Insights into the Mechanism of <i>n</i>-Hexane Reforming over a Single-Site Platinum Catalyst

We demonstrate that the single-site catalyst Pt₁/CeO₂ greatly enhances the selectivity of cyclization and aromatization in the <i>n</i>-hexane reforming reaction. Specifically, the selectivity of single-site Pt₁/CeO₂ toward both cyclization and aromatization is above 86% at 350 °C. The turnover frequency of Pt₁/CeO₂ is 58.8 h^-1 at 400 °C, which is close to that of Pt cluster/CeO₂ (61.4 h^-1) and much higher than that of Pt nanoparticle/CeO₂ with Pt sizes of 2.5 and 7 nm. On the basis of the catalytic results for methylcyclopentane reforming, the dehydrocyclization and further aromatization of <i>n</i>-hexane are attributed to the prominent adsorption of ring intermediate products on the single-site Pt₁/CeO₂ catalysts. On the other side, with the multiple Pt adjacent active sites, the cluster and nanoparticle Pt/CeO₂ samples favor the C-C bond cracking reaction. Ultimately, this in-depth study unravels the principles of hydrocarbon activation with different Pt sizes and represents a key step toward the rational design of new heterogeneous catalysts.