Metal-organic frameworks（MOFs） are a unique class of porous crystalline materials that have shown promise for a wide range of applications. MOFs have been explored as a new type of heterogeneous catalytic materials,...Metal-organic frameworks（MOFs） are a unique class of porous crystalline materials that have shown promise for a wide range of applications. MOFs have been explored as a new type of heterogeneous catalytic materials, because of their high surface area, uniform and tunable pores, facile functionalization and incorporation of catalytic active sites. The use of multi-functional sites MOF materials as catalysts for synergistic catalysis and tandem reactions has attracted increasing attention. In this review, we aim to introduce the construction of bi-or multi-functional MOF catalysts with cooperative or cascade functions via post-synthetic modification（PSM）.展开更多
A series of efficient ruthenium chloride (RuCl_3)-anchored MOF catalysts,such as RuCl_3@MIL-101 (Cr)-Sal,and RuCl_3@MIL-101 (Cr)-DPPB, have been successfully synthesized by post-synthetic modification (PSM)of the term...A series of efficient ruthenium chloride (RuCl_3)-anchored MOF catalysts,such as RuCl_3@MIL-101 (Cr)-Sal,and RuCl_3@MIL-101 (Cr)-DPPB, have been successfully synthesized by post-synthetic modification (PSM)of the terminal amino of MIL-101(Cr)-NH_2 with salicylaldehyde, 2-diphenylphosphinobenzaldehyde (DPPBde) and anchoring of Ru (Ⅲ) ions. The stronger coordination electron donor interaction between Ru (Ⅲ) ions and chelating groups in the RuCl_3@MIL-101 (Cr)-DPPB enhances its catalytic performance for CO_2 hydrogenation to formic acid. The turnover number (TON) of formic acid was up to 831 in reaction time of 2 h with dimethyl sulfoxide (DMSO) and water (H_2O) as mixed solvent, trimethylamine (Et_3N) as organic base, and PPh_3 as electronic additive.展开更多
Post-synthetic modifications(PSM)have drawn great attention as a vigoroso tool to tune or enhance the performance of metal-organic frameworks(MOFs).However,the current PSM method usually have to sacrifice the porosity...Post-synthetic modifications(PSM)have drawn great attention as a vigoroso tool to tune or enhance the performance of metal-organic frameworks(MOFs).However,the current PSM method usually have to sacrifice the porosity of MOFs to enrich their functionality,such as pore space partition(PSP)and postsynthetic elimination and insertion(PSE&I),causing a trade-off in this aspect.To address this issue,we herein propose a new PSM strategy of using the size-matching ligands as the bolts to lock MOFs'pores,which could be anchored onto open metal sites(OMSs)after vip loading through a stepwise manipulation.As a result,the loaded cargoes undergo a controlled releasing process with respect to different bolt ligands.Our proposed strategy provides a promising way to balance the functionality and porosity of MOFs.展开更多
Post-synthetic installation strategy is an effective approach to improve the functions of metal-organic frameworks(MOFs).Herein,a pair of chiral MOFs is successfully constructed through solvothermal subcomponent self-...Post-synthetic installation strategy is an effective approach to improve the functions of metal-organic frameworks(MOFs).Herein,a pair of chiral MOFs is successfully constructed through solvothermal subcomponent self-assembly and exhibit circularly polarized luminescence(CPL).These MOFs contain coordinatively unsaturated Zn sites and channels,which allow the installation of pyridyl-terminated pillars into the original structure.Such a post-synthetic installation process reinforces the MOFs'rigidity and increases the photoluminescence quantum yields(PLQYs).Furthermore,the luminescence dissymmetry factors(glum)of these post-modified MOFs are amplified after installing the pillars.This work provides an appealing strategy for boosting the CPL performance of chiral MOFs.展开更多
Metal-organic frameworks(MOFs)are a subclass of porous materials that have gained considerable at-tention recently due to their unique properties and potential applications.However,MOFs may exhibit defects affecting t...Metal-organic frameworks(MOFs)are a subclass of porous materials that have gained considerable at-tention recently due to their unique properties and potential applications.However,MOFs may exhibit defects affecting their gas separation performance,limiting their practical applications.This review arti-cle focuses on defects in MOFs and their impact on gas separation.Additionally,the reports explore the potential of De novo and post-synthetic modification(PSM)to improve the gas separation properties by tuning their defects.The PSM of MOFs is discussed in detail,including the different types of modifications and their effects on the MOF properties.Finally,the article discusses the potential of PSM for practical gas separation applications,highlighting recent examples of MOF-based membranes and adsorbents with improved gas separation performance resulting from PSM.It is strategically reasonable to have defects inside the MOFs,but why is it so fascinating in gas separation applications?In this present review,we have tried to uncover the mystery of defects.Overall,this review highlights the importance of defects in MOFs and the potential of PSM strategies to enhance their gas separation properties.展开更多
Since the early reports of MOFs and their interesting properties,research involving these materials has grown wide in scope and applications.Various synthetic approaches have ensued in view of obtaining materials with...Since the early reports of MOFs and their interesting properties,research involving these materials has grown wide in scope and applications.Various synthetic approaches have ensued in view of obtaining materials with optimised properties,the extensive scope of application spanning from energy,gas sorption,catalysis biological applications has meant exponentially evolved over the years.The far-reaching synthetic and PSM approaches and porosity control possibilities have continued to serve as a motivation for research on these materials.With respect to the biological applications,MOFs have shown promise as good candidates in applicati ons involving drug delivery,BioMOFs,sensing,imaging amongst others.Despite being a while away from successful entry into the market,observed results in sensing,drug delivery,and imaging put these materials on the spot light as candidates poised to usher in a revolution in biology.In this regard,this review article focuses current approaches in synthesis,post functionalization and biological applications of these materials with particular attention on drug delivery,imaging,sensing and BioMOFs.展开更多
