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

• Published in: Angewandte Chemie International Edition 2020-01, Vol.59 (3), p.1216-1219
• Main Authors: Shen, Qikai, Cao, Changyan, Huang, Runkun, Zhu, Lei, Zhou, Xin, Zhang, Qinghua, Gu, Lin, Song, Weiguo
• Format: Article
• Language: English
• Subjects: Catalysis; Catalysts; Catalytic converters; Chromium; Direct conversion; Electron paramagnetic resonance; heterogeneous catalysis; Hydrogen peroxide; Methane; Methyl radicals; Nanoparticles; Organic chemistry; Oxidants; Oxidation; Oxidizing agents; Oxygenation; Reaction kinetics; Selectivity; single atoms; synergistic catalysis; Synergistic effect; Titanium; Titanium dioxide
• ISSN: 1433-7851; 1521-3773
• DOI: 10.1002/anie.201913309

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 molCr−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. Single chromium atoms supported on titanium dioxide nanoparticles are an efficient synergistic heterogeneous catalyst. This system was used for direct methane oxidation to C1 oxygenated products with H2O2 as oxidant under mild conditions.