Against the backdrop of escalating global climate change and energy crises,the resource utilization of carbon dioxide(CO_(2)),a major greenhouse gas,has become a crucial pathway for achieving carbon peaking and carbon...Against the backdrop of escalating global climate change and energy crises,the resource utilization of carbon dioxide(CO_(2)),a major greenhouse gas,has become a crucial pathway for achieving carbon peaking and carbon neutrality goals.The hydrogenation of CO_(2)to methanol not only enables carbon sequestration and recycling,but also provides a route to produce high value-added fuels and basic chemical feedstocks,holding significant environmental and economic potential.However,this conversion process is thermodynamically and kinetically limited,and traditional catalyst systems(e.g.,Cu/ZnO/Al_(2)O_(3))exhibit inadequate activity,selectivity,and stability under mild conditions.Therefore,the development of novel high-performance catalysts with precisely tunable structures and functionalities is imperative.Metal-organic frameworks(MOFs),as crystalline porous materials with high surface area,tunable pore structures,and diverse metal-ligand compositions,have the great potential in CO_(2)hydrogenation catalysis.Their structural design flexibility allows for the construction of well-dispersed active sites,tailored electronic environments,and enhanced metal-support interactions.This review systematically summarizes the recent advances in MOF-based and MOF-derived catalysts for CO_(2)hydrogenation to methanol,focusing on four design strategies:(1)spatial confinement and in situ construction,(2)defect engineering and ion-exchange,(3)bimetallic synergy and hybrid structure design,and(4)MOF-derived nanomaterial synthesis.These approaches significantly improve CO_(2)conversion and methanol selectivity by optimizing metal dispersion,interfacial structures,and reaction pathways.The reaction mechanism is further explored by focusing on the three main reaction pathways:the formate pathway(HCOO*),the RWGS(Reverse Water Gas Shift reaction)+CO*hydrogenation pathway,and the trans-COOH pathway.In situ spectroscopic studies and density functional theory(DFT)calculations elucidate the formation and transformation of key intermediates,as well as the roles of active sites,metal-support interfaces,oxygen vacancies,and promoters.Additionally,representative catalytic performance data for MOFbased systems are compiled and compared,demonstrating their advantages over traditional catalysts in terms of CO_(2)conversion,methanol selectivity,and space-time yield.Future perspectives for MOF-based CO_(2)hydrogenation catalysts will prioritize two main directions:structural design and mechanistic understanding.The precise construction of active sites through multi-metallic synergy,defect engineering,and interfacial electronic modulation should be made to enhance catalyst selectivity and stability.In addition,advanced in situ characterization techniques combined with theoretical modeling are essential to unravel the detailed reaction mechanisms and intermediate behaviors,thereby guiding rational catalyst design.Moreover,to enable industrial application,challenges related to thermal/hydrothermal stability,catalyst recyclability,and cost-effective large-scale synthesis must be addressed.The development of green,scalable preparation methods and the integration of MOF catalysts into practical reaction systems(e.g.,flow reactors)will be crucial for bridging the gap between laboratory research and commercial deployment.Ultimately,multi-scale structure-performance optimization and catalytic system integration will be vital for accelerating the industrialization of MOF-based CO_(2)-to-methanol technologies.展开更多
In this study,using 3,5‑di(3′,5′‑dicarboxylphenyl)‑1H‑1,2,4‑triazole(H4L)as ligands,a gadolinia‑based organic framework complex{[GdNa(L)(H_(2)O)3]·2H_(2)O}_(n)(Gd‑Na‑MOF)was successfully designed and synthesize...In this study,using 3,5‑di(3′,5′‑dicarboxylphenyl)‑1H‑1,2,4‑triazole(H4L)as ligands,a gadolinia‑based organic framework complex{[GdNa(L)(H_(2)O)3]·2H_(2)O}_(n)(Gd‑Na‑MOF)was successfully designed and synthesized by hydrothermal method.The structure and properties were systematically characterized and tested by techniques such as single‑crystal X‑ray diffraction,powder X‑ray diffraction,thermogravimetric analysis,infrared spectroscopy,and fluorescence spectroscopy.The results indicate that this complex has a unique 3D structure,excellent thermal stability,and outstanding luminescent performance.Based on its luminescent properties,a polymer‑embedding method was employed to fabricate the Gd‑Na‑MOF into a flexible,washable composite fluorescent film,Gd‑Na‑MOF@PMMA/BMA(PMMA=polymethyl methacrylate,BMA=butyl methacrylate).This fluorescent film exhibited highly sensitive recognition capability for tyramine,with a low detection limit of 1.66μmol·L^(-1).It was used for the detection of tyramine in bananas,with a recovery rate of 96.92%‑100.26%.CCDC:2466949.展开更多