Porous organic cages(POCs)have shown great potential in many applications,and post-synthetic modification(PSM)has been confirmed to be an effective strategy to tailor their structures and related functionalities.Howev...Porous organic cages(POCs)have shown great potential in many applications,and post-synthetic modification(PSM)has been confirmed to be an effective strategy to tailor their structures and related functionalities.However,it is extremely challenging to develop a general platform for simple-to-make functional POCs for advanced applications by PSM method.Herein,we reported that octahedral calix[4]resorcinarene-based hydrazone-linked porous organic cage(HPOC-401)provides an excellent platform for post-synthetic metalation by various transition metal(TM)ions under mild conditions due to the abundance of coordination sites in its skeleton.Such metalated products(HPOC-401-TM)exhibit Brunauer-Emmett-Teller(BET)surface area up to1,456 m^(2)g^(-1),much higher than that of the pristine HPOC-401,which has a BET value of 474 m^(2)g^(-1).Moreover,the metalation and porosity increases further influence their gas capture,separation,as well as catalytic performance.For instance,HPOC-401-TM products exhibit higher CO_(2),H_(2),and C2 hydrocarbon gas uptake,as well as higher C_(2)H_(6)/C_(2)H_(4) selectivity than HPOC-401.Moreover,the HPOC-401-TM also shows better catalytic performance in the cycloaddition of CO_(2) with epoxides compared to HPOC-401.These findings uncover a simple yet effective approach for modifying the porosity characteristics of organic cages,which will undoubtedly expand their future implementations.展开更多
The development of preparation methods for XOFs,as a new class of organic frameworks,plays a crucial role in shaping their structures,functions,and potential applications.In this study,we presented the construction of...The development of preparation methods for XOFs,as a new class of organic frameworks,plays a crucial role in shaping their structures,functions,and potential applications.In this study,we presented the construction of chiral supramolecular 2D halogen-bonded organic frameworks(XOFs)through a post-synthetic modification strategy.A linear halogen-bonded organic polymer(XOP),XOP-DPBA,decorated with aldehyde groups,was initially prepared to validate the feasibility of post-synthetic modification for XOF construction and functionalization.XOP-DPBA exhibited excellent reactivity with amines,forming imine bonds.By utilizing this reactivity,a series of cross-linked 2D XOFs were efficiently prepared through post-synthetic modified cross-linking reactions.Furthermore,we successfully introduced chiralα/β-cyclodextrins(α/β-CD)into the XOF skeletons via host-vip interactions,resulting in the fabrication of chiral supramolecular 2D XOFs.These chiral XOFs displayed the induced circular dichroism(ICD)signals and assembled them into helical fibers.The post-synthetic modification strategy demonstrated its versatility and simplicity for the construction and functionalization of XOFs.展开更多
Although many racemic M4L6cages have been synthesized,little attention has been paid to the resolution of M4L6cages because resolution of these cages is very difficult.To explore the use of optically pure M4L6cages in...Although many racemic M4L6cages have been synthesized,little attention has been paid to the resolution of M4L6cages because resolution of these cages is very difficult.To explore the use of optically pure M4L6cages in chiral applications,it is important to obtain a single enantiomer.In this work,the anionicΛΛΛΛ-Zr_(4)L_(6)andΛΛΛΛ-Zr_(4)L_(6)(L=embonate)cages have been completely separated by introducing chiral organic ligands R/S-BINAP and 1S,2S/1R,2R-DPEN,respectively,and the active vertex of homochiral Zr_(4)L_(6)cage trapsπ-conjugated coordination silver cations(such as[Ag_(2)(DPPM)_(2)]^(2+),chiral[Ag_(2)(PPh_(3))_(2)(DPEN)]^(2+)and[Ag(PPh_(3))(DPEN)]^(+)),obtaining two pair of pure enantiomers(PTC-375(Λ/Λ)and PTC-376(Λ/Λ)).Interestingly,the chiral resolution and surface modification of such zirconium cage endow it with homochirality and significant circularly polarized luminescence(CPL)response,and PTC-376 enantiomers show a CPL output with glumvalues up to~1.4×10^(-2).This work not only provides a new resolution strategy for metal-organic cages,but also expands their chiral application especially in CPL field.展开更多
Mixed-lanthanide(Ln) luminescent materials have important application values in ratiometric temperature sensing.Hydrogen-bonded organic frameworks(HOFs) offer a self-supporting network to conveniently tune multiple Ln...Mixed-lanthanide(Ln) luminescent materials have important application values in ratiometric temperature sensing.Hydrogen-bonded organic frameworks(HOFs) offer a self-supporting network to conveniently tune multiple Ln^(3+)ions,but challenges still exist in material design.In this work,we selected two simple organic molecules as hydrogen-bonded building blocks,which are melamine(MA) and 2,5-pyridinedicarboxylic acid(PDC) owning the suitable energy to sensitize Tb^(3+)and Eu^(3+)ions.MA assists PDC molecules to support the network in a new HOF(MA-PDC),where the abundant carboxylic groups enable Ln^(3+)ions to combine with the HOF.Based on the effective energy transfer process,the emission of Tb^(3+)and Eu^(3+)from TbxEu1-x@MA-PDC(x=0.75,0.85,0.90) shows the obvious temperature dependence,which benefits ratiometric temperature detection.Taking Tb0.85Eu0.15@MA-PDC as an example,when temperature varies from 303 to 443 K,the intensity ratio exhibits distinct S-type response based on Mott-Seitz model.It also behaves good relative sensitivity(1.03%/K at 383 K),low temperature resolution(0.059 K) and large reproducibility(>96%).This work demonstrates that functionalization of a simple-component HOF with mixed Ln^(3+)ions is a fantastic strategy to develop novel ratiometric thermometers of both low cost and good performance.展开更多
