Ln@MOFs by anchoring rare metal ions(Ln) into metal-organic frameworks(MOFs) are proved to have great potential in the field of luminescent molecular thermometer.Nevertheless,the current research indicated that the po...Ln@MOFs by anchoring rare metal ions(Ln) into metal-organic frameworks(MOFs) are proved to have great potential in the field of luminescent molecular thermometer.Nevertheless,the current research indicated that the poor structural stability and low sensitivity hindered their application scope.In this work,a new MOF Zn-450 luminescent thermometer with multiple emission fluorescence characteristics was synthesized by the combination of 3,3,5,5-biphenyl tetracarboxylic acid(H4L) and Zn2+ ion under solvothermal conditions.Interestingly,a high relative sensitivity of 1.43 % K-1 was found within 80-300 K based on Zn-450.Subsequently,two high-sensitivity luminescent Ln@MOFs(Ln = Eu and Tb) were further fabricated by doping rare earth ions into Zn-450 based on the post-synthesis strategy.Among them,the Eu@Zn-450 demonstrates various luminous behaviors while achieving an increased relative sensitivity of 1.63 % K-1.In addition,the continuously visible red,pink,and purple luminescent emissions at the same temperature range were observed,suggesting that the Eu@Zn-450 could be utilized as a luminescent colorimetric molecular thermometer.Importantly,this work can present new possibilities for the development of rare earth-doped luminescence and its temperature sensing properties.展开更多
To improve the flame-retardant performance of epoxy resin(EP),EP composites were developed using aluminum diethylphosphonate(ADP)and melamine polyphosphate(MPP)as a compound flame retardant,and calcium-based MOF(calci...To improve the flame-retardant performance of epoxy resin(EP),EP composites were developed using aluminum diethylphosphonate(ADP)and melamine polyphosphate(MPP)as a compound flame retardant,and calcium-based MOF(calcium terephthalate,CaT)as a synergist(MOF refers to metal-organic frameworks).The results demonstrated that the combination of CaT and ADP/MPP significantly enhanced the flameretardant properties of EP.With only 2%CaT and 5%ADP/MPP(relative to the mass of EP),the LOI value of EP composite reached 33.8%,and UL-94 V-0 grade was achieved.The peak heat release rate,the total heat release and the total smoke production values decreased by 44.2%,25.6%,and 52.0%,respectively.The addition of a small amount of CaT improved the mechanical strength and toughness of EP.The relevant mechanism was discussed to explain the synergistic effect of CaT and ADP/MPP in EP.The results indicated that the incorporation of CaT not only enhanced the stability of char layer but also suppressed the release of toxic gases during combustion.As a cost-effective MOF material,CaT has a potential application in improving the fire safety of EP.展开更多
Aqueous Zn-ion batteries provide an alternative solution to grid energy storage,but their development has been hindered by dendrite formation and parasitic reactions on Zn anodes.Artificial protective layers hold grea...Aqueous Zn-ion batteries provide an alternative solution to grid energy storage,but their development has been hindered by dendrite formation and parasitic reactions on Zn anodes.Artificial protective layers hold great potential for alleviating these issues,in which the coordination between zincophilic sites and Zn2+plays a crucial role.However,the coordination mode,a key descriptor of interactions,is largely overlooked.Herein,we present a strategy to govern Zn2+diffusion and deposition behavior by changing its coordination mode in the metal–organic framework(MOF)protective layer by installing bidentate dihydroxyanthraquinone(AQOH)and monodentate anthraquinone(AQ)groups onto UiO-66 to afford UiOAQOH and UiO-AQ.Thanks to the superior chelating ability of the adjacent dual oxygen sites,the bidentate coordination is demonstrated to enable UiO-AQOH as a powerful ion-trapper to modulate Zn2+more effectively than UiO-AQ.Specifically,this coordination mode expedites the desolvation of hydrated Zn2+by kicking off more coordinated water than monodentate coordination,thereby suppressing waterinduced side reactions.Meanwhile,it contributes to improving Zn2+transport kinetics and guiding the diffusion of captured Zn2+along the target-distributed sites in nanochannels,ensuring a homogeneous Zn deposition.Notably,the assembled Zn||MnO2 full cell achieves an impressive ultra-long cycle life of10,000 cycles at 3 A g-1,surpassing most reported cases.This work provides new insights into designing advanced Zn anodes for high-performing aqueous batteries.展开更多
