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
Metal-organic frameworks(MOFs)are becoming more and more popular as the fillers in polymer electrolytes in recent years.In this study,a series of MOFs(NH_(2)-MIL-101(Fe),MIL-101(Fe),activated NH_(2)-MIL-101(Fe)and act...Metal-organic frameworks(MOFs)are becoming more and more popular as the fillers in polymer electrolytes in recent years.In this study,a series of MOFs(NH_(2)-MIL-101(Fe),MIL-101(Fe),activated NH_(2)-MIL-101(Fe)and activated MIL-101(Fe))were synthesized and added to PEO-based solid composite electrolytes(SCEs).Furthermore,the role of the—NH_(2)groups and open metal sites(OMSs)were both examined.Different ratios of MOFs vs polymers were also studied by the electrochemical characterizations.At last,we successfully designed a novel solid composite electrolyte containing activated NH_(2)-MIL-101(Fe),PEO,Li TFSI and PVDF for the high-performance all-solid-state lithium-metal batteries.This work might provide new insight to understand the interactions between polymers and functional groups or OMSs of MOFs better.展开更多
A novel adsorbent(MTZ-MOFs)was synthesized by a one-step reaction of zinc nitrate hexahydrate and 1-(2-dimethylaminoethyl)-1H-5-mercaptotetrazole to remove mercury from waste water.The results showed that MTZ-MOFs had...A novel adsorbent(MTZ-MOFs)was synthesized by a one-step reaction of zinc nitrate hexahydrate and 1-(2-dimethylaminoethyl)-1H-5-mercaptotetrazole to remove mercury from waste water.The results showed that MTZ-MOFs had excellent selectivity and repeatability for Hg(Ⅱ),the optimum pH was 3.0,the maximum adsorption capacity was 872.8 mg/g,and the process was a spontaneous exothermic reaction.The adsorption behavior was chemisorption,which conformed to the pseudo-second-order kinetic and Freundlich isothermal model.Moreover,the adsorption mechanism showed that the adsorption process mainly depended on ion exchange and chelation,and the synergistic action of S and N atoms played a key role.So,MTZ-MOFs were an efficient adsorbent for mercury ion removal.展开更多
Unsatisfactory conductivity and volume effects have hindered the commercial application of siliconbased materials as advanced anode materials for high-performance lithium-ion batteries. Herein, nitrogen doped carbon s...Unsatisfactory conductivity and volume effects have hindered the commercial application of siliconbased materials as advanced anode materials for high-performance lithium-ion batteries. Herein, nitrogen doped carbon silicon matrix composite with atomically dispersed Co sites(Si/Co-N-C) is obtained via the design of the frame structure loaded with nano-components and the multi-element hybrid strategy. Co atoms are uniformly fixed to the N-C frame and tightly packed with nanoscale silicon particles as an activation and protection building block. The mechanism of the N-C framework of loaded metal Co in the Si alloying process is revealed by electrochemical kinetic analysis and ex situ characterization tests.Impressively, the nitrogen-doped Co site activates the intercalation of the outer carbon matrix to supplement the additional capacity. The Co nanoparticles with high conductivity and support enhance the conductivity and structural stability of the composite, accelerating the Li^(+)/Na^(+) diffusion kinetics. Density functional theory(DFT) calculation confirms that the hetero-structure Si/Co-N-C adjusts the electronic structure to obtain good lithium-ion adsorption energy, reduces the Li^(+)/Na^(+) migration energy barrier.This work provides meaningful guidance for the development of high-performance metal/non-metal modified anode materials.展开更多