CuBi_(2)O_(4)(CBO)photocathodes hold significant promise for efficient photoelectrochemical(PEC)water splitting due to their favorable band gap and theoretical onset potential.However,their practical application is hi...CuBi_(2)O_(4)(CBO)photocathodes hold significant promise for efficient photoelectrochemical(PEC)water splitting due to their favorable band gap and theoretical onset potential.However,their practical application is hindered by poor charge separation efficiency.Herein,we introduce a characteristic in-situ solution Fe-doping strategy that markedly improves photoelectrochemical performance of CBO,doubling the photocurrent density and achieving an unprecedented 190 mV anodic shift in the onset potential.By integrating with an electrochemical oxidation post-treatment,a record incident photon-to-current efficiency(IPCE)exceeding 40% at 0.6 V vs.RHE under visible light illumination is achieved.The versatility of the doping strategy is demonstrated across CBO photocathodes synthesized by different methods with various morphologies,grain sizes,and crystallinities.Mechanistic studies reveal that the gradient distribution of Fe^(3+)ions generates an internal electric field that facilitates efficient charge separation and increases acceptor density.The strong Fe-O bonding also enhances structural stability against photoinduced corrosion.Notably,our investigation uncovers the non-temperature-dependent nature of CBO photocurrent,indicating that PEC performance enhancement primarily depends on reducing carrier recombination rather than improving bulk conductivity.This work lays the groundwork for future advancements in water splitting performance of CBO photocathodes,offering a complementary strategy to conventional methods for enhancing charge separation efficiency.展开更多
By anchoring Tb^(3+)ions on its free carboxyl groups of the nanocaged NiMOF,a dual-emission self-calibrating sensor of Tb^(3+)@NiMOF was fabricated through coordination post-synthetic modification(PSM)strategy.With Tb...By anchoring Tb^(3+)ions on its free carboxyl groups of the nanocaged NiMOF,a dual-emission self-calibrating sensor of Tb^(3+)@NiMOF was fabricated through coordination post-synthetic modification(PSM)strategy.With Tb^(3+)ions as the secondary fluorescent signal and sensing active sites,Tb^(3+)@NiMOF presents great potentials in visually and efficiently monitoring EPI in serum,with high sensitivity and selectivity,fast response,excellent recyclable,and the low detection limit(LOD,3.06 ng/mL).Furthermore,a tandem combinational logic gate based intelligent detection system was constructed to improve the practicability and convenience of epinephrine(EPI)detection in serum by comparing the light emitted colour with the series standard colour cards preset in the smartphone.This work provides a promising approach of developing metal-organic frameworks(MOFs)based self-calibrating sensors for intelligent detection of bioactive molecules.展开更多
The designed synthesis of chiral covalent organic frameworks(COFs) featuring intriguing properties is fairly scant and remains a daunting synthetic challenge.Here we develop a de novo synthesis of an enantiomeric pair...The designed synthesis of chiral covalent organic frameworks(COFs) featuring intriguing properties is fairly scant and remains a daunting synthetic challenge.Here we develop a de novo synthesis of an enantiomeric pair of 2 D hydroxyl-functionalized hydrazone-linked chiral COFs,(S)-and(R)-HthBta-OH COFs,using enantiopure 2,5-bis(2-hydroxypropoxy)terephthalohydrazide(Hth) as monomers.The fo rmation process of hydroxyl-functionalized chiral COFs was monitored using rigorous time-dependent PXRD,vibrational circular dichroism(VCD),and electronic circular dichroism(ECD) studies.Remarkably,VCD spectra indicated a unique chiral signal inversion from the positive Cotton effect of(S)-Hth monomer to the negative Cotton effect of(S)-HthBta-OH COF,which has never been reported in chiral COFs.Moreover,two unprecedented carboxyl-functionalized chiral COFs,(S)-and(R)-HthBta-COOH,were constructed by a post-synthetic modification of the corresponding hydroxyl chiral COFs with succinic anhydride.Notably,carboxyl-functionalized COFs retained homochirality and crystallinity without linker racemization and structural collapse after the chemical modification due to the chemically robust nature of pristine hydrazone-linked chiral COFs.展开更多
Metal–organic frameworks(MOFs)represent a unique class of porous materialswith tremendous potential for diverse applications.A key factor contributing totheir versatility is their ability to precisely introduce funct...Metal–organic frameworks(MOFs)represent a unique class of porous materialswith tremendous potential for diverse applications.A key factor contributing totheir versatility is their ability to precisely introduce functional groups at specificpositions within pores and crystals.This review explores two prominent strategiesfor achieving the positional functionalization of MOFs:post-synthetic ligand exchange(PSE)and MOF-on-MOF.In PSE,the existing ligands within solid-stateMOFs can be selectively replaced by the desired functional groups in solutionthrough ligand dynamics.This invasive functionalization provides a flexibleapproach to fine-tuning the surface of the MOFs with the target functionality.Conversely,MOF-on-MOF strategies are additive methodologies involving thecontrolled growth of one MOF layer onto another.The functionality of the core andshell(or surface)can be independently controlled.This review critically examinesthe examples,strengths,limitations,and applications of these strategies,emphasizingtheir significance in advancing the field of MOF functionalization andpaving the way for tailored multifunctional materials with precise and specificproperties.展开更多
The unique structure of zero-dimensional(0D)perovskite-analogues has attracted a great amount of research interest in recent years.To date,the current compositional library of 0D perovskites is largely limited to the ...The unique structure of zero-dimensional(0D)perovskite-analogues has attracted a great amount of research interest in recent years.To date,the current compositional library of 0D perovskites is largely limited to the lead-based Cs4PbX6(X=Cl,Br,and I)systems.In this work,we report a new synthesis of lead-free 0D Cs3BiX6(X=Cl,Br)perovskite-analogue nanocrystals(NCs)with a uniform cubic shape.We observe a broad photoluminescence peak centered at 390 nm for the 0D Cs3BiCl6 NCs at low temperatures.This feature originates from a self-trapped exciton mechanism.In situ thermal stability studies show that Cs3BiX6 NCs remain stable upon heating up to 200°C without crystal structural degradation.Moreover,we demonstrate that the Cs3BiX6 NCs can transform into other bismuth-based perovskite-analogues via facile anion exchange or metal ion insertion reactions.Our study presented here offers the opportunity for further understanding of the structure-property relationship of 0D perovskite-analogue materials,leading toward their future optoelectronic applications.展开更多
