nanoalloys formed on anatase TiO2 via strong metal–support interaction (SMSI) sustain aqueous ethane-to-ethanol oxidation at 125 °C for 48 h without measurable deactivation, maintaining 54–66% ethanol selectivity and delivering ∼670 mol of C2 oxygenates per molPt. Microscopy and spectroscopy indicate that Pt–Ti alloying stabilizes adjacent Ptδ+/Pt0 ensembles while suppressing CO-driven sintering. Mechanistic evidence supports a sequential pathway in which the CO-driven water–gas shift reaction generates H2, which in turn promotes in situ H2O2 formation from H2 and O2; the resulting H2O2 oxidizes ethane via an ethyl hydroperoxide intermediate to yield ethanol. These results establish SMSI-enabled Pt–Ti alloying as a viable materials strategy to couple selectivity with durability in CO-assisted aqueous ethane oxidation.
Oda et al. (Thu,) studied this question.