The combination of nano sizes,large pore sizes and green synthesis is recognized as one of the most crucial and challenging problems in constructing metal-organic frameworks(MOFs).Herein,a water-based strategy is prop...The combination of nano sizes,large pore sizes and green synthesis is recognized as one of the most crucial and challenging problems in constructing metal-organic frameworks(MOFs).Herein,a water-based strategy is proposed for the synthesis of nanoscale hierarchical MOFs(NH-MOFs)with high crystallinity and excellent stability.This approach allows the morphology and porosity of MOFs to be fine tuned,thereby enabling the nanoscale crystal generation and a well-defined hierarchical system.The aqueous solution facilitates rapid nucleation kinetics,and the introduced modulator acts as a deprotonation agent to accelerate the deprotonation of the organic ligand as well as a structure-directing agent(SDA)to guide the formation of hierarchical networks.The assynthesized NH-MOFs(NH-ZIF-67)were assessed as efficient adsorbents and heterogeneous catalysts to facilitate the diffusion of guest molecules,outperforming the parent microZIF-67.This study focuses on understanding the NH-MOF growth rules,which could allow tailor-designing NH-MOFs for various functions.展开更多
Exploring electrode materials with attractive specific capacity and prominent cyclic durability is of the essence for promoting lithium ion batteries(LIBs).In2O3 has shown an extraordinary promise for LIBs with advant...Exploring electrode materials with attractive specific capacity and prominent cyclic durability is of the essence for promoting lithium ion batteries(LIBs).In2O3 has shown an extraordinary promise for LIBs with advantageous gravimetric capacity(theoretically 965 mA h g-1) and low working voltage.However,In2O3 still suffers from the inherent weaknesses of metal oxides in practical application,especially low conductivity and incorrigible volume expansion upon the cycling process.Here,we demonstrate the architecture of metal-organic framework(MOF)-derived In2O3 nanocrystals/hierarchically porous nitrogen-doped carbon composite(In2O3/HPNC) for ultra-stable LIBs anode.This hierarchically porous structure(micro/meso/macro-pores) with nitrogen doping not only ensures exceptional mechanical strength and accommodates the volume expansion of In2O3 nanocrystals,but also offers electrons and lithium ions efficient interpenetrating pathways to migrate rapidly during charge/discharge processes.Thus,In2O3/HPNC exhibits excellent cyclic stability with a high specific capacity of 623 mA h g-1 over2000 cycles at 1000 mA g-1,corresponding to an ultra-low specific capacity decay of 0.017% per cycle(the best among the ln203-based anode for LIBs),and outstanding rate performance,suggesting a critical step toward achieving long-life and high-rate LIBs in practical devices.展开更多
Introduction of multiple pore size regimes into metalorganic frameworks(MOFs)to form hierarchical porous structures can lead to improved performance of the material in various applications.In many cases,where interact...Introduction of multiple pore size regimes into metalorganic frameworks(MOFs)to form hierarchical porous structures can lead to improved performance of the material in various applications.In many cases,where interactions with bulky molecules are involved,enlarging the pore size of typically microporous MOF adsorbents or MOF catalysts is crucial for enhancing both mass transfer and molecular accessibility.In this review,we examine the range of synthetic strategies which have been reported thus far to prepare hierarchical MOFs or MOF composites with added macroporosity.These fabrication techniques can be either pre-or post-synthetic and include using hard or soft structural template agents,defect formation,routes involving supercritical CO2,and 3D printing.We also discuss potential applications and some of the challenges involved with current techniques,which must be addressed if any of these approaches are to be taken forward for industrial applications.展开更多