Safely and highly selective acetylene(C_(2)H_(2))capture is a great challenge,because of its highly explosive nature,as well as its nearly similar molecule size and boiling point toward the main impurity of carbon dio...Safely and highly selective acetylene(C_(2)H_(2))capture is a great challenge,because of its highly explosive nature,as well as its nearly similar molecule size and boiling point toward the main impurity of carbon dioxide(CO_(2)).Adsorption separation has shown a promising future.Herein,a new nanoporous coordination polymer(PCP)adsorbent with fixed and free Cu ions(termed NTU-66-Cu)was prepared through post-synthetic approach via cation exchanging from the pristine NTU-66,an anionic framework with new 3,4,6-c topology and two kinds of cages.The NTU-66-Cu shows significantly improved C_(2)H_(2)/CO_(2)selectivity from 6 to 32(v/v:1/1)or 4 to 4_(2)(v/v:1/4)at low pressure under 298 K,along with enhanced C_(2)H_(2)capacity(from 89.22to 111.53 cm^(3)·g^(-1)).More importantly,this observation was further validated by density functional theory(DFT)calculations and breakthrough experiments under continuous and dynamic conditions.Further,the excellent chemical stability enables this adsorbent to achieve recycle C_(2)H_(2)/CO_(2)separation without loss of C_(2)H_(2)capacity.展开更多
Covalent organic frameworks(COFs) have recently emerged as a new class of photocatalysts.However,integrated design is crucial to maximizing the performance of COF-incorporating photocatalytic systems.Herein,we compare...Covalent organic frameworks(COFs) have recently emerged as a new class of photocatalysts.However,integrated design is crucial to maximizing the performance of COF-incorporating photocatalytic systems.Herein,we compare two strategies of installing earth-abundant metal-based catalytic centers into the matrice of a 2 D COF named NUS-55.Compared to NUS-55(Co)prepared from the post-synthetic metalation of coordination sites within the COF,the molecular co-catalyst impregnated NUS-55/[Co(bpy)3]Cl2 achieves a seven-fold improvement in visible light-driven H2 evolution rate to 2,480 μmol g^-1h^-1,with an apparent quantum efficiency(AQE) of 1.55% at 450 nm.Our results show that the rational design of molecular anchoring sites in COFs for the introduction of catalytic metal sites can be a viable strategy for the development of highly efficient photocatalysts with enhanced stability and photocatalytic activities.展开更多
Zirconium terephthalate UiO-66 has aroused great interest in catalysis since it exhibits significant flexibility and compatibility for accommodating a high number of defects as well as exceptional thermal and chemical...Zirconium terephthalate UiO-66 has aroused great interest in catalysis since it exhibits significant flexibility and compatibility for accommodating a high number of defects as well as exceptional thermal and chemical stability.Until now,many works have focused on the modulations of the Zr6-oxo clusters in UiO-66 in terms of diverse synthesis,advanced characterizations,and their catalytic applications.To achieve high catalytic efficiency,it is still highly desired for rationally constructing and modulating the Zr6-oxo clusters with exposed catalytic sites and diverse microenvironments for advanced catalysis.In this review,we provide a comprehensive summary of recent progress on the synthesis of defective UiO-66,qualitative and quantitative characterizations,as well as a logical overview of heterogeneous catalytic applications over the past few years.Finally,the outlooks for the research paradigm of defective UiO-66 are discussed.展开更多
Porphyrinoid metal-organic frameworks(MOFs)with dual effective uranium uptake sites were synthesized through combined insitu and post-synthetic method.The MOF10@5 demonstrates the uptake amount of uranium reaches 1476...Porphyrinoid metal-organic frameworks(MOFs)with dual effective uranium uptake sites were synthesized through combined insitu and post-synthetic method.The MOF10@5 demonstrates the uptake amount of uranium reaches 1476 mg/g under visiblelight irradiation.The PN-MOF10@5 with dual uranyl uptake sites yields the amount of extracting uranyl of 1590 mg/g under visible-light irradiation.The density functional theory(DFT)calculations reveal strong interaction between uranyl and dual uranyl effective active sites.These MOFs demonstrate a powerful synthesis strategy for uranium extraction materials with dual effective active sites.展开更多
Porphyrins and their derivatives have been extensively applied in various fields owing to their photophysical and electrochemical properties.However,the drawbacks of self-aggregation and self-quenching in aqueous medi...Porphyrins and their derivatives have been extensively applied in various fields owing to their photophysical and electrochemical properties.However,the drawbacks of self-aggregation and self-quenching in aqueous media limit their biological applications.Porphyrinic metal-organic frameworks(PMOFs)have attracted considerable attention because the introduction of porphyrins as organic linker into frameworks overcomes the limitations of free porphyrins.This review summarizes the strategies for the construction of PMOFs and their biological applications.The challenges and chances displayed by this class of emerging materials are also discussed.展开更多
基金supported by the National Natural Science Foundation of China (Nos. 21371069 and 21621001)
文摘Metal-organic frameworks（MOFs） are a unique class of porous crystalline materials that have shown promise for a wide range of applications. MOFs have been explored as a new type of heterogeneous catalytic materials, because of their high surface area, uniform and tunable pores, facile functionalization and incorporation of catalytic active sites. The use of multi-functional sites MOF materials as catalysts for synergistic catalysis and tandem reactions has attracted increasing attention. In this review, we aim to introduce the construction of bi-or multi-functional MOF catalysts with cooperative or cascade functions via post-synthetic modification（PSM）.