High-performance bifunctional oxygen electrocatalysts are urgently required for rechargeable zinc-air batteries(ZABs)due to sluggish kinetics of oxygen reduction/evolution reactions(ORR/OER)at the air cathode.In this ...High-performance bifunctional oxygen electrocatalysts are urgently required for rechargeable zinc-air batteries(ZABs)due to sluggish kinetics of oxygen reduction/evolution reactions(ORR/OER)at the air cathode.In this study,an iron single-atom catalyst(Fe-SAC,FeTCPP@UiO-66–800)is synthesized by direct pyrolysis of a metalloporphyrin-incorporated multivariate MOF.The spatial separation effect of the framework linkers endows Fe-SAC with hierarchical porosity,improved metal utilization efficiency,and enhanced site accessibility by suppressing the metal agglomeration during pyrolysis.Moreover,the possible formation of di-or tri-atomic iron sites facilitates the OER activity via the oxide pathway mechanism(OPM),contributing to the excellent bifunctional ORR/OER performance with aΔE of 0.59 V.Both liquid and flexible ZAB assembled with FeTCPP@UiO-66–800 demonstrate enhanced activity,long-term durability,and anti-deformation ability(340.5 mW/cm2peak power density in liquid device).This study presents a novel strategy for preparing MOF-derived SACs with highly accessible single-atom sites,offering a promising route to high-performance energy conversion devices.展开更多
Morphological imperfections and phase segregation at the buried perovskite interface have posed significant challenges to further enhancing the efficiency of perovskite solar cells(PSCs).In this work,a halogen‑functio...Morphological imperfections and phase segregation at the buried perovskite interface have posed significant challenges to further enhancing the efficiency of perovskite solar cells(PSCs).In this work,a halogen‑functionalized porphyrin‑based metal‑organic framework(MOF)nanosheet,Cu‑TCPP(I),is introduced as a multifunctional buffer layer at the SnO2/perovskite interface.The Cu‑TCPP(I)nanosheets effectively passivate interfacial defects,regulate crystallization kinetics,and stabilize the photoactiveα‑phase perovskite against undesirable transition to theδ‑phase.This interfacial engineering strategy enhances charge extraction efficiency and suppresses non‑radiative recombination,enabling devices to achieve a champion power conversion efficiency(PCE)of 24.62%with negligible hysteresis.The optimized devices retain 92%of their initial PCE after 1600 h of storage under ambient conditions,demonstrating excellent operational stability.Importantly,the Cu‑TCPP(I)interlayer exhibits strong lead‑chelating capability,significantly reducing the risk of lead leakage.This multifunctional interfacial design presents a promising route toward high‑efficiency,stable,and environmentally friendly PSCs for large‑scale photovoltaic applications.展开更多
Because magnetic permeability is an intrinsic property of materials,achieving the regulation of magnetic loss is one of the challenges for electromagnetic wave absorption materials.This paper focuses on the research i...Because magnetic permeability is an intrinsic property of materials,achieving the regulation of magnetic loss is one of the challenges for electromagnetic wave absorption materials.This paper focuses on the research idea of in situ growth of dispersed nanocrystalline FeSiB in an amorphous FeSiB matrix to regulate magnetic properties.On the other hand,based on impedance matching,composite MOFs‐derived porous carbon is used to optimize dielectric loss characteristics.The dual regulation of magnetism and dielectric properties aims to improve the electromagnetic wave absorption performance of composite materials.The research results show that,when the MIL‐101(Fe)composite is 10 wt%and 20 wt%,the reflection loss(RL)reaches−55.34 and−59.11 dB,corresponding to coating thicknesses(d)of 1.54 and 1.45 mm and frequencies(f)of 17.24 and 16.05 GHz,respectively.The effective absorption bandwidths(EAB,RL≤−10 dB)are 6.78 and 3.58 GHz at d=2.4 and 2.0 mm,respectively.This study provides a useful reference idea for constructing FeSiB soft magnetic composite electromagnetic wave absorption materials.展开更多
