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Efficient Electrooxidation of Methane to Formic Acid by Optimizing Both the Inner-Sphere and Outer-Sphere Reactions
Mingjie Cheng1,2, Chunjun Chen1,2, Yingxuan Liu1,2
1Shanghai Key Laboratory of Green Chemistry and Chemical Processes, State Key Laboratory of Petroleum Molecular & Process Engineering, School of Chemistry and Molecular Engineering, East China Normal University, Shanghai200062, China.
Abstract:
Electrooxidation CH4 into valuable, easily transportable liquid fuels offers a highly promising route for the energy-efficient use of CH4. However, achieving high apparent Faradaic efficiency (aFE) and product formation rate is challenging. In this work, we report a heterogeneous WO3 modified Bi (WO3-Bi) incorporated with homogeneous Fe2+ catalytic system in 0.1 M HClO4, which can efficiently electrooxidation CH4 into HCOOH by O2 at the cathode. The aFE of HCOOH can reach up to 96.0%, and the formation rate of HCOOH is 7.9 μmol h-1 cm-2. Experiments and theoretical calculations indicate that the WO3 can not only improve the formation of H2O2 from O2 by enhancing the adsorption of *OOH but also promote the decomposition of H2O2 into •OH radicals by tuning the hydrogen-bond structure of interfacial H2O. The synergy between these two parts facilitates the oxidation of CH4 into HCOOH.
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