基金Financial support from the National Natural Science Foundation of China(NSFC, Nos. 21776211, 21325626)the Program for New Century Excellent Talents in University(No. NCET-13-0411)the Program of Introducing Talents of Discipline to Universities(No. B06006)
文摘A series of efficient ruthenium chloride (RuCl_3)-anchored MOF catalysts,such as RuCl_3@MIL-101 (Cr)-Sal,and RuCl_3@MIL-101 (Cr)-DPPB, have been successfully synthesized by post-synthetic modification (PSM)of the terminal amino of MIL-101(Cr)-NH_2 with salicylaldehyde, 2-diphenylphosphinobenzaldehyde (DPPBde) and anchoring of Ru (Ⅲ) ions. The stronger coordination electron donor interaction between Ru (Ⅲ) ions and chelating groups in the RuCl_3@MIL-101 (Cr)-DPPB enhances its catalytic performance for CO_2 hydrogenation to formic acid. The turnover number (TON) of formic acid was up to 831 in reaction time of 2 h with dimethyl sulfoxide (DMSO) and water (H_2O) as mixed solvent, trimethylamine (Et_3N) as organic base, and PPh_3 as electronic additive.
基金financially supported by Natural Science Foundation of Beijing,China(No.2212006)National Natural Science Foundation of China(Nos.22171144,21501012,21806011 and 21761026)+1 种基金the Fundamental Research Funds for the Central Universities(Nankai University)High-level Teachers in Beijing Municipal Universities in the Period of 13th Five–year Plan(No.CIT&TCD201904044)。
文摘Post-synthetic modifications(PSM)have drawn great attention as a vigoroso tool to tune or enhance the performance of metal-organic frameworks(MOFs).However,the current PSM method usually have to sacrifice the porosity of MOFs to enrich their functionality,such as pore space partition(PSP)and postsynthetic elimination and insertion(PSE&I),causing a trade-off in this aspect.To address this issue,we herein propose a new PSM strategy of using the size-matching ligands as the bolts to lock MOFs'pores,which could be anchored onto open metal sites(OMSs)after vip loading through a stepwise manipulation.As a result,the loaded cargoes undergo a controlled releasing process with respect to different bolt ligands.Our proposed strategy provides a promising way to balance the functionality and porosity of MOFs.
基金financially supported by the National Natural Science Foundation of China(Nos.21731002,21871172,21975104,22171106,22301103,22375075,and 82227802)the Guangdong Major Project of Basic and Applied Research(No.2019B030302009)+4 种基金Guangdong Natural Science Foundation(No.2022A1515011937)the Guangzhou Science and Technology Program(Nos.202002030411,202201020022)Guangdong Basic and Applied Basic Research Foundation(No.2022A1515110523)the China Postdoctoral Science Foundation(Nos.2023T160269,2023M741374)Jinan University。
文摘Post-synthetic installation strategy is an effective approach to improve the functions of metal-organic frameworks(MOFs).Herein,a pair of chiral MOFs is successfully constructed through solvothermal subcomponent self-assembly and exhibit circularly polarized luminescence(CPL).These MOFs contain coordinatively unsaturated Zn sites and channels,which allow the installation of pyridyl-terminated pillars into the original structure.Such a post-synthetic installation process reinforces the MOFs'rigidity and increases the photoluminescence quantum yields(PLQYs).Furthermore,the luminescence dissymmetry factors(glum)of these post-modified MOFs are amplified after installing the pillars.This work provides an appealing strategy for boosting the CPL performance of chiral MOFs.
基金support through the National Research Foundation of Korea(NRF)grant funded by the Ko-rean government(MSIT)(Nos.NRF-2022R1C1C1003313 and NRF-2020M3H4A3106356)supported by the Technology Innovation Program(No.20010846)+2 种基金funded by the Ministry of Trade,Industry&Energy(MOTIE,Korea)supported by the“Regional Innovation Strategy(RIS)”through the National Research Foundation of Korea(NRF)funded by the Ministry of Education(MOE)(No.2023RIS-007)support through the Korea Environ-ment Industry&Technology Institute,funded by the Korea Ministry。
文摘Metal-organic frameworks(MOFs)are a subclass of porous materials that have gained considerable at-tention recently due to their unique properties and potential applications.However,MOFs may exhibit defects affecting their gas separation performance,limiting their practical applications.This review arti-cle focuses on defects in MOFs and their impact on gas separation.Additionally,the reports explore the potential of De novo and post-synthetic modification(PSM)to improve the gas separation properties by tuning their defects.The PSM of MOFs is discussed in detail,including the different types of modifications and their effects on the MOF properties.Finally,the article discusses the potential of PSM for practical gas separation applications,highlighting recent examples of MOF-based membranes and adsorbents with improved gas separation performance resulting from PSM.It is strategically reasonable to have defects inside the MOFs,but why is it so fascinating in gas separation applications?In this present review,we have tried to uncover the mystery of defects.Overall,this review highlights the importance of defects in MOFs and the potential of PSM strategies to enhance their gas separation properties.
文摘Since the early reports of MOFs and their interesting properties,research involving these materials has grown wide in scope and applications.Various synthetic approaches have ensued in view of obtaining materials with optimised properties,the extensive scope of application spanning from energy,gas sorption,catalysis biological applications has meant exponentially evolved over the years.The far-reaching synthetic and PSM approaches and porosity control possibilities have continued to serve as a motivation for research on these materials.With respect to the biological applications,MOFs have shown promise as good candidates in applicati ons involving drug delivery,BioMOFs,sensing,imaging amongst others.Despite being a while away from successful entry into the market,observed results in sensing,drug delivery,and imaging put these materials on the spot light as candidates poised to usher in a revolution in biology.In this regard,this review article focuses current approaches in synthesis,post functionalization and biological applications of these materials with particular attention on drug delivery,imaging,sensing and BioMOFs.