The development of gradient lubrication materials is critical for numerous biomedical applications,particularly in magnifying mechanical properties and service longevity.Herein,we present an innovative approach to fab...The development of gradient lubrication materials is critical for numerous biomedical applications,particularly in magnifying mechanical properties and service longevity.Herein,we present an innovative approach to fabricate biomimetic gradient lubrication hydrogel through the synergistic integration of three-dimensional(3D)printed metal-organic frameworks(MOFs)nanoparticle network hydrogel skeletons with bioinspired lubrication design.Specifically,robust hydrogel skeletons were engineered through single or multi-material 3D printing,followed by the in situ growth of MOFs nanoparticles within this hydrogel network to create a reinforced,load-bearing architecture.Subsequently,biomimetic lubrication capability was enabled by mechanically coupling another lubricating hydrogel within 3D-printed MOFs nanoparticle network hydrogel skeleton.The superficial layer is highly lubricious to ensure low coefficient of friction(~0.1141)and wear resistance(40,000 cycles),while the deeper layer is stiffer to afford the obligatory mechanical support(fracture strength~2.50 MPa).Furthermore,the gradient architecture stiffness of the hydrogel can be modulated by manipulating the spatial distribution of MOFs within the 3D-printed hydrogel skeleton.As a proof-of-concept,biomimetic gradient hydrogel meniscus structures with C-and O-shaped configurations were constructed by leveraging multi-material 3D printing,demonstrating exceptional lubrication performance.This innovative biomimetic design opens new avenues for creating implantable biomedical gradient lubricating materials with reinforced mechanical and lubrication performance.展开更多
基金supported by the National Natural Science Foundation of China (No.21801111)the Training Plan for Young Core Teachers in Higher Education of Henan Province (No.2021GGJS131)+1 种基金Natural Science Foundation of Henan Province (No.232300421232)the Heluo Young Talent Lifting Project (No.2023HLTJ02)。
摘要Ln@MOFs by anchoring rare metal ions(Ln) into metal-organic frameworks(MOFs) are proved to have great potential in the field of luminescent molecular thermometer.Nevertheless,the current research indicated that the poor structural stability and low sensitivity hindered their application scope.In this work,a new MOF Zn-450 luminescent thermometer with multiple emission fluorescence characteristics was synthesized by the combination of 3,3,5,5-biphenyl tetracarboxylic acid(H4L) and Zn2+ ion under solvothermal conditions.Interestingly,a high relative sensitivity of 1.43 % K-1 was found within 80-300 K based on Zn-450.Subsequently,two high-sensitivity luminescent Ln@MOFs(Ln = Eu and Tb) were further fabricated by doping rare earth ions into Zn-450 based on the post-synthesis strategy.Among them,the Eu@Zn-450 demonstrates various luminous behaviors while achieving an increased relative sensitivity of 1.63 % K-1.In addition,the continuously visible red,pink,and purple luminescent emissions at the same temperature range were observed,suggesting that the Eu@Zn-450 could be utilized as a luminescent colorimetric molecular thermometer.Importantly,this work can present new possibilities for the development of rare earth-doped luminescence and its temperature sensing properties.
基金Funded by Basic Research Program of Jiangsu Province(Natural Science Foundation)(No.BK20230642)。
摘要To improve the flame-retardant performance of epoxy resin(EP),EP composites were developed using aluminum diethylphosphonate(ADP)and melamine polyphosphate(MPP)as a compound flame retardant,and calcium-based MOF(calcium terephthalate,CaT)as a synergist(MOF refers to metal-organic frameworks).The results demonstrated that the combination of CaT and ADP/MPP significantly enhanced the flameretardant properties of EP.With only 2%CaT and 5%ADP/MPP(relative to the mass of EP),the LOI value of EP composite reached 33.8%,and UL-94 V-0 grade was achieved.The peak heat release rate,the total heat release and the total smoke production values decreased by 44.2%,25.6%,and 52.0%,respectively.The addition of a small amount of CaT improved the mechanical strength and toughness of EP.The relevant mechanism was discussed to explain the synergistic effect of CaT and ADP/MPP in EP.The results indicated that the incorporation of CaT not only enhanced the stability of char layer but also suppressed the release of toxic gases during combustion.As a cost-effective MOF material,CaT has a potential application in improving the fire safety of EP.
