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The molecular and electronic structures and chemical properties of the active sites on the surface of supported Na 2 WO 4 /SiO 2 catalysts used for oxidative coupling of methane (OCM) are poorly understood. Model SiO 2 -supported, Na-promoted tungsten oxide catalysts (Na–WO x /SiO 2 ) were systematically prepared using various Na- and W-precursors using carefully controlled Na/W molar ratios and examined with in situ Raman, UV-vis DR, CO 2 -TPD-DRIFT and NH 3 -TPD-DRIFT spectroscopies. The traditionally-prepared catalysts corresponding to 5% Na 2 WO 4 nominal loading, with Na/W molar ratio of 2, were synthesized from the aqueous Na 2 WO 4 ·2H 2 O precursor. After calcination at 800 °C, the initially amorphous SiO 2 support crystallized to the cristobalite phase and the supported sodium tungstate phase consisted of both crystalline Na 2 WO 4 nanoparticles (Na/W = 2) and dispersed phase Na–WO 4 surface sites (Na/W < 2). On the other hand, the catalysts prepared via a modified impregnation method using individual precursors of NaOH + AMT, such that the Na/W molar ratio remained well below 2, resulted in: (i) SiO 2 remaining amorphous (ii) only dispersed phase Na–WO 4 surface sites. The dispersed Na–WO 4 surface sites were isolated, more geometrically distorted, less basic in nature, and more reducible than the crystalline Na 2 WO 4 nanoparticles. The CH 4 + O 2 -TPSR results reveal that the isolated, dispersed phase Na–WO 4 surface sites were significantly more C 2 selective, but slightly less active than the traditionally-prepared catalysts that contain crystalline Na 2 WO 4 nanoparticles (Na/W = 2). These findings demonstrate that the isolated, dispersed phase Na–WO 4 sites on the SiO 2 support surface are the selective-active sites for the OCM reaction.
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New Mechanistic and Reaction Pathway Insights for Oxidative Coupling of Methane (OCM) over Supported Na 2 WO 4 /SiO 2 Catalysts
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 Na2WO4/SiO2catalysts. The present study demonstrates, with the aid of in situ Raman spectroscopy and chemical probe (H2‐TPR, TAP and steady‐state kinetics) experiments, that the long speculated crystalline Na2WO4active phase is unstable and melts under OCM reaction conditions, partially transforming to thermally stable surface Na‐WOxsites. Kinetic analysis via temporal analysis of products (TAP) and steady‐state OCM reaction studies demonstrate that (i) surface Na‐WOxsites are responsible for selectively activating CH4to C2Hxand over‐oxidizing CHyto CO and (ii) molten Na2WO4phase is mainly responsible for over‐oxidation of CH4to CO2and also assists in oxidative dehydrogenation of C2H6to C2H4. These new insights reveal the nature of catalytic active sites and resolve the OCM reaction mechanism over supported Na2WO4/SiO2catalysts.
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- Award ID(s):
- 1706581
- PAR ID:
- 10289531
- Publisher / Repository:
- Wiley Blackwell (John Wiley & Sons)
- Date Published:
- Journal Name:
- Angewandte Chemie International Edition
- Volume:
- 60
- Issue:
- 39
- ISSN:
- 1433-7851
- Format(s):
- Medium: X Size: p. 21502-21511
- Size(s):
- p. 21502-21511
- Sponsoring Org:
- National Science Foundation
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