Aqueous hybrid-ion batteries(AHBs)are a promising class of energy storage devices characterized by low cost,high safety,and high energy density.However,aqueous Cu-Al hybrid-ion batteries face challenges such as sluggi...Aqueous hybrid-ion batteries(AHBs)are a promising class of energy storage devices characterized by low cost,high safety,and high energy density.However,aqueous Cu-Al hybrid-ion batteries face challenges such as sluggish reaction kinetics and severe structural collapse of cathode materials,which limit their practical application.Here,a high-performance aqueous Cu-Al hybrid-ion battery is developed using aluminum pre-inserted Cu_(9)S_(5)(Al-Cu_(9)S_(5))as the cathode material,derived from CuAl-layered double hydroxide(CuAl-LDH).The Al^(3+)pre-intercalation strategy narrows the band gap,enhancing electron transport and improving electrochemical kinetics.The battery exhibits excellent rate performance(463 and 408 mA h g^(-1)at current densities of 500 and 1000 mA g^(-1),respectively)and good cycle stability(with a capacity retention ratio of 81% after 300 cycles at a current density of 1000 mA g^(-1)).Its performance surpasses that of most reported Al-ion batteries.Ex situ characterization and density functional theory(DFT)calculations reveal that the pre-intercalated Al^(3+)in Al-Cu9S5participates in the reversible embedding/removal of Al ions during charge/discharge processes.These findings provide valuable insights for designing pre-intercalated cathodes in aqueous Cu-Al hybrid-ion batteries with stable cycle life.展开更多
The structure-performance relationship of Cu/Al_(2)O_(3) catalysts in the hydrogenation of diethyl oxalate(DEO)for the synthesis of alcohol ether esters has been investigated by various characterization techniques inc...The structure-performance relationship of Cu/Al_(2)O_(3) catalysts in the hydrogenation of diethyl oxalate(DEO)for the synthesis of alcohol ether esters has been investigated by various characterization techniques including XRD,XPS,N2O titration,and 27Al MAS-NMR.The results showed that when the crystal configurations of Al_(2)O_(3) were the same,increasing the specific surface area could effectively refine the size of copper nanoparticles(Cu NPs),and ultimately improve the conversion of DEO.Meanwhile,the smaller size ofγ-Al_(2)O_(3)(HSAl and SBAl)loaded Cu NPs promotes the reaction towards the deep hydrogenation to produce ethanol(EtOH)and ethylene glycol(EG).Besides,the larger size of Cu NPs on the surface of amorphous Al_(2)O_(3)(HTAl and SolAl)resulted in a lower conversion rate,where ethyl glycolate(Egly)is the main product.Despite there are differences in Al^(3+)ionic coordination in Al_(2)O_(3) with different crystal structures,the experimental data showed that the differences in Al^(3+)ionic coordination did not significantly affect the catalytic performance in the hydrogenation reaction.The formation of alcohol-ether ester chemicals is critically dependent on the interactions between Cu sites and acidic sites.Among them,EG and EtOH were dehydrated to form 2-ethoxyethanol via the SN2 mechanism,while Egly and EtOH were reacted to form ethyl ethoxyacetate(EEA)via the SN2 mechanism.This study provides a theoretical basis for the optimization of the coal-based glycol processes to achieve a diversified product portfolio.展开更多
Cu nanoparticles supported on a variety of oxide supports, including SiO2, TiO2, ZrO2, Al2O3, MgO and ZnO, were investigated for the hydrogenolysis of biomass‐derived furfuryl alcohol to1,2‐pentanediol and 1,5‐pent...Cu nanoparticles supported on a variety of oxide supports, including SiO2, TiO2, ZrO2, Al2O3, MgO and ZnO, were investigated for the hydrogenolysis of biomass‐derived furfuryl alcohol to1,2‐pentanediol and 1,5‐pentanediol. A Cu‐Al2O3 catalyst with 10 wt% Cu loading prepared by a co‐precipitation method exhibited the best performance in terms of producing pentanediols compared with the other materials. This catalyst generated an 85.8% conversion and a 70.3% combined selectivity for the target pentanediols at 413 K and 8 MPa H2 over an 8‐h reaction. The catalyst could also be recycled over repeated reaction trials without any significant decrease in productivity. Characterizations with X‐ray diffraction, NH3/CO2‐temperature programmed desorption, N2 adsorption,transmission electron microscopy and N2 O chemisorption demonstrated that intimate and effective interactions between Cu particles and the acidic Al2O3 support in this material greatly enhanced its activity and selectivity. The promotion of the hydrogenolysis reaction was found to be especially sensitive to the Cu particle size, and the catalyst with Cu particles 1.9 to 2.4 nm in size showed the highest turnover frequency during the synthesis of pentanediols.展开更多
