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, CH3OH and CH2O, in the temperature range of 393-600K. The resulting cluster ions RhVO3CO- after CH3OH 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 -> CH3OH+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.