基金supported by the National Natural Science Foundation of China(22071244)the Youth Innovation Promotion Association CAS(2022305)+1 种基金the Natural Science Foundation of Fujian Province of China(2022J01503,2020J05087)the China Postdoctoral Science Foundation(2020M671954)。
文摘Porous organic cages(POCs)have shown great potential in many applications,and post-synthetic modification(PSM)has been confirmed to be an effective strategy to tailor their structures and related functionalities.However,it is extremely challenging to develop a general platform for simple-to-make functional POCs for advanced applications by PSM method.Herein,we reported that octahedral calix[4]resorcinarene-based hydrazone-linked porous organic cage(HPOC-401)provides an excellent platform for post-synthetic metalation by various transition metal(TM)ions under mild conditions due to the abundance of coordination sites in its skeleton.Such metalated products(HPOC-401-TM)exhibit Brunauer-Emmett-Teller(BET)surface area up to1,456 m^(2)g^(-1),much higher than that of the pristine HPOC-401,which has a BET value of 474 m^(2)g^(-1).Moreover,the metalation and porosity increases further influence their gas capture,separation,as well as catalytic performance.For instance,HPOC-401-TM products exhibit higher CO_(2),H_(2),and C2 hydrocarbon gas uptake,as well as higher C_(2)H_(6)/C_(2)H_(4) selectivity than HPOC-401.Moreover,the HPOC-401-TM also shows better catalytic performance in the cycloaddition of CO_(2) with epoxides compared to HPOC-401.These findings uncover a simple yet effective approach for modifying the porosity characteristics of organic cages,which will undoubtedly expand their future implementations.
基金supported by the National Natural Science Foundation of China(22371218,21702153,21801194)the Wuhan Science and Technology Bureau(whkxjsj009)+1 种基金the support of the Core Facility of Wuhan Universitythe Large-scale Instrument and Equipment Sharing Foundation of Wuhan University。
文摘The development of preparation methods for XOFs,as a new class of organic frameworks,plays a crucial role in shaping their structures,functions,and potential applications.In this study,we presented the construction of chiral supramolecular 2D halogen-bonded organic frameworks(XOFs)through a post-synthetic modification strategy.A linear halogen-bonded organic polymer(XOP),XOP-DPBA,decorated with aldehyde groups,was initially prepared to validate the feasibility of post-synthetic modification for XOF construction and functionalization.XOP-DPBA exhibited excellent reactivity with amines,forming imine bonds.By utilizing this reactivity,a series of cross-linked 2D XOFs were efficiently prepared through post-synthetic modified cross-linking reactions.Furthermore,we successfully introduced chiralα/β-cyclodextrins(α/β-CD)into the XOF skeletons via host-vip interactions,resulting in the fabrication of chiral supramolecular 2D XOFs.These chiral XOFs displayed the induced circular dichroism(ICD)signals and assembled them into helical fibers.The post-synthetic modification strategy demonstrated its versatility and simplicity for the construction and functionalization of XOFs.
基金supported by the National Natural Science Foundation of China(Nos.92261108 and 2022YFA1503303)the STS Project of Fujian-CAS(No.2023T3054)。
文摘Although many racemic M4L6cages have been synthesized,little attention has been paid to the resolution of M4L6cages because resolution of these cages is very difficult.To explore the use of optically pure M4L6cages in chiral applications,it is important to obtain a single enantiomer.In this work,the anionicΛΛΛΛ-Zr_(4)L_(6)andΛΛΛΛ-Zr_(4)L_(6)(L=embonate)cages have been completely separated by introducing chiral organic ligands R/S-BINAP and 1S,2S/1R,2R-DPEN,respectively,and the active vertex of homochiral Zr_(4)L_(6)cage trapsπ-conjugated coordination silver cations(such as[Ag_(2)(DPPM)_(2)]^(2+),chiral[Ag_(2)(PPh_(3))_(2)(DPEN)]^(2+)and[Ag(PPh_(3))(DPEN)]^(+)),obtaining two pair of pure enantiomers(PTC-375(Λ/Λ)and PTC-376(Λ/Λ)).Interestingly,the chiral resolution and surface modification of such zirconium cage endow it with homochirality and significant circularly polarized luminescence(CPL)response,and PTC-376 enantiomers show a CPL output with glumvalues up to~1.4×10^(-2).This work not only provides a new resolution strategy for metal-organic cages,but also expands their chiral application especially in CPL field.
基金Project supported by the Zhejiang Provincial Natural Science Foundation of China (LY24E020005)Industrial Key Projects of Jinhua City(2023-1-090)。
文摘Mixed-lanthanide(Ln) luminescent materials have important application values in ratiometric temperature sensing.Hydrogen-bonded organic frameworks(HOFs) offer a self-supporting network to conveniently tune multiple Ln^(3+)ions,but challenges still exist in material design.In this work,we selected two simple organic molecules as hydrogen-bonded building blocks,which are melamine(MA) and 2,5-pyridinedicarboxylic acid(PDC) owning the suitable energy to sensitize Tb^(3+)and Eu^(3+)ions.MA assists PDC molecules to support the network in a new HOF(MA-PDC),where the abundant carboxylic groups enable Ln^(3+)ions to combine with the HOF.Based on the effective energy transfer process,the emission of Tb^(3+)and Eu^(3+)from TbxEu1-x@MA-PDC(x=0.75,0.85,0.90) shows the obvious temperature dependence,which benefits ratiometric temperature detection.Taking Tb0.85Eu0.15@MA-PDC as an example,when temperature varies from 303 to 443 K,the intensity ratio exhibits distinct S-type response based on Mott-Seitz model.It also behaves good relative sensitivity(1.03%/K at 383 K),low temperature resolution(0.059 K) and large reproducibility(>96%).This work demonstrates that functionalization of a simple-component HOF with mixed Ln^(3+)ions is a fantastic strategy to develop novel ratiometric thermometers of both low cost and good performance.
