A sequential improvement strategy has been devised and implemented on a 3D open framework In-BQ showing 2D intersected channels filled by dimethylamine and its protonated cation constructed by-COOCH_(3)-functionalized...A sequential improvement strategy has been devised and implemented on a 3D open framework In-BQ showing 2D intersected channels filled by dimethylamine and its protonated cation constructed by-COOCH_(3)-functionalized anilicate linkers.In situ aliovalent metal substitution and post-synthetic ligand esterolysis led to Cd-BQ-COOH with a doubling of Me_(2)NH_(2)^(+)carriers and a great number of residual-COOH groups,resulting in maximum proton concentration and frequent jumping sites.As a result,the modified Cd-BQ-COOH exhibits a 300-fold enhanced value of proton conductivity compared with that of pristine In-BQ,reaching 6.06×10^(-2) S cm^(-1).MD calculations reveal that the entire process of proton transportation in Cd-BQ-COOH is achieved by the vehicle mechanism.展开更多
The high porosity,excellent water stability and optimized supramolecular host–vip interactions of MOFs are the three key factors for their potential practical applications in many important areas including gas stor...The high porosity,excellent water stability and optimized supramolecular host–vip interactions of MOFs are the three key factors for their potential practical applications in many important areas including gas storage/separation,catalysis and so on.In this study,we designed and constructed a highly porous(3,36)-connected txt-type acylamide-functionalized metal–organic framework(HNUST-8)from a pyridine-based acylamide-linking diisophthalate and dicopper(II)-paddlewheel clusters.展开更多
Herein,by using pillaring ligands with different lengths,two copper-based metal–organic frameworks,compounds 1 (Cu_(2)(bada)_(2)(dabco)) and 2 (Cu_(2)(bada)_(2)(bipy)) (bada=4,4′-carbonylbis(azanediyl)dibenzoic acid...Herein,by using pillaring ligands with different lengths,two copper-based metal–organic frameworks,compounds 1 (Cu_(2)(bada)_(2)(dabco)) and 2 (Cu_(2)(bada)_(2)(bipy)) (bada=4,4′-carbonylbis(azanediyl)dibenzoic acid,dabco=1,4-diazabicyclo[2.2.2]octane,bipy=4,4′-bipyridine) with the urea-functionalized ligand bada,have been successfully synthesized using a pillared-layer strategy.Both 1 and 2 exhibit two-dimensional square lattice (sql) layers pillared by dabco and bipy,respectively,and feature pcu topology.Different to dabco in 1,the pillaring ligand 4,4′-bipyridine with longer length forms a doubly interpenetrated structure of 2.Both compounds display good thermal stabilities and permanent porosities.1 exhibits good performance for CO_(2)(32 cm^(3) g^(-1)),C_(2)H_(6) (58 cm^(3) g^(-1)),and C_(3)H_(8) (105 cm^(3) g^(-1)) capture among MOFs without open metal sites.In particular,1 possesses high Q_st for CO_(2)(32.8 kJ mol^(-1)),C_(2)H_(6) (37.2 kJ mol^(-1)),and C_(3)H_(8) (40.3 kJ mol^(-1)) adsorption and outstanding selectivities for CO_(2)(5.7),C_(2)H_(6) (28),and C_(3)H_(8) (224) over CH_(4) at 298 K.Density functional theory (DFT)-based calculations further prove the hydrogen-bond interactions and σ–π interactions between gas molecules and urea-based ligands.2 exhibits a gate-opening behavior for N_(2),Ar and CO_(2).Compound 1 could be seen as a significant potential material for gas storage and separation.展开更多
Hydrogen spillover mechanism of metal-supported covalent-organic frameworks COF-105 is investigated by means of the density functional theory, and the effects of metal catalysts M_4（Pt_4, Pd_4, and Ni_4） on the whol...Hydrogen spillover mechanism of metal-supported covalent-organic frameworks COF-105 is investigated by means of the density functional theory, and the effects of metal catalysts M_4（Pt_4, Pd_4, and Ni_4） on the whole spillover process are systematically analyzed. These three metal catalysts exhibit several similar phenomena：（i） they prefer to deposit on the tetra（_4-dihydroxyborylphenyl） silane（TBPS） cluster with surface-contacted configuration;（ii） only the H atoms at the bridge site can migrate to 2,3,6,7,10,11-hexahydroxy triphenylene（HHTP） and TBPS surfaces, and the migration process is an endothermic reaction and not stable;（iii） the introduction of M_4 catalyst can greatly reduce the diffusion energy barrier of H atoms, which makes it easier for the H atoms to diffuse on the substrate surface. Differently, all of the H2 molecules spontaneously dissociate into H atoms onto Pt_4 and Pd_4clusters. However, the adsorbed H2 molecules on Ni_4 cluster show two types of adsorption states： one activated state with stretched H–H bond length of 0.88 ？A via the Kubas interaction and five dissociated states with separated hydrogen atoms. Among all the M_4 catalysts, the orders of the binding energy of M_4 deposited on the substrate and average chemisorption energy per H2 molecule are Pt_4〉Ni_4〉Pd_4. On the contrary, the orders of the migration and diffusion barriers of H atoms are Pt_4展开更多