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(H_(4)L) and Zn^(2+) 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
Singlet oxygen(^(1)O_(2))is recognized as one of the most effective and selective oxygen agents.However,the explorative study of photocatalysts(PCs)for effective ^(1)O_(2)-based photocatalytic oxidation remains challe...Singlet oxygen(^(1)O_(2))is recognized as one of the most effective and selective oxygen agents.However,the explorative study of photocatalysts(PCs)for effective ^(1)O_(2)-based photocatalytic oxidation remains challenging and critical.In this study,a novel donor-acceptor metal-organic framework(D-A MOF)has been developed by engineering the D-A system,which was then evaluated as a photocatalyst for ^(1)O_(2)-based oxidation.By regulating the donor component of the D-A systematic framework,the MOF(B1)exhibits delayed fluorescence(DF)behavior with a reduced singlet-triplet gap.Given the significantly improved electron transfer behavior in combination with an efficient energy transfer process,the optimal B1 demonstrates remarkable activity toward ^(1)O_(2)generation under suitable photoexcitation conditions.Therefore,it can be utilized for the photocatalytic oxidation of 1,5-dioxynaphthalene(1,5-DHN)to Juglone,achieving the highest yield(conversion>99%at 25℃ in 30 min)and selectivity among all previously reported MOF photocatalysts.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
Metal-organic frameworks(MOFs)have attracted significant interest as self-templates and precursors for the synthesis of carbon-based composites aimed at electromagnetic wave(EMW)absorption.However,the utilization of h...Metal-organic frameworks(MOFs)have attracted significant interest as self-templates and precursors for the synthesis of carbon-based composites aimed at electromagnetic wave(EMW)absorption.However,the utilization of high-temperature treatments has introduced uncertainties regarding the compositions and microstructures of resulting derivatives.Additionally,complete carbonization has led to diminished yields of the produced carbon composites,significantly limiting their practical applications.Consequently,the exploration of pristine MOF-based EMW absorbers presents an intriguing yet challenging endeavor,primarily due to inherently low electrical conductivity.In this study,we showcase the utilization of structurally robust Zr-MOFs as scaffolds to build highly conductive Zr-MOF/PPy composites via an inner-outer dual-modification approach,which involves the production of conducting polypyrrole(PPy)both within the confined nanoporous channels and the external surface of Zr-MOFs via post-synthetic modification.The interconnection of confined PPy and surface-lined PPy together leads to a consecutive and extensive conducting network to the maximum extent.This therefore entails outstanding conductivity up to~14.3 S cm^(-1) in Zr-MOF/PPy composites,which is approximately 1-2 orders of magnitude higher than that for conductive MOF nanocomposites constructed from either inner or outer modification.Benefiting from the strong and tunable conduction loss,as well as the induced dielectric polarization originated from the porous structures and MOF-polymer interfaces,Zr-MOF/PPy exhibits excellent microwave attenuation capabilities and a tunable absorption frequency range.Specifically,with only 15 wt.%loading,the minimum reflection loss(RLmin)can reach up to-67.4 dB,accompanied by an effective absorption bandwidth(EAB)extending to 6.74 GHz.Furthermore,the microwave absorption characteristics can be tailored from the C-band to the Ku-band by adjusting the loading of PPy.This work provides valuable insights into the fabrication of conductive MOF composites by presenting a straightforward pathway to enhance and reg-ulate electrical conduction in MOF-based nanocomposites,thus paving a way to facilely fabricate pristine MOF-based microwave absorbers.展开更多
基金Supported by the National Key Research and Development Program of China(2023YFB4104500,2023YFB4104502)the National Natural Science Foundation of China(22138013)the Taishan Scholar Project(ts201712020).
