Highly active and stable electrocatalysts for ethanol oxidation reaction(EOR)are critical for the widespread adoption of direct ethanol fuel cells(DEFCs).However,the low efficiency of C–C bond cleavage of commercial ...Highly active and stable electrocatalysts for ethanol oxidation reaction(EOR)are critical for the widespread adoption of direct ethanol fuel cells(DEFCs).However,the low efficiency of C–C bond cleavage of commercial electrocatalysts not only leads to incomplete ethanol oxidation but also results in the accumulation of poisoning CO species.In this work,silver-platinum hollow nanocubes(AgPt hNCs)are designed and synthesized to achieve high selectivity for the complete 12-electron EOR in an alkaline electrolyte.AgPt h NCs demonstrate a Faradaic efficiency of up to 88.2%at the potential of 0.70 V for the C1 pathway and exhibit a 6.3-fold EOR mass activity than commercial Pt black at the potential of 0.81 V.Moreover,the oxyphilic nature of Ag imparts exceptional long-term stability to AgPt h NCs.Theoretical calculations reveal that the electronic interaction between Pt and Ag effectively modifies the d-band properties of surface Pt atoms,thereby optimizing the adsorption behavior of key intermediates,promoting the dehydrogenation of CH_(3)CO^(*)to CH_(2)CO^(*),and facilitating C–C bond cleavage.The present work provides both theoretical and experimental insights into the utilization of Ag-based alloy catalysts for highperformance DEFCs.展开更多
Ultrasensitive detection of multiple diseases markers is of great importance in improving diagnostic accuracy,precision,and efficiency.A versatile Au nanozyme Raman probe strategy was employed to develop an ultrasensi...Ultrasensitive detection of multiple diseases markers is of great importance in improving diagnostic accuracy,precision,and efficiency.A versatile Au nanozyme Raman probe strategy was employed to develop an ultrasensitive multiplex surface-enhanced Raman scattering(SERS)immunosensor using encoded silica photonic crystal beads(SPCBs).The efficient Au nanozyme Raman probe strategy was constructed using a robust Au nanozyme with high dual enzyme-like activity and SERS activity.On the one hand,Au nanozyme tags with oxidase-like activity can catalyze the oxidation of Raman-inactive 3,3,5,5-tetramethylbenzidine(TMB)to Raman-active oxidized TMB(ox-TMB)in the presence of O_(2).On the other hand,Au nanozyme tags with peroxidase-like activity can catalyze Raman-inactive TMB to Ramanactive ox-TMB in the presence of H_(2)O_(2).This dual catalysis action results in many Raman-active reporter molecules(ox-TMB)enabling highly sensitive detection.Meanwhile,the Au nanozyme as an extraordinary SERS substrate further enhances the detection signals of these Raman reporter molecules.Using reflection peaks of different SPCBs to encode tumor markers,an ultrasensitive multiplex SERS immunosensor was developed for detection of carcinoembryonic antigen(CEA)and alpha-fetoprotein(AFP),which exhibited wide linear ranges of 0.001-100 ng/m L for CEA and 0.01-1000 ng/m L for AFP,accompanied by low detection limits of 0.66 pg/m L for CEA and 9.5 pg/m L for AFP,respectively.This work demonstrates a universal and promising nanozyme Raman probe strategy to develop ultrasensitive multiplex SERS immunosensors for precise clinical diagnosis of disease.展开更多
Fast-charging technology is indeed a critical technical problem for electric vehicles today.Improving the conductivity of electrode materials is one of the effective ways to solve this technical bottleneck.Here,we inc...Fast-charging technology is indeed a critical technical problem for electric vehicles today.Improving the conductivity of electrode materials is one of the effective ways to solve this technical bottleneck.Here,we incorporated highly conductive MXene and carbon nanotubes into the electrode materials of Li_(4)Ti_(5)O_(12)(LTO)and LiFePO_(4)(LFP)to construct the composite electrode material 3D-LTO-CNT-MXene and 3D-LFP-CNT-MXene(named 3D-LTO and 3D-LFP).The 3D-LTO we synthesized demonstrated an impressive capacity of 146.2 mAh g^(-1)at a 20C rate(where 1C=175 mA g^(-1)),the 3D-LFP