基金the financial support of the National Natural Science Foundation of China(22308062,22371054)the Foundation of Basic and Applied Basic Research of Guangdong Province(2024A1515010423)Science and Technology Planning Project of Guangdong Province(2025A1515011851)。
摘要Aqueous Zn-ion batteries provide an alternative solution to grid energy storage,but their development has been hindered by dendrite formation and parasitic reactions on Zn anodes.Artificial protective layers hold great potential for alleviating these issues,in which the coordination between zincophilic sites and Zn2+plays a crucial role.However,the coordination mode,a key descriptor of interactions,is largely overlooked.Herein,we present a strategy to govern Zn2+diffusion and deposition behavior by changing its coordination mode in the metal–organic framework(MOF)protective layer by installing bidentate dihydroxyanthraquinone(AQOH)and monodentate anthraquinone(AQ)groups onto UiO-66 to afford UiOAQOH and UiO-AQ.Thanks to the superior chelating ability of the adjacent dual oxygen sites,the bidentate coordination is demonstrated to enable UiO-AQOH as a powerful ion-trapper to modulate Zn2+more effectively than UiO-AQ.Specifically,this coordination mode expedites the desolvation of hydrated Zn2+by kicking off more coordinated water than monodentate coordination,thereby suppressing waterinduced side reactions.Meanwhile,it contributes to improving Zn2+transport kinetics and guiding the diffusion of captured Zn2+along the target-distributed sites in nanochannels,ensuring a homogeneous Zn deposition.Notably,the assembled Zn||MnO2 full cell achieves an impressive ultra-long cycle life of10,000 cycles at 3 A g-1,surpassing most reported cases.This work provides new insights into designing advanced Zn anodes for high-performing aqueous batteries.
基金the financial support provided by the National Natural Science Foundation of China(Nos.52102294,52331009,52272088).
摘要High-performance bifunctional oxygen electrocatalysts are urgently required for rechargeable zinc-air batteries(ZABs)due to sluggish kinetics of oxygen reduction/evolution reactions(ORR/OER)at the air cathode.In this study,an iron single-atom catalyst(Fe-SAC,FeTCPP@UiO-66–800)is synthesized by direct pyrolysis of a metalloporphyrin-incorporated multivariate MOF.The spatial separation effect of the framework linkers endows Fe-SAC with hierarchical porosity,improved metal utilization efficiency,and enhanced site accessibility by suppressing the metal agglomeration during pyrolysis.Moreover,the possible formation of di-or tri-atomic iron sites facilitates the OER activity via the oxide pathway mechanism(OPM),contributing to the excellent bifunctional ORR/OER performance with aΔE of 0.59 V.Both liquid and flexible ZAB assembled with FeTCPP@UiO-66–800 demonstrate enhanced activity,long-term durability,and anti-deformation ability(340.5 mW/cm2peak power density in liquid device).This study presents a novel strategy for preparing MOF-derived SACs with highly accessible single-atom sites,offering a promising route to high-performance energy conversion devices.
基金National Natural Science Foundation of China(22575068,22505235)Natural Science Foundation of Heilongjiang Youth Fund(YQ2024B004).
摘要Morphological imperfections and phase segregation at the buried perovskite interface have posed significant challenges to further enhancing the efficiency of perovskite solar cells(PSCs).In this work,a halogen‑functionalized porphyrin‑based metal‑organic framework(MOF)nanosheet,Cu‑TCPP(I),is introduced as a multifunctional buffer layer at the SnO2/perovskite interface.The Cu‑TCPP(I)nanosheets effectively passivate interfacial defects,regulate crystallization kinetics,and stabilize the photoactiveα‑phase perovskite against undesirable transition to theδ‑phase.This interfacial engineering strategy enhances charge extraction efficiency and suppresses non‑radiative recombination,enabling devices to achieve a champion power conversion efficiency(PCE)of 24.62%with negligible hysteresis.The optimized devices retain 92%of their initial PCE after 1600 h of storage under ambient conditions,demonstrating excellent operational stability.Importantly,the Cu‑TCPP(I)interlayer exhibits strong lead‑chelating capability,significantly reducing the risk of lead leakage.This multifunctional interfacial design presents a promising route toward high‑efficiency,stable,and environmentally friendly PSCs for large‑scale photovoltaic applications.