As a new emerging class of highly crystalline advanced porous materials,metal–organic frameworks(MOFs)and covalent organic frameworks(COFs)have gained significant attention for photodynamic therapy(PDT)due to their s...As a new emerging class of highly crystalline advanced porous materials,metal–organic frameworks(MOFs)and covalent organic frameworks(COFs)have gained significant attention for photodynamic therapy(PDT)due to their structural regularity,inherent porosity,extensive functionality,design flexibility,and good biocompatibility.In this review,we summarize and illustrate the recent developments of MOF-and COF-based nanomedicines for PDT and its combined antitumor treatments.Furthermore,major challenges and future development prospects in this field are also discussed.展开更多
The luminescence response application in chemical sensing by metal–organic frameworks(MOFs)and their hybrid materials has been reported extensively in recent years.However,the reviews on this topic are mainly focused...The luminescence response application in chemical sensing by metal–organic frameworks(MOFs)and their hybrid materials has been reported extensively in recent years.However,the reviews on this topic are mainly focused on the sensing materials(MOFs and their functionalized hybrid materials)and analytes(all types of species).In this comprehensive review,the luminescence response mode and chemical sensing mechanism for lanthanide-functionalized MOF hybrids(abbreviated as LnFMOFH)are systematically summarized.Specifically,ten sections are subdivided,and importantly involve three main topics.Firstly,LnFMOFH and the luminescence responsive chemical sensing for these hybrids are introduced.Secondly,three single luminescence response modes,including“Turn-Off”,“Turn-On”“Turn–Off–On”and dual mode,as ratiometric luminescence(RL)for chemical sensing in LnFMOFH materials are summarized.Thirdly,some types of chemical sensing mechanisms observed in LnFMOFH materials are outlined,which involve the ligand–metal energy transfer(LMET)for the luminescence response in chemical sensing of enhanced or weakened analytes.展开更多
In light of the escalating energy crises and environmental concerns,the photocatalytic conversion of CO_(2)has emerged as a promising strategy for sustainable energy solutions[1].Since the pioneering use of TiO_(2)as ...In light of the escalating energy crises and environmental concerns,the photocatalytic conversion of CO_(2)has emerged as a promising strategy for sustainable energy solutions[1].Since the pioneering use of TiO_(2)as a photocatalyst in 1979[2],numerous inorganic semiconductors,including doped SrTiO_(3),BiVO_(4),and CdS,have been investigated for photocatalytic CO_(2)reduction reactions(CO_(2)RR)[3].展开更多
Lithium sulfur batteries(LSBs)show great promise as next-generation batteries due to their high energy density.However,commercialization is hindered by limited cycle life,fast capacity decay and poor sulfur utilizatio...Lithium sulfur batteries(LSBs)show great promise as next-generation batteries due to their high energy density.However,commercialization is hindered by limited cycle life,fast capacity decay and poor sulfur utilization,primarily due to the intricate phase evolution during battery operation and insulating characteristics of sulfur,leading to uncontrollable sulfur and polysulfide distribution and inefficient conversion kinetics.Therefore,the incorporation of metal and covalent organic frameworks(MOFs and COFs)has been widely employed in LSBs to serve as hosts,enabling the regulation of conversion and diffusion behavior of vip species,including lithium ions,sulfur and polysulfides,within their well-defined nanosized cavities.Nevertheless,pristine frameworks often fail to meet the requisite standards,and framework functionalization offers unique opportunities to