material exhibited a capacity of 104.6 mAh g^(-1)at a 20C rate(where 1C=170 mA g^(-1)).This remarkable rate capability can be attributed to the constructed three-dimensional conductive network,which facilitates enhanced electrical conductivity and electron migration rates,thereby promoting rapid charging and discharging of the batteries.Furthermore,we assembled a 3D-LTO‖3D-LFP full cell,which demonstrated exceptional performance at a high rate of 10C(1C=170 mA g^(-1)),achieving an energy density of 68.34 Wh kg^(-1)and a power density of 1547.5 W kg^(-1).This work demonstrates the feasibility of constructing 3D highly conductive electrode materials for rapid charging and discharging at high rates.It paves the way for the commercial application of truly ultra-fast charging in electric vehicles.展开更多
This study reports the development of a novel amino‐functionalized ionic liquid catalyst,namely 1‐butyl‐3‐methylimidazolium amino triazole([EMIM]ATZ),for the efficient and sustainable synthesis of ethyl methyl car...This study reports the development of a novel amino‐functionalized ionic liquid catalyst,namely 1‐butyl‐3‐methylimidazolium amino triazole([EMIM]ATZ),for the efficient and sustainable synthesis of ethyl methyl carbonate(EMC)via transesterification of dimethyl carbonate(DMC)and ethanol(C_(2)H_(5)OH)at room temperature.Addressing the limitations of conventional catalytic systems that require elevated temperatures(>75℃),[EMIM]ATZ achieves 62%DMC conversion and 56%EMC yield within 8 h under room temperature(25℃),while conventional ionic liquids([EMIM]Cl,[EMIM]BF_(4),[EMIM]PF_(6) etc.)showed almost no activity at room temperature.The catalyst's superior activity stems from its strong basicity(pH≈9.2)and enhanced CO_(2) absorption capacity(200 mg·g^(−)1),which synergistically activate C2H5OH and stabilize reaction intermediates.Structural characterization via FTIR and thermogravimetric analysis(TGA)confirmed the catalyst's thermal stability and recyclability,with no significant degradation observed over five reuse cycles(89%activity retention).In addition,the ionic liquid was also able to catalyze the synthesis of methyl propyl carbonate(PMC)and methyl butyl carbonate(BMC)at room temperature.展开更多
Modifying the electronic density of states and the synergistic effect of the active centers by introducing a second metal present an efficient strategy to tune physi/chemi-sorption,probably lead to improving catalytic...Modifying the electronic density of states and the synergistic effect of the active centers by introducing a second metal present an efficient strategy to tune physi/chemi-sorption,probably lead to improving catalytic performances.Herein,bimetallic Ni_(3)Mo/Al_(2)O_(3)catalyst was demonstrated and exhibited over 5 times more active than Pt/Al_(2)O_(3)toward the ethane dehydrogenation(EDH)as well as 2-10 times activity enhancement compared with their monometallic Ni and Mo counterparts and other Ni-based bimetallic nanoparticles.Kinetic studies revealed that the activation energy over Ni_(3)Mo/Al_(2)O_(3)(111 kJ mol^(-1))was much lower than that of Ni(157 kJ mol^(-1))and Mo(171 kJ·mol^(-1)).DFT calculations showed ethane was adsorbed on the Ni or Mo surface in a more parallel configuration,whereas over Ni_(3)Mo it adopted an inclined configuration.This change promoted ethane adsorption and pre-activation of the C-H bond,thereby benefiting the ethane dehydrogenation process on the Ni_(3)Mo surface.展开更多
Developing high-efficiency catalyst is crucial for electrochemical conversion of carbon dioxide(CO_(2))to high-value products.In the present work,a three-chamber electrolysis cell has been developed for CO_(2)reductio...Developing high-efficiency catalyst is crucial for electrochemical conversion of carbon dioxide(CO_(2))to high-value products.In the present work,a three-chamber electrolysis cell has been developed for CO_(2)reduction to carbon monoxide(CO)in an organic electrolyte,with sodium hydroxide(NaOH)and chlorine(Cl_(2))produced as byproducts.In order to improve the performance of the three-chamber electrolyzer,a gallium-based(Ga-based)ternary-porous catalyst(Ga-In_(4)Ag_(9))has