基金supported by the National Natural Science Foundation of China(Nos.22278020 and 2177060378)the Fundamental Research Funds for the Central Universities(Nos.12060093063 and XK1803-05)the Program for Changjiang Scholars and Innovative Research Teams in University(No.IRT1205)。
文摘Aqueous hybrid-ion batteries(AHBs)are a promising class of energy storage devices characterized by low cost,high safety,and high energy density.However,aqueous Cu-Al hybrid-ion batteries face challenges such as sluggish reaction kinetics and severe structural collapse of cathode materials,which limit their practical application.Here,a high-performance aqueous Cu-Al hybrid-ion battery is developed using aluminum pre-inserted Cu_(9)S_(5)(Al-Cu_(9)S_(5))as the cathode material,derived from CuAl-layered double hydroxide(CuAl-LDH).The Al^(3+)pre-intercalation strategy narrows the band gap,enhancing electron transport and improving electrochemical kinetics.The battery exhibits excellent rate performance(463 and 408 mA h g^(-1)at current densities of 500 and 1000 mA g^(-1),respectively)and good cycle stability(with a capacity retention ratio of 81% after 300 cycles at a current density of 1000 mA g^(-1)).Its performance surpasses that of most reported Al-ion batteries.Ex situ characterization and density functional theory(DFT)calculations reveal that the pre-intercalated Al^(3+)in Al-Cu9S5participates in the reversible embedding/removal of Al ions during charge/discharge processes.These findings provide valuable insights for designing pre-intercalated cathodes in aqueous Cu-Al hybrid-ion batteries with stable cycle life.
文摘The structure-performance relationship of Cu/Al_(2)O_(3) catalysts in the hydrogenation of diethyl oxalate(DEO)for the synthesis of alcohol ether esters has been investigated by various characterization techniques including XRD,XPS,N2O titration,and 27Al MAS-NMR.The results showed that when the crystal configurations of Al_(2)O_(3) were the same,increasing the specific surface area could effectively refine the size of copper nanoparticles(Cu NPs),and ultimately improve the conversion of DEO.Meanwhile,the smaller size ofγ-Al_(2)O_(3)(HSAl and SBAl)loaded Cu NPs promotes the reaction towards the deep hydrogenation to produce ethanol(EtOH)and ethylene glycol(EG).Besides,the larger size of Cu NPs on the surface of amorphous Al_(2)O_(3)(HTAl and SolAl)resulted in a lower conversion rate,where ethyl glycolate(Egly)is the main product.Despite there are differences in Al^(3+)ionic coordination in Al_(2)O_(3) with different crystal structures,the experimental data showed that the differences in Al^(3+)ionic coordination did not significantly affect the catalytic performance in the hydrogenation reaction.The formation of alcohol-ether ester chemicals is critically dependent on the interactions between Cu sites and acidic sites.Among them,EG and EtOH were dehydrated to form 2-ethoxyethanol via the SN2 mechanism,while Egly and EtOH were reacted to form ethyl ethoxyacetate(EEA)via the SN2 mechanism.This study provides a theoretical basis for the optimization of the coal-based glycol processes to achieve a diversified product portfolio.
基金supported by the National Natural Science Foundation of China(2113301121203221+1 种基金21473224)the Natural Science Foundation of Gansu Province(1308RJZA281)~~
文摘Cu nanoparticles supported on a variety of oxide supports, including SiO2, TiO2, ZrO2, Al2O3, MgO and ZnO, were investigated for the hydrogenolysis of biomass‐derived furfuryl alcohol to1,2‐pentanediol and 1,5‐pentanediol. A Cu‐Al2O3 catalyst with 10 wt% Cu loading prepared by a co‐precipitation method exhibited the best performance in terms of producing pentanediols compared with the other materials. This catalyst generated an 85.8% conversion and a 70.3% combined selectivity for the target pentanediols at 413 K and 8 MPa H2 over an 8‐h reaction. The catalyst could also be recycled over repeated reaction trials without any significant decrease in productivity. Characterizations with X‐ray diffraction, NH3/CO2‐temperature programmed desorption, N2 adsorption,transmission electron microscopy and N2 O chemisorption demonstrated that intimate and effective interactions between Cu particles and the acidic Al2O3 support in this material greatly enhanced its activity and selectivity. The promotion of the hydrogenolysis reaction was found to be especially sensitive to the Cu particle size, and the catalyst with Cu particles 1.9 to 2.4 nm in size showed the highest turnover frequency during the synthesis of pentanediols.
