Ag(0) dimers within a thioether-functionalized MOF catalyze the CO to CH hydrogenation reaction.

Ultrasmall silver clusters in reduced state are difficult to synthesize since silver atoms tend to rapidly aggregate into bigger entities. Here, we show that dimers of reduced silver (Ag) are formed within the framework of a metal-organic framework provided with thioether arms in their walls (methioMOF), after reduction with NaBH of the corresponding Ag-methioMOF precursor. The resulting Ag-methioMOF catalyzes the methanation reaction of carbon dioxide (CO to CH hydrogenation reaction) under mild reaction conditions (1 atm CO, 4 atm H, 140 °C), with production rates much higher than Ag on alumina and even comparable to the state-of-the-art Ru on alumina catalyst (Ru-AlO) under these reaction conditions, according to literature results.