New Mechanistic and Reaction Pathway Insights for Oxidative Coupling of Methane (OCM) over Supported Na 2 WO 4 /SiO 2 Catalysts

Sourav, Sagar; Wang, Yixiao; Kiani, Daniyal; Baltrusaitis, Jonas; Fushimi, Rebecca R.; Wachs, Israel E.

doi:10.1002/ange.202108201

New Mechanistic and Reaction Pathway Insights for Oxidative Coupling of Methane (OCM) over Supported Na ₂ WO ₄ /SiO ₂ Catalysts

Journal Article · Mon Aug 16 00:00:00 EDT 2021 · Angewandte Chemie

DOI:https://doi.org/10.1002/ange.202108201· OSTI ID:1813634

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Biological and Chemical Science and Engineering Energy Environment Science &, Technology Idaho National Laboratory Idaho Falls ID 83415 USA, Department of Chemical and Biomolecular Engineering Lehigh University Bethlehem PA 18015 USA
Biological and Chemical Science and Engineering Energy Environment Science &, Technology Idaho National Laboratory Idaho Falls ID 83415 USA
Department of Chemical and Biomolecular Engineering Lehigh University Bethlehem PA 18015 USA

Abstract

The complex structure of the catalytic active phase, and surface‐gas reaction networks have hindered understanding of the oxidative coupling of methane (OCM) reaction mechanism by supported Na ₂ WO ₄ /SiO ₂ catalysts. The present study demonstrates, with the aid of in situ Raman spectroscopy and chemical probe (H ₂ ‐TPR, TAP and steady‐state kinetics) experiments, that the long speculated crystalline Na ₂ WO ₄ active phase is unstable and melts under OCM reaction conditions, partially transforming to thermally stable surface Na‐WO _x sites. Kinetic analysis via temporal analysis of products (TAP) and steady‐state OCM reaction studies demonstrate that ( i ) surface Na‐WO _x sites are responsible for selectively activating CH ₄ to C ₂ H _x and over‐oxidizing CH _y to CO and ( ii ) molten Na ₂ WO ₄ phase is mainly responsible for over‐oxidation of CH ₄ to CO ₂ and also assists in oxidative dehydrogenation of C ₂ H ₆ to C ₂ H ₄ . These new insights reveal the nature of catalytic active sites and resolve the OCM reaction mechanism over supported Na ₂ WO ₄ /SiO ₂ catalysts.

View Accepted Manuscript (Publisher)

Sponsoring Organization:: USDOE

Grant/Contract Number:: NONE; AC07-05ID14517

OSTI ID:: 1813634

Journal Information:: Angewandte Chemie, Journal Name: Angewandte Chemie Journal Issue: 39 Vol. 133; ISSN 0044-8249

Publisher:: Wiley Blackwell (John Wiley & Sons)Copyright Statement

Country of Publication:: Germany

Language:: English

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