Acetate-based imidazolium ionic liquids(ILs)are of great importance and widely applied in biomass processing and engineering but under stability issue due to the structure self–rearrangement induced by C2–H deproton...Acetate-based imidazolium ionic liquids(ILs)are of great importance and widely applied in biomass processing and engineering but under stability issue due to the structure self–rearrangement induced by C2–H deprotonation,by which the IL based biomass processing will be challenging.Herein,we demonstrated that the thermal stability of normal acetate-based imidazolim[C8C1Im][OAc]could be significantly improved by changing its cation and anion environment with the presence of 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide IL([C4C1Im][NTf2]).When the molar fraction of[C8C1Im][OAc]was 0.3,the thermal stability of[C8C1Im][OAc]could be significantly improved(ΔT5%dec=+43°C).Detailed information obtained from thermal gravimetric analysis(TGA)and nuclear magnetic resonance(NMR)revealed that the addition of[C4C1 Im][NTf2]played a significant role in enhancing the thermal stability of[C8C1Im][OAc].It was proposed that the formation of an anion–π+structure network between[C8C1 Im][OAc]and[C4C1Im][NTf2]via strong hydrogen bond interactions greatly affects the environment of hydrogen atom in the imidazolium ring of each IL.展开更多
Low cost processing of lignocellulosic biomass is of great importance for sustainable chemistry and engineering.Herein,a low cost system composed of 1-butyl-3-methylimidazolium chloride([C_(4)C_(1) im]Cl),HCl and form...Low cost processing of lignocellulosic biomass is of great importance for sustainable chemistry and engineering.Herein,a low cost system composed of 1-butyl-3-methylimidazolium chloride([C_(4)C_(1) im]Cl),HCl and formaldehyde(FA)was developed for the pretreatment of corn stalk at 80℃.The efficiency of this technology was compared with that in dioxane system or without FA addition.Due to FA stabilization,the extent of acid-hydrolysis of carbohydrate fraction can be significantly decreased while 70%above of lignin was removed with the pretreatment of[C_(4)C_(1) im]Cl/HCl/FA system at 80℃for 2 h.A maximum reducing sugar yield of 93.7%and glucose concentration of 7.0 mg·ml^(-1) were subsequently obtained from enzymatic hydrolysis of the slurry.There were great differences in compositions of small molecule degraded products obtained with FA addition or not.The present[C_(4)C_(1) im]C_(l) based system exhibits great potential of substituting volatile organic solvents(i.e.dioxane)in developing low cost lignocellulosic biomass pretreatment at low temperature.Also,this work would gain insight into understanding on the roles of stabilization methods on the economic improvement of IL based biomass processing.展开更多
基金financially supported by the National Natural Science Foundation of China(21776026)the Liaoning Revitalization Talents Program(XLYC1902037)the start-up research funding of Beijing Institute of Technology(3160011181808)。
文摘Acetate-based imidazolium ionic liquids(ILs)are of great importance and widely applied in biomass processing and engineering but under stability issue due to the structure self–rearrangement induced by C2–H deprotonation,by which the IL based biomass processing will be challenging.Herein,we demonstrated that the thermal stability of normal acetate-based imidazolim[C8C1Im][OAc]could be significantly improved by changing its cation and anion environment with the presence of 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide IL([C4C1Im][NTf2]).When the molar fraction of[C8C1Im][OAc]was 0.3,the thermal stability of[C8C1Im][OAc]could be significantly improved(ΔT5%dec=+43°C).Detailed information obtained from thermal gravimetric analysis(TGA)and nuclear magnetic resonance(NMR)revealed that the addition of[C4C1 Im][NTf2]played a significant role in enhancing the thermal stability of[C8C1Im][OAc].It was proposed that the formation of an anion–π+structure network between[C8C1 Im][OAc]and[C4C1Im][NTf2]via strong hydrogen bond interactions greatly affects the environment of hydrogen atom in the imidazolium ring of each IL.
基金supported by the National Natural Science Foun-dation of China(21776026,22078023)Liaoning Revitalization Talents Program(XLYC1902037).
文摘Low cost processing of lignocellulosic biomass is of great importance for sustainable chemistry and engineering.Herein,a low cost system composed of 1-butyl-3-methylimidazolium chloride([C_(4)C_(1) im]Cl),HCl and formaldehyde(FA)was developed for the pretreatment of corn stalk at 80℃.The efficiency of this technology was compared with that in dioxane system or without FA addition.Due to FA stabilization,the extent of acid-hydrolysis of carbohydrate fraction can be significantly decreased while 70%above of lignin was removed with the pretreatment of[C_(4)C_(1) im]Cl/HCl/FA system at 80℃for 2 h.A maximum reducing sugar yield of 93.7%and glucose concentration of 7.0 mg·ml^(-1) were subsequently obtained from enzymatic hydrolysis of the slurry.There were great differences in compositions of small molecule degraded products obtained with FA addition or not.The present[C_(4)C_(1) im]C_(l) based system exhibits great potential of substituting volatile organic solvents(i.e.dioxane)in developing low cost lignocellulosic biomass pretreatment at low temperature.Also,this work would gain insight into understanding on the roles of stabilization methods on the economic improvement of IL based biomass processing.