Metal–organic framework(MOF)-based materials with high porosity,tunable compositions,diverse structures,and versatile functionalities provide great scope for next-generation rechargeable battery applications.Herein,t...Metal–organic framework(MOF)-based materials with high porosity,tunable compositions,diverse structures,and versatile functionalities provide great scope for next-generation rechargeable battery applications.Herein,this review summarizes recent advances in pristine MOFs,MOF composites,MOF derivatives,and MOF composite derivatives for high-performance sodium-ion batteries,potassiumion batteries,Zn-ion batteries,lithium–sulfur batteries,lithium–oxygen batteries,and Zn–air batteries in which the unique roles of MOFs as electrodes,separators,and even electrolyte are highlighted.Furthermore,through the discussion of MOFbased materials in each battery system,the key principles for controllable synthesis of diverse MOF-based materials and electrochemical performance improvement mechanisms are discussed in detail.Finally,the major challenges and perspectives of MOFs are also proposed for next-generation battery applications.展开更多
As a new generation of artificial enzymes,nanozymes show outstanding advantages such as high stability,low cost,and facile synthesis,which endow them with promising applications in biomedical and environmental fields....As a new generation of artificial enzymes,nanozymes show outstanding advantages such as high stability,low cost,and facile synthesis,which endow them with promising applications in biomedical and environmental fields.Among the various reported nanozymes,metal-organic frameworks(MOFs)could mimic the active center of natural enzymes and provide a hydrophobic environment,which makes MOFs attractive alternatives to natural enzymes.Owing to the highly structural diversity and tailorability of MOFs,rational design will contribute to improve the activity of MOF-based nanozymes and promote their potential applications in both biomedical and environmental fields.Therefore,a comprehensiye suminary of activity regulatory strategies of MOF-based nanozymes is urgently needed.Firstly,we summarized the activity regulatory strategies of MOFs with intrinsic enzyme-like activities via modulation of metal nodes,ligands,structures and morphologies.Then the applications of MOF-based nanozymes in biosensing,hazardous degradation,antibacterial,and cancer therapy were also introduced.Finally,the current challenges and future perspectives were discussed in depth.It is highly expected that this review will provide a better understanding on the rational design of novel high-performance MOF-based nanozymes.展开更多
In the present work,a zinc-based metal-organic framework{[Zn(ddpd)_(0.5)(bipy)_(0.5)]·H_(2)O]}_(n)(1-Zn)(where ddpd=2,5-di(2',4'-dic arboxylphenyl)-1,4-difluorobenzene,bipy=4,4-bipyridine)was synthesized ...In the present work,a zinc-based metal-organic framework{[Zn(ddpd)_(0.5)(bipy)_(0.5)]·H_(2)O]}_(n)(1-Zn)(where ddpd=2,5-di(2',4'-dic arboxylphenyl)-1,4-difluorobenzene,bipy=4,4-bipyridine)was synthesized by a solvothermal method.Complex 1-Zn features a threedimensional(2,4,6)-connected network with{4^2.6^2.8^2}_(2){4^4.6^6.8^5}{6}topology.Meanwhile,without the assistance of other reagents,complex 1-Zn not only exhibited an exceeded 95%photodegradation efficiency for rhodamine B(Rh B),methyl blue(MB)and methyl orange(MO)within 40 min,but also showed high stability and recyclability.In addition,free radical quenching experiments and electron spin resonance(ESR)spectroscopy verified that the main active species in the photodegradation process were·O_(2)^(-)and OH,and a more indepth degradation mechanism was further elucidated by density functional theory(DFT)calculations.展开更多
For several decades,the promise of implementing of lithium(Li)metal anodes for Li batteries has been a"holy grail"for researchers.Herein,we have proposed a facile design of a MOF-derived Co_(3)O_(4)nanoparti...For several decades,the promise of implementing of lithium(Li)metal anodes for Li batteries has been a"holy grail"for researchers.Herein,we have proposed a facile design of a MOF-derived Co_(3)O_(4)nanoparticles modified nickel foam,i.e.,Co_(3)O_(4)-NF,as a 3D host to achieve a uniform infusion of the molten Li.The molten Li was uniformly absorbed on the Co_(3)O_(4)-NF host only in 10 s due to its high Li lithiophilicity.The obtained Li-Co_(3)O_(4)-NF composite electrode shows high cycling stability in symmetric cells with low voltage hysteresis even at a high current density of 5 mA/cm2.The full cells of Li-Co_(3)O_(4)-NF/LiFePO_(4)can cycle for more than 500 cycles at 2C without obvious capacity decay.SEM after cycling and in situ optical microscope results suggest that the unique 3D host structure of the Li-Co_(3)O_(4)-NF anode plays key roles on suppressing the dendrite growth and decreasing the local current inhomogeneity.We believe this work might provide a new strategy for fabricating dendrite-free Li metal anodes and facilitate practical applications in Li batteries.展开更多
