A novel porous lanthanide-organic coordination polymer, [Nd(H2O)(HnicO)(TP)]·2H2O (1) (H2nicO=2-hydroxynicotinic acid, TP= terephthalate), was prepared under hydrothermal condition and characterized by ...A novel porous lanthanide-organic coordination polymer, [Nd(H2O)(HnicO)(TP)]·2H2O (1) (H2nicO=2-hydroxynicotinic acid, TP= terephthalate), was prepared under hydrothermal condition and characterized by single-crystal X-ray diffraction, thermogravimetric analysis and infrared spectroscopy. Compound 1 exhibited a flexible coordination geometry of lanthanide ions, which possessed a three-dimensional (3D) open framework with one-dimensional (1D) channels containing lattice water molecules. This framework structure exhibited a high stability up to 330℃ after removing free water molecules. A homometallic supramolecular framework (Zn(HnicO)2(H2O)2 (2)) was obtained due to the competitive reaction between organic ligands, Nd3+ and Zn2+ ions. The results showed that on the basis of the soft-hard/acid-base principle the coordination selection between metal ions and organic ligands played an essential role in the smart construction of lanthanide architectures.展开更多
Porous features of mesoporous metal nanocrystals are critically important for their applications in catalysis,sorption,and biomedicine and bioimaging.However,precisely engineering porous architectures of mesoporous me...Porous features of mesoporous metal nanocrystals are critically important for their applications in catalysis,sorption,and biomedicine and bioimaging.However,precisely engineering porous architectures of mesoporous metals is still highly challenging.Herein,we report a facile soft-templating strategy to precisely engineer porous architectures of multicomponent PdCuBP mesoporous nanospheres(MSs)by using the surfactants with different amphiphilic features.Three kinds of MSs with distinct porous architectures,including three-dimensional(3D)opened/interconnected dendritic mesopores(dMSs),one-dimensional(1D)cylindered mesopores(cMSs),and zero-dimensional(0D)spherical mesopores(sMSs),are prepared.This surfactant-templating method is generally extended to regulate elemental compositions of multicomponent MSs.The resultant Pd-based MSs have been evaluated as the electrocatalysts for ethanol oxidation reaction(EOR).Our results show that quaternary PdCuBP dMSs display remarkably high catalytic activity and better stability for electrocatalytic EOR,compared to those of multicomponent MSs with other porous architectures and less elemental compositions.Mechanism studies reveal that PdCuBP dMSs combine multiple structural and compositional advantages,which kinetically accelerate the electron/mass transfers and also improve the tolerances to poisoning intermediates.We believe that the porous architecture engineering in mesoporous metal electrocatalysts will present a new way to design highly efficient electrocatalysts with desired porous systems and explore their relations towards(electro)catalysis.展开更多
The practical application of lithium-sulfur batteries is severely hampered by the poor conductivity,polysulfide shuttle effect and sluggish reaction kinetics of sulfur cathodes.Herein,a hierarchi-cally porous three-di...The practical application of lithium-sulfur batteries is severely hampered by the poor conductivity,polysulfide shuttle effect and sluggish reaction kinetics of sulfur cathodes.Herein,a hierarchi-cally porous three-dimension(3D)carbon architecture assembled by cross-linked carbon leaves with implanted atomic Co-N4 has been deli-cately developed as an advanced sulfur host through a SiO_(2)-mediated zeolitic imidazolate framework-L(ZIF-L)strategy.The unique 3D architectures not only provide a highly conductive network for fast electron transfer and buffer the volume change upon lithiation-delithi-ation process but also endow rich interface with full exposure of Co-N4 active sites to boost the lithium polysulfides adsorption and conversion.Owing to the accelerated kinetics and suppressed shuttle effect,the as-prepared sulfur cathode exhibits a superior electrochemical perfor-mance with a high reversible specific capacity of 695 mAh g^(−1) at 5 C and a low capacity fading rate of 0.053%per cycle over 500 cycles at 1 C.This work may provide a promising solution for the design of an advanced sulfur-based cathode toward high-performance Li-S batteries.展开更多