基金financial support by the National Natural Science Foundation of China(NSFC,Grant No.22379153 and 22109128)the Ningbo Key Research and Development Project(2023Z147)the Ningbo 3315 Program。
文摘CuBi_(2)O_(4)(CBO)photocathodes hold significant promise for efficient photoelectrochemical(PEC)water splitting due to their favorable band gap and theoretical onset potential.However,their practical application is hindered by poor charge separation efficiency.Herein,we introduce a characteristic in-situ solution Fe-doping strategy that markedly improves photoelectrochemical performance of CBO,doubling the photocurrent density and achieving an unprecedented 190 mV anodic shift in the onset potential.By integrating with an electrochemical oxidation post-treatment,a record incident photon-to-current efficiency(IPCE)exceeding 40% at 0.6 V vs.RHE under visible light illumination is achieved.The versatility of the doping strategy is demonstrated across CBO photocathodes synthesized by different methods with various morphologies,grain sizes,and crystallinities.Mechanistic studies reveal that the gradient distribution of Fe^(3+)ions generates an internal electric field that facilitates efficient charge separation and increases acceptor density.The strong Fe-O bonding also enhances structural stability against photoinduced corrosion.Notably,our investigation uncovers the non-temperature-dependent nature of CBO photocurrent,indicating that PEC performance enhancement primarily depends on reducing carrier recombination rather than improving bulk conductivity.This work lays the groundwork for future advancements in water splitting performance of CBO photocathodes,offering a complementary strategy to conventional methods for enhancing charge separation efficiency.
基金Project supported by the National Natural Science Foundation of China(21801230,21905255)Natural Science Foundation of Shanxi Province(202203021211090)+2 种基金Young Academic Leader Supported Program of North University of China(QX201904)Shanxi Key Laboratory of Advanced Carbon Electrode Materials(202104010910019)The Key Laboratory Research Foundation of North University of China。
文摘By anchoring Tb^(3+)ions on its free carboxyl groups of the nanocaged NiMOF,a dual-emission self-calibrating sensor of Tb^(3+)@NiMOF was fabricated through coordination post-synthetic modification(PSM)strategy.With Tb^(3+)ions as the secondary fluorescent signal and sensing active sites,Tb^(3+)@NiMOF presents great potentials in visually and efficiently monitoring EPI in serum,with high sensitivity and selectivity,fast response,excellent recyclable,and the low detection limit(LOD,3.06 ng/mL).Furthermore,a tandem combinational logic gate based intelligent detection system was constructed to improve the practicability and convenience of epinephrine(EPI)detection in serum by comparing the light emitted colour with the series standard colour cards preset in the smartphone.This work provides a promising approach of developing metal-organic frameworks(MOFs)based self-calibrating sensors for intelligent detection of bioactive molecules.
基金We are grateful for the financial support from the National Natural Science Foundation of China(Nos.21603076 and 21571070)the Natural Science Foundation of Guangdong Province(No.2018A030313193).
文摘The designed synthesis of chiral covalent organic frameworks(COFs) featuring intriguing properties is fairly scant and remains a daunting synthetic challenge.Here we develop a de novo synthesis of an enantiomeric pair of 2 D hydroxyl-functionalized hydrazone-linked chiral COFs,(S)-and(R)-HthBta-OH COFs,using enantiopure 2,5-bis(2-hydroxypropoxy)terephthalohydrazide(Hth) as monomers.The fo rmation process of hydroxyl-functionalized chiral COFs was monitored using rigorous time-dependent PXRD,vibrational circular dichroism(VCD),and electronic circular dichroism(ECD) studies.Remarkably,VCD spectra indicated a unique chiral signal inversion from the positive Cotton effect of(S)-Hth monomer to the negative Cotton effect of(S)-HthBta-OH COF,which has never been reported in chiral COFs.Moreover,two unprecedented carboxyl-functionalized chiral COFs,(S)-and(R)-HthBta-COOH,were constructed by a post-synthetic modification of the corresponding hydroxyl chiral COFs with succinic anhydride.Notably,carboxyl-functionalized COFs retained homochirality and crystallinity without linker racemization and structural collapse after the chemical modification due to the chemically robust nature of pristine hydrazone-linked chiral COFs.
基金supported by the National Research Foundation of Korea(NRF)funded by the Ministry of Science and ICT(2022R1A2C1009706).
文摘Metal–organic frameworks(MOFs)represent a unique class of porous materialswith tremendous potential for diverse applications.A key factor contributing totheir versatility is their ability to precisely introduce functional groups at specificpositions within pores and crystals.This review explores two prominent strategiesfor achieving the positional functionalization of MOFs:post-synthetic ligand exchange(PSE)and MOF-on-MOF.In PSE,the existing ligands within solid-stateMOFs can be selectively replaced by the desired functional groups in solutionthrough ligand dynamics.This invasive functionalization provides a flexibleapproach to fine-tuning the surface of the MOFs with the target functionality.Conversely,MOF-on-MOF strategies are additive methodologies involving thecontrolled growth of one MOF layer onto another.The functionality of the core andshell(or surface)can be independently controlled.This review critically examinesthe examples,strengths,limitations,and applications of these strategies,emphasizingtheir significance in advancing the field of MOF functionalization andpaving the way for tailored multifunctional materials with precise and specificproperties.
基金support from Brown University startup funds and the National Science Foundation(OIA-1538893)K.H.-K.is supported by the U.S.Department of Education GAANN research fellowship(P200A150037)。
文摘The unique structure of zero-dimensional(0D)perovskite-analogues has attracted a great amount of research interest in recent years.To date,the current compositional library of 0D perovskites is largely limited to the lead-based Cs4PbX6(X=Cl,Br,and I)systems.In this work,we report a new synthesis of lead-free 0D Cs3BiX6(X=Cl,Br)perovskite-analogue nanocrystals(NCs)with a uniform cubic shape.We observe a broad photoluminescence peak centered at 390 nm for the 0D Cs3BiCl6 NCs at low temperatures.This feature originates from a self-trapped exciton mechanism.In situ thermal stability studies show that Cs3BiX6 NCs remain stable upon heating up to 200°C without crystal structural degradation.Moreover,we demonstrate that the Cs3BiX6 NCs can transform into other bismuth-based perovskite-analogues via facile anion exchange or metal ion insertion reactions.Our study presented here offers the opportunity for further understanding of the structure-property relationship of 0D perovskite-analogue materials,leading toward their future optoelectronic applications.