Developing advanced oxygen reduction reaction(ORR)electrocatalysts with rapid mass/electron transport as well as conducting relevant kinetics investigations is essential for energy technologies,but both still face ong...Developing advanced oxygen reduction reaction(ORR)electrocatalysts with rapid mass/electron transport as well as conducting relevant kinetics investigations is essential for energy technologies,but both still face ongoing challenges.Herein,a facile approach was reported for achieving the highly dispersed Co nanoparticles anchored hierarchically porous N-doped carbon fibers(Co@N-HPCFs),which were assembled by core-shell MOFs-derived hollow polyhedrons.Notably,the unique one-dimensional(1D)carbon fibers with hierarchical porosity can effectively improve the exposure of active sites and facilitate the electron transfer and mass transfer,resulting in the enhanced reaction kinetics.As a result,the ORR performance of the optimal Co@N-HPCF catalysts remarkably outperforms that of commercial Pt/C in alkaline solution,reaching a limited diffusion current density(J)of 5.85 m A cm^(-2)and a half-wave potential(E_(1/2))of 0.831 V.Particularly,the prepared Co@N-HPCF catalysts can be used as an excellent air-cathode for liquid/solid-state Zn-air batteries,exhibiting great potentiality in portable/wearable energy devices.Furthermore,the reaction kinetic during ORR process is deeply explored by finite element simulation,so as to intuitively grasp the kinetic control region,diffusion control region,and mixing control region of the ORR process,and accurately obtain the relevant kinetic parameters.This work offers an effective strategy and a reliable theoretical basis for the engineering of first-class ORR electrocatalysts with fast electronic/mass transport.展开更多
Heat treatment of metal-organic frameworks(MOFs)has provided a wide variety of functional carbons coordinated with metal compounds.In this study,two kinds of zinc-based MOF(ZMOF),C_(16)H_(10)O_(4)Zn(ZMOF1)and C_(8)H_(...Heat treatment of metal-organic frameworks(MOFs)has provided a wide variety of functional carbons coordinated with metal compounds.In this study,two kinds of zinc-based MOF(ZMOF),C_(16)H_(10)O_(4)Zn(ZMOF1)and C_(8)H_(4)O_(4)Zn(ZMOF2),were prepared.ZMOF1 and ZMOF2 were carbonized at 1000℃,forming CZMOF1 and CZMOF2,respectively.The specific surface area(S_(BET))of CZMOF2 was~2700 m^(2)g^(−1),much higher than that of CZMOF1(~1300 m^(2)g^(−1)).A supercapacitor electrode based on CZMOF2 achieved specific capacitances of 360,278,and 221 F g^(−1)at 50,250,and 1000 mA g^(−1)in an aqueous electrolyte(H2SO_(4)),respectively,the highest values reported to date for ZMOF-derived electrodes under identical conditions.The practical applicability of the CZMOF-based supercapacitor was verified in non-aqueous electrolytes.The initial capacitance retention was 78%after 100000 charge/discharge cycles at 10 A g^(−1).Crucially,the high capacitance of CZMOF2 arises from pore generation during carbonization.Below 1000℃,pore generation is dominated by the Zn/C ratio of ZMOFs,as carbon atoms reduce the zinc oxides formed during carbonization.Above 1000℃,a high O/C ratio becomes essential for pore generation because the oxygen functional groups are pyrolyzed.These findings will provide insightful information for other metal-based MOFderived multifunctional carbons.展开更多
The development of microwave absorption materials(MAMs) is a considerable important topic because our living space is crowed with electromagnetic wave which threatens human’s health.And MAMs are also used in radar st...The development of microwave absorption materials(MAMs) is a considerable important topic because our living space is crowed with electromagnetic wave which threatens human’s health.And MAMs are also used in radar stealth for protecting the weapons from being detected.Many nanomaterials were studied as MAMs,but not all of them have the satisfactory performance.Recently,metal-organic frameworks(MOFs) have attracted tremendous attention owing to their tunable chemical structures,diverse properties,large specific surface area and uniform pore distribution.MOF can transform to porous carbon(PC) which is decorated with metal species at appropriate pyrolysis temperature.However,the loss mechanism of pure MOF-derived PC is often relatively simple.In order to further improve the MA performance,the MOFs coupled with other loss materials are a widely studied method.In this review,we summarize the theories of MA,the progress of different MOF-derived PC-based MAMs,tunable chemical structures incorporated with dielectric loss or magnetic loss materials.The different MA performance and mechanisms are discussed in detail.Finally,the shortcomings,challenges and perspectives of MOF-derived PC-based MAMs are also presented.We hope this review could provide a new insight to design and fabricate MOF-derived PC-based MAMs with better fundamental understanding and practical application.展开更多
