Direct coupling of CH4 and CO2 into acetic acid over CuPdO2/Al2O3 in the presence of H2O2

Abstract

Direct conversion of methane and carbon dioxide into acetic acid is a dream way to address the two greenhouse gases, but is challenged by their chemical inertness. Cu and Pd are promising candidates both in CH4 and CO2 activation as well as the subsequent C-C coupling reactions at low temperature. Herein, we report that acetic acid can be produced by the direct coupling of CH4 and CO2 in the presence of H2O2 over Cu-Pd/Al2O3 catalysts at 50 °C. Results show that the acetic acid yield reaches 48.1 μmol·gcat−1·h−1 on the optimized reaction condition over Cu3.8-Pd1.6/Al2O3 catalyst, which is higher than that of either mono-Cu or mono-Pd catalyst. Extensive characterization indicates the higher activity of Cu3.8-Pd1.6/Al2O3 catalyst is attributed to the strong synergistic effect between Cu and Pd, which results in the formation of CuPdO2 phase, and thus promoting the electron transfer from Cu to Pd. DRIFTS experiments reveal that acetic acid is produced by the coupling of CH3* and COOH* over CuPdO2 active sites via Langmuir-Hinshelwood mechanism, where CH3* is originated from CH4 dehydrogenation step, and COOH* may formed by the activation of CO2 by H2O2. This study provides a new approach for the co-conversion of CH4 and CO2 into acetic acid at low temperature.