Advantages and limitations of hydrogen peroxide for direct oxidation of methane to methanol at mono-copper active sites in Cu-exchanged zeolites

doi:10.1016/S1872-2067(23)64485-7

Abstract

Abstract:

The efficiency of direct catalytic oxidation of methane to methanol (DMTM) is significantly influenced by oxidants. However, realizing a one-pot DMTM using dioxygen remains challenging. Hydrogen peroxide is still the most frequently reported green oxidant for DMTM, with high selectivity for methanol. To gain insight into the influence of oxidants on DMTM performance, we computationally investigated the reaction mechanisms involved in DMTM using H₂O₂ at mono-copper sites in three types of Cu-exchanged zeolites with different micropore sizes. We identified the advantages and limitations of H₂O₂ as an oxidant. In contrast to the O-O bond in O₂, the O-O bond in H₂O₂ can be easily broken to produce reactive surface oxygen species, which enable the facile C-H bond activation of methane at a low temperature. However, because of the radical-like process of C-H bond activation at mono-copper sites, actualizing the preferential C-H bond activation of methane is kinetically challenging compared to that of methanol. Moreover, the lower O-H bonding energy of H₂O₂ would result in self-decomposition of H₂O₂. Despite these bottlenecks, kinetic analysis shows that improving catalysts to boost the DMTM performance using H₂O₂ is a promising approach.

Key words: Density functional theory, Cu-exchanged zeolite, Hydrogen peroxide, Methane partial oxidation, Methanol

Lu Cheng, Xuning Chen, P. Hu, Xiao-Ming Cao. Advantages and limitations of hydrogen peroxide for direct oxidation of methane to methanol at mono-copper active sites in Cu-exchanged zeolites[J]. Chinese Journal of Catalysis, 2023, 51: 135-144.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(23)64485-7

https://www.cjcatal.com/EN/Y2023/V51/I8/135

Figures/Tables 8

Fig. 1. The optimized structure of H-ZSM-5 with a unit cell of 20.517 ? × 20.293 ? × 13.627 ? (a), H-MOR with a unit cell of 18.279 ? × 20.463 ? × 7.546 ? (b), and H-SSZ-13 with a unit cell of 13.686 ? × 13.686 ? × 14.771 ? (c), from a Z-axis view. The most stable substituted single Al cations are located on the γ-8MR at the intersection of the straight and sine channels of ZSM-5 zeolite, on the 6MR of SSZ-13 zeolite, and on the 12MR of the straight channel of MOR zeolite. The H, C, O, Si, Al, and Cu atoms are displayed in white, gray, red, yellow, magenta, and orange, respectively.

Fig. 2. (a) The Gibbs free energies of different mononuclear copper species against ΔμO2 at the reaction temperature of 323 K with 10?2 mbar H2O. (b) The phase diagram of Z[CuxOyHz] before the catalysis, where the dotted line represents the most stable copper species before DMTM at 323 K with 10?2 mbar H2O. The optimized structures of the most stable mono-copper species at 323 K: [Cu]+/ZSM-5 (c), [Cu]+/MOR (d), and [Cu]+/SSZ-13 (e).

Fig. 3. (a) The standard free energies of adsorption for O2 and H2O2 at Z[Cu]+ site in the copper-exchanged zeolites. (b) Standard free energies of activation for the first C-H bond breaking of CH4 at [CuO2]+ and [Cu(OH)2]+ sites in the copper-exchanged zeolites at 323 K. (c) Free-energy profiles of the water-mediated and direct O-O bond activations of H2O2 catalyzed by [Cu]+/ZSM-5 at 323 K. (d) Free energies of activation for direct and water-mediated cleavage of the O-O bond of H2O2 at Cu-ZSM-5, Cu-MOR, and Cu-SSZ-13.

Fig. 4. The reaction network of methane conversion towards methanol in Cu-ZSM-5 starts with the black pathway. The blue and the orange arrows are the reaction cycles of regenerating Z[Cu(OH)2]+ and Z[CuOH]+ sites, respectively. The black and red numbers represent the free energies of variation and activation, respectively, for each elementary step, in eV. The structures of some key transition states are also shown.

Fig. 5. Gibbs free-energy profiles of H2O2 oxidation at the [Cu(OH)2]+/ZSM-5 site at 323 K with the geometry structures of the corresponding transition states and intermediate states.

Fig. 6. The cumulative bar graph for the activation free energies ΔG≠ of the first C-H bond breaking of methane and methanol and the first O-H bond breaking of H2O2 at [Cu(OH)2]+/ZSM-5 (a) and [CuOH]+/ZSM-5 (b) sites. For each activation free energy, ΔH≠ and TΔS≠ represent the contribution of enthalpic and entropic contributions to the free-energy barrier. Δμ corresponds to the influence of pressure and concentration on the free-energy barrier at 323 K: 30 bar CH4, 100 μmol CH3OH/10 mL H2O, and 0.51 mol/L H2O2.

Fig. 7. The relationship between the conversion rate and methanol selectivity at different times: the red and blue lines correspond to the Z[CuOH]+ and Z[Cu(OH)2]+ sites, respectively. Reaction conditions: 28 mg catalysts dispersed in 10 mL of 0.51 mol/L H2O2 aqueous solution, 30 bar CH4 for 30 min at 323 K.

Fig. 8. Ratio of the conversion rate of methane and H2O2 oxidation, against the difference in the free energy of activation between the first C-H bond breaking of methane and the second O-H bond breaking of H2O2 versus temperature.

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