Nanoscale hierarchically porous metal–organic frameworks(NHP-MOFs)have received unprecedented attention in many fields owing to their integration of the strengths of nanoscale size(<1μm)and hierarchical porous st...Nanoscale hierarchically porous metal–organic frameworks(NHP-MOFs)have received unprecedented attention in many fields owing to their integration of the strengths of nanoscale size(<1μm)and hierarchical porous structure(micro-,meso-and/or macro-pores)of MOFs.This review focuses on recent advances in the main synthetic strategies for NHP-MOFs based on different metal ions(e.g.,Cu,Fe,Co,Zn,Al,Zr,and Cr),including the template method,composite technology,post-synthetic modification,in situ growth and the grind method.In addition,the mechanisms of synthesis,regulation techniques and the advantages and disadvantages of various methods are discussed.Finally,the challenges and prospects of the commercialisation of promising NHP-MOFs are also presented.The purpose of this review is to provide a road map for future design and development of NHP-MOFs for practical application.展开更多
Hierarchical porous TiOnanopills were synthesized using a titanium metal-organic framework MIL-125(Ti) as precursor. The as-synthesized TiOnanopills owned a large specific surface area of 102 m/g and unique porous s...Hierarchical porous TiOnanopills were synthesized using a titanium metal-organic framework MIL-125(Ti) as precursor. The as-synthesized TiOnanopills owned a large specific surface area of 102 m/g and unique porous structure. Furthermore, the obtained TiOnanopills were applied as anode materials for Na-ion batteries for the first time. The as-synthesized TiOnanopills achieved a high discharge capacity of 196.4 m Ah/g at a current density of 0.1 A/g. A discharge capacity of 115.9 m Ah/g was obtained at a high current density of 0.5 A/g and the capacity retention was remained as high as 90% even after 3000 cycles. The excellent electrochemical performance can be attributed to its unique hierarchical porous feature.展开更多
Increasing the mass diffusion efficiency is a major challenge in the realm of metal-organic frameworks(MOFs).Construction of hierarchically porous,typically microporous MOF adsorbents or catalysts is crucial for enhan...Increasing the mass diffusion efficiency is a major challenge in the realm of metal-organic frameworks(MOFs).Construction of hierarchically porous,typically microporous MOF adsorbents or catalysts is crucial for enhancing both mass transfer and molecular accessibility.Many strategies have been proposed for the synthesis of hierarchically porous MOFs(HP-MOFs),with some striking results.In this paper,we proposed a facile and versatile strategy,termed the MOF-Template strategy,for fabricating hierarchical pores in MOF particle.The highly controlled crystalline sizes and morphologies of the unstable Cu-MOFs Cu_(3)(BTC)_(2) and Cu(Qc)_(2) have been exploited in their utilization as sacrificial agents by uniformly dispersing them during the shaping process of ZIF-8.Through a facile treatment with alkaline solution,tunable mesopores and macropores could be easily introduced in the shaped ZIF-8 spheres.This strategy could effectively improve the adsorption kinetics and separation productivity of MOF materials while maintaining high mechanical stability,offering promising prospects for industrial application.展开更多
Surface-functionalized nitrogen/carbon co-doped polymorphic TiO_(2) phase junction nanoparticles uniformly distributed in porous carbon matrix were synthesized by a simple one-step pyrolysis of titanium based metal-or...Surface-functionalized nitrogen/carbon co-doped polymorphic TiO_(2) phase junction nanoparticles uniformly distributed in porous carbon matrix were synthesized by a simple one-step pyrolysis of titanium based metal-organic framework(MOF),NH_(2)-MIL^(-1)25(Ti) at 700℃ under water vapour atmosphere.Introducing water vapour during the pyrolysis of NH_(2)-MIL^(-1)25(Ti) not only functionalizes the derived porous carbon matrix with carboxyl groups but also forms additional oxygen-rich N like interstitial/intraband states lying above the valence band of TiO2 along with the self-doped carbo n,which further narrows the energy band gaps of polymorphic TiO2 nanoparticles that enhance photocatalytic charge transfer efficiency.Without co-catalyst,sample N-C-TiO2/CArW demonstrates H_(2) evolution activity of 426 μmol gcat-1h^(-1),which remarkably outperforms commercial TiO_(2)(P-25) and N-C-TiO_(2)/CAr with a 5-fold and 3-fold H_(2) generation,respectively.This study clearly shows that water vapour atmosphere during the pyrolysis increases the hydrophilicity of the Ti-MOF derived composites by functionalizing porous carbon matrix with carboxylic groups,as well as enhancing the electrical conductivity and charge transfer efficiency due to the formation of additional localized oxygen-rich N like interstitial/intraband states.This work also demonstrates that by optimizing the anatase-rutile phase composition of the TiO2 polymorphs,tuning the energy band gaps by N/C co-doping and functionalizing the porous carbon matrix in the N-C-TiO2/C nanocomposites,the photocatalytic H_(2) generation activity can be further enhanced.展开更多
