Reactive Species and Reaction Pathways for the Oxidative Cleavage of 4-Octene and Oleic Acid with H2O2 over Tungsten Oxide Catalysts

Yun, Danim; Ayla, E. Zeynep; Bregante, Daniel T.; Flaherty, David W.

doi:10.1021/acscatal.0c05393

Title: Reactive Species and Reaction Pathways for the Oxidative Cleavage of 4-Octene and Oleic Acid with H₂O₂ over Tungsten Oxide Catalysts

Journal Article · Wed Feb 24 00:00:00 EST 2021 · ACS Catalysis

DOI:https://doi.org/10.1021/acscatal.0c05393· OSTI ID:1807582

^[1]; Ayla, E. Zeynep ^[2];

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Univ. of Illinois at Urbana-Champaign, IL (United States); Center for Advanced Bioenergy and Bioproducts Innovation (CABBI), Urbana, IL (United States)
Univ. of Illinois at Urbana-Champaign, IL (United States)

The oxidative cleavage of carbon-carbon double bonds (C=C) in alkenes and fatty acids produces aldehydes and acids valued as chemical intermediates. Solid tungsten oxide catalysts are low cost, non-toxic, and selective for the oxidative cleavage of C=C bonds with hydrogen peroxide (H₂O₂) and are, therefore, a promising option for continuous processes. Despite the relevance of these materials, the elementary steps involved and their sensitivity to the form of W sites present on surfaces have not been described. In this work, we combine in situ spectroscopy and rate measurements to identify significant steps in the reaction, the reactive species present on catalysts, and examine differences between the kinetics of this reaction on isolated W atoms grafted to alumina and on those exposed on crystalline WO₃ nanoparticles. Raman spectroscopy shows that W-peroxo complexes (W-(η²-O₂) formed from H₂O₂) react in a kinetically relevant step to produce epoxides, which undergo hydrolysis at protic surface sites. Subsequently, the CH₃CN solvent deprotonates diols to form alpha hydroxy ketones that react to form aldehydes and water following nucleophilic attack of H₂O₂. Turnover rates for oxidative cleavage, determined by in situ site titrations, on WO_x-Al₂O₃ are 75% greater than those on WO₃ at standard conditions. These differences reflect activation enthalpies (ΔH^‡) for oxidative cleavage of 4-octene that are much lower for the isolated WO_x sites (36±3 and 60±6 kJ∙mol^-1 for WO_x-Al₂O₃ and WO₃, respectively) and correlate strongly with the difference between enthalpies of adsorption for epoxyoctane (ΔH_ads,epox), which resembles the transition state for epoxidation. The WO_x-Al₂O₃ catalysts mediate oxidative cleavage of oleic acid with H₂O₂ following a mechanism comparable to that for 4-octene. The WO₃ materials, however, form only the epoxide and do not cleave the C-C bond or produce aldehydes and acids. These differences reflect the distinct site requirements for these reaction pathways and indicate that acid sites required for diol formation are strongly inhibited by oleic acids and epoxides on WO₃ whereas the Al₂O₃ support provides sites competent for this reaction and increase the yield of the oxidative cleavage products.

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Research Organization:: Center for Advanced Bioenergy and Bioproducts Innovation (CABBI), Urbana, IL (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Biological and Environmental Research (BER); US Army Research Office (ARO)

Grant/Contract Number:: SC0018420; W911NF-18-1-0100

OSTI ID:: 1807582

Journal Information:: ACS Catalysis, Vol. 11, Issue 5; ISSN 2155-5435

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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unsaturated fatty acids
in situ spectroscopy
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Title: Reactive Species and Reaction Pathways for the Oxidative Cleavage of 4-Octene and Oleic Acid with H2O2 over Tungsten Oxide Catalysts

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Title: Reactive Species and Reaction Pathways for the Oxidative Cleavage of 4-Octene and Oleic Acid with H₂O₂ over Tungsten Oxide Catalysts