Modeling Oxidative Dehydrogenation of Propane with Supported Vanadia Catalysts Using Multireference Methods

Mandal, Mukunda; Hermes, Matthew R.; Berger, Fabian; Sauer, Joachim; Gagliardi, Laura

doi:10.1021/acs.jpcc.5c04695

Modeling Oxidative Dehydrogenation of Propane with Supported Vanadia Catalysts Using Multireference Methods

Journal Article · Thu Jul 31 04:00:00 EDT 2025 · Journal of Physical Chemistry. C

DOI:https://doi.org/10.1021/acs.jpcc.5c04695· OSTI ID:2587283

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University of Chicago, IL (United States)
Humboldt-Universität zu Berlin (Germany); University of Cambridge (United Kingdom)
Humboldt-Universität zu Berlin (Germany)

The oxidative dehydrogenation of propane over supported vanadium oxide catalysts poses significant computational challenges due to complex electronic structure changes along the reaction coordinate, driven primarily by changes in the oxidation states of vanadium. To address these challenges, we systematically test quantum chemical methods, including multireference (MR) approaches, domain-based local pair natural orbital coupled cluster theory (DLPNO-CCSD(T)), and density functional theory (DFT). The initial C–H bond-breaking transition state requires MR treatment due to its multireference character, while subsequent steps permit efficient single-reference calculations. For the rate-limiting C–H activation step mediated by the vanadyl moiety, complete 1 active space second-order perturbation theory (CASPT2) yields an apparent activation barrier (E_app^600K) of 138 kJ/mol, consistent with experimental values (134 ± 4 kJ/mol; Gruene et al. Catal. Today 2010, 157, 137). In contrast, DLPNO-CCSD(T) overestimates this barrier (198 kJ/mol), whereas DFT predictions span 125–150 kJ/mol, depending on the functional. Our multireference investigation of this transition metal oxide-catalyzed process demonstrates that an active space that incorporates the C–H σ and V=O σ/π bonding orbitals, oxygen lone pairs, and their antibonding counterparts adequately captures electronic structure changes along the chemical transformation. Furthermore, these findings provide a general strategy for active space selection in transition metal oxide-catalyzed C/O–H bond activation reactions. The reference dataset from this work, which includes MR calculations with manually selected active spaces for all intermediates and transition states in the propane ODH reaction network, will serve as a benchmark for automating active space selection in similar systems.

View Accepted Manuscript (DOE)

Research Organization:: University of Chicago, IL (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0023383

OSTI ID:: 2587283

Journal Information:: Journal of Physical Chemistry. C, Journal Name: Journal of Physical Chemistry. C; ISSN 1932-7455; ISSN 1932-7447

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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