In this work, a series of MIL-101-SO3H（x） polymeric materials were prepared and further used for the first time as efficient heterogeneous catalysts for the conversion of fructose-based carbohydrates into 5-ethoxyme...In this work, a series of MIL-101-SO3H（x） polymeric materials were prepared and further used for the first time as efficient heterogeneous catalysts for the conversion of fructose-based carbohydrates into 5-ethoxymethylfurfural（EMF） in a renewable mixed solvent system consisting of ethanol and tetrahydrofuran（THF）. The influence of –SO3H content on the acidity as well as on the catalytic activity of the porous coordination polymers in EMF production was also studied. High EMF yields of 67.7% and 54.2% could be successively obtained from fructose and inulin in the presence of MIL-101-SO;H（100） at 130 °C for 15 h.The catalyst could be reused for five times without significant loss of its activity and the recovery process was facile and simple. This work provides a new platform by application of porous coordination polymers（PCPs） for the production of the potential liquid fuel molecule EMF from biomass in a sustainable solvent system.展开更多
Currently,it is of great significance to develop new proton-conduction materials with high proton conductivity,high stability,and good conducting durability to meet the demands of fuel cell and sensors.Herein,we prepa...Currently,it is of great significance to develop new proton-conduction materials with high proton conductivity,high stability,and good conducting durability to meet the demands of fuel cell and sensors.Herein,we prepared two composites DETA-HPW@MIL-101-SO_(3)H 1 and TETA-HPW@MIL-101-SO3H 2(DETA=diethylenetriamine,HPW=H_(3)PW_(12))_(4)0·xH_(2)O,MIL=Material Institut Lavoisier,TETA=triethylenetetramine)by encapsulating polyoxometalate(POM)and organic amine into a sulfonated MIL-101 through a step-by-step dipping method.Delightedly,1 and 2 have high proton conductivities of 6.4×10^(−2) and 2.9×10^(−2) S·cm^(−1) at 65℃ and 95%relative humidity(RH),respectively,which can be attributed to the fast proton transfer among acid–base pairs formed between HPW and organic amine as well between sulfonic acid and organic amine.Moreover,the time-dependent test in proton conductivity displays that their proton-conduction properties have good stability and durability,which benefit from that the electrostatic interactions among acid–base pairs and the limitation of opening size of MIL-101-SO3H make HPW and organic amine stably exist in the cages of MIL-101-SO_(3)H.The remarkable proton-conduction properties(high proton conductivity and high stability)of the two composites make them become promising proton-conduction materials.展开更多
基金financially supported by the Natural Science Foundation of China(no.21576059)the Key Technologies R&D Program(no.2011BAE06B02)+1 种基金the International Science&Technology Cooperation Program of China(2010DFB60840)the Science and Technology Project of Guizhou Province(nos.[2012]6012 and[2011]3016)
文摘In this work, a series of MIL-101-SO3H（x） polymeric materials were prepared and further used for the first time as efficient heterogeneous catalysts for the conversion of fructose-based carbohydrates into 5-ethoxymethylfurfural（EMF） in a renewable mixed solvent system consisting of ethanol and tetrahydrofuran（THF）. The influence of –SO3H content on the acidity as well as on the catalytic activity of the porous coordination polymers in EMF production was also studied. High EMF yields of 67.7% and 54.2% could be successively obtained from fructose and inulin in the presence of MIL-101-SO;H（100） at 130 °C for 15 h.The catalyst could be reused for five times without significant loss of its activity and the recovery process was facile and simple. This work provides a new platform by application of porous coordination polymers（PCPs） for the production of the potential liquid fuel molecule EMF from biomass in a sustainable solvent system.
基金financially supported by the National Natural Science Foundation of China (Grant Nos. 22071019 and 21872021)
文摘Currently,it is of great significance to develop new proton-conduction materials with high proton conductivity,high stability,and good conducting durability to meet the demands of fuel cell and sensors.Herein,we prepared two composites DETA-HPW@MIL-101-SO_(3)H 1 and TETA-HPW@MIL-101-SO3H 2(DETA=diethylenetriamine,HPW=H_(3)PW_(12))_(4)0·xH_(2)O,MIL=Material Institut Lavoisier,TETA=triethylenetetramine)by encapsulating polyoxometalate(POM)and organic amine into a sulfonated MIL-101 through a step-by-step dipping method.Delightedly,1 and 2 have high proton conductivities of 6.4×10^(−2) and 2.9×10^(−2) S·cm^(−1) at 65℃ and 95%relative humidity(RH),respectively,which can be attributed to the fast proton transfer among acid–base pairs formed between HPW and organic amine as well between sulfonic acid and organic amine.Moreover,the time-dependent test in proton conductivity displays that their proton-conduction properties have good stability and durability,which benefit from that the electrostatic interactions among acid–base pairs and the limitation of opening size of MIL-101-SO3H make HPW and organic amine stably exist in the cages of MIL-101-SO_(3)H.The remarkable proton-conduction properties(high proton conductivity and high stability)of the two composites make them become promising proton-conduction materials.