Under the joint assistance of its excellent storage strength, accessible long storage lifespan, and high heat utilization efficiency, salt hydrate-based thermochemical heat storage(THS) materials give renewable energy...Under the joint assistance of its excellent storage strength, accessible long storage lifespan, and high heat utilization efficiency, salt hydrate-based thermochemical heat storage(THS) materials give renewable energy an important outlet to alleviate the pressure of underutilization. Herein, an activated hollow spherical carbon(AHSC) with hierarchical porous architectures converted from covalent-organic frameworks(COFs) is constructed and utilized as the supporting matrix for Li OH.THS composite material for the first time. The obtained Li/AHSC_(3) composites have distinguished hydration performance while manifesting impressive storage ability up to 1916.4 k J kg^(-1)with low operating temperature stemming from the collective effect of the void spherical framework, multimodal porosity, and high surface area of AHSC3. And the Li/AHSC3-40 composite with evidently progressed thermal conductivity is capable of realizing 94.5% heat preservation after twenty-five adsorption-desorption cycles, exhibiting its eminent cyclability and great heat transfer performance. This study not only brings new hope for overcoming the underutilization of low-grade heat but also may enlighten new ideas for enriching the application scenarios of COFs-derived carbonaceous materials.展开更多
Well-defined platelet-like hydrazine-cadmium tellurite hybrid microcrystals have been synthesized by a solvothermal reaction of cadmium chloride,sodium tellurite,and hydrazine hydrate in a mixed solvent containing n-p...Well-defined platelet-like hydrazine-cadmium tellurite hybrid microcrystals have been synthesized by a solvothermal reaction of cadmium chloride,sodium tellurite,and hydrazine hydrate in a mixed solvent containing n-propylamine and deionized water.The formula of the hybrid platelet-like microcrystals has been proposed based on a combination of powder X-ray diffraction pattern(PXRD),elemental analysis,thermogravimetic analysis(TGA),and X-ray photoelectron spectroscopy(XPS).Controlled thermal decomposition of this hybrid precursor can lead to the formation of porous platelet-like microarchitectures.Pure porous cadmium telluride architectures were obtained by using hydrochloric acid to dissolve CdTeO3 remaining in the sample after thermal decomposition at 450°C.In addition,unique nanoporous tellurium architectures were obtained by using hydrochloric acid to dissolve the amorphous Cd(N2H4)TeO3 formed after thermal decomposition at 300°C,followed by an in situ topotactic reaction between the residual three-dimensional(3-D)skeleton of cadmium telluride nanocrystallites and−23TeO.Brunauer-Emmett-Teller(BET)analysis and a study of the optical properties of these porous cadmium telluride and tellurium materials have also been carried out.展开更多
Although carbon coating can improve the cycle life of anode for alkaline Zn batteries, the specific capacity reported is still lower compared with nanosized ZnO. Herein, carbon-coated nanosized ZnO(nano-ZnO@C) was syn...Although carbon coating can improve the cycle life of anode for alkaline Zn batteries, the specific capacity reported is still lower compared with nanosized ZnO. Herein, carbon-coated nanosized ZnO(nano-ZnO@C) was synthesized by one-step heat treatment from a gel precursor in N2. Commercial ZnO and homemade ZnO prepared similarly in air atmosphere were studied for comparison. Structure analysis displayed that both nano-ZnO@C and homemade ZnO had a porous hierarchical agglomerated architecture produced from primary nanoparticles with a diameter of approximately 100 nm as building blocks. Electrochemical performance measurements showed that nano-ZnO@C displayed the highest electrochemical activity, the lowest electrode resistance, the highest discharge capacity(622 m A·h/g), and the best cyclic stability. These properties were due to the combination of nanosized ZnO and the physical capping of carbon, which maintained the high utilization efficiency of nano-ZnO, and simultaneously prevented dendrite growth and densification of the anode.展开更多
Electronic skins are artificial skin-type multifunctional sensors,which hold great potentials in intelligent robotics,limb prostheses and human health monitoring.However,it is a great challenge to independently and ac...Electronic skins are artificial skin-type multifunctional sensors,which hold great potentials in intelligent robotics,limb prostheses and human health monitoring.However,it is a great challenge to independently and accurately read various physical signals without power supplies.Here,a self-powered flexible temperature-pressure bimodal sensor based on high-performance thermoelectric films and porous microconed conductive elastic materials is presented.Through introducing flexible heat-sink design and harvesting body heat energy,the thin-film thermoelectric device could not only precisely sense temperature signal but also drive the pressure sensor for detecting external tactile stimulus.The integration of Bi-Te based thermoelectric film with high stability in wide temperature range enables the sensor to sense the ambient temperature with high resolution(<0.1 K)as well as excellent sensitivity(3.77 mV K^(-1)).Meanwhile,the porous microconed elastomer responds to pressure variation with low-pressure detection(16 Pa)and a high sensitivity of 37 kPa^(-1).Furthermore,the bimodal sensor could accurately and simultaneously monitor human wrist pulse and body temperature in real time,which demonstrates promising applications in self-powered electronic skins for human health monitoring systems.展开更多
