The SAPO-34 catalyst was fine-tuned with zinc cations through a straightforward template-assisted ion incorporation (TH) process, without the necessary template pre-removal and the preparation of NH4- SAPO-34 intermed...The SAPO-34 catalyst was fine-tuned with zinc cations through a straightforward template-assisted ion incorporation (TH) process, without the necessary template pre-removal and the preparation of NH4- SAPO-34 intermediate, which is more facile, efficient and cost-effective than the conventional ion exchange process. The template-assisted zinc cations incorporated SAPO-34 catalysts were characterized by XRD, XRF, N2 adsorption-desorption, XPS, SEM, EDX,NMR, respectively. Enhanced selectivity to ethylene and ratio of ethylene to propylene in MTO reaction are observed over the zinc cations modified SAPO-34 catalysts, due to the facilitated formation of lower methylbenzenes that favour the ethylene gen eration, as well as the increased diffusion hindrance originated from the zinc cations incorporation and the facil让ated generation of aromatics compound.展开更多
A serial of protonated and layered transition metal oxides, including layered HTaWO6, HNbMoO6 as well as HNbWO6, were synthesized by solid-state reaction and ion-exchange. The layered HTaWO6 has been systematically st...A serial of protonated and layered transition metal oxides, including layered HTaWO6, HNbMoO6 as well as HNbWO6, were synthesized by solid-state reaction and ion-exchange. The layered HTaWO6 has been systematically studied as a solid acid to realize the dehydration of fructose to 5-hydroxymethylfurfural (HMF). The transition metal oxide samples were characterized with ICP-OES, EDS, XRD, XPS, SEM, TGA, FT-IR, N-2 adsorption-desorption and NH3-TPD. The influential factors such as reaction temperature, reaction time, solvent, catalyst amount and substrate concentration were deeply investigated. The optimized fructose conversion rate of 99% with HMF yield of 67% were achieved after 30 min at 140 degrees C in dimethylsulfoxide. (C) 2016 Science Press and Dalian Institute of Chemical Physics, Chinese Academy of Sciences. Published by Elsevier B.V. and Science Press. All rights reserved.展开更多
The conversion of inexpensive,available C1 feedstock of carbon dioxide(CO_(2))into value-added fine chemicals via homogeneous or heterogeneous catalysis has attracted great recent interest.Coinagemetal-based(Cu,Ag,and...The conversion of inexpensive,available C1 feedstock of carbon dioxide(CO_(2))into value-added fine chemicals via homogeneous or heterogeneous catalysis has attracted great recent interest.Coinagemetal-based(Cu,Ag,and Au)catalysis has emerged as a synthetic strategy for a wide range of organic chemical reactions in past decades.In coinage-metal-catalyzed carboxylation,CO_(2)is adopted as a carboxylation reagent,while coinage-metal salts,complexes,and nanoparticles(NPs)serve as a Lewis acid catalyst to activate unsaturated chemicals,particularly alkynes.This mini-review focuses on the recent advances of coinage-metal-catalyzed carboxylation of terminal alkynes with CO_(2).Other respects,such as the role of bases,the influence of trace water,and solvent effects are also highlighted.展开更多
Gel polymer electrolytes(GPEs) are promising alternatives to liquid electrolytes applied in high-energydensity batteries.Here superior SiO_(2) nanofiber composite gel polymer electrolytes(SNCGPEs) are developed via in...Gel polymer electrolytes(GPEs) are promising alternatives to liquid electrolytes applied in high-energydensity batteries.Here superior SiO_(2) nanofiber composite gel polymer electrolytes(SNCGPEs) are developed via in-situ ionic ring-opening polymerization of 1,3-dioxolane(DOL) monomers in SiO_(2) nanofiber membrane(PDOL-SiO_(2)) for lithium metal batteries.The oxygen atoms of PDOL together with Si-O of SiO_(2) construct a more efficient channel for Li^(+) migration.Consequently,the lithium ion transference number(t_(Li^(+)) and ionic conductivity(σ) at 30℃ of PDOL-SiO_(2) are 0.80 and 1.68×10^(-4)S/cm separately.PDOL-SiO_(2) manifests the electrochemical decomposition potentials of 4.90 V.At 0.5 mA/cm^(2),Li|PDOL-SiO_(2) |Li cell shows a steady cycling performance for nearly 1400 h.LFP|PDOL-SiO_(2) |Li battery can steadily cycle at 0.5 C with a capacity retention rate of 89% after 200 cycles.While cycling at 2 C,the capacity retention rate can maintain at 78% after 300 cycles.This contribution provides a innovative strategy for accelerating Li^(+)transportation via designing PDOL molecular chains throughout the SiO_(2) nanofiber framework,which is crucial for high-energy-density LMBs.展开更多