been fabricated.During the long-term electrolysis process,Ga-In_(4)Ag_(9)catalyst exhibits good performance toward CO_(2)reduction reaction(CO_(2)RR),the CO partial current density achieves to 139.21 mA·cm^(-2)at-2.4 V(vs.SHE),with the Faraday efficiency(FE)of CO formation stabled at 92.3%.Density functional theory(DFT)analysis reveals that the position of the d-band center of Ga-In_(4)Ag_(9)is regulated by silver(Ag)atoms,which is beneficial for enhancing the binding ability between the catalyst and the intermediate.Owing to the adsorption of Cl^(-)on the surface of Ga-In_(4)Ag_(9),the reconfiguration of electron density has been altered,which is beneficial for the stabilization of*CO_(2)-intermediate.This work provides valuable insights for designing Ga-based metal catalysts toward CO_(2)electrolysis to produce high-value chemicals.展开更多
The Sun is the primary energy source driving the Earth's climate system.A prevailing hypothesis suggests that even minor variations in solar activity,when amplified by climate system feedback mechanisms,can induce...The Sun is the primary energy source driving the Earth's climate system.A prevailing hypothesis suggests that even minor variations in solar activity,when amplified by climate system feedback mechanisms,can induce significant climatic changes on decadal to centennial timescales.However,the limited availability of historical winter climate proxies has impeded consensus on how solar variability influences the long-term winter climate in Northeast Asia,particularly during Grand Solar Minima(GMs).In this study,we analyzed daily-resolution snowfall records in Seoul from 1625 to 1907 CE,derived from the Korean official historical chronicle Seungjeongweon Ilgi.This period encompasses both the Maunder Minimum(1645–1715 CE)and the Dalton Minimum(1790–1830 CE)of solar activity.Our findings indicate that during the GMs,the first date of annual snowfall(FDS)was delayed by approximately 10 days,and the average annual snowfall frequency(ASF)was reduced by half compared to non-GM periods.Additionally,while an 11-year solar cycle was evident in the ASF during non-GM periods,this cycle was replaced by a shortened 8-to 9-year cycle during the GMs.These variations suggest a differential regional climatic response to prolonged changes in solar activity,and provide historical insights that enhance our understanding of the potential impact of low solar activity on the winter climate in Northeast Asia.展开更多
基金supported by the National Natural Science Foundation of China(22272103)the China Postdoctoral Science Foundation(2023TQ0204)+3 种基金the Fundamental Research Funds for the Central Universities(GK202304011)the Natural Science Foundation of Shaanxi Province(JC-YBQN-0088)the Science and Technology Innovation Team of Shaanxi Province(2023-CX-TD-27)the Sanqin scholars innovation teams in Shaanxi Province,China。
文摘Highly active and stable electrocatalysts for ethanol oxidation reaction(EOR)are critical for the widespread adoption of direct ethanol fuel cells(DEFCs).However,the low efficiency of C–C bond cleavage of commercial electrocatalysts not only leads to incomplete ethanol oxidation but also results in the accumulation of poisoning CO species.In this work,silver-platinum hollow nanocubes(AgPt hNCs)are designed and synthesized to achieve high selectivity for the complete 12-electron EOR in an alkaline electrolyte.AgPt h NCs demonstrate a Faradaic efficiency of up to 88.2%at the potential of 0.70 V for the C1 pathway and exhibit a 6.3-fold EOR mass activity than commercial Pt black at the potential of 0.81 V.Moreover,the oxyphilic nature of Ag imparts exceptional long-term stability to AgPt h NCs.Theoretical calculations reveal that the electronic interaction between Pt and Ag effectively modifies the d-band properties of surface Pt atoms,thereby optimizing the adsorption behavior of key intermediates,promoting the dehydrogenation of CH_(3)CO^(*)to CH_(2)CO^(*),and facilitating C–C bond cleavage.The present work provides both theoretical and experimental insights into the utilization of Ag-based alloy catalysts for highperformance DEFCs.
