Selective Catalytic Oxidation of Methane to Methanol in Aqueous Medium over Copper Cations Promoted by Atomically Dispersed Rhodium on TiO2. (7th March 2022)

• Record Type: Journal Article
• Authors: Gu, Fubo; Qin, Xuetao; Li, Mengwei; Xu, Yao; Hong, Song; Ouyang, Mengyao; Giannakakis, Georgios; Cao, Sufeng; Peng, Mi; Xie, Jinling; Wang, Meng; Han, Dongmei; Xiao, Dequan; Wang, Xiayan; Wang, Zhihua; Ma, Ding
• Is Part Of: Angewandte Chemie. Volume 134:Number 18(2022)
• Page Start: n/a
• Page End: n/a
• Publication Date: 2022-03-07
• Subjects: Atomic Dispersion -- Copper Cations -- Methane -- Methanol -- Rhodium; Chemistry -- Periodicals; 540
• DOI: 10.1002/ange.202201540
• Languages: English
• ISSNs: 0044-8249

Abstract

Abstract: Direct conversion of methane into value‐added chemicals, such as methanol under mild conditions, is a promising route for industrial applications. In this work, atomically dispersed Rh on TiO2 suspended in an aqueous solution was used for the oxidation of methane to methanol. Promoted by copper cations (as co‐catalyst) in solution, the catalysts exhibited high activity and selectivity for the production of methanol using molecular oxygen with the presence of carbon monoxide at 150 °C with a reaction pressure of 31 bar. Millimole level yields of methanol were reached with the selectivity higher than 99 % using the Rh/TiO2 catalysts with the promotion of the copper cation. CO was the reductive agent to generate H2 from H2 O, which led to the formation of H2 O2 through the reaction of H2 and O2 . Atomically dispersed Rh activated the C−H bond in CH4 and catalyzed the oxidation using H2 O2 . Copper cations maintained the low‐valence state of Rh. Moreover, copper acted as a scavenger for suppressing the overoxidation, thus leading to the high selectivity of methanol. Abstract : Atomically dispersed Rh on TiO2 was used for the oxidation of methane to methanol with molecular oxygen under mild conditions. Promoted by copper cations, the Rh/TiO2 catalysts produced a millimole level of methanol with a selectivity higher than 99 %. Copper maintained the low‐valence state of Rh. Moreover, copper acted as a scavenger for suppressing the overoxidation, thus leading to the high selectivity of methanol.