采用微波辅助合成方法将WO3固载到金属有机骨架MIL-101(Cr)上,借助于沉积沉淀–光还原方法将Ag/AgCl和WO3/MIL-101复合在一起,制备出Ag/AgCl@WO3/MIL-101可见光催化剂。利用FT-IR、XRD、UV-Vis-DRS和XPS测试技术对该催化剂进行了表征。...采用微波辅助合成方法将WO3固载到金属有机骨架MIL-101(Cr)上,借助于沉积沉淀–光还原方法将Ag/AgCl和WO3/MIL-101复合在一起,制备出Ag/AgCl@WO3/MIL-101可见光催化剂。利用FT-IR、XRD、UV-Vis-DRS和XPS测试技术对该催化剂进行了表征。结果表明,Ag/AgCl和WO3的引入没有改变MIL-101的结构,催化剂在可见光区有强烈的光吸收。当WO3的负载量为0.3(w)%,Ag的负载量为3.4(w)%时,Ag/AgCl@WO3/MIL-101对70 mL 20 mg/L的罗丹明B溶液的降解率达到100%,并且该催化剂具有较好的稳定性。展开更多
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
A series of efficient ruthenium chloride (RuCl_3)-anchored MOF catalysts,such as RuCl_3@MIL-101 (Cr)-Sal,and RuCl_3@MIL-101 (Cr)-DPPB, have been successfully synthesized by post-synthetic modification (PSM)of the term...A series of efficient ruthenium chloride (RuCl_3)-anchored MOF catalysts,such as RuCl_3@MIL-101 (Cr)-Sal,and RuCl_3@MIL-101 (Cr)-DPPB, have been successfully synthesized by post-synthetic modification (PSM)of the terminal amino of MIL-101(Cr)-NH_2 with salicylaldehyde, 2-diphenylphosphinobenzaldehyde (DPPBde) and anchoring of Ru (Ⅲ) ions. The stronger coordination electron donor interaction between Ru (Ⅲ) ions and chelating groups in the RuCl_3@MIL-101 (Cr)-DPPB enhances its catalytic performance for CO_2 hydrogenation to formic acid. The turnover number (TON) of formic acid was up to 831 in reaction time of 2 h with dimethyl sulfoxide (DMSO) and water (H_2O) as mixed solvent, trimethylamine (Et_3N) as organic base, and PPh_3 as electronic additive.展开更多
Metal-organic frameworks possessing relatively large pores,high surface areas,and unsaturated metal sites are attractive materials for use as electrocatalysts in the reduction of N_(2)to NH_(3).In this work,a MIL-101(...Metal-organic frameworks possessing relatively large pores,high surface areas,and unsaturated metal sites are attractive materials for use as electrocatalysts in the reduction of N_(2)to NH_(3).In this work,a MIL-101(Fe)/MoS_(3)hybrid catalyst,prepared by using a precursor-transformation strategy,is shown to be an effective electrocatalyst for the N_(2)reduction reaction(NRR).Under solvothermal conditions,micro-sized octahedral MIL-101(Fe)precursors are converted into ultra-small nanodots,while amorphous MoS_(3)derived from(NH_(4))_(2)MoS_(4)provides a surface suitable for anchoring the MIL-101(Fe)nanodots.The asprepared composite exhibits excellent electrocatalytic activity and durability for the NRR with a Faraday efficiency of 36.71%and an NH_(3)yield of 25.7μg h^(-1)mg_(cat)^(-1)at-0.1 V vs.RHE in 0.1 M HCl.The results show that the dispersion and adherence of MIL-101(Fe)nanodots on amorphous MoS_(3)improves the exposure of active centers and aids mass transfer,resulting in greatly enhanced catalytic activity and stability.展开更多
MIL-101(Fe)-NH_(2)@Al_(2)O_(3)(MA)catalysts were successfully synthesized by reactive seeding(RS)method onα-Al_(2)O_(3)substrate,which demonstrated excellent photo-Fenton degradation performance toward fluoroquinolon...MIL-101(Fe)-NH_(2)@Al_(2)O_(3)(MA)catalysts were successfully synthesized by reactive seeding(RS)method onα-Al_(2)O_(3)substrate,which demonstrated excellent photo-Fenton degradation performance toward fluoroquinolone antibiotics(i.e.,norfloxacin,ciprofloxacin,and enrofloxacin).The structure and morphology of the obtained MA were characterized by transmission electron microscopy(TEM),high-resolution transmission electron microscopy(HRTEM),atomic force microscope(AFM).The as-prepared MA could accomplish>90%of norfloxacin degradation efficiency for 10 cycles’photo-Fenton processes,owing to its excellent chemical and water stability.In addition,the effects of operational factors including H_(2)O_(2)concentration,foreign ions,and pH on the photo-Fenton degradation of norfloxacin over MA were clarified.The ESR spectra further document that^(•)O_(2)^(−),1O_(2)and•OH radicals are prominent in the decomposition process of antibiotic molecules.Finally,the plausible photo-Fenton norfloxacin degradation mechanisms were proposed and verified.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
