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Computational Study of Methane Direct Oxidation to Methanol on g-C3N4-Based Single Metal Atom Catalysts
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DOI：10.1021/acs.jpcc.6c02426.png)
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Abstract
En 中文
The direct conversion of methane to methanol is a promising strategy for the utilization of abundant natural resources with significant economic benefits. However, this process still faces substantial challenges in both activity and selectivity. In this work, based on density functional theory calculations, the potential of single-atom catalysts TM@g-C3N4 (TM = Cr, Fe, Co, Ni, Cu) for the oxidation of methane to methanol with N2O as the oxidant was systematically investigated. The results show that, except for Fe, TM@g-C3N4 can be easily oxidized to the TM-O@g-C3N4 species, which effectively suppresses side reactions and exhibits excellent selectivity toward methane-to-methanol conversion via a radical mechanism. Notably, the first C–H bond activation of CH4 is identified as the rate-determining step for all TM-O@g-C3N4 species, and the reaction activity increases in the order of the periodic table. Electronic structure analysis reveals that the oxygen atom in Cu-O@g-C3N4 carries the highest negative charge, leading to the strongest C–H···O interaction and the lowest energy barrier for C–H bond cleavage. The energy barrier for C–H activation (0.44 eV) is similar to that for the formation of Cu-O@g-C3N4 (0.47 eV). Additionally, the excellent stability of Cu@g-C3N4 and Cu-O@g-C3N4 guarantees superior catalytic performance under ambient conditions, confirming that Cu@g-C3N4 is an ideal catalyst for methane-to-methanol conversion. Our findings open a new avenue for the rational design of single-atom catalysts for methane oxidation to methanol.
Keywords:
Alcohols
Catalysts
Hydrocarbons
Inorganic carbon compounds
Oxidation
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