基金financially supported by Jiangxi Province Outstanding Youth Fund(Grant No.20242BAB23033)the National Natural Science Foundation of China(Grant No.52001147)Jiangxi Province Key Laboratory of Magnetic Metallic Materials and Devices(Grant No.2024SSY05061).
摘要Because magnetic permeability is an intrinsic property of materials,achieving the regulation of magnetic loss is one of the challenges for electromagnetic wave absorption materials.This paper focuses on the research idea of in situ growth of dispersed nanocrystalline FeSiB in an amorphous FeSiB matrix to regulate magnetic properties.On the other hand,based on impedance matching,composite MOFs‐derived porous carbon is used to optimize dielectric loss characteristics.The dual regulation of magnetism and dielectric properties aims to improve the electromagnetic wave absorption performance of composite materials.The research results show that,when the MIL‐101(Fe)composite is 10 wt%and 20 wt%,the reflection loss(RL)reaches−55.34 and−59.11 dB,corresponding to coating thicknesses(d)of 1.54 and 1.45 mm and frequencies(f)of 17.24 and 16.05 GHz,respectively.The effective absorption bandwidths(EAB,RL≤−10 dB)are 6.78 and 3.58 GHz at d=2.4 and 2.0 mm,respectively.This study provides a useful reference idea for constructing FeSiB soft magnetic composite electromagnetic wave absorption materials.
基金support from the National Key Research and Development Program of China(2022YFB4600101)the National Natural Science Foundation of China(52505231 and 52175201)+5 种基金the Key R&D Program of Shandong Province(2024CXPT035)the Research Program of Science and Technology Department of Gansu Province(24JRRA059,24JRRA044 and 24ZDGA014)the Science Fund of Shandong Laboratory of Advanced Materials and Green Manufacturing at Yantai(AMGM2024F12)the Innovation and Entrepreneurship Team Prject of YEDA(2021TD007)the Special Supporting Project for Provincial Leading Talents of Yantai,the Major Program(ZYFZFX-2)the Fundamental Research Special Zone Project of the Lanzhou Institute of Chemical Physics,CAS,the Special Research Assistant Project of the Chinese Academy of Sciences,and the Taishan Scholars Program.
摘要The development of gradient lubrication materials is critical for numerous biomedical applications,particularly in magnifying mechanical properties and service longevity.Herein,we present an innovative approach to fabricate biomimetic gradient lubrication hydrogel through the synergistic integration of three-dimensional(3D)printed metal-organic frameworks(MOFs)nanoparticle network hydrogel skeletons with bioinspired lubrication design.Specifically,robust hydrogel skeletons were engineered through single or multi-material 3D printing,followed by the in situ growth of MOFs nanoparticles within this hydrogel network to create a reinforced,load-bearing architecture.Subsequently,biomimetic lubrication capability was enabled by mechanically coupling another lubricating hydrogel within 3D-printed MOFs nanoparticle network hydrogel skeleton.The superficial layer is highly lubricious to ensure low coefficient of friction(~0.1141)and wear resistance(40,000 cycles),while the deeper layer is stiffer to afford the obligatory mechanical support(fracture strength~2.50 MPa).Furthermore,the gradient architecture stiffness of the hydrogel can be modulated by manipulating the spatial distribution of MOFs within the 3D-printed hydrogel skeleton.As a proof-of-concept,biomimetic gradient hydrogel meniscus structures with C-and O-shaped configurations were constructed by leveraging multi-material 3D printing,demonstrating exceptional lubrication performance.This innovative biomimetic design opens new avenues for creating implantable biomedical gradient lubricating materials with reinforced mechanical and lubrication performance.