tailor desired attributes and facilitate selective host-vip interactions in LSBs.However,a thorough understanding on how to precisely customize the nano-channels with functional groups to promote such interactions remains largely unexplored.In this review,we provide a systematic discussion on how the grafting of functional groups containing various active sites can play a role in host-vip chemistry,and focus on the latest advancements in engineering functionalized MOFs and COFs as charged-species regulators to tackle the problems causing poor LSB electrochemical performance.The concepts of electrophilic and nucleophilic effects are proposed,uncovering the mechanisms of framework functionalization in LSBs and serving as guidance for future developments.展开更多
Metal-organic frameworks(MOFs)have attracted considerable research attention as a new type of porous material for catalytic applications.Herein,2,5-dihydroxyterephthalic acid was proposed to replace conventional terep...Metal-organic frameworks(MOFs)have attracted considerable research attention as a new type of porous material for catalytic applications.Herein,2,5-dihydroxyterephthalic acid was proposed to replace conventional terephthalic acid and reacted with chromic nitrate nonahydrate to synthesize a functional metal–organic framework(FMIL-101).This was then used to immobilize various compound ionic liquids to prepare three ionic liquids immobilized on FMIL-101 catalysts,namely,FMIL-101-[HeMIM]Cl/(ZnBr_(2))_(2),FMIL-101-[CeMIM]Cl/(ZnBr_(2))_(2),and FMIL-101-[AeMIM]Br/(ZnBr_(2))_(2).After characterization by Fourier-transform infrared spectroscopy,X-ray diffraction,ultraviolet spectroscopy,thermogravimetry,specific surface area analysis,and scanning electron microscopy,the catalysts were used to mediate cycloaddition reactions between carbon dioxide(CO_(2))and propylene oxide.The effects of reaction temperature,reaction pressure,reaction time,and catalyst dosage on the catalytic performance were investigated.The results revealed that the FMIL-101-supported CIL catalysts afforded the target product propylene carbonate with good catalytic performance and thermal stability.The optimal catalyst,FMIL-101-[CeMIM]Cl/(ZnBr_(2))_(2),displayed a propylene oxide conversion of 98.64%and a propylene carbonate selectivity of 96.63%at a reaction temperature of 110℃,a reaction pressure of 2.0 MPa,a catalyst dosage of 2.0%relative to propylene oxide,and a reaction time of 2.5 h.In addition,the conversion and selectivity of the catalyst decreased slightly after four cycles.Additionally,the catalyst decreased slightly in catalytic performance after being recycled four times.展开更多
基金support of NSFC(21871167)1331 Project of Shanxi,Shanxi Province Science Foundation for Youths(201901D211391)+1 种基金research project supported by Shanxi Scholarship Council of China(2020-088)the Technology Innovation Team(CX201904).
文摘A sequential improvement strategy has been devised and implemented on a 3D open framework In-BQ showing 2D intersected channels filled by dimethylamine and its protonated cation constructed by-COOCH_(3)-functionalized anilicate linkers.In situ aliovalent metal substitution and post-synthetic ligand esterolysis led to Cd-BQ-COOH with a doubling of Me_(2)NH_(2)^(+)carriers and a great number of residual-COOH groups,resulting in maximum proton concentration and frequent jumping sites.As a result,the modified Cd-BQ-COOH exhibits a 300-fold enhanced value of proton conductivity compared with that of pristine In-BQ,reaching 6.06×10^(-2) S cm^(-1).MD calculations reveal that the entire process of proton transportation in Cd-BQ-COOH is achieved by the vehicle mechanism.
基金supported by the National Natural Science Foundation of China(Grant No.21401055,21371150 and 21201062)Hunan Provincial Natural Science Foundation of China(Grant No.2018JJ2113 and 2017JJ2095)State Key Laboratory of Coordination Chemistry(Grant No.SKLCC1417).
文摘The high porosity,excellent water stability and optimized supramolecular host–vip interactions of MOFs are the three key factors for their potential practical applications in many important areas including gas storage/separation,catalysis and so on.In this study,we designed and constructed a highly porous(3,36)-connected txt-type acylamide-functionalized metal–organic framework(HNUST-8)from a pyridine-based acylamide-linking diisophthalate and dicopper(II)-paddlewheel clusters.
