With the acceleration of global industrialization,the human society has an increasing demand for high-value chemicals.Such chemicals are mostly derived from non-renewable fossil fuels,causing inevitable energy shortag...With the acceleration of global industrialization,the human society has an increasing demand for high-value chemicals.Such chemicals are mostly derived from non-renewable fossil fuels,causing inevitable energy shortage and accompanied environmental pollution issues during the conversion processes[1].Recently,biomass-derived platform molecules with abundant source,low price,and variable chemical structure have attracted tremendous attention from researchers,and their catalytic oxidation has become a promising route to reduce the dependence of fossil fuels and alleviate the harmful impact of environmental pollution for the production of high-value chemicals[2].展开更多
An iron（Ⅲ）-catalyzed selective oxidation of 5-HMF to 2,5-DFF in air at room temperature was developed.This approach gives 2,5-DFF with good selectivity and yields. Additionally, a two-step process was developed for...An iron（Ⅲ）-catalyzed selective oxidation of 5-HMF to 2,5-DFF in air at room temperature was developed.This approach gives 2,5-DFF with good selectivity and yields. Additionally, a two-step process was developed for the oxidation of 2,5-DFF to 2,5-FDCA at remarkably high substrate concentrations. This work demonstrates unequivocally the great potential of iron as a cheap and earth-abundant catalyst for the development of new protocols for the conversion of biomass to value-added chemicals.展开更多
The synthesis of new and potentially“green”solvents and other small molecules/intermediates from glycerol and associated derivatives is promising for expanding glycerol valorization.Previously,we showed that elimina...The synthesis of new and potentially“green”solvents and other small molecules/intermediates from glycerol and associated derivatives is promising for expanding glycerol valorization.Previously,we showed that eliminating H-bonding reduces solvent–solvent interactions and increases CO_(2)solubility in 1,3-diether-2-ketones compared to 1,3-diether-2-alcohols based on glycerol skeletons.Further exploration of glycerol-derived 1,3-diether-2-propanol compounds into corresponding 1,3-diether-2-alkenes can yield valuable insights into structure–property relationships as well as new chemical intermediates.In the current work five symmetric glycerol-derived(E/Z)-1,3-diether-2-alkenes were synthesized:1,3-dimethoxyprop-1-ene([M,A,M]),1,3-diethoxyprop-1-ene([E,A,E]),2,5,9,12-tetraoxatridec-6-ene([ME,A,ME]),1,3-bis(2,2,2-trifluoromethoxy)prop-1-ene([F,A,F]),and prop-1-ene-1,3-diylbis(oxy)bis(methylene)dibenzene([Bn,A,Bn]),using a three-step strategy starting from epichlorohydrin.All compounds were purified using thorough distillation and drying methods.The E:Z ratio in all products was close to 1:1.Thermophysical properties of the synthesized(E/Z)-1,3-diether-2-alkenes(e.g.,density,refractive index,viscosity)were measured over the range of T=293.15–333.15 or 343.15 K.CO_(2)absorption capacities(Henry’s constants)of[F,A,F]were measured at T=303.15,318.15,333.15,and 348.15 K and pressures in the range of P=2–10 atm.Density,viscosity,vapor pressure,enthalpy of vaporization,and dipole moment were also calculated for each compound.Additionally,it was demonstrated that the C=C bond remains accessible for further reactions and can undergo bromination and thus may also have applications as intermediates for more complex molecules that are based on glycerol skeletons.展开更多
基金supported by CAS Key Laboratory of Renewable Energy,Guangzhou Institute of Energy Conversion(E229kf1201)the National Natural Science Foundation of China(22078374,22378434,and 22309210)the Scientific and Technological Planning Project of Guangzhou(202206010145 and 2024A04J4353).
文摘With the acceleration of global industrialization,the human society has an increasing demand for high-value chemicals.Such chemicals are mostly derived from non-renewable fossil fuels,causing inevitable energy shortage and accompanied environmental pollution issues during the conversion processes[1].Recently,biomass-derived platform molecules with abundant source,low price,and variable chemical structure have attracted tremendous attention from researchers,and their catalytic oxidation has become a promising route to reduce the dependence of fossil fuels and alleviate the harmful impact of environmental pollution for the production of high-value chemicals[2].
基金the National Basic Research Program of China (Nos. 2013CB228103, 2012CB215306)NNSFC (Nos. 21472033, 21325208, 21172209)+3 种基金FRFCU (No. WK2060190025)SRFDP (No. 20123402130008)CAS (No. KJCX2-EW-J02)Fok Ying Tung Education Foundation for the financial support
文摘An iron（Ⅲ）-catalyzed selective oxidation of 5-HMF to 2,5-DFF in air at room temperature was developed.This approach gives 2,5-DFF with good selectivity and yields. Additionally, a two-step process was developed for the oxidation of 2,5-DFF to 2,5-FDCA at remarkably high substrate concentrations. This work demonstrates unequivocally the great potential of iron as a cheap and earth-abundant catalyst for the development of new protocols for the conversion of biomass to value-added chemicals.
基金Support from the U.S.National Science Foundation(EFMA-2029387)is gratefully acknowledgedfinancial support from the University of Alabama Graduate School as a Graduate Council Fellow.
文摘The synthesis of new and potentially“green”solvents and other small molecules/intermediates from glycerol and associated derivatives is promising for expanding glycerol valorization.Previously,we showed that eliminating H-bonding reduces solvent–solvent interactions and increases CO_(2)solubility in 1,3-diether-2-ketones compared to 1,3-diether-2-alcohols based on glycerol skeletons.Further exploration of glycerol-derived 1,3-diether-2-propanol compounds into corresponding 1,3-diether-2-alkenes can yield valuable insights into structure–property relationships as well as new chemical intermediates.In the current work five symmetric glycerol-derived(E/Z)-1,3-diether-2-alkenes were synthesized:1,3-dimethoxyprop-1-ene([M,A,M]),1,3-diethoxyprop-1-ene([E,A,E]),2,5,9,12-tetraoxatridec-6-ene([ME,A,ME]),1,3-bis(2,2,2-trifluoromethoxy)prop-1-ene([F,A,F]),and prop-1-ene-1,3-diylbis(oxy)bis(methylene)dibenzene([Bn,A,Bn]),using a three-step strategy starting from epichlorohydrin.All compounds were purified using thorough distillation and drying methods.The E:Z ratio in all products was close to 1:1.Thermophysical properties of the synthesized(E/Z)-1,3-diether-2-alkenes(e.g.,density,refractive index,viscosity)were measured over the range of T=293.15–333.15 or 343.15 K.CO_(2)absorption capacities(Henry’s constants)of[F,A,F]were measured at T=303.15,318.15,333.15,and 348.15 K and pressures in the range of P=2–10 atm.Density,viscosity,vapor pressure,enthalpy of vaporization,and dipole moment were also calculated for each compound.Additionally,it was demonstrated that the C=C bond remains accessible for further reactions and can undergo bromination and thus may also have applications as intermediates for more complex molecules that are based on glycerol skeletons.
