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CH4.pdf (2.4 MB)
Selective Activation of Methane C-H Bond in the Presence of Methanol
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methane to methanol (MTM) conversion over heterogeneous catalysts is a
promising route for valorization of methane. The methane C-H bond activation is
considered as the key step of the MTM and is the focus of considerable research
activity. However, the formed methanol typically suffers from overoxidation largely
due to the cleavage of a methanol C-H bond, whose bond dissociation energy is
ca. 0.5 eV lower than that of the methane C-H bond, which usually translates to
a transition state energy of the methanol C-H bond cleavage that is ca. 0.55 eV
lower than that of methane whenever the reactions proceed through a radical
mechanism. Here, we propose a general approach for decreasing the transition
state energy difference between the CH4 and CH3OH C-H bond dissociation. When a
metal-oxide supported cationic transition metal atom and a neighboring oxygen
on the oxide surface serve as the active site, the transition state energy
difference through a surface-stabilized pathway can be noticeably narrowed as
compared with that of a radical pathway.