Single Chromium Atoms Supported on Titanium Dioxide Nanoparticles for Synergic Catalytic Methane Conversion under Mild Conditions

Direct conversion of methane to value‐added chemicals with high selectivity under mild conditions remains a great challenge in catalysis. Now, single chromium atoms supported on titanium dioxide nanoparticles are reported as an efficient heterogeneous catalyst for direct methane oxidation to C1 oxygenated products with H₂O₂ as oxidant under mild conditions. The highest yield for C1 oxygenated products can be reached as 57.9 mol mol_Cr^?1 with selectivity of around 93 % at 50 °C for 20 h, which is significantly higher than those of most reported catalysts. The superior catalytic performance can be attributed to the synergistic effect between single Cr atoms and TiO₂ support. Combining catalytic kinetics, electron paramagnetic resonance, and control experiment results, the methane conversion mechanism was proposed as a methyl radical pathway to form CH₃OH and CH₃OOH first, and then the generated CH₃OH is further oxidized to HOCH₂OOH and HCOOH.