Zinc-ion hybrid supercapacitors(ZHSCs)have been widely considered as promising candidates for flexible electrochemical energy storage devices.The key challenge is to develop hydrogel electrolytes with high hydrophilic...Zinc-ion hybrid supercapacitors(ZHSCs)have been widely considered as promising candidates for flexible electrochemical energy storage devices.The key challenge is to develop hydrogel electrolytes with high hydrophilicity,anti-freezing,bending resistance,and stable interface with electrodes.This study reported a hydrogel electrolyte system that can meet the above functions,in which the zincophilic and negatively charged SO_(3)^(−),migratable Na^(+),abundant hydrophilic functional groups,gum xanthan,and porous architecture could effectively promote the electrochemical performance of ZHSCs.ZHSCs with such hydrogel electrolytes not only exhibited good low-temperature performance but also showed excellent bending resistance ability.A high specific capacitance could be kept after a long air-working lifespan over 10,000 cycles under a wide operation voltage of 1.85 V at−10℃.Furthermore,flexible ZHSCs could maintain the capacitance retention of 93.18%even after continuous 500 bends at an angle of 180°.The designed hydrogel electrolytes could be also used for other electrochemical energy storage devices with anti-freezing and bending resistance by changing electrolyte salt.展开更多
基金Program for New Century Excellent Talents in University (NCET-05-0278)the National Natural Science Foundation of China (50872016)the Foundation for the Author of National Excellent Doctoral Dissertation of China (200322)
文摘A novel porous lanthanide-organic coordination polymer, [Nd(H2O)(HnicO)(TP)]·2H2O (1) (H2nicO=2-hydroxynicotinic acid, TP= terephthalate), was prepared under hydrothermal condition and characterized by single-crystal X-ray diffraction, thermogravimetric analysis and infrared spectroscopy. Compound 1 exhibited a flexible coordination geometry of lanthanide ions, which possessed a three-dimensional (3D) open framework with one-dimensional (1D) channels containing lattice water molecules. This framework structure exhibited a high stability up to 330℃ after removing free water molecules. A homometallic supramolecular framework (Zn(HnicO)2(H2O)2 (2)) was obtained due to the competitive reaction between organic ligands, Nd3+ and Zn2+ ions. The results showed that on the basis of the soft-hard/acid-base principle the coordination selection between metal ions and organic ligands played an essential role in the smart construction of lanthanide architectures.
基金supported by the Natural Science Foundation of Jiangsu Province(Nos.BK20191366 and BK20180723),Priority Academic Program Development of Jiangsu Higher Education Institutions,National and Local Joint Engineering Research Center of Biomedical Functional Materials.
文摘Porous features of mesoporous metal nanocrystals are critically important for their applications in catalysis,sorption,and biomedicine and bioimaging.However,precisely engineering porous architectures of mesoporous metals is still highly challenging.Herein,we report a facile soft-templating strategy to precisely engineer porous architectures of multicomponent PdCuBP mesoporous nanospheres(MSs)by using the surfactants with different amphiphilic features.Three kinds of MSs with distinct porous architectures,including three-dimensional(3D)opened/interconnected dendritic mesopores(dMSs),one-dimensional(1D)cylindered mesopores(cMSs),and zero-dimensional(0D)spherical mesopores(sMSs),are prepared.This surfactant-templating method is generally extended to regulate elemental compositions of multicomponent MSs.The resultant Pd-based MSs have been evaluated as the electrocatalysts for ethanol oxidation reaction(EOR).Our results show that quaternary PdCuBP dMSs display remarkably high catalytic activity and better stability for electrocatalytic EOR,compared to those of multicomponent MSs with other porous architectures and less elemental compositions.Mechanism studies reveal that PdCuBP dMSs combine multiple structural and compositional advantages,which kinetically accelerate the electron/mass transfers and also improve the tolerances to poisoning intermediates.We believe that the porous architecture engineering in mesoporous metal electrocatalysts will present a new way to design highly efficient electrocatalysts with desired porous systems and explore their relations towards(electro)catalysis.