基金financially supported by National Natural Science Foundation of China(Nos.21475116,21575125 and 22474124)the National Natural Science Foundation of Jiangsu Province(Nos.BK20221370,BK20211362)+5 种基金Key University Natural Science Foundation of Jiangsu-Province(No.20KJA150004)the Project for Science and Technology of Yangzhou(No.YZ2022074)the Project for Yangzhou City and Yangzhou University corporation(No.YZ2023204)Cross cooperation project of Subei Peoples’Hospital of Jiangsu Province(No.SBJC220009)the Open Research Fund of State Key Laboratory of Analytical Chemistry for Life Science(No.SKLACLS2405)Postgraduate Research&Practice Innovation Program of Jiangsu Province(No.KYCX24_3728)。
文摘Ultrasensitive detection of multiple diseases markers is of great importance in improving diagnostic accuracy,precision,and efficiency.A versatile Au nanozyme Raman probe strategy was employed to develop an ultrasensitive multiplex surface-enhanced Raman scattering(SERS)immunosensor using encoded silica photonic crystal beads(SPCBs).The efficient Au nanozyme Raman probe strategy was constructed using a robust Au nanozyme with high dual enzyme-like activity and SERS activity.On the one hand,Au nanozyme tags with oxidase-like activity can catalyze the oxidation of Raman-inactive 3,3,5,5-tetramethylbenzidine(TMB)to Raman-active oxidized TMB(ox-TMB)in the presence of O_(2).On the other hand,Au nanozyme tags with peroxidase-like activity can catalyze Raman-inactive TMB to Ramanactive ox-TMB in the presence of H_(2)O_(2).This dual catalysis action results in many Raman-active reporter molecules(ox-TMB)enabling highly sensitive detection.Meanwhile,the Au nanozyme as an extraordinary SERS substrate further enhances the detection signals of these Raman reporter molecules.Using reflection peaks of different SPCBs to encode tumor markers,an ultrasensitive multiplex SERS immunosensor was developed for detection of carcinoembryonic antigen(CEA)and alpha-fetoprotein(AFP),which exhibited wide linear ranges of 0.001-100 ng/m L for CEA and 0.01-1000 ng/m L for AFP,accompanied by low detection limits of 0.66 pg/m L for CEA and 9.5 pg/m L for AFP,respectively.This work demonstrates a universal and promising nanozyme Raman probe strategy to develop ultrasensitive multiplex SERS immunosensors for precise clinical diagnosis of disease.
基金supported by Xinjiang Uygur Autonomous Region Graduate Research Innovation Project (No.XJ2024G195)Xinjiang Key Research and Development Project (No.2021B01001-1)+2 种基金the National Natural Science Foundation of China (No.22169020)the Natural Science Foundation of University in Jiangsu province (No.22KJB150003)the National Natural Science Foundation of China (No.22309068)
文摘Fast-charging technology is indeed a critical technical problem for electric vehicles today.Improving the conductivity of electrode materials is one of the effective ways to solve this technical bottleneck.Here,we incorporated highly conductive MXene and carbon nanotubes into the electrode materials of Li_(4)Ti_(5)O_(12)(LTO)and LiFePO_(4)(LFP)to construct the composite electrode material 3D-LTO-CNT-MXene and 3D-LFP-CNT-MXene(named 3D-LTO and 3D-LFP).The 3D-LTO we synthesized demonstrated an impressive capacity of 146.2 mAh g^(-1)at a 20C rate(where 1C=175 mA g^(-1)),the 3D-LFP material exhibited a capacity of 104.6 mAh g^(-1)at a 20C rate(where 1C=170 mA g^(-1)).This remarkable rate capability can be attributed to the constructed three-dimensional conductive network,which facilitates enhanced electrical conductivity and electron migration rates,thereby promoting rapid charging and discharging of the batteries.Furthermore,we assembled a 3D-LTO‖3D-LFP full cell,which demonstrated exceptional performance at a high rate of 10C(1C=170 mA g^(-1)),achieving an energy density of 68.34 Wh kg^(-1)and a power density of 1547.5 W kg^(-1).This work demonstrates the feasibility of constructing 3D highly conductive electrode materials for rapid charging and discharging at high rates.It paves the way for the commercial application of truly ultra-fast charging in electric vehicles.
基金supported by Shandong Energy Institute(SEI U202321)Gansu Province Young Talents(Team Project)(2025QNTD41)+2 种基金Natural Science Foundation of Shandong(ZR2024QB172)The Major Project of Gansu Province(21ZD4WA021,23JRRA603)Natural Science Foundation of Gansu(24JRRA060).
文摘This study reports the development of a novel amino‐functionalized ionic liquid catalyst,namely 1‐butyl‐3‐methylimidazolium amino triazole([EMIM]ATZ),for the efficient and sustainable synthesis of ethyl methyl carbonate(EMC)via transesterification of dimethyl carbonate(DMC)and ethanol(C_(2)H_(5)OH)at room temperature.Addressing the limitations of conventional catalytic systems that require elevated temperatures(>75℃),[EMIM]ATZ achieves 62%DMC conversion and 56%EMC yield within 8 h under room temperature(25℃),while conventional ionic liquids([EMIM]Cl,[EMIM]BF_(4),[EMIM]PF_(6) etc.)showed almost no activity at room temperature.The catalyst's superior activity stems from its strong basicity(pH≈9.2)and enhanced CO_(2) absorption capacity(200 mg·g^(−)1),which synergistically activate C2H5OH and stabilize reaction intermediates.Structural characterization via FTIR and thermogravimetric analysis(TGA)confirmed the catalyst's thermal stability and recyclability,with no significant degradation observed over five reuse cycles(89%activity retention).In addition,the ionic liquid was also able to catalyze the synthesis of methyl propyl carbonate(PMC)and methyl butyl carbonate(BMC)at room temperature.
