Related Experiment Video
Updated: Jan 9, 2026
Development of Heterogeneous Enantioselective Catalysts using Chiral Metal-Organic Frameworks MOFs
Published on: January 17, 2020
Reactant-dependent volcano trends in Pt-catalyzed cycloalkane dehydrogenation: orbital hybridization-guided design of
Yongxiao Tuo1, Jingying Qu2, Huailu Sun2
1State Key Laboratory of Heavy Oil Processing, College of New Energy, China University of Petroleum (East China), 66 West Changjiang Road, Qingdao, Shandong, China.
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 (CNPt-Pt). Using a tunable Pt/MgAl2O4 system, we identify optimal CNPt-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 energy of aromatic products as a universal electronic descriptor that serves as a proxy for π* orbital energy. LUMO energy shows strong linear correlations with the d-band center of Pt at the optimal CNPt-Pt, enabling rational tuning of electronic interactions across diverse reactants. The optimized Pt/MgAl2O4 catalyst delivers 2-3 times higher activity with >100 h stability under industrial conditions at only 300 oC, offering a robust strategy for hydrogen release and active-site engineering in dehydrogenation catalysis.
More Related Videos
07:36Versatile CO2 Transformations into Complex Products: A One-pot Two-step Strategy
Published on: November 9, 2019
12:08Catalytic Reactions at Amine-Stabilized and Ligand-Free Platinum Nanoparticles Supported on Titania During Hydrogenation of Alkenes and Aldehydes
Published on: June 24, 2022
Related Concept Videos
01:16Cycloaddition Reactions: MO Requirements for Thermal Activation
01:17Thermal Electrocyclic Reactions: Stereochemistry
Selection Rules: Thermal Activation
Conjugated systems containing an even number of π-electron pairs undergo a conrotatory ring closure. For example, thermal electrocyclization of (2E,4E)-2,4-hexadiene, a conjugated diene containing two π-electron pairs, gives trans-3,4-dimethylcyclobutene.
01:16Cycloaddition Reactions: Overview
02:36Regioselectivity and Stereochemistry of Hydroboration
Hydroboration proceeds in a concerted fashion with the attack of borane on the π bond, giving a cyclic four-centered transition state. The –BH2 group is bonded to the less substituted carbon and –H to the more substituted carbon. The concerted nature requires the simultaneous addition of –H and –BH2 across the same face of the alkene giving syn stereochemistry.
02:17Regioselectivity of Electrophilic Additions to Alkenes: Markovnikov's Rule
The hydrohalogenation of an unsymmetrical alkene can yield two haloalkane products, depending on which vinylic carbon takes up the halogen. However, one product usually predominates, where hydrogen adds to the vinylic carbon bearing the...
01:28Reduction of Benzene to Cyclohexane: Catalytic Hydrogenation