Lithium-selenium(Li-Se)battery has attracted growing attention.Nevertheless,its practical application is still impeded by the shuttle effect of the formed polyselenides.Herein,we report in-situ hydrothermal weaving th...Lithium-selenium(Li-Se)battery has attracted growing attention.Nevertheless,its practical application is still impeded by the shuttle effect of the formed polyselenides.Herein,we report in-situ hydrothermal weaving the three-dimensional(3 D)highly conductive hierarchically interconnected nanoporous web by threading microporous metal organic framework MIL-68(Al)crystals onto multi-walled carbon nanotubes(MWCNTs).Such 3 D hierarchically nanoporous web(3 D MIL-68(Al)@MWCNTs web)with a very high surface area,a large amount of micropores,electrical conductivity and elasticity strongly traps the soluble polyselenides during the electrochemical reaction and significantly facilitates lithium ion diffusion and electron transportation.Molecular dynamic calculation confirmed the strong affinity of MIL-68(Al)for the adsorption of polyselenides,quite suitable for Li-Se battery.Their hexahedral channels(1.56 nm)are more efficient for the confinement of polyselenides and for the diffusion of electrolytes compared to their smaller triangular channels(0.63 nm).All these excellent characteristics of 3 D MIL-68(Al)@MWCNTs web with suitable confinement of a large amount of selenium and the conductive linkage between MIL-68(Al)host by MWCNTs result in a high capacity of 453 m Ah/g at 0.2 C with 99.5%coulombic efficiency after 200 cycles with significantly improved cycle stability and rate performance.The 3 D MIL-68(Al)@MWCNTs web presents a good performance in Li-Se battery in term of the specific capacity and cycling stability and also in terms of rate performance compared with all the metal-organic framework(MOF)based or MOF derived porous carbons used in Li-Se battery.展开更多
The development of anode materials with high rate capability and long charge-discharge plateau is the key to improve per-formance of lithium-ion capacitors(LICs).Herein,the porous graphitic carbon(PGC-1300)derived fro...The development of anode materials with high rate capability and long charge-discharge plateau is the key to improve per-formance of lithium-ion capacitors(LICs).Herein,the porous graphitic carbon(PGC-1300)derived from a new triply interpenetrated co-balt metal-organic framework(Co-MOF)was prepared through the facile and robust carbonization at 1300°C and washing by HCl solu-tion.The as-prepared PGC-1300 featured an optimized graphitization degree and porous framework,which not only contributes to high plateau capacity(105.0 mAh·g^(−1)below 0.2 V at 0.05 A·g^(−1)),but also supplies more convenient pathways for ions and increases the rate capability(128.5 mAh·g^(−1)at 3.2 A·g^(−1)).According to the kinetics analyses,it can be found that diffusion regulated surface induced capa-citive process and Li-ions intercalation process are coexisted for lithium-ion storage.Additionally,LIC PGC-1300//AC constructed with pre-lithiated PGC-1300 anode and activated carbon(AC)cathode exhibited an increased energy density of 102.8 Wh·kg^(−1),a power dens-ity of 6017.1 W·kg^(−1),together with the excellent cyclic stability(91.6%retention after 10000 cycles at 1.0 A·g^(−1)).展开更多
Multiple space from the interior of metal-organic polyhedra(MOPs),the exterior among MOPs,and the inherent nature of big organic molecules makes MOPs as promising platform with hierarchical porous structures,especiall...Multiple space from the interior of metal-organic polyhedra(MOPs),the exterior among MOPs,and the inherent nature of big organic molecules makes MOPs as promising platform with hierarchical porous structures,especially when well-elucidated reticular chemistry principles were used.Herein we describe the preparation of a series of isoreticular octahedral MOPs featuring Zn4-p-tert-butylsulfonylcalix[4]arene clusters by the metal-directed assembly of three rigid organic ligands with different lengths.Intercage hydrogen-bonds and hydrophobic interactions between sulfonylcalix[4]arene groups direct the stacking of discrete MOPs into a novel permanent hierarchical porous material.More importantly,the optimal MOP 1-Zn exhibits high adsorption capacity of Xe and excellent Xe/Kr(20/80,v/v)separation performance,as demonstrated by adsorption isotherms,breakthrough experiments,and density functional theory calculations.Additionally,grand canonical Monte Carlo(GCMC)and dispersion-corrected density functional theory(DFT-D)theoretical calculations provide molecular-level insight over the adsorption/separation mechanism.展开更多
