The direct conversion of cheap syngas into value-added ethanol at an industrial scale is in high demand.Herein we disclose a one-pot homogeneous homologation of methanol to ethanol with syngas via a rhodium/ruthenium ...The direct conversion of cheap syngas into value-added ethanol at an industrial scale is in high demand.Herein we disclose a one-pot homogeneous homologation of methanol to ethanol with syngas via a rhodium/ruthenium bimetallic catalytic approach.By introducing a catalytic amount of methyl iodide,methanol can be converted to ethanol with high selectivity(>91%ethanol).A syngas ratio of H_(2)/CO=4:1 was found to be optimal.Among various phosphine ligands tested,Rh-dppp catalyst gave the highest aldehyde pathway selectivity,thus providing an effective route for the synthesis of ethanol upon coupling with a Ru hydrogenation catalyst.The bite angle of the bisphosphine ligands dramatically influences the selectivity of the dual Rh/Ru metallic cascade catalysts.In line with the experimental findings,theoretical calculations predicted a rational trend of the selectivity of different bisphosphine ligands via varying bite angle properties.展开更多
基金This experimental investigation was financially supported by the National Natural Science Foundation of China(grant no.21991113)the Guangdong Provincial Key Laboratory of Catalysis(grant no.2020B121201002)+1 种基金the Science,Technology,and Innovation Commission of Shenzhen(grant no.20200925161222002)Theoretical calculations were supported by the National Natural Science Foundation of China(grant nos.22033005 and 22103035).
文摘The direct conversion of cheap syngas into value-added ethanol at an industrial scale is in high demand.Herein we disclose a one-pot homogeneous homologation of methanol to ethanol with syngas via a rhodium/ruthenium bimetallic catalytic approach.By introducing a catalytic amount of methyl iodide,methanol can be converted to ethanol with high selectivity(>91%ethanol).A syngas ratio of H_(2)/CO=4:1 was found to be optimal.Among various phosphine ligands tested,Rh-dppp catalyst gave the highest aldehyde pathway selectivity,thus providing an effective route for the synthesis of ethanol upon coupling with a Ru hydrogenation catalyst.The bite angle of the bisphosphine ligands dramatically influences the selectivity of the dual Rh/Ru metallic cascade catalysts.In line with the experimental findings,theoretical calculations predicted a rational trend of the selectivity of different bisphosphine ligands via varying bite angle properties.
