Ru single-atom catalyst anchored on sulfated zirconia for direct methane conversion to methanol

doi:10.1016/S1872-2067(22)64191-3

Abstract

Abstract:

The direct CH₄ conversion (DMC) to methanol is a challenging topic. In this study, the Ru/SZ (sulfated zirconia) single-atom catalysts (SACs) were synthesized and utilized to the DMC to methanol under mild conditions (70 °C). The yield over the Ru/SZ SACs (18.32 µmol, TOF ≥ 80 h^-1) significantly exceeded the sum of the yields over the SZ (0.67 µmol) and Ru/ZrO₂ (0.29 µmol), indicating that a new active center was formed on the Ru/SZ SACs. Combined with the results of the ¹³CH₄ isotope labeling experiments and various characterizations including the pyridine adsorption infrared spectroscopy, electron paramagnetic resonance and X-ray photoelectron spectroscopy, an unprecedented synergy effect between the single-atom and the super acid sites was pictured: The strong acidity of the Ru/SZ SACs could effectively promote the decomposition of H₂O₂ into the ^•OH, and the Ru^δ⁺ (δ > 4) and the adjacent Zr^γ⁺-^•OH (γ > 4) could synergistically catalyze the CH₄ to methanol.

Key words: Ru single atom, Sulfated zirconia, Strong acid site, Direct methane conversion, Synergistic catalysis

Hua Liu, Leilei Kang, Hua Wang, Qike Jiang, Xiao Yan Liu, Aiqin Wang. Ru single-atom catalyst anchored on sulfated zirconia for direct methane conversion to methanol[J]. Chinese Journal of Catalysis, 2023, 46: 64-71.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(22)64191-3

https://www.cjcatal.com/EN/Y2023/V46/I3/64

Figures/Tables 6

Fig. 1. (a) XRD patterns of the ZrO2, SZ and Ru/SZ catalysts. AC-HAADF-STEM images of the 0.05Ru/SZ (b), 0.1Ru/SZ (c) and 0.3Ru/SZ catalysts (d).

Fig. 2. (a) Catalytic performance of DMC on ZrO2, 0.1Ru/ZrO2, SZ and Ru/SZ catalysts. (b) The TOF of oxygenates on Ru/SZ catalysts for the DMC reaction.

Fig. 3. PY-IR spectra (a) and NH3-TPD results (b) of the ZrO2, 0.1Ru/ZrO2, SZ and 0.1Ru/SZ catalysts.

Fig. 4. EPR spectra of the DMC on the ZrO2, 0.1Ru/ZrO2, SZ and 0.1Ru/SZ catalysts.

Fig. 5. 13C NMR spectra of reaction products from the DMC.

Fig. 6. Reaction mechanism for the DMC over the Ru/SZ SACs.

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