Catalytic dehydrogenative aromatization(CDA)has emerged as a powerful strategy for the synthesis of substituted phenols.However,most of the known CDA methods suffer from limited functional group compatibility due to t...Catalytic dehydrogenative aromatization(CDA)has emerged as a powerful strategy for the synthesis of substituted phenols.However,most of the known CDA methods suffer from limited functional group compatibility due to the use of strong oxidants,reductants,or bases.Herein,we report a(cis-P_(2)Cl)Ir-catalyzed CDA reaction enabled by transfer dehydrogenation(TD).This catalytic system is effective for CDA of both cyclohexanone and cyclohexanol derivatives and demonstrates excellent tolerance toward a variety of functional groups,including readily oxidizable electron-rich heterocycles.DFT studies further reveal that the(cis-P_(2)Cl)Ir catalyst is thermodynamically disfavored for the formation of a potential out-of-cycle catalyst species,iridium phenoxyl hydride complex,via oxidative addition of the phenol O–H bond,thereby preventing catalyst inhibition observed in the previously reported TD system.展开更多
Phenol is extensively utilized in various industries involving paints,rubber,textiles,explosives,plastics,etc.Compared to the conventional distillation or extraction technologies,pervaporation(PV)membrane process can ...Phenol is extensively utilized in various industries involving paints,rubber,textiles,explosives,plastics,etc.Compared to the conventional distillation or extraction technologies,pervaporation(PV)membrane process can be operated at a low temperature and has a low energy consumption as well as a high separation efficiency for phenol recovery.Thus,to meet the high demand for phenol recovery,the application of PV has been encouraged,and reached a new level.The PV process is governed by the properties of the membrane materials that significantly influence the energy costs associated with the separation unit,and the membrane types include polymer membranes,inorganic membranes,and mixed matrix membranes.Although recent literatures show that PV membranes have been continuously updated,no review has reported the latest development about it.In this work,the material types,separation properties and preparation methods of hydrophobic PV membranes for phenol recovery are summarized.Furthermore,the key preparation methods and application challenges associated with membranes are summarized,along with an overview of the opportunities and challenges posed by hydrophobic PV membranes for phenol recovery.展开更多
基金support from the National Key R&D Program of China(2021YFA1501700)National Natural Science Foundation of China(22425012,22293013)+3 种基金the Shanghai Sailing Program(24YF2756700)the Strategic Priority Research Program of the Chinese Academy of Sciences(XDB0610000,XDB1180000)CAS Project for Young Scientists in Basic Research(YSBR-O94)Science and Technology Commission of Shanghai Municipality(23JC1404400).
文摘Catalytic dehydrogenative aromatization(CDA)has emerged as a powerful strategy for the synthesis of substituted phenols.However,most of the known CDA methods suffer from limited functional group compatibility due to the use of strong oxidants,reductants,or bases.Herein,we report a(cis-P_(2)Cl)Ir-catalyzed CDA reaction enabled by transfer dehydrogenation(TD).This catalytic system is effective for CDA of both cyclohexanone and cyclohexanol derivatives and demonstrates excellent tolerance toward a variety of functional groups,including readily oxidizable electron-rich heterocycles.DFT studies further reveal that the(cis-P_(2)Cl)Ir catalyst is thermodynamically disfavored for the formation of a potential out-of-cycle catalyst species,iridium phenoxyl hydride complex,via oxidative addition of the phenol O–H bond,thereby preventing catalyst inhibition observed in the previously reported TD system.
基金funded by National Natural Science Foundation of China(22278023,22208010)S&T Program of Hebei(24464301D)SINOPEC Group(24-ZS-0447).
文摘Phenol is extensively utilized in various industries involving paints,rubber,textiles,explosives,plastics,etc.Compared to the conventional distillation or extraction technologies,pervaporation(PV)membrane process can be operated at a low temperature and has a low energy consumption as well as a high separation efficiency for phenol recovery.Thus,to meet the high demand for phenol recovery,the application of PV has been encouraged,and reached a new level.The PV process is governed by the properties of the membrane materials that significantly influence the energy costs associated with the separation unit,and the membrane types include polymer membranes,inorganic membranes,and mixed matrix membranes.Although recent literatures show that PV membranes have been continuously updated,no review has reported the latest development about it.In this work,the material types,separation properties and preparation methods of hydrophobic PV membranes for phenol recovery are summarized.Furthermore,the key preparation methods and application challenges associated with membranes are summarized,along with an overview of the opportunities and challenges posed by hydrophobic PV membranes for phenol recovery.