基金supported by the National Natural Science Foundation of China(No.21771078,21671074,and 21621001)the 111 Project(B17020)the National Key Research and Development Program of China(2016YFB0701100)。
文摘Herein,by using pillaring ligands with different lengths,two copper-based metal–organic frameworks,compounds 1 (Cu_(2)(bada)_(2)(dabco)) and 2 (Cu_(2)(bada)_(2)(bipy)) (bada=4,4′-carbonylbis(azanediyl)dibenzoic acid,dabco=1,4-diazabicyclo[2.2.2]octane,bipy=4,4′-bipyridine) with the urea-functionalized ligand bada,have been successfully synthesized using a pillared-layer strategy.Both 1 and 2 exhibit two-dimensional square lattice (sql) layers pillared by dabco and bipy,respectively,and feature pcu topology.Different to dabco in 1,the pillaring ligand 4,4′-bipyridine with longer length forms a doubly interpenetrated structure of 2.Both compounds display good thermal stabilities and permanent porosities.1 exhibits good performance for CO_(2)(32 cm^(3) g^(-1)),C_(2)H_(6) (58 cm^(3) g^(-1)),and C_(3)H_(8) (105 cm^(3) g^(-1)) capture among MOFs without open metal sites.In particular,1 possesses high Q_st for CO_(2)(32.8 kJ mol^(-1)),C_(2)H_(6) (37.2 kJ mol^(-1)),and C_(3)H_(8) (40.3 kJ mol^(-1)) adsorption and outstanding selectivities for CO_(2)(5.7),C_(2)H_(6) (28),and C_(3)H_(8) (224) over CH_(4) at 298 K.Density functional theory (DFT)-based calculations further prove the hydrogen-bond interactions and σ–π interactions between gas molecules and urea-based ligands.2 exhibits a gate-opening behavior for N_(2),Ar and CO_(2).Compound 1 could be seen as a significant potential material for gas storage and separation.
基金Project supported by the National Natural Science Foundation of China(Grant Nos.11304079,11304140,11404094,and 11504088)the China National Scholarship Foundation(Grant No.201508410255)+4 种基金the Foundation for Young Core Teachers of Higher Education Institutions of Henan Province of Chinathe Foundation for Young Core Teachers of Henan University of Technology in Chinathe Korea Institute of Science and Technology(KIST)Institutional Program(Grant No.2E26291)Flag Program(Grant No.2E26300)the Research Grants of NRF funded by the National Research Foundation under the Ministry of Science,ICT&Future,Korea(Grant No.NRF-2015H1D3A1036078)
文摘Hydrogen spillover mechanism of metal-supported covalent-organic frameworks COF-105 is investigated by means of the density functional theory, and the effects of metal catalysts M_4（Pt_4, Pd_4, and Ni_4） on the whole spillover process are systematically analyzed. These three metal catalysts exhibit several similar phenomena：（i） they prefer to deposit on the tetra（_4-dihydroxyborylphenyl） silane（TBPS） cluster with surface-contacted configuration;（ii） only the H atoms at the bridge site can migrate to 2,3,6,7,10,11-hexahydroxy triphenylene（HHTP） and TBPS surfaces, and the migration process is an endothermic reaction and not stable;（iii） the introduction of M_4 catalyst can greatly reduce the diffusion energy barrier of H atoms, which makes it easier for the H atoms to diffuse on the substrate surface. Differently, all of the H2 molecules spontaneously dissociate into H atoms onto Pt_4 and Pd_4clusters. However, the adsorbed H2 molecules on Ni_4 cluster show two types of adsorption states： one activated state with stretched H–H bond length of 0.88 ？A via the Kubas interaction and five dissociated states with separated hydrogen atoms. Among all the M_4 catalysts, the orders of the binding energy of M_4 deposited on the substrate and average chemisorption energy per H2 molecule are Pt_4〉Ni_4〉Pd_4. On the contrary, the orders of the migration and diffusion barriers of H atoms are Pt_4
基金support from the NSFC(Grant No.21971153 and 21671122)Chang Jiang Scholars Program of ChinaTaishan Scholars Construction Project of Shandong Province.
文摘As a new emerging class of highly crystalline advanced porous materials,metal–organic frameworks(MOFs)and covalent organic frameworks(COFs)have gained significant attention for photodynamic therapy(PDT)due to their structural regularity,inherent porosity,extensive functionality,design flexibility,and good biocompatibility.In this review,we summarize and illustrate the recent developments of MOF-and COF-based nanomedicines for PDT and its combined antitumor treatments.Furthermore,major challenges and future development prospects in this field are also discussed.
基金supported by the National Natural Science Foundation of China(21971194).