Mercury(Hg)ions can lead to a serious impact on the environment;therefore,it was necessary to find an effective method for absorbing these toxic Hg ions.Here,the adsorbent(Zn-AHMT)was synthesized from zinc nitrate and...Mercury(Hg)ions can lead to a serious impact on the environment;therefore,it was necessary to find an effective method for absorbing these toxic Hg ions.Here,the adsorbent(Zn-AHMT)was synthesized from zinc nitrate and 4-amino 3-hydrazine-5 mercapto-1,2,4-triazole(AHMT)by one-step method and,characterized the microstruc-ture and absorption performance by fourier transform infrared spectroscopy(FTIR),field emission scanning electron microscopy(FESEM),X-ray diffraction(XRD),Brunauer-Emmett Teller(BET),Thermal Gravimetric Analyzer(TGA)and X-ray photoelectron spectroscopy(XPS).Through a plethora of measurements,we found that the maximum adsorption capacity was 802.8 mg/g when the optimal pH of Zn-AHMT was 3.0.The isothermal and kinetic experiments confirm that the reaction process of Zn-AHMT was chemisorption,while the adsorption process conforms to the Hill model and pseudo second order kinetic model.Thermodynamic experiments showed that the adsorption process was spontaneous and exothermic.Selective experiments were performed in the simulated wastewater containing Mn,Mg,Cr,Al,Co,Ni,Hg ions.Our results showed that the Zn-AHMT has a stronger affinity for Hg ions.The removal rate of Zn-AHMT remained above 98%,indicating that the Zn-AHMT had a good stability validated by three adsorption-desorption repeatable tests.According to the XPS results,the adsorption reaction of Zn-AHMT was mainly attributed to the chelation and ion exchange.This was further explained by both density functional theory(DFT)calculation and frontier molecular orbital theory.We therefore propose the adsorption mechanism of Zn-AHMT.The adsorption reaction facilitates via the synergistic action of S and N atoms.Moreover,the bonding between the adsorbent and the N atom has been proved to be more stable.Our study demonstrated that Zn-AHMT had a promising application prospect in mercury removal.展开更多
Construction of metal-organic-frame works-based composite photocatalysts has attracted much attention for the reasonable band gap and high surface areas to improve the photocatalytic activity.In this study,the ternary...Construction of metal-organic-frame works-based composite photocatalysts has attracted much attention for the reasonable band gap and high surface areas to improve the photocatalytic activity.In this study,the ternary heterojunction Pd@UiO-66-NH_(2)@ZnIn_(2)S_(4)nanocomposites were facilely prepared for the first time by a two-step method.The visible-light-promoted hydrogen production rate of 0.3%Pd@UiO-66-NH_(2)@ZnIn_(2)S_(4)reaches up to 5.26 mmol g^(-1)h^(-1),which is evidently much higher than pure UiO-66-NH_(2),ZnIn_(2)S_(4)and binary UiO-66-NH_(2)/ZnIn_(2)S_(4)composites.Such a huge improvement in the photocatalytic performance is mainly attributed to the matched band gap of ZnIn_(2)S_(4)and UiO-66-NH_(2),and the introduction of Pd NPs into photocatalysts that broaden spectral response range and promote the photon induced charge carrier separation.This work may provide a feasible approach for the design and construction of metal-organic-frameworks-based photocatalytic materials.展开更多