All-solid-state lithium batteries(ASSLB) are promising candidates for next-generation energy storage devices.Nevertheless,the large-scale commercial application of high energy density AS S LB with the polymer electrol...All-solid-state lithium batteries(ASSLB) are promising candidates for next-generation energy storage devices.Nevertheless,the large-scale commercial application of high energy density AS S LB with the polymer electrolyte still faces challenges.In this study,a thin solid polymer composite electrolyte(SPCE) is prepared through a facile and cost-effective strategy with an infiltration of thermoplastic polyurethane(TPU),lithium salt(LiTFSI or LiFSI),and halloysite nanotubes(HNTs) in a porous framework of polyethylene separator(PE)(TPU-HNTs-LiTFSI-PE or TPU-HNTs-LiFSI-PE).The composition,electrochemical performance,and especially the effect of anions(TFSI-and FSI-) on cycling performance are investigated.The results reveal that the flexible TPU-HNTs-LiTFSI-PE and TPU-HNTs-LiFSI-PE with a thickness of 34 μm exhibit wide electrochemical windows of 4.9 and 5.1 V(vs.Li+/Li) at 60℃,respectively.Reduction in FSI-tends to form more LiF and sulfur compounds at the interface between TPU-HNTs-LiFSI-PE and Li metal anode,thus enhancing the interfacial stability.As a result,cell composed of TPU-HNTs-LiFSI-PE exhibits a smaller increase in interfacial resistance of solid electrolyte interphase(SEI) with a distinct decrease in charge-transfer resistance during cycling.Li|Li symmetric cell with TPU-HNTs-LiFSI-PE could keep its stable overpotential profile for nearly 1300 h with a low hysteresis of approximately39 mV at a current density of 0.1 mA cm-2,while a sudden voltage rise with internal cell impedance-surge signals was observed within 600 h for cell composed of TPU-HNTs-LiTFSI-PE.The initial capacities of NCMITPU-HNTs-LiTFSIPEILi and NCMITPU-HNTs-LiFSI-PEILi cells were 149 and 114 mAh g-1,with capacity retention rates of 83.52% and89.99% after 300 cycles at 0.5 C,respectively.This study provides a valuable guideline for designing flexible SPCE,which shows great application prospect in the practice of ASSLB.展开更多
基金supported by the Key Research Program of Frontier Sciences,CAS(QYZDY-SSW-JSC024)the Youth Innovation Promotion Association of the CAS(2014165)the National Natural Science Foundation of China(21603223,21473182,91334205,91545104)~~
基金the National Natural Science Foundation of China(21603223,91745109,91545104,21473182,91334205)the Youth Innovation Promotion Association of the Chinese Academy of Sciences(2014165)for financial support
文摘The SAPO-34 catalyst was fine-tuned with zinc cations through a straightforward template-assisted ion incorporation (TH) process, without the necessary template pre-removal and the preparation of NH4- SAPO-34 intermediate, which is more facile, efficient and cost-effective than the conventional ion exchange process. The template-assisted zinc cations incorporated SAPO-34 catalysts were characterized by XRD, XRF, N2 adsorption-desorption, XPS, SEM, EDX,NMR, respectively. Enhanced selectivity to ethylene and ratio of ethylene to propylene in MTO reaction are observed over the zinc cations modified SAPO-34 catalysts, due to the facilitated formation of lower methylbenzenes that favour the ethylene gen eration, as well as the increased diffusion hindrance originated from the zinc cations incorporation and the facil让ated generation of aromatics compound.
基金supported by the National Natural Science Foundation of China (21472189)National Basic Research Program of China (973 Program, 2012CB215304)+2 种基金the Natural Science Foundation of Guangdong Province, China (2015A030312007)Guangdong Key Laboratory of New and Renewable Energy Research and Development (Y607jl1001)Science and Technology Planning Project of Guangdong Province, China (2015A010106010)
文摘A serial of protonated and layered transition metal oxides, including layered HTaWO6, HNbMoO6 as well as HNbWO6, were synthesized by solid-state reaction and ion-exchange. The layered HTaWO6 has been systematically studied as a solid acid to realize the dehydration of fructose to 5-hydroxymethylfurfural (HMF). The transition metal oxide samples were characterized with ICP-OES, EDS, XRD, XPS, SEM, TGA, FT-IR, N-2 adsorption-desorption and NH3-TPD. The influential factors such as reaction temperature, reaction time, solvent, catalyst amount and substrate concentration were deeply investigated. The optimized fructose conversion rate of 99% with HMF yield of 67% were achieved after 30 min at 140 degrees C in dimethylsulfoxide. (C) 2016 Science Press and Dalian Institute of Chemical Physics, Chinese Academy of Sciences. Published by Elsevier B.V. and Science Press. All rights reserved.