文摘The luminescence response application in chemical sensing by metal–organic frameworks(MOFs)and their hybrid materials has been reported extensively in recent years.However,the reviews on this topic are mainly focused on the sensing materials(MOFs and their functionalized hybrid materials)and analytes(all types of species).In this comprehensive review,the luminescence response mode and chemical sensing mechanism for lanthanide-functionalized MOF hybrids(abbreviated as LnFMOFH)are systematically summarized.Specifically,ten sections are subdivided,and importantly involve three main topics.Firstly,LnFMOFH and the luminescence responsive chemical sensing for these hybrids are introduced.Secondly,three single luminescence response modes,including“Turn-Off”,“Turn-On”“Turn–Off–On”and dual mode,as ratiometric luminescence(RL)for chemical sensing in LnFMOFH materials are summarized.Thirdly,some types of chemical sensing mechanisms observed in LnFMOFH materials are outlined,which involve the ligand–metal energy transfer(LMET)for the luminescence response in chemical sensing of enhanced or weakened analytes.
基金supported by the National Key R&D Program of China(2022YFE0114800 and 2021YFA1502100)the Natural Science Foundation of Fujian Province(2024J01238)111 Project(D16008)。
文摘In light of the escalating energy crises and environmental concerns,the photocatalytic conversion of CO_(2)has emerged as a promising strategy for sustainable energy solutions[1].Since the pioneering use of TiO_(2)as a photocatalyst in 1979[2],numerous inorganic semiconductors,including doped SrTiO_(3),BiVO_(4),and CdS,have been investigated for photocatalytic CO_(2)reduction reactions(CO_(2)RR)[3].
基金supported by the Singapore Ministry of Education,and the National Research Foundation(NRF)for research conducted at the National University of Singapore(CRP NRF-CRP26-2021-0003).
文摘Lithium sulfur batteries(LSBs)show great promise as next-generation batteries due to their high energy density.However,commercialization is hindered by limited cycle life,fast capacity decay and poor sulfur utilization,primarily due to the intricate phase evolution during battery operation and insulating characteristics of sulfur,leading to uncontrollable sulfur and polysulfide distribution and inefficient conversion kinetics.Therefore,the incorporation of metal and covalent organic frameworks(MOFs and COFs)has been widely employed in LSBs to serve as hosts,enabling the regulation of conversion and diffusion behavior of vip species,including lithium ions,sulfur and polysulfides,within their well-defined nanosized cavities.Nevertheless,pristine frameworks often fail to meet the requisite standards,and framework functionalization offers unique opportunities to tailor desired attributes and facilitate selective host-vip interactions in LSBs.However,a thorough understanding on how to precisely customize the nano-channels with functional groups to promote such interactions remains largely unexplored.In this review,we provide a systematic discussion on how the grafting of functional groups containing various active sites can play a role in host-vip chemistry,and focus on the latest advancements in engineering functionalized MOFs and COFs as charged-species regulators to tackle the problems causing poor LSB electrochemical performance.The concepts of electrophilic and nucleophilic effects are proposed,uncovering the mechanisms of framework functionalization in LSBs and serving as guidance for future developments.
基金supported by the National Natural Science Foundation of China (Grant No.22278271)the Key Project of Education Department of Liaoning Province(Grant No.LZGD2020005)
文摘Metal-organic frameworks(MOFs)have attracted considerable research attention as a new type of porous material for catalytic applications.Herein,2,5-dihydroxyterephthalic acid was proposed to replace conventional terephthalic acid and reacted with chromic nitrate nonahydrate to synthesize a functional metal–organic framework(FMIL-101).This was then used to immobilize various compound ionic liquids to prepare three ionic liquids immobilized on FMIL-101 catalysts,namely,FMIL-101-[HeMIM]Cl/(ZnBr_(2))_(2),FMIL-101-[CeMIM]Cl/(ZnBr_(2))_(2),and FMIL-101-[AeMIM]Br/(ZnBr_(2))_(2).After characterization by Fourier-transform infrared spectroscopy,X-ray diffraction,ultraviolet spectroscopy,thermogravimetry,specific surface area analysis,and scanning electron microscopy,the catalysts were used to mediate cycloaddition reactions between carbon dioxide(CO_(2))and propylene oxide.The effects of reaction temperature,reaction pressure,reaction time,and catalyst dosage on the catalytic performance were investigated.The results revealed that the FMIL-101-supported CIL catalysts afforded the target product propylene carbonate with good catalytic performance and thermal stability.The optimal catalyst,FMIL-101-[CeMIM]Cl/(ZnBr_(2))_(2),displayed a propylene oxide conversion of 98.64%and a propylene carbonate selectivity of 96.63%at a reaction temperature of 110℃,a reaction pressure of 2.0 MPa,a catalyst dosage of 2.0%relative to propylene oxide,and a reaction time of 2.5 h.In addition,the conversion and selectivity of the catalyst decreased slightly after four cycles.Additionally,the catalyst decreased slightly in catalytic performance after being recycled four times.