Nitrogen-doped carbon materials as promising oxygen reduction reaction(ORR) electrocatalysts attract great interest in fuel cells and metal-air batteries because of their relatively high activity, high surface area, h...Nitrogen-doped carbon materials as promising oxygen reduction reaction(ORR) electrocatalysts attract great interest in fuel cells and metal-air batteries because of their relatively high activity, high surface area, high conductivity and low cost. To maximize their catalytic efficiency, rational design of efficient electrocatalysts with rich exposed active sites is highly desired. Besides, due to the complexity of nitrogen species, the identification of active nitrogen sites for ORR remains challenging. Herein, we develop a facile and scalable template method to construct high-concentration nitrogen-doped carbon hollow frameworks(NC), and reveal the effect of different nitrogen species on theirORRactivity on basis of experimental analysis and theoretical calculations. The formation mechanism is clearly revealed, including low-pressure vapor superassembly of thin zeolitic imidazolate framework(ZIF-8) shell on ZnO templates,in situ carbonization and template removal. The obtained NC-800 displays better ORR activity compared with other NC-700 and NC-900 samples. Our results indicate that the superior ORR activity of NC-800 is mainly attributed to its content balance of three nitrogen species. The graphitic N and pyrrolic N sites are responsible for lowering the working function, while the pyridinic N and pyrrolic N sites as possible active sites are beneficial for increasing the density of states.展开更多
Constructing molecule@support composites is an attractive strategy to realize heterogeneous molecular electrocatalysis.Herein,we synthesized metal-organic framework(MOF)-supported molecular catalysts for hydrogen evol...Constructing molecule@support composites is an attractive strategy to realize heterogeneous molecular electrocatalysis.Herein,we synthesized metal-organic framework(MOF)-supported molecular catalysts for hydrogen evolution and oxygen reduction reaction(HER/ORR).Ligand exchange strategy was used to prepare molecule@support hybrids due to the same functional group.A series of hybrids were obtained using Co porphyrin(1)and different MOFs including MIL-88(Fe),MOF-5(NiCo)and UIO-66(Zr).The1@MOF-5(NiCo)had the best HER and ORR activity compared with 1@MIL-88(Fe)and 1@MOF-5(NiCo).These hybrids also exhibited tunable selectivity for ORR with four-electron process,which can be attributed to the synergistic effect of porphyrin molecules and MOFs.This work provides a possibility for molecular catalysts to improve activity of HER and tune selectivity of ORR.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.
基金financially supported by National Natural Science Foundation of China(21701083)Postgraduate Research&Practice Innovation Program of Jiangsu Province(KYCX20_3137)。
文摘Metal-organic frameworks(MOFs)are becoming more and more popular as the fillers in polymer electrolytes in recent years.In this study,a series of MOFs(NH_(2)-MIL-101(Fe),MIL-101(Fe),activated NH_(2)-MIL-101(Fe)and activated MIL-101(Fe))were synthesized and added to PEO-based solid composite electrolytes(SCEs).Furthermore,the role of the—NH_(2)groups and open metal sites(OMSs)were both examined.Different ratios of MOFs vs polymers were also studied by the electrochemical characterizations.At last,we successfully designed a novel solid composite electrolyte containing activated NH_(2)-MIL-101(Fe),PEO,Li TFSI and PVDF for the high-performance all-solid-state lithium-metal batteries.This work might provide new insight to understand the interactions between polymers and functional groups or OMSs of MOFs better.
基金supported by the Hubei Provincial Department of Education Science and Technology Research Program Young Talent Project,China (No. Q20201102)the National Natural Science Foundation of China (Nos. 51864042, 51804220)
文摘A novel adsorbent(MTZ-MOFs)was synthesized by a one-step reaction of zinc nitrate hexahydrate and 1-(2-dimethylaminoethyl)-1H-5-mercaptotetrazole to remove mercury from waste water.The results showed that MTZ-MOFs had excellent selectivity and repeatability for Hg(Ⅱ),the optimum pH was 3.0,the maximum adsorption capacity was 872.8 mg/g,and the process was a spontaneous exothermic reaction.The adsorption behavior was chemisorption,which conformed to the pseudo-second-order kinetic and Freundlich isothermal model.Moreover,the adsorption mechanism showed that the adsorption process mainly depended on ion exchange and chelation,and the synergistic action of S and N atoms played a key role.So,MTZ-MOFs were an efficient adsorbent for mercury ion removal.