基金financially supported by the National Natural Science Foundation of China(Grant Nos.51871060,52071084 and 51831009)Recruit Program of Global Youth Experts and Fudan’s Undergraduate Research Opportunities Program(FDUROP)。
文摘The practical application of lithium-sulfur batteries is severely hampered by the poor conductivity,polysulfide shuttle effect and sluggish reaction kinetics of sulfur cathodes.Herein,a hierarchi-cally porous three-dimension(3D)carbon architecture assembled by cross-linked carbon leaves with implanted atomic Co-N4 has been deli-cately developed as an advanced sulfur host through a SiO_(2)-mediated zeolitic imidazolate framework-L(ZIF-L)strategy.The unique 3D architectures not only provide a highly conductive network for fast electron transfer and buffer the volume change upon lithiation-delithi-ation process but also endow rich interface with full exposure of Co-N4 active sites to boost the lithium polysulfides adsorption and conversion.Owing to the accelerated kinetics and suppressed shuttle effect,the as-prepared sulfur cathode exhibits a superior electrochemical perfor-mance with a high reversible specific capacity of 695 mAh g^(−1) at 5 C and a low capacity fading rate of 0.053%per cycle over 500 cycles at 1 C.This work may provide a promising solution for the design of an advanced sulfur-based cathode toward high-performance Li-S batteries.
基金the support from the Key-Area Research and Development Program of Guangdong Province (2020B0202010004)the National Natural Science Foundation of China (52071192)the Key Research Program of Frontier Sciences, CAS (QYZDY-SSW-JSC038)。
文摘Under the joint assistance of its excellent storage strength, accessible long storage lifespan, and high heat utilization efficiency, salt hydrate-based thermochemical heat storage(THS) materials give renewable energy an important outlet to alleviate the pressure of underutilization. Herein, an activated hollow spherical carbon(AHSC) with hierarchical porous architectures converted from covalent-organic frameworks(COFs) is constructed and utilized as the supporting matrix for Li OH.THS composite material for the first time. The obtained Li/AHSC_(3) composites have distinguished hydration performance while manifesting impressive storage ability up to 1916.4 k J kg^(-1)with low operating temperature stemming from the collective effect of the void spherical framework, multimodal porosity, and high surface area of AHSC3. And the Li/AHSC3-40 composite with evidently progressed thermal conductivity is capable of realizing 94.5% heat preservation after twenty-five adsorption-desorption cycles, exhibiting its eminent cyclability and great heat transfer performance. This study not only brings new hope for overcoming the underutilization of low-grade heat but also may enlighten new ideas for enriching the application scenarios of COFs-derived carbonaceous materials.
基金This work was supported by the National Basic Research Priorities Program of China(No.2010CB934700)the National Natural Science Foundation of China(NSFC)(Nos.50732006 and 20671085)+1 种基金the Program of International S and T Cooperation(No.S2010GR0314)and the Partner-Group of the Chinese Academy of Sciences-the Max Planck Society.
文摘Well-defined platelet-like hydrazine-cadmium tellurite hybrid microcrystals have been synthesized by a solvothermal reaction of cadmium chloride,sodium tellurite,and hydrazine hydrate in a mixed solvent containing n-propylamine and deionized water.The formula of the hybrid platelet-like microcrystals has been proposed based on a combination of powder X-ray diffraction pattern(PXRD),elemental analysis,thermogravimetic analysis(TGA),and X-ray photoelectron spectroscopy(XPS).Controlled thermal decomposition of this hybrid precursor can lead to the formation of porous platelet-like microarchitectures.Pure porous cadmium telluride architectures were obtained by using hydrochloric acid to dissolve CdTeO3 remaining in the sample after thermal decomposition at 450°C.In addition,unique nanoporous tellurium architectures were obtained by using hydrochloric acid to dissolve the amorphous Cd(N2H4)TeO3 formed after thermal decomposition at 300°C,followed by an in situ topotactic reaction between the residual three-dimensional(3-D)skeleton of cadmium telluride nanocrystallites and−23TeO.Brunauer-Emmett-Teller(BET)analysis and a study of the optical properties of these porous cadmium telluride and tellurium materials have also been carried out.