文摘Against the backdrop of escalating global climate change and energy crises,the resource utilization of carbon dioxide(CO_(2)),a major greenhouse gas,has become a crucial pathway for achieving carbon peaking and carbon neutrality goals.The hydrogenation of CO_(2)to methanol not only enables carbon sequestration and recycling,but also provides a route to produce high value-added fuels and basic chemical feedstocks,holding significant environmental and economic potential.However,this conversion process is thermodynamically and kinetically limited,and traditional catalyst systems(e.g.,Cu/ZnO/Al_(2)O_(3))exhibit inadequate activity,selectivity,and stability under mild conditions.Therefore,the development of novel high-performance catalysts with precisely tunable structures and functionalities is imperative.Metal-organic frameworks(MOFs),as crystalline porous materials with high surface area,tunable pore structures,and diverse metal-ligand compositions,have the great potential in CO_(2)hydrogenation catalysis.Their structural design flexibility allows for the construction of well-dispersed active sites,tailored electronic environments,and enhanced metal-support interactions.This review systematically summarizes the recent advances in MOF-based and MOF-derived catalysts for CO_(2)hydrogenation to methanol,focusing on four design strategies:(1)spatial confinement and in situ construction,(2)defect engineering and ion-exchange,(3)bimetallic synergy and hybrid structure design,and(4)MOF-derived nanomaterial synthesis.These approaches significantly improve CO_(2)conversion and methanol selectivity by optimizing metal dispersion,interfacial structures,and reaction pathways.The reaction mechanism is further explored by focusing on the three main reaction pathways:the formate pathway(HCOO*),the RWGS(Reverse Water Gas Shift reaction)+CO*hydrogenation pathway,and the trans-COOH pathway.In situ spectroscopic studies and density functional theory(DFT)calculations elucidate the formation and transformation of key intermediates,as well as the roles of active sites,metal-support interfaces,oxygen vacancies,and promoters.Additionally,representative catalytic performance data for MOFbased systems are compiled and compared,demonstrating their advantages over traditional catalysts in terms of CO_(2)conversion,methanol selectivity,and space-time yield.Future perspectives for MOF-based CO_(2)hydrogenation catalysts will prioritize two main directions:structural design and mechanistic understanding.The precise construction of active sites through multi-metallic synergy,defect engineering,and interfacial electronic modulation should be made to enhance catalyst selectivity and stability.In addition,advanced in situ characterization techniques combined with theoretical modeling are essential to unravel the detailed reaction mechanisms and intermediate behaviors,thereby guiding rational catalyst design.Moreover,to enable industrial application,challenges related to thermal/hydrothermal stability,catalyst recyclability,and cost-effective large-scale synthesis must be addressed.The development of green,scalable preparation methods and the integration of MOF catalysts into practical reaction systems(e.g.,flow reactors)will be crucial for bridging the gap between laboratory research and commercial deployment.Ultimately,multi-scale structure-performance optimization and catalytic system integration will be vital for accelerating the industrialization of MOF-based CO_(2)-to-methanol technologies.
文摘In this study,using 3,5‑di(3′,5′‑dicarboxylphenyl)‑1H‑1,2,4‑triazole(H4L)as ligands,a gadolinia‑based organic framework complex{[GdNa(L)(H_(2)O)3]·2H_(2)O}_(n)(Gd‑Na‑MOF)was successfully designed and synthesized by hydrothermal method.The structure and properties were systematically characterized and tested by techniques such as single‑crystal X‑ray diffraction,powder X‑ray diffraction,thermogravimetric analysis,infrared spectroscopy,and fluorescence spectroscopy.The results indicate that this complex has a unique 3D structure,excellent thermal stability,and outstanding luminescent performance.Based on its luminescent properties,a polymer‑embedding method was employed to fabricate the Gd‑Na‑MOF into a flexible,washable composite fluorescent film,Gd‑Na‑MOF@PMMA/BMA(PMMA=polymethyl methacrylate,BMA=butyl methacrylate).This fluorescent film exhibited highly sensitive recognition capability for tyramine,with a low detection limit of 1.66μmol·L^(-1).It was used for the detection of tyramine in bananas,with a recovery rate of 96.92%‑100.26%.CCDC:2466949.
