Selective activation of methane C–H bond in the presence of methanol

Xi, Yongjie; Heyden, Andreas

doi:10.1016/j.jcat.2020.03.036

Selective activation of methane C–H bond in the presence of methanol

Journal Article · Wed Apr 08 00:00:00 EDT 2020 · Journal of Catalysis

DOI:https://doi.org/10.1016/j.jcat.2020.03.036· OSTI ID:3001233

Xi, Yongjie ^[1]; ^[1]

University of South Carolina, Columbia, SC (United States)

Direct 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. Furthermore, 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. For Ir, Pt and Rh-doped anatase TiO₂(101), the CH₄ C-H bond activation can be preferred over that of CH₃OH at significant methanol mole fraction. Also, for PdAu alloys containing adsorbed oxygen and positively charged Pd, calculations suggest in agreement with recent experiments (Science 367 (6474), 193-197) that the CH₄ C-H bond can be selectively activated in the presence of CH₃OH.

View Accepted Manuscript (DOE)

Research Organization:: University of South Carolina, Columbia, SC (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0007167; AC02-05CH11231

OSTI ID:: 3001233

Alternate ID(s):: OSTI ID: 1615176
OSTI ID: 1656892

Journal Information:: Journal of Catalysis, Journal Name: Journal of Catalysis Vol. 386; ISSN 0021-9517

Publisher:: Elsevier BVCopyright Statement

Country of Publication:: United States

Language:: English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
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Selective activation of methane C–H bond in the presence of methanol

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