Direct Conversion of Methane with Carbon Dioxide Mediated by RhVO3 - Cluster Anions.

Direct conversion of methane with carbon dioxide to value-added chemicals is attractive but extremely challenging because of the thermodynamic stability and kinetic inertness of both molecules. Herein, the first dinuclear cluster species, RhVO3 - , has been designed to mediate the co-conversion of CH4 and CO2 to oxygenated products, CH3 OH and CH2 O, in the temperature range of 393-600 K. The resulting cluster ions RhVO3 CO- after CH3 OH formation can further desorb the [CO] unit to regenerate the RhVO3 - cluster, leading to the successful establishment of a catalytic cycle for methanol production from CH4 and CO2 (CH4 +CO2 →CH3 OH+CO). The exceptional activity of Rh-V dinuclear oxide cluster (RhVO3 - ) identified herein provides a new mechanism for co-conversion of two very stable molecules CH4 and CO2 .