Mechanistic study of heterogeneous propene metathesis on WOx/SiO2 catalysts

Le, Anne V.; Rajbanshi, Biplab; Lobo, Raul F.; Bai, Peng

doi:10.1016/j.jcat.2023.115117

Mechanistic study of heterogeneous propene metathesis on WO_x/SiO₂ catalysts

Journal Article · Sat Sep 09 00:00:00 EDT 2023 · Journal of Catalysis

DOI:https://doi.org/10.1016/j.jcat.2023.115117· OSTI ID:2001049

^[1]; Rajbanshi, Biplab ^[2]; Lobo, Raul F. ^[3]; Bai, Peng ^[4]

University of Massachusetts, Amherst, MA (United States); University of Delaware, Newark, DE (United States); University of Delaware
University of Massachusetts, Amherst, MA (United States); University of Delaware, Newark, DE (United States); Visva-Bharati University, West Bengal (India)
University of Delaware, Newark, DE (United States)
University of Massachusetts, Amherst, MA (United States); University of Delaware, Newark, DE (United States)

Silica-supported tungsten oxides are widely used industrial catalysts for olefin metathesis due to their low cost and robustness, yet the mechanisms for heterogeneously catalyzed metathesis reactions remain comparatively less understood. In this work, density-functional theory (DFT) calculations were used to study the model reactions of propene metathesis. Our calculations confirm that the metathesis reactions catalyzed by WO_x/SiO₂ largely follow the Chauvin cycle, with an overall energetic barrier of 142 kJ/mol. To understand how the initial alkylidene active sites are generated, three mechanisms were examined: The pseudo-Wittig mechanism was found to be most favorable and proceeds with a metallacycle intermediate, while the allylic and vinylic C-H activations are much more difficult and require the reduction of surface sites to W(+4). Relative to the adsorbed reactant state, the overall intrinsic barriers for three mechanisms were computed to be 193, 261, and 355 kJ/mol, respectively. In conclusion, the higher barriers for active-site formation than for the metathesis cycle are consistent with the difficult, high-temperature pretreatment required in experiments to activate WO_x/SiO₂ catalysts.

View Accepted Manuscript (DOE)

Research Organization:: University of Delaware, Newark, DE (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities (SUF); National Science Foundation (NSF)

Grant/Contract Number:: SC0021166; AC02-05CH11231

OSTI ID:: 2001049

Alternate ID(s):: OSTI ID: 2001336

Journal Information:: Journal of Catalysis, Journal Name: Journal of Catalysis Vol. 427; ISSN 0021-9517

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
heterogeneous catalysis
olefin metathesis
silica-supported tungsten oxides

Mechanistic study of heterogeneous propene metathesis on WOx/SiO2 catalysts

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Mechanistic study of heterogeneous propene metathesis on WO_x/SiO₂ catalysts