基金Research and Development Plan Project in Key Fields of Guangdong Province (2020B0101030005)Basic and Applied Basic Research Fund of Guangdong Province (2019B1515120027)+1 种基金Scientific Research Innovation Project of Graduate School of South China Normal University (2024KYLX050)Special Funds for the Cultivation of Guangdong College Students’ Scientific and Technological Innovation (“Climbing Program” Special Funds, pdjh2024a109)。
文摘Unsatisfactory conductivity and volume effects have hindered the commercial application of siliconbased materials as advanced anode materials for high-performance lithium-ion batteries. Herein, nitrogen doped carbon silicon matrix composite with atomically dispersed Co sites(Si/Co-N-C) is obtained via the design of the frame structure loaded with nano-components and the multi-element hybrid strategy. Co atoms are uniformly fixed to the N-C frame and tightly packed with nanoscale silicon particles as an activation and protection building block. The mechanism of the N-C framework of loaded metal Co in the Si alloying process is revealed by electrochemical kinetic analysis and ex situ characterization tests.Impressively, the nitrogen-doped Co site activates the intercalation of the outer carbon matrix to supplement the additional capacity. The Co nanoparticles with high conductivity and support enhance the conductivity and structural stability of the composite, accelerating the Li^(+)/Na^(+) diffusion kinetics. Density functional theory(DFT) calculation confirms that the hetero-structure Si/Co-N-C adjusts the electronic structure to obtain good lithium-ion adsorption energy, reduces the Li^(+)/Na^(+) migration energy barrier.This work provides meaningful guidance for the development of high-performance metal/non-metal modified anode materials.
基金supported by the National Natural Science Foundation of China(51972030,51772030)the S&T Major Project of Inner Mongolia Autonomous Region in China(2020ZD0018)+1 种基金Beijing Outstanding Young Scientists Program(BJJWZYJH01201910007023)Guangdong Key Laboratory of Battery Safety(2019B121203008)。
文摘Metal–organic framework(MOF)-based materials with high porosity,tunable compositions,diverse structures,and versatile functionalities provide great scope for next-generation rechargeable battery applications.Herein,this review summarizes recent advances in pristine MOFs,MOF composites,MOF derivatives,and MOF composite derivatives for high-performance sodium-ion batteries,potassiumion batteries,Zn-ion batteries,lithium–sulfur batteries,lithium–oxygen batteries,and Zn–air batteries in which the unique roles of MOFs as electrodes,separators,and even electrolyte are highlighted.Furthermore,through the discussion of MOFbased materials in each battery system,the key principles for controllable synthesis of diverse MOF-based materials and electrochemical performance improvement mechanisms are discussed in detail.Finally,the major challenges and perspectives of MOFs are also proposed for next-generation battery applications.
基金financially supported by the National Natural Science Foundation of China(Nos.31901000 and 22022609)the Natural Science Foundation of Jiangsu Higher Education Institutes of China(No.19KJA610003)+1 种基金the Postdoctoral Science Foundation of Jiangsu Province(No.2019K152)the Collaborative Innovation Center of Radiological Medicine of Jiangsu Higher Education Institutions。
文摘As a new generation of artificial enzymes,nanozymes show outstanding advantages such as high stability,low cost,and facile synthesis,which endow them with promising applications in biomedical and environmental fields.Among the various reported nanozymes,metal-organic frameworks(MOFs)could mimic the active center of natural enzymes and provide a hydrophobic environment,which makes MOFs attractive alternatives to natural enzymes.Owing to the highly structural diversity and tailorability of MOFs,rational design will contribute to improve the activity of MOF-based nanozymes and promote their potential applications in both biomedical and environmental fields.Therefore,a comprehensiye suminary of activity regulatory strategies of MOF-based nanozymes is urgently needed.Firstly,we summarized the activity regulatory strategies of MOFs with intrinsic enzyme-like activities via modulation of metal nodes,ligands,structures and morphologies.Then the applications of MOF-based nanozymes in biosensing,hazardous degradation,antibacterial,and cancer therapy were also introduced.Finally,the current challenges and future perspectives were discussed in depth.It is highly expected that this review will provide a better understanding on the rational design of novel high-performance MOF-based nanozymes.
