H 2 -reduced phosphomolybdate promotes room-temperature aerobic oxidation of methane to methanol

The selective partial oxidation of methane to methanol using molecular oxygen (O 2 ) represents a long-standing challenge, inspiring extensive study for many decades. However, considerable challenges still prevent low-temperature methane activation via the aerobic route. Here we report a precipitated Pd-containing phosphomolybdate, which, after activation by molecular hydrogen (H 2 ), converts methane and O 2 almost exclusively to methanol at room temperature. The highest activity reaches 67.4 μmol g cat −1 h −1 . Pd enables rapid H 2 activation and H spillover to phosphomolybdate for Mo reduction, while facile O 2 activation and subsequent methane activation occur on the reduced phosphomolybdate sites. Continuous production of methanol from methane was also achieved by concurrently introducing H 2 , O 2 and methane into the system, where H 2 assists in maintaining a moderately reduced state of phosphomolybdate. This work reveals the underexplored potential of such a Mo-based catalyst for aerobic methane oxidation and highlights the importance of regulating the chemical valence state to construct methane active sites.