文摘The conversion of inexpensive,available C1 feedstock of carbon dioxide(CO_(2))into value-added fine chemicals via homogeneous or heterogeneous catalysis has attracted great recent interest.Coinagemetal-based(Cu,Ag,and Au)catalysis has emerged as a synthetic strategy for a wide range of organic chemical reactions in past decades.In coinage-metal-catalyzed carboxylation,CO_(2)is adopted as a carboxylation reagent,while coinage-metal salts,complexes,and nanoparticles(NPs)serve as a Lewis acid catalyst to activate unsaturated chemicals,particularly alkynes.This mini-review focuses on the recent advances of coinage-metal-catalyzed carboxylation of terminal alkynes with CO_(2).Other respects,such as the role of bases,the influence of trace water,and solvent effects are also highlighted.
基金supported by the Department of Science and Technology of Zhuhai City(No.ZH22017001200059PWC)the Department of Science and Technology of Guangdong Province,China(No.2019A050510043)。
文摘Gel polymer electrolytes(GPEs) are promising alternatives to liquid electrolytes applied in high-energydensity batteries.Here superior SiO_(2) nanofiber composite gel polymer electrolytes(SNCGPEs) are developed via in-situ ionic ring-opening polymerization of 1,3-dioxolane(DOL) monomers in SiO_(2) nanofiber membrane(PDOL-SiO_(2)) for lithium metal batteries.The oxygen atoms of PDOL together with Si-O of SiO_(2) construct a more efficient channel for Li^(+) migration.Consequently,the lithium ion transference number(t_(Li^(+)) and ionic conductivity(σ) at 30℃ of PDOL-SiO_(2) are 0.80 and 1.68×10^(-4)S/cm separately.PDOL-SiO_(2) manifests the electrochemical decomposition potentials of 4.90 V.At 0.5 mA/cm^(2),Li|PDOL-SiO_(2) |Li cell shows a steady cycling performance for nearly 1400 h.LFP|PDOL-SiO_(2) |Li battery can steadily cycle at 0.5 C with a capacity retention rate of 89% after 200 cycles.While cycling at 2 C,the capacity retention rate can maintain at 78% after 300 cycles.This contribution provides a innovative strategy for accelerating Li^(+)transportation via designing PDOL molecular chains throughout the SiO_(2) nanofiber framework,which is crucial for high-energy-density LMBs.
基金financially supported by the National Natural Science Foundation of China(No.21673051)the Department of Science and Technology of Guangdong Province,China(No.2019A050510043)。
文摘All-solid-state lithium batteries(ASSLB) are promising candidates for next-generation energy storage devices.Nevertheless,the large-scale commercial application of high energy density AS S LB with the polymer electrolyte still faces challenges.In this study,a thin solid polymer composite electrolyte(SPCE) is prepared through a facile and cost-effective strategy with an infiltration of thermoplastic polyurethane(TPU),lithium salt(LiTFSI or LiFSI),and halloysite nanotubes(HNTs) in a porous framework of polyethylene separator(PE)(TPU-HNTs-LiTFSI-PE or TPU-HNTs-LiFSI-PE).The composition,electrochemical performance,and especially the effect of anions(TFSI-and FSI-) on cycling performance are investigated.The results reveal that the flexible TPU-HNTs-LiTFSI-PE and TPU-HNTs-LiFSI-PE with a thickness of 34 μm exhibit wide electrochemical windows of 4.9 and 5.1 V(vs.Li+/Li) at 60℃,respectively.Reduction in FSI-tends to form more LiF and sulfur compounds at the interface between TPU-HNTs-LiFSI-PE and Li metal anode,thus enhancing the interfacial stability.As a result,cell composed of TPU-HNTs-LiFSI-PE exhibits a smaller increase in interfacial resistance of solid electrolyte interphase(SEI) with a distinct decrease in charge-transfer resistance during cycling.Li|Li symmetric cell with TPU-HNTs-LiFSI-PE could keep its stable overpotential profile for nearly 1300 h with a low hysteresis of approximately39 mV at a current density of 0.1 mA cm-2,while a sudden voltage rise with internal cell impedance-surge signals was observed within 600 h for cell composed of TPU-HNTs-LiTFSI-PE.The initial capacities of NCMITPU-HNTs-LiTFSIPEILi and NCMITPU-HNTs-LiFSI-PEILi cells were 149 and 114 mAh g-1,with capacity retention rates of 83.52% and89.99% after 300 cycles at 0.5 C,respectively.This study provides a valuable guideline for designing flexible SPCE,which shows great application prospect in the practice of ASSLB.