Metal-organic frameworks(MOFs)have a high specific surface area,adjustable pores and can be used to obtain functional porous materials with diverse and well-ordered structures through coordination and self-assembly,wh...Metal-organic frameworks(MOFs)have a high specific surface area,adjustable pores and can be used to obtain functional porous materials with diverse and well-ordered structures through coordination and self-assembly,which has intrigued wide interest in a broad range of disciplines.In the arena of biomedical engineering,the functionalized modification of MOFs has produced drug carriers with excellent dispersion and functionalities such as target delivery and response release,with promising applications in bio-detection,disease therapy,tissue healing,and other areas.This review summa-rizes the present state of research on the functionalization of MOFs by physical binding or chemical cross-linking of small molecules.polvmers.bioma romolecules.and hvdrogels and evaluates the role and approach of MOFs functionalization in boosting the reactivity of materials.On this basis,research on the application of functionalized MOFs composites in biomedical engineering fields such as drug delivery,tissue repair,disease treatment,bio-detection and imaging is surveyed,and the development trend and application prospects of functionalized MOFs as an important new class of biomedical materials in the biomedical field are anticipated,which may provide some inspiration and reference for further development of MOF for bio-medical applications.展开更多
Multiple enzymes-induced biological cascade catalysis is indispensable in biotechnology and industrial processes. Nevertheless,the drawbacks of most natural enzymes, including poor stability and recyclability and sens...Multiple enzymes-induced biological cascade catalysis is indispensable in biotechnology and industrial processes. Nevertheless,the drawbacks of most natural enzymes, including poor stability and recyclability and sensitivity to the environment, have hindered their broader application. Here, we report a facile strategy to prepare a biomimetic cascade reaction system by combining the advantages of enzyme immobilization and biomimetic catalysis in a one-pot reaction system based on the hierarchically porous metal-organic frameworks(HP-MOFs). The hierarchically porous zirconium-porphyrin-based MOF(HPPCN-222(Fe)) synthesized by modulator-induced strategy possessed tunable hierarchical porous and peroxidase-like activity,permitting them to act as not only an efficient immobilization matrix for glucose oxidase(GOx) but also peroxidase mimics to catalyze the cascade for glucose detection. A stable, anti-interference and reusable colorimetric biosensor for glucose detection was successfully established through GOx@HP-PCN-222(Fe) on the basis of the artificial tandem catalysis. Moreover, the GOx@HP-PCN-222(Fe)-fabricated electrode was available for glucose detection by electrochemical method. This work provides a potentially universal method to design functional multi-enzymatic cascade reaction systems by integrating the merits of enzyme encapsulation and biomimetic catalysis in HP-MOFs.展开更多
Hierarchically porous materials play an important role in facilitating mass transport and improving efficiency of adsorption and separation processes. In this paper, a new strategy is proposed to realize a hierarchica...Hierarchically porous materials play an important role in facilitating mass transport and improving efficiency of adsorption and separation processes. In this paper, a new strategy is proposed to realize a hierarchically porous metal-organic framework ([Cu2(OH)(L)]'(DMF)0.8 (FJU-11, H3L=3,5-(4-carboxybenzyloxy)benzoic acid, DMF= N,N-dimethylformamide) via using semi-rigid multi-carboxylic acids. Interestingly, FJU-11 possesses the large adsorption capacities and small isosteric heats toward CO2. The column breakthrough experiment for FJU-11 highlights its potential application in the separation of the flue gas.展开更多
