Reactant-dependent volcano trends in Pt-catalyzed cycloalkane dehydrogenation: orbital hybridization-guided design of active sites.

ABSTRACT: Catalyst design is often reaction-specific due to the lack of universal descriptors linking molecular structures to optimal active-site configurations. Here, we uncover a reactant-dependent volcano relationship in Pt-catalyzed dehydrogenation, governed by the Pt-Pt coordination number (CN_Pt-Pt). Using a tunable Pt/MgAl₂O₄ system, we identify optimal CN_Pt-Pt values of ~2.5, ~4.7, and ~7.0 for cyclohexane, methylcyclohexane, and decalin, respectively. This activity trend is explained by an orbital hybridization-guided mechanism, where optimal activity emerges from a balance between C-H bond activation and product desorption, mediated by the interactions between Pt d-orbitals and the π* orbitals of dehydrogenated intermediates. We introduce the LUMO

SUBMITTER: Tuo Y 

PROVIDER: S-EPMC12770571 | biostudies-literature | 2025 Dec

REPOSITORIES: biostudies-literature