文摘Modifying the electronic density of states and the synergistic effect of the active centers by introducing a second metal present an efficient strategy to tune physi/chemi-sorption,probably lead to improving catalytic performances.Herein,bimetallic Ni_(3)Mo/Al_(2)O_(3)catalyst was demonstrated and exhibited over 5 times more active than Pt/Al_(2)O_(3)toward the ethane dehydrogenation(EDH)as well as 2-10 times activity enhancement compared with their monometallic Ni and Mo counterparts and other Ni-based bimetallic nanoparticles.Kinetic studies revealed that the activation energy over Ni_(3)Mo/Al_(2)O_(3)(111 kJ mol^(-1))was much lower than that of Ni(157 kJ mol^(-1))and Mo(171 kJ·mol^(-1)).DFT calculations showed ethane was adsorbed on the Ni or Mo surface in a more parallel configuration,whereas over Ni_(3)Mo it adopted an inclined configuration.This change promoted ethane adsorption and pre-activation of the C-H bond,thereby benefiting the ethane dehydrogenation process on the Ni_(3)Mo surface.
基金supported by the National Natural Science Foundation of China(Nos.52164048 and 52067012)the Natural Science Foundation of Kunming University of Science and Technology(No.KKZ3202437105)the Analysis and Testing Foundation of Kunming University of Science and Technology(No.2023P20221102026).
文摘Developing high-efficiency catalyst is crucial for electrochemical conversion of carbon dioxide(CO_(2))to high-value products.In the present work,a three-chamber electrolysis cell has been developed for CO_(2)reduction to carbon monoxide(CO)in an organic electrolyte,with sodium hydroxide(NaOH)and chlorine(Cl_(2))produced as byproducts.In order to improve the performance of the three-chamber electrolyzer,a gallium-based(Ga-based)ternary-porous catalyst(Ga-In_(4)Ag_(9))has been fabricated.During the long-term electrolysis process,Ga-In_(4)Ag_(9)catalyst exhibits good performance toward CO_(2)reduction reaction(CO_(2)RR),the CO partial current density achieves to 139.21 mA·cm^(-2)at-2.4 V(vs.SHE),with the Faraday efficiency(FE)of CO formation stabled at 92.3%.Density functional theory(DFT)analysis reveals that the position of the d-band center of Ga-In_(4)Ag_(9)is regulated by silver(Ag)atoms,which is beneficial for enhancing the binding ability between the catalyst and the intermediate.Owing to the adsorption of Cl^(-)on the surface of Ga-In_(4)Ag_(9),the reconfiguration of electron density has been altered,which is beneficial for the stabilization of*CO_(2)-intermediate.This work provides valuable insights for designing Ga-based metal catalysts toward CO_(2)electrolysis to produce high-value chemicals.
基金supported by the National Natural Science Foundation of China(Grant No.42388101)the National Natural Science Foundation of China(42241106)CAS Youth Interdisciplinary Team(JCTD-2021-05).
文摘The Sun is the primary energy source driving the Earth's climate system.A prevailing hypothesis suggests that even minor variations in solar activity,when amplified by climate system feedback mechanisms,can induce significant climatic changes on decadal to centennial timescales.However,the limited availability of historical winter climate proxies has impeded consensus on how solar variability influences the long-term winter climate in Northeast Asia,particularly during Grand Solar Minima(GMs).In this study,we analyzed daily-resolution snowfall records in Seoul from 1625 to 1907 CE,derived from the Korean official historical chronicle Seungjeongweon Ilgi.This period encompasses both the Maunder Minimum(1645–1715 CE)and the Dalton Minimum(1790–1830 CE)of solar activity.Our findings indicate that during the GMs,the first date of annual snowfall(FDS)was delayed by approximately 10 days,and the average annual snowfall frequency(ASF)was reduced by half compared to non-GM periods.Additionally,while an 11-year solar cycle was evident in the ASF during non-GM periods,this cycle was replaced by a shortened 8-to 9-year cycle during the GMs.These variations suggest a differential regional climatic response to prolonged changes in solar activity,and provide historical insights that enhance our understanding of the potential impact of low solar activity on the winter climate in Northeast Asia.