基金the National Natural Science Foundation of China(No.21671102,21973029)the Innovative Research Team Program by the Ministry of Education of China(No.IRT-17R54)+2 种基金the Hunan Provincial Natural Science Foundation of China(No.2020JJ4290)the Young and Middle-aged Academic Leader of Jiangsu Provincial Blue Project,the Six Talent Peaks Project in Jiangsu Province(No.JY-030)the State Key Laboratory of Materials-Oriented Chemical Engineering(No.ZK201803).We also thank Prof.M.O’Keeffe and Prof.M.Li for valuable suggestion on topology analysis.
文摘Safely and highly selective acetylene(C_(2)H_(2))capture is a great challenge,because of its highly explosive nature,as well as its nearly similar molecule size and boiling point toward the main impurity of carbon dioxide(CO_(2)).Adsorption separation has shown a promising future.Herein,a new nanoporous coordination polymer(PCP)adsorbent with fixed and free Cu ions(termed NTU-66-Cu)was prepared through post-synthetic approach via cation exchanging from the pristine NTU-66,an anionic framework with new 3,4,6-c topology and two kinds of cages.The NTU-66-Cu shows significantly improved C_(2)H_(2)/CO_(2)selectivity from 6 to 32(v/v:1/1)or 4 to 4_(2)(v/v:1/4)at low pressure under 298 K,along with enhanced C_(2)H_(2)capacity(from 89.22to 111.53 cm^(3)·g^(-1)).More importantly,this observation was further validated by density functional theory(DFT)calculations and breakthrough experiments under continuous and dynamic conditions.Further,the excellent chemical stability enables this adsorbent to achieve recycle C_(2)H_(2)/CO_(2)separation without loss of C_(2)H_(2)capacity.
基金supported by the National Research Foundation of Singapore(NRF2018-NRF-ANR007 POCEMON)the Ministry of Education-Singapore(MOE AcRF Tier 1 R-279-000-540-114,Tier 2 MOE2018-T2-2-148)+1 种基金the Agency for Science,Technology and Research(IRG A1783c0015,IAF-PP A1789a0024)the Jiangsu Overseas Visiting Scholar Program for University Prominent Young&Middle-Aged Teachers and Presidents
文摘Covalent organic frameworks(COFs) have recently emerged as a new class of photocatalysts.However,integrated design is crucial to maximizing the performance of COF-incorporating photocatalytic systems.Herein,we compare two strategies of installing earth-abundant metal-based catalytic centers into the matrice of a 2 D COF named NUS-55.Compared to NUS-55(Co)prepared from the post-synthetic metalation of coordination sites within the COF,the molecular co-catalyst impregnated NUS-55/[Co(bpy)3]Cl2 achieves a seven-fold improvement in visible light-driven H2 evolution rate to 2,480 μmol g^-1h^-1,with an apparent quantum efficiency(AQE) of 1.55% at 450 nm.Our results show that the rational design of molecular anchoring sites in COFs for the introduction of catalytic metal sites can be a viable strategy for the development of highly efficient photocatalysts with enhanced stability and photocatalytic activities.
基金the National Key Research and Development Program of China(No.2021YFA1500403,G.D.L.,Nos.2021YFA1200302 and 2022YFA1205400,Z.Y.T.)Strategic Priority Research Program of Chinese Academy of Sciences(No.XDB36000000,Z.Y.T.and G.D.L.)+1 种基金National Natural Science Foundation of China(Nos.92356304 and 92056204,Z.Y.T.,Nos.52372079 and 22173024,G.D.L.,No.52003066,L.C.)Youth Innovation Promotion Association of CAS(G.D.L.).
文摘Zirconium terephthalate UiO-66 has aroused great interest in catalysis since it exhibits significant flexibility and compatibility for accommodating a high number of defects as well as exceptional thermal and chemical stability.Until now,many works have focused on the modulations of the Zr6-oxo clusters in UiO-66 in terms of diverse synthesis,advanced characterizations,and their catalytic applications.To achieve high catalytic efficiency,it is still highly desired for rationally constructing and modulating the Zr6-oxo clusters with exposed catalytic sites and diverse microenvironments for advanced catalysis.In this review,we provide a comprehensive summary of recent progress on the synthesis of defective UiO-66,qualitative and quantitative characterizations,as well as a logical overview of heterogeneous catalytic applications over the past few years.Finally,the outlooks for the research paradigm of defective UiO-66 are discussed.
基金supported by the National Natural Science Foundation of China(No.22301108)the Project Startup Foundation for Distinguished Scholars of Jiangsu University(No.4111310026).
文摘Porphyrinoid metal-organic frameworks(MOFs)with dual effective uranium uptake sites were synthesized through combined insitu and post-synthetic method.The MOF10@5 demonstrates the uptake amount of uranium reaches 1476 mg/g under visiblelight irradiation.The PN-MOF10@5 with dual uranyl uptake sites yields the amount of extracting uranyl of 1590 mg/g under visible-light irradiation.The density functional theory(DFT)calculations reveal strong interaction between uranyl and dual uranyl effective active sites.These MOFs demonstrate a powerful synthesis strategy for uranium extraction materials with dual effective active sites.
基金National Natural Science Foundation of China(21934002)Fundamental Research Funds for the Central Universities(JUSRP121005)Collaborative Innovation Center of Food Safety and Quality Control in Jiangsu Province.
文摘Porphyrins and their derivatives have been extensively applied in various fields owing to their photophysical and electrochemical properties.However,the drawbacks of self-aggregation and self-quenching in aqueous media limit their biological applications.Porphyrinic metal-organic frameworks(PMOFs)have attracted considerable attention because the introduction of porphyrins as organic linker into frameworks overcomes the limitations of free porphyrins.This review summarizes the strategies for the construction of PMOFs and their biological applications.The challenges and chances displayed by this class of emerging materials are also discussed.