文摘采用微波辅助合成方法将WO3固载到金属有机骨架MIL-101(Cr)上,借助于沉积沉淀–光还原方法将Ag/AgCl和WO3/MIL-101复合在一起,制备出Ag/AgCl@WO3/MIL-101可见光催化剂。利用FT-IR、XRD、UV-Vis-DRS和XPS测试技术对该催化剂进行了表征。结果表明,Ag/AgCl和WO3的引入没有改变MIL-101的结构,催化剂在可见光区有强烈的光吸收。当WO3的负载量为0.3(w)%,Ag的负载量为3.4(w)%时,Ag/AgCl@WO3/MIL-101对70 mL 20 mg/L的罗丹明B溶液的降解率达到100%,并且该催化剂具有较好的稳定性。
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Financial support from the National Natural Science Foundation of China(NSFC, Nos. 21776211, 21325626)the Program for New Century Excellent Talents in University(No. NCET-13-0411)the Program of Introducing Talents of Discipline to Universities(No. B06006)
文摘A series of efficient ruthenium chloride (RuCl_3)-anchored MOF catalysts,such as RuCl_3@MIL-101 (Cr)-Sal,and RuCl_3@MIL-101 (Cr)-DPPB, have been successfully synthesized by post-synthetic modification (PSM)of the terminal amino of MIL-101(Cr)-NH_2 with salicylaldehyde, 2-diphenylphosphinobenzaldehyde (DPPBde) and anchoring of Ru (Ⅲ) ions. The stronger coordination electron donor interaction between Ru (Ⅲ) ions and chelating groups in the RuCl_3@MIL-101 (Cr)-DPPB enhances its catalytic performance for CO_2 hydrogenation to formic acid. The turnover number (TON) of formic acid was up to 831 in reaction time of 2 h with dimethyl sulfoxide (DMSO) and water (H_2O) as mixed solvent, trimethylamine (Et_3N) as organic base, and PPh_3 as electronic additive.
基金supported by the National Natural Science Foundation of China(21773163,21531006,22001021)the State Key Laboratory of Organometallic Chemistry of Shanghai Institute of Organic Chemistry(KF2021005)+3 种基金Natural Science Foundation of Jiangsu Province(BK20201048)Natural Science Research Project of Higher Education Institutions in Jiangsu Province(20KJB150008)Collaborative Innovation Center of Suzhou Nano Science and Technologythe Project of Scientific and Technologic Infrastructure of Suzhou(SZS201905)。
文摘Metal-organic frameworks possessing relatively large pores,high surface areas,and unsaturated metal sites are attractive materials for use as electrocatalysts in the reduction of N_(2)to NH_(3).In this work,a MIL-101(Fe)/MoS_(3)hybrid catalyst,prepared by using a precursor-transformation strategy,is shown to be an effective electrocatalyst for the N_(2)reduction reaction(NRR).Under solvothermal conditions,micro-sized octahedral MIL-101(Fe)precursors are converted into ultra-small nanodots,while amorphous MoS_(3)derived from(NH_(4))_(2)MoS_(4)provides a surface suitable for anchoring the MIL-101(Fe)nanodots.The asprepared composite exhibits excellent electrocatalytic activity and durability for the NRR with a Faraday efficiency of 36.71%and an NH_(3)yield of 25.7μg h^(-1)mg_(cat)^(-1)at-0.1 V vs.RHE in 0.1 M HCl.The results show that the dispersion and adherence of MIL-101(Fe)nanodots on amorphous MoS_(3)improves the exposure of active centers and aids mass transfer,resulting in greatly enhanced catalytic activity and stability.
基金supported by National Natural Science Foundation of China(No.22176012)Beijing Natural Science Foundation(No.8202016)。
文摘MIL-101(Fe)-NH_(2)@Al_(2)O_(3)(MA)catalysts were successfully synthesized by reactive seeding(RS)method onα-Al_(2)O_(3)substrate,which demonstrated excellent photo-Fenton degradation performance toward fluoroquinolone antibiotics(i.e.,norfloxacin,ciprofloxacin,and enrofloxacin).The structure and morphology of the obtained MA were characterized by transmission electron microscopy(TEM),high-resolution transmission electron microscopy(HRTEM),atomic force microscope(AFM).The as-prepared MA could accomplish>90%of norfloxacin degradation efficiency for 10 cycles’photo-Fenton processes,owing to its excellent chemical and water stability.In addition,the effects of operational factors including H_(2)O_(2)concentration,foreign ions,and pH on the photo-Fenton degradation of norfloxacin over MA were clarified.The ESR spectra further document that^(•)O_(2)^(−),1O_(2)and•OH radicals are prominent in the decomposition process of antibiotic molecules.Finally,the plausible photo-Fenton norfloxacin degradation mechanisms were proposed and verified.
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.