The exploitation of electromagnetic wave absorption(EMA) materials has attracted ever-increasing attention,not only because electromagnetic wave(EMW) originated from overuse of electronic products has threatened human...The exploitation of electromagnetic wave absorption(EMA) materials has attracted ever-increasing attention,not only because electromagnetic wave(EMW) originated from overuse of electronic products has threatened human' health seriously,but also because EMA materials can effectively protect radar stealth from being detected.However,it is still a challenge to obtain broadband and efficient EMA materials to satisfy practical applications.In this work,we developed a series of hierarchical CoFe alloy/porous carbon@carbon nanotubes(CoFe/PC@CNTs) nanocomposites through revising the proportion of Fe^(2+) in the metal-organic frameworks(MOFs)(CoFe-ZIF) precursor and one-step simple pyrolysis process.The cross deposition between CoFe alloy,carbon nanotubes(CNTs),and porous carbon(PC) formed a double conductive network,favoring for achieving excellent EMA property.Surprisingly,when the filler mass ratio is only 10 wt%,the optimized CoFe/PC@CNTs nanocomposites display the best EMA capability,whose minimum reflection loss(RL_(min)) value is-68.94 dB at 13.69 GHz and the effective absorption band(EAB,<-10 dB) reaches up 9.14 GHz with a matching thickness of 2.63 mm.In addition,the largest EAB can achieve up to 11 GHz(3.35-14.35 GHz) during all matching thicknesses.The splendid EMA performance benefits the favorable dielectric loss provided by the double conductive network,the good magnetic loss benefited from the evenly distributed CoFe alloy,the excellent impedance matching,rich transmission paths,and multiple polarization.Therefore,such EMA materials with super broadband absorbing provide desirable candidates for lightweight and high-efficient microwave absorbers.展开更多
The ferrocene(Fc)-based metal-organic frameworks(MOFs)are regarded as compelling platforms for the construction of efficient and robust oxygen evolution reaction(OER)electrocatalysts due to their superior conductivity...The ferrocene(Fc)-based metal-organic frameworks(MOFs)are regarded as compelling platforms for the construction of efficient and robust oxygen evolution reaction(OER)electrocatalysts due to their superior conductivity and flexible electronic structure.Herein,density functional theory simulations were addressed to predict the electronic structure regulations of CoFc-MOF by nickel doping,which demonstrated that the well-proposed CoNiFc-MOFs delivered a small energy barrier,promoted conductivity,and well-regulated d-band center.Inspired by these,a series of sea-urchin-like CoNiFc-MOFs were successfully synthesized via a facile solvothermal method.Moreover,the synchrotron X-ray and X-ray photoelectron spectroscopy measurements manifested that the introduction of nickel could tailor the electronic structure of the catalyst and induce the directional transfer of electrons,thus optimizing the rate-determining step of^(*)O→^(*)OOH during the OER process and yielding decent overpotentials of 209 and 252 mV at 10 and 200 mA cm^(−2),respectively,with a small Tafel slope of 39 mV dec^(−1).This work presents a new paradigm for developing highly efficient and durable MOF-based electrocatalysts for OER.展开更多
The rational integration of multi-functional components with metal–organic frameworks(MOFs) to form MOF-based catalysts can often afford enhanced catalytic activity for specific reactions. Herein, we propose a novel ...The rational integration of multi-functional components with metal–organic frameworks(MOFs) to form MOF-based catalysts can often afford enhanced catalytic activity for specific reactions. Herein, we propose a novel strategy for the synthesis of hierarchically porous MOFs(e.g., MIL-101)-encapsulated N-doped nanocarbon(CN@MIL) by controlled pyrolysis of ionic liquids@MIL-101 precursors(ILs@MIL). The obtained CN@MIL composites not only possess abundant enlarged mesopores,but also show multi-active sites without the sacrifice of their structure stability. The CN@MIL can efficiently facilitate the mass transfer of substrates, exhibiting excellent catalytic performance in the synthesis of cyclic carbonates from epoxides and CO_(2) under mild and co-catalyst-free conditions(i.e., 90 ℃ and ambient pressure of CO_(2)). Furthermore, the multi-active Lewis acid sites and nucleophilic sites(Br ions) as well as the strong affinity of catalysts toward CO_(2)also contribute to the excellent catalytic activity of the CN@MIL. This study might open a new avenue for the rational design of MOF-based composites by employing ILs@MOF as precursors for advanced heterogeneous catalysis.展开更多