基金the financial support of this work by the National Natural Science Foundation of China(No.U1904199)the Program for Science&Technology Innovation Team in Universities of Henan Province(No.21IRTSTHN004)+3 种基金the Program for Science and Technology Innovation Talents at the University of Henan Province(No.22HASTIT007)Science Foundation for Excellent Youth of Henan Province(No.212300410064)the Young Backbone Teachers in Colleges and Universities of Henan Province(No.2018GGJS119)Nanyang Normal University。
文摘In the present work,a zinc-based metal-organic framework{[Zn(ddpd)_(0.5)(bipy)_(0.5)]·H_(2)O]}_(n)(1-Zn)(where ddpd=2,5-di(2',4'-dic arboxylphenyl)-1,4-difluorobenzene,bipy=4,4-bipyridine)was synthesized by a solvothermal method.Complex 1-Zn features a threedimensional(2,4,6)-connected network with{4^2.6^2.8^2}_(2){4^4.6^6.8^5}{6}topology.Meanwhile,without the assistance of other reagents,complex 1-Zn not only exhibited an exceeded 95%photodegradation efficiency for rhodamine B(Rh B),methyl blue(MB)and methyl orange(MO)within 40 min,but also showed high stability and recyclability.In addition,free radical quenching experiments and electron spin resonance(ESR)spectroscopy verified that the main active species in the photodegradation process were·O_(2)^(-)and OH,and a more indepth degradation mechanism was further elucidated by density functional theory(DFT)calculations.
基金This work was financially supported by National Natural Science Foundation of China(No.21701083)Fok Ying-Tong Education Foundation of China(No.171064)Natural Science Foundation of Hebei Province(Nos.B2022203018,B2018203297).
文摘For several decades,the promise of implementing of lithium(Li)metal anodes for Li batteries has been a"holy grail"for researchers.Herein,we have proposed a facile design of a MOF-derived Co_(3)O_(4)nanoparticles modified nickel foam,i.e.,Co_(3)O_(4)-NF,as a 3D host to achieve a uniform infusion of the molten Li.The molten Li was uniformly absorbed on the Co_(3)O_(4)-NF host only in 10 s due to its high Li lithiophilicity.The obtained Li-Co_(3)O_(4)-NF composite electrode shows high cycling stability in symmetric cells with low voltage hysteresis even at a high current density of 5 mA/cm2.The full cells of Li-Co_(3)O_(4)-NF/LiFePO_(4)can cycle for more than 500 cycles at 2C without obvious capacity decay.SEM after cycling and in situ optical microscope results suggest that the unique 3D host structure of the Li-Co_(3)O_(4)-NF anode plays key roles on suppressing the dendrite growth and decreasing the local current inhomogeneity.We believe this work might provide a new strategy for fabricating dendrite-free Li metal anodes and facilitate practical applications in Li batteries.
基金the Hubei Provincial Department of Education Science and Technology Research Program Young Talent Project(Q20201102)the National Natural Science Foundation of China(51864042 and 51804220).
文摘Mercury(Hg)ions can lead to a serious impact on the environment;therefore,it was necessary to find an effective method for absorbing these toxic Hg ions.Here,the adsorbent(Zn-AHMT)was synthesized from zinc nitrate and 4-amino 3-hydrazine-5 mercapto-1,2,4-triazole(AHMT)by one-step method and,characterized the microstruc-ture and absorption performance by fourier transform infrared spectroscopy(FTIR),field emission scanning electron microscopy(FESEM),X-ray diffraction(XRD),Brunauer-Emmett Teller(BET),Thermal Gravimetric Analyzer(TGA)and X-ray photoelectron spectroscopy(XPS).Through a plethora of measurements,we found that the maximum adsorption capacity was 802.8 mg/g when the optimal pH of Zn-AHMT was 3.0.The isothermal and kinetic experiments confirm that the reaction process of Zn-AHMT was chemisorption,while the adsorption process conforms to the Hill model and pseudo second order kinetic model.Thermodynamic experiments showed that the adsorption process was spontaneous and exothermic.Selective experiments were performed in the simulated wastewater containing Mn,Mg,Cr,Al,Co,Ni,Hg ions.Our results showed that the Zn-AHMT has a stronger affinity for Hg ions.The removal rate of Zn-AHMT remained above 98%,indicating that the Zn-AHMT had a good stability validated by three adsorption-desorption repeatable tests.According to the XPS results,the adsorption reaction of Zn-AHMT was mainly attributed to the chelation and ion exchange.This was further explained by both density functional theory(DFT)calculation and frontier molecular orbital theory.We therefore propose the adsorption mechanism of Zn-AHMT.The adsorption reaction facilitates via the synergistic action of S and N atoms.Moreover,the bonding between the adsorbent and the N atom has been proved to be more stable.Our study demonstrated that Zn-AHMT had a promising application prospect in mercury removal.
