Dry Reforming\nof Methane to Syngas Mediated by Rhodium–Cobalt\nOxide Cluster Anions Rh<sub>2</sub>CoO<sup>–</sup>

Dry reforming of methane (DRM) to\nsyngas is an important\nroute\nto co-convert CH<sub>4</sub> and CO<sub>2</sub>. However, the highly\nendothermic nature of DRM induces the thermocatalysis to commonly\noperate at high temperatures that inevitably causes coke deposition\nthrough pyrolysis of methane. Herein, benefiting from the mass spectrometric\nexperiments complemented with quantum chemical calculations, we have\ndiscovered that the bimetallic oxide cluster Rh<sub>2</sub>CoO<sup>–</sup> can mediate the co-conversion of CH<sub>4</sub> and\nCO<sub>2</sub> at room temperature giving rise to two free H<sub>2</sub> molecules and two adsorbed CO molecules (CO<sub>ads</sub>). The\nonly elementary step requiring the input of external energy (e.g.,\nhigh temperature) is desorption of CO<sub>ads</sub> from the reaction\nintermediate Rh<sub>2</sub>CoOC<sub>2</sub>O<sub>2</sub><sup>–</sup>. The doping effect of Co has also been clarified that the Co could\ntune the charge distribution and orbital energy of the active metal\nRh, enabling the enhancement of cluster reactivity toward C–H\nactivation, which is essential to facilitating the DRM to syngas.\nThis work not only underlines the importance of temperature control\nover elementary steps in practical thermocatalysis but also identifies\na promising active species containing the late 3d transition metal\nto drive DRM to syngas. The findings could provide novel insights\ninto design of bimetallic catalysts for co-conversion of CH<sub>4</sub> and CO<sub>2</sub> at low temperatures.