Development of simple methods for controlled integration of DNA molecules with metal-organic frameworks(MOFs)is important for various biomedical applications,yet remains a challenge.Herein,a simple and general approac...Development of simple methods for controlled integration of DNA molecules with metal-organic frameworks(MOFs)is important for various biomedical applications,yet remains a challenge.Herein,a simple and general approach to load DNA on the surface of MOFs is developed via one-pot self-assembly of DNA and FeII ions on nanoscale MOFs,resulting in hierarchical core-shell nanostructures of metal-organic@metal-DNA coordination polymers.The strategy enables assembly of DNA molecules on MOFs with ultra-high contents and precise controllability.By incorporation of a chemotherapeutic drug into the Fe-DNA shell,the systems allow to integrate chemotherapy and gene therapy with photodynamic therapy for combinational tumor treatment.Moreover,the hybrid nanostructures enable light-triggered production of cytotoxic singlet oxygen,which further boosts the endosomal escape of the system for an enhanced gene silencing efficacy and thus improved therapeutic outcome.This work highlights a robust approach for the construction of coordination-based drug delivery systems to combat tumor.展开更多
基金the National Key Research and Development Program(2019YFC1805804)the National Natural Science Foundation of China(22008032)+3 种基金the Guangdong Natural Science Foundation(2022A1515011192)the Guangdong Basic and Applied Basic Research Foundation(2019A1515110706)the Guangdong Provincial Key Lab of Green Chemical Product Technology(GC202111)the China Postdoctoral Science Foundation(2021M691059).
文摘The combination of nano sizes,large pore sizes and green synthesis is recognized as one of the most crucial and challenging problems in constructing metal-organic frameworks(MOFs).Herein,a water-based strategy is proposed for the synthesis of nanoscale hierarchical MOFs(NH-MOFs)with high crystallinity and excellent stability.This approach allows the morphology and porosity of MOFs to be fine tuned,thereby enabling the nanoscale crystal generation and a well-defined hierarchical system.The aqueous solution facilitates rapid nucleation kinetics,and the introduced modulator acts as a deprotonation agent to accelerate the deprotonation of the organic ligand as well as a structure-directing agent(SDA)to guide the formation of hierarchical networks.The assynthesized NH-MOFs(NH-ZIF-67)were assessed as efficient adsorbents and heterogeneous catalysts to facilitate the diffusion of guest molecules,outperforming the parent microZIF-67.This study focuses on understanding the NH-MOF growth rules,which could allow tailor-designing NH-MOFs for various functions.
基金the financial support from the Fundamental Research Funds of the Central Universities(No.531118010112)the Double First-Class University Initiative of Hunan University(No.531109100004)+1 种基金the Fundamental Research Funds of the Central Universities(no.531107051048)the support from the Hunan Key Laboratory of Two-Dimensional Materials(No.801200005)
文摘Exploring electrode materials with attractive specific capacity and prominent cyclic durability is of the essence for promoting lithium ion batteries(LIBs).In2O3 has shown an extraordinary promise for LIBs with advantageous gravimetric capacity(theoretically 965 mA h g-1) and low working voltage.However,In2O3 still suffers from the inherent weaknesses of metal oxides in practical application,especially low conductivity and incorrigible volume expansion upon the cycling process.Here,we demonstrate the architecture of metal-organic framework(MOF)-derived In2O3 nanocrystals/hierarchically porous nitrogen-doped carbon composite(In2O3/HPNC) for ultra-stable LIBs anode.This hierarchically porous structure(micro/meso/macro-pores) with nitrogen doping not only ensures exceptional mechanical strength and accommodates the volume expansion of In2O3 nanocrystals,but also offers electrons and lithium ions efficient interpenetrating pathways to migrate rapidly during charge/discharge processes.Thus,In2O3/HPNC exhibits excellent cyclic stability with a high specific capacity of 623 mA h g-1 over2000 cycles at 1000 mA g-1,corresponding to an ultra-low specific capacity decay of 0.017% per cycle(the best among the ln203-based anode for LIBs),and outstanding rate performance,suggesting a critical step toward achieving long-life and high-rate LIBs in practical devices.
