Molecular structure and catalytic promotional effect of Mn on supported Na2WO4/SiO2 catalysts for oxidative coupling of methane (OCM) reaction

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

doi:10.1016/j.cattod.2022.07.005

Molecular structure and catalytic promotional effect of Mn on supported Na₂WO₄/SiO₂ catalysts for oxidative coupling of methane (OCM) reaction

Journal Article · Wed Jul 13 00:00:00 EDT 2022 · Catalysis Today

DOI:https://doi.org/10.1016/j.cattod.2022.07.005· OSTI ID:2006594

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Lehigh Univ., Bethlehem, PA (United States); Idaho National Laboratory (INL), Idaho Falls, ID (United States)
Lehigh Univ., Bethlehem, PA (United States)
Idaho National Laboratory (INL), Idaho Falls, ID (United States)

The structure and promotional effect of Mn in supported Mn-Na₂WO₄/SiO₂ catalysts for the oxidative coupling of methane (OCM) reaction has been debated for a longtime in the literature. In the current investigation, with the aid of multiple in-situ characterization studies, we show that the freshly calcined supported 1.2Mn-5Na₂WO₄/SiO₂ catalyst possesses crystalline Na₂WO₄, Mn₂O₃ and SiO₂(cristobalite phase) along with surface MnO_x and Na-WO_x sites at low temperature and oxidizing environments. Under the OCM reaction environment (T>800°C), the crystalline Na₂WO₄ phase melts and Mn₂O₃ phase reduces. In contrast, the surface MnO_x and Na-WO_x sites exhibit excellent thermal and chemical stability. Exposure of the 1.2Mn-5Na₂WO₄/SiO₂ catalyst to the OCM reaction environment redisperses the molten Na₂WO₄ phase on the SiO₂ support to form new surface WO_x sites. Interestingly, the stable MnO_x species interacts with both molten Na₂WO₄ phase and surface Na-WO_x sites during OCM reaction. Controlled transient kinetic experiments in TAP and detailed steady state OCM fixed-bed reaction studies reveal the role and promotional effect of Mn in the 1.2Mn-5Na₂WO₄/SiO₂ catalyst. The W-oxides (both molten Na₂WO₄ and surface Na-WO_x sites) are the active sites for the catalytic OCM reaction and the MnO_xspecies only function as promoters. The promotion of MnO_x strongly depends on the gas phase O₂ partial pressure and the MnO_x species act as mediators for oxygen exchange between the gas phase molecular O₂ and catalyst lattice oxygen. In conclusion, the temperature dependent MnO_x promotion reveals that the MnO_x species selectively promote the molten Na₂WO₄ phase at lower reaction temperature and the surface Na-WO_x sites at higher temperature.

View Accepted Manuscript (DOE)

Research Organization:: Idaho National Laboratory (INL), Idaho Falls, ID (United States)

Sponsoring Organization:: National Science Foundation (NSF); USDOE Office of Energy Efficiency and Renewable Energy (EERE)

Grant/Contract Number:: AC07-05ID14517

OSTI ID:: 2006594

Report Number(s):: INL/JOU--22-66369-Rev000

Journal Information:: Catalysis Today, Journal Name: Catalysis Today Vol. 416; ISSN 0920-5861

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

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Mn promotional effect
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TAP
active site
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in-situ spectroscopy
kinetics

Molecular structure and catalytic promotional effect of Mn on supported Na2WO4/SiO2 catalysts for oxidative coupling of methane (OCM) reaction

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Molecular structure and catalytic promotional effect of Mn on supported Na₂WO₄/SiO₂ catalysts for oxidative coupling of methane (OCM) reaction