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)。
文摘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(H_(4)L) and Zn^(2+) 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supported by the National Key R&D Program of China(2022YFA1503301)the National Natural Science Foundation of China(NSFC)(22375104,22035003,22201143,22371134)+1 种基金the China Postdoctoral Science Foundation(2022M711699)the Haihe Laboratory of Sustainable Chemical Transformations(YYJC202101)。
文摘Singlet oxygen(^(1)O_(2))is recognized as one of the most effective and selective oxygen agents.However,the explorative study of photocatalysts(PCs)for effective ^(1)O_(2)-based photocatalytic oxidation remains challenging and critical.In this study,a novel donor-acceptor metal-organic framework(D-A MOF)has been developed by engineering the D-A system,which was then evaluated as a photocatalyst for ^(1)O_(2)-based oxidation.By regulating the donor component of the D-A systematic framework,the MOF(B1)exhibits delayed fluorescence(DF)behavior with a reduced singlet-triplet gap.Given the significantly improved electron transfer behavior in combination with an efficient energy transfer process,the optimal B1 demonstrates remarkable activity toward ^(1)O_(2)generation under suitable photoexcitation conditions.Therefore,it can be utilized for the photocatalytic oxidation of 1,5-dioxynaphthalene(1,5-DHN)to Juglone,achieving the highest yield(conversion>99%at 25℃ in 30 min)and selectivity among all previously reported MOF photocatalysts.
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.
文摘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.
基金supported by the Fundamental Research Funds for the Central Universities(Nos.2232023D-01 and 2232023D-07)the Shanghai Science&Technology Committee(No.22ZR1403300)the National Natural Science Foundation of China(No.52372040).
文摘Metal-organic frameworks(MOFs)have attracted significant interest as self-templates and precursors for the synthesis of carbon-based composites aimed at electromagnetic wave(EMW)absorption.However,the utilization of high-temperature treatments has introduced uncertainties regarding the compositions and microstructures of resulting derivatives.Additionally,complete carbonization has led to diminished yields of the produced carbon composites,significantly limiting their practical applications.Consequently,the exploration of pristine MOF-based EMW absorbers presents an intriguing yet challenging endeavor,primarily due to inherently low electrical conductivity.In this study,we showcase the utilization of structurally robust Zr-MOFs as scaffolds to build highly conductive Zr-MOF/PPy composites via an inner-outer dual-modification approach,which involves the production of conducting polypyrrole(PPy)both within the confined nanoporous channels and the external surface of Zr-MOFs via post-synthetic modification.The interconnection of confined PPy and surface-lined PPy together leads to a consecutive and extensive conducting network to the maximum extent.This therefore entails outstanding conductivity up to~14.3 S cm^(-1) in Zr-MOF/PPy composites,which is approximately 1-2 orders of magnitude higher than that for conductive MOF nanocomposites constructed from either inner or outer modification.Benefiting from the strong and tunable conduction loss,as well as the induced dielectric polarization originated from the porous structures and MOF-polymer interfaces,Zr-MOF/PPy exhibits excellent microwave attenuation capabilities and a tunable absorption frequency range.Specifically,with only 15 wt.%loading,the minimum reflection loss(RLmin)can reach up to-67.4 dB,accompanied by an effective absorption bandwidth(EAB)extending to 6.74 GHz.Furthermore,the microwave absorption characteristics can be tailored from the C-band to the Ku-band by adjusting the loading of PPy.This work provides valuable insights into the fabrication of conductive MOF composites by presenting a straightforward pathway to enhance and reg-ulate electrical conduction in MOF-based nanocomposites,thus paving a way to facilely fabricate pristine MOF-based microwave absorbers.
