Methane oxidation to acetic acid catalyzed by Pd2+ cations in the presence of oxygen |
| |
| Affiliation: | 1. Shanghai Engineering Research Center for Multi-Media Environmental Catalysis and Resource Utilization, Key Lab for Advanced Materials and Joint International Research Laboratory of Precision Chemistry and Molecular Engineering, Feringa Nobel Prize Scientist Joint Research Center, Institute of Fine Chemicals, School of Chemistry and Molecular Engineering, East China University of Science & Technology, 130 Meilong Road, Shanghai 200237, China;1. Shenzhen Key Laboratory of Nanobiomechanics, Shenzhen Institutes of Advanced Technology, Chinese Academy of Sciences, Shenzhen 518055, Guangdong, China;2. Department of Chemical and Biomolecular Engineering, Yonsei University, 50 Yonsei-ro, Seodaemun-gu, Seoul, 120-749, Republic of Korea;3. Department of Chemical and Biomolecular Engineering, Sogang University, 1 Sinsu-dong, Mapo-gu, Seoul, Republic of Korea |
| |
| Abstract: | Synthesis of acetic acid from methane catalyzed by Pd2+ cations dissolved in sulfuric acid was investigated to determine the effects of reaction conditions and the mechanism. Acetic acid yield was found to be a strong function of CH4 and O2 partial pressures. High O2/CH4 ratio and high total pressure delivered the highest yield of acetic acid (14.2 turnovers of Pd2+) and the highest retention of Pd2+ in solution (96%). Byproducts were sulfur containing compounds (most notably methyl bisulfate) and COx, but the acetic acid selectivity was maximized (82%) by lowering the reaction temperature. Methane is activated by Pd(OSO3H)2, forming (CH3)Pd(OSO3H). CO, generated from the oxidation of methyl bisulfate, inserts into the CH3 Pd bond creating a (CH3CO)Pd(OSO3H) species. Reaction of this complex with H2SO4 produces acetic acid. Pd2+ is reduced to Pd0 during the oxidation of methyl bisulfate or CO, and Pd0 is reoxidized to Pd2+ by H2SO4 and O2. |
| |
| Keywords: | |
| 本文献已被 ScienceDirect 等数据库收录！ |
|