基金the Natural Science Foundation of Shanghai(No.19ZR1403500)the National Natural Science Foundation of China(No.21373054)the Natural Science Foundation of Shanghai Science and Technology Committee(No.19DZ2270100)。
文摘Construction of metal-organic-frame works-based composite photocatalysts has attracted much attention for the reasonable band gap and high surface areas to improve the photocatalytic activity.In this study,the ternary heterojunction Pd@UiO-66-NH_(2)@ZnIn_(2)S_(4)nanocomposites were facilely prepared for the first time by a two-step method.The visible-light-promoted hydrogen production rate of 0.3%Pd@UiO-66-NH_(2)@ZnIn_(2)S_(4)reaches up to 5.26 mmol g^(-1)h^(-1),which is evidently much higher than pure UiO-66-NH_(2),ZnIn_(2)S_(4)and binary UiO-66-NH_(2)/ZnIn_(2)S_(4)composites.Such a huge improvement in the photocatalytic performance is mainly attributed to the matched band gap of ZnIn_(2)S_(4)and UiO-66-NH_(2),and the introduction of Pd NPs into photocatalysts that broaden spectral response range and promote the photon induced charge carrier separation.This work may provide a feasible approach for the design and construction of metal-organic-frameworks-based photocatalytic materials.
基金supported by the National Natural Science Foundation of China (51832004 and 51521001)the National Key Research and Development Program of China (2016YFA0202603)+2 种基金the Natural Science Foundation of Hubei Province (2019CFA001)the Programme of Introducing Talents of Discipline to Universities (B17034)the Yellow Crane Talent (Science & Technology) Program of Wuhan City。
文摘Nitrogen-doped carbon materials as promising oxygen reduction reaction(ORR) electrocatalysts attract great interest in fuel cells and metal-air batteries because of their relatively high activity, high surface area, high conductivity and low cost. To maximize their catalytic efficiency, rational design of efficient electrocatalysts with rich exposed active sites is highly desired. Besides, due to the complexity of nitrogen species, the identification of active nitrogen sites for ORR remains challenging. Herein, we develop a facile and scalable template method to construct high-concentration nitrogen-doped carbon hollow frameworks(NC), and reveal the effect of different nitrogen species on theirORRactivity on basis of experimental analysis and theoretical calculations. The formation mechanism is clearly revealed, including low-pressure vapor superassembly of thin zeolitic imidazolate framework(ZIF-8) shell on ZnO templates,in situ carbonization and template removal. The obtained NC-800 displays better ORR activity compared with other NC-700 and NC-900 samples. Our results indicate that the superior ORR activity of NC-800 is mainly attributed to its content balance of three nitrogen species. The graphitic N and pyrrolic N sites are responsible for lowering the working function, while the pyridinic N and pyrrolic N sites as possible active sites are beneficial for increasing the density of states.
基金support from National Natural Science Foundation of China(Nos.21808138,22178213 and 21773146)Fundamental Research Funds for the Central Universities(No.GK202103029)Young Talent fund of University Association for Science and Technology in Shaanxi,China(No.20200602)。
文摘Constructing molecule@support composites is an attractive strategy to realize heterogeneous molecular electrocatalysis.Herein,we synthesized metal-organic framework(MOF)-supported molecular catalysts for hydrogen evolution and oxygen reduction reaction(HER/ORR).Ligand exchange strategy was used to prepare molecule@support hybrids due to the same functional group.A series of hybrids were obtained using Co porphyrin(1)and different MOFs including MIL-88(Fe),MOF-5(NiCo)and UIO-66(Zr).The1@MOF-5(NiCo)had the best HER and ORR activity compared with 1@MIL-88(Fe)and 1@MOF-5(NiCo).These hybrids also exhibited tunable selectivity for ORR with four-electron process,which can be attributed to the synergistic effect of porphyrin molecules and MOFs.This work provides a possibility for molecular catalysts to improve activity of HER and tune selectivity of ORR.
