Reaction Energy Landscape of Propane Oxidative Dehydrogenation on Liquid Boron Oxide‐Germinated Catalytic Sites in the Presence of Dioxygen: An Orbitals‐Driven Mechanistic Study
Year: 2026
Type: article
Abstract: ABSTRACT Recently, boron‐based catalysts have gained significant attention for the oxidative dehydrogenation of propane into propene and ethene. In this study, we present an electronic‐level understanding of propane oxidation via a triplet dioxygen molecule over liquid boron oxide motifs, including cyclic B−O−B sites (8‐, 6‐, and 4‐membered rings) and edge B−OH and B−B sites. Our computations reveal that cyclic B−O−B and edge B−OH motifs exhibit higher activation barriers for C 3 H 6 (55–71 kcal mol −1 ) and C 2 H 4 (80–95 kcal mol −1 ) formation. In contrast, the B−B site requires the lowest barrier among all sites. Orbital analysis reveals that 3 O 2 activation at cyclic B−O−B sites proceeds via an electron transfer from O(2p) orbital into the antibonding orbitals of 3 O 2 . Over edge B−OH sites, the σ(O−H) bonding orbital facilitates 3 O 2 activation. At the B−B site, the σ(B−B) bonding orbital transfers an electron into the antibonding orbital of 3 O 2 . Furthermore, transfer of an electron from the σ(C−H) of C 3 H 8 to another antibonding orbital of 3 O 2 , leading to the generation of C 3 H 7 radical. C 2 H 4 formation over the B−B site has the lowest barrier, arising from the least strained seven‐membered ring and the simultaneous cleavage of σ(C−C) and σ(C−O) bonds. This study underscores the industrial potential of boron‐based catalysts.
Source: Chemistry - A European Journal
DOI: 10.1002/chem.71795
Institution: Indian Institute of Technology Roorkee
Language: English
Subfield: Catalysis
Field: Chemical Engineering
Domain: Physical Sciences
Open Access status: bronze
OpenAlex ID: W7221823085