基金Project(51674301) supported by the National Natural Science Foundation of China
文摘Although carbon coating can improve the cycle life of anode for alkaline Zn batteries, the specific capacity reported is still lower compared with nanosized ZnO. Herein, carbon-coated nanosized ZnO(nano-ZnO@C) was synthesized by one-step heat treatment from a gel precursor in N2. Commercial ZnO and homemade ZnO prepared similarly in air atmosphere were studied for comparison. Structure analysis displayed that both nano-ZnO@C and homemade ZnO had a porous hierarchical agglomerated architecture produced from primary nanoparticles with a diameter of approximately 100 nm as building blocks. Electrochemical performance measurements showed that nano-ZnO@C displayed the highest electrochemical activity, the lowest electrode resistance, the highest discharge capacity(622 m A·h/g), and the best cyclic stability. These properties were due to the combination of nanosized ZnO and the physical capping of carbon, which maintained the high utilization efficiency of nano-ZnO, and simultaneously prevented dendrite growth and densification of the anode.
基金supported by the National Key R&D Program of China(Grant No.2018YFA0702100)the Zhejiang Provincial Key R&D Program of China(Grant No.2021C05002)+1 种基金the Beijing Nova Programme Interdisciplinary Cooperation Project(Grant Nos.Z191100001119019 and Z191100001119013)the Fundamental Research Funds for the Central Universities。
文摘Electronic skins are artificial skin-type multifunctional sensors,which hold great potentials in intelligent robotics,limb prostheses and human health monitoring.However,it is a great challenge to independently and accurately read various physical signals without power supplies.Here,a self-powered flexible temperature-pressure bimodal sensor based on high-performance thermoelectric films and porous microconed conductive elastic materials is presented.Through introducing flexible heat-sink design and harvesting body heat energy,the thin-film thermoelectric device could not only precisely sense temperature signal but also drive the pressure sensor for detecting external tactile stimulus.The integration of Bi-Te based thermoelectric film with high stability in wide temperature range enables the sensor to sense the ambient temperature with high resolution(<0.1 K)as well as excellent sensitivity(3.77 mV K^(-1)).Meanwhile,the porous microconed elastomer responds to pressure variation with low-pressure detection(16 Pa)and a high sensitivity of 37 kPa^(-1).Furthermore,the bimodal sensor could accurately and simultaneously monitor human wrist pulse and body temperature in real time,which demonstrates promising applications in self-powered electronic skins for human health monitoring systems.
基金The financial support from National Natural Science Foundation of China(2210910352205489,and 21875144)Shenzhen Science and Technology Research Grant(JCYJ20200109105003940)is gratefully acknowledged.
文摘Zinc-ion hybrid supercapacitors(ZHSCs)have been widely considered as promising candidates for flexible electrochemical energy storage devices.The key challenge is to develop hydrogel electrolytes with high hydrophilicity,anti-freezing,bending resistance,and stable interface with electrodes.This study reported a hydrogel electrolyte system that can meet the above functions,in which the zincophilic and negatively charged SO_(3)^(−),migratable Na^(+),abundant hydrophilic functional groups,gum xanthan,and porous architecture could effectively promote the electrochemical performance of ZHSCs.ZHSCs with such hydrogel electrolytes not only exhibited good low-temperature performance but also showed excellent bending resistance ability.A high specific capacitance could be kept after a long air-working lifespan over 10,000 cycles under a wide operation voltage of 1.85 V at−10℃.Furthermore,flexible ZHSCs could maintain the capacitance retention of 93.18%even after continuous 500 bends at an angle of 180°.The designed hydrogel electrolytes could be also used for other electrochemical energy storage devices with anti-freezing and bending resistance by changing electrolyte salt.