Revisiting the catalytic role of supported Na2WO4 for oxidative coupling of methane reaction

doi:10.1016/S1872-2067(26)65212-6

Abstract

Abstract:

Na₂WO₄-based catalysts have shown great promise in the oxidative coupling of methane (OCM). Nevertheless, conventional studies have generally limited Na₂WO₄ loading to relatively low levels (<10 wt%), thereby revealing only the role of the Na-WOₓ species in activating methane to generate methyl radicals. Herein, we systematically investigate the loading-dependent structural evolution of Na₂WO₄ over an exceptionally wide range (0-50 wt%) and reveal a dual role for Na₂WO₄, i.e., surface Na-WO_x sites for CH₄ activation and small Na₂WO₄ clusters for heterogeneous ^•CH₃ coupling. This finding revises the traditional heterogeneous-homogeneous mechanism for OCM and fills the knowledge gap regarding the structure-dependent catalytic function of Na₂WO₄ across a broad loading range. The in-depth understanding of these structure-dependent catalytic functions of various Na₂WO₄ species will substantially contribute to the design of more efficient catalysts to break through the inherent C₂ yield limitation of conventional OCM processes.

Key words: Methane, Oxidative coupling of methane, Na₂WO₄, Cluster, ^•CH₃ radical

Zejing Wei, Kunkun Wei, Xutao Chen, Yang Pan, Chengyuan Liu, Liping Xiao, Yifeng Shi, Shihui Zou, Jie Fan. Revisiting the catalytic role of supported Na₂WO₄ for oxidative coupling of methane reaction[J]. Chinese Journal of Catalysis, 2027, 92: 376-386.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(26)65212-6

https://www.cjcatal.com/EN/Y2027/V92/I1/376

Figures/Tables 7

Fig. 1. XRD patterns and Raman spectra of fresh Na2WO4/SiO2 (a,c), fresh Na2WO4/ZrO2 (b,d), spent Na2WO4/SiO2 (e,g) and spent Na2WO4/ZrO2 (f,h) catalysts with different Na2WO4 loadings.

Fig. 2. HRTEM images (a,c,e) and EDS elemental mappings (b,d,f) of Na2WO4/ZrO2 with different loadings. (a,b) 5Na2WO4/ZrO2; (c,d) 30Na2WO4/ZrO2; (e,f) 30Na2WO4/ZrO2-w. Typical Na-WOx and Na2WO4 clusters are marked by orange and green circles, respectively. The inset shows the size distribution of the tungstate species.

Fig. 3. OCM performances of Na2WO4/SiO2 (a) and Na2WO4/ZrO2 (b) catalysts under oxygen-lean atmosphere. Reaction conditions: 300 mg catalyst, total gas flow rate 67 mL min-1, CH4:O2:N2 = 30:10:27, GHSV = 13400 mL gcatalyst-1 h-1.

Fig. 4. Comparison of C2 selectivity of Na2WO4/SiO2 (a) and Na2WO4/ZrO2 (b) catalysts at a fixed CH4 conversion under oxygen-rich atmosphere. Reaction conditions: 300 mg catalyst, total gas flow rate 67 mL min-1, CH4:O2:N2 = 2:8:60, GHSV = 13400 mL gcatalyst-1 h-1.

Fig. 5. H2-TPR profiles of Na2WO4/SiO2 (a) and Na2WO4/ZrO2 (b) with different loadings. 30 wt%-w represents the corresponding catalysts (30 wt% Na2WO4/SiO2 or 30 wt% Na2WO4/ZrO2) after the ammonia-washing treatment. The reduction was performed using 50 mg of catalyst under a 10% H2/He flow (30 mL min-1) with a heating rate of 10 °C min-1.

Fig. 6. Schematic illustration and the results of in-situ SVUV‐PIMS studies of Na2WO4/SiO2 and Na2WO4/ZrO2. [CH3]Q and [CH3]C denote the signal intensities of methyl radicals detected downstream of the Quartz control bed and the Catalyst bed, respectively. Reaction conditions: 200 mg of Sm2O3 was placed upstream and 200 mg catalyst was placed downstream separately, CH4:O2 = 30:10, pressure equaled to 2 Torr.

Fig. 7. Schematic illustration of loading-dependent structural evolution and catalytic behaviors of Na2WO4 in the oxidative coupling of methane.

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Revisiting the catalytic role of supported Na₂WO₄ for oxidative coupling of methane reaction

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