基金financially supported by the Vietnamese Ministry of Education and Training and the UK Engineering and Physical Sciences Research Council (EP/R01650X/1 and EP/L016028/1)
文摘Introduction of multiple pore size regimes into metalorganic frameworks(MOFs)to form hierarchical porous structures can lead to improved performance of the material in various applications.In many cases,where interactions with bulky molecules are involved,enlarging the pore size of typically microporous MOF adsorbents or MOF catalysts is crucial for enhancing both mass transfer and molecular accessibility.In this review,we examine the range of synthetic strategies which have been reported thus far to prepare hierarchical MOFs or MOF composites with added macroporosity.These fabrication techniques can be either pre-or post-synthetic and include using hard or soft structural template agents,defect formation,routes involving supercritical CO2,and 3D printing.We also discuss potential applications and some of the challenges involved with current techniques,which must be addressed if any of these approaches are to be taken forward for industrial applications.
基金The financial support of the Natural Science Foundation of China(21802079 and 22075159)the Postdoctoral Science Foundation of China(2018 M642605)+1 种基金the Youth Innovation Team Project of Shandong Provincial Education Department(2019KJC023)the Taishan Scholar Program for L.Zhang(202103058)are appreciated。
文摘Developing advanced oxygen reduction reaction(ORR)electrocatalysts with rapid mass/electron transport as well as conducting relevant kinetics investigations is essential for energy technologies,but both still face ongoing challenges.Herein,a facile approach was reported for achieving the highly dispersed Co nanoparticles anchored hierarchically porous N-doped carbon fibers(Co@N-HPCFs),which were assembled by core-shell MOFs-derived hollow polyhedrons.Notably,the unique one-dimensional(1D)carbon fibers with hierarchical porosity can effectively improve the exposure of active sites and facilitate the electron transfer and mass transfer,resulting in the enhanced reaction kinetics.As a result,the ORR performance of the optimal Co@N-HPCF catalysts remarkably outperforms that of commercial Pt/C in alkaline solution,reaching a limited diffusion current density(J)of 5.85 m A cm^(-2)and a half-wave potential(E_(1/2))of 0.831 V.Particularly,the prepared Co@N-HPCF catalysts can be used as an excellent air-cathode for liquid/solid-state Zn-air batteries,exhibiting great potentiality in portable/wearable energy devices.Furthermore,the reaction kinetic during ORR process is deeply explored by finite element simulation,so as to intuitively grasp the kinetic control region,diffusion control region,and mixing control region of the ORR process,and accurately obtain the relevant kinetic parameters.This work offers an effective strategy and a reliable theoretical basis for the engineering of first-class ORR electrocatalysts with fast electronic/mass transport.
基金partially supported by a Grant-in-Aid for Scientific Research(KAKENHI)from the Japan Society for the Promotion of Science(JSPS)(grant number 19H05332)。
文摘Heat treatment of metal-organic frameworks(MOFs)has provided a wide variety of functional carbons coordinated with metal compounds.In this study,two kinds of zinc-based MOF(ZMOF),C_(16)H_(10)O_(4)Zn(ZMOF1)and C_(8)H_(4)O_(4)Zn(ZMOF2),were prepared.ZMOF1 and ZMOF2 were carbonized at 1000℃,forming CZMOF1 and CZMOF2,respectively.The specific surface area(S_(BET))of CZMOF2 was~2700 m^(2)g^(−1),much higher than that of CZMOF1(~1300 m^(2)g^(−1)).A supercapacitor electrode based on CZMOF2 achieved specific capacitances of 360,278,and 221 F g^(−1)at 50,250,and 1000 mA g^(−1)in an aqueous electrolyte(H2SO_(4)),respectively,the highest values reported to date for ZMOF-derived electrodes under identical conditions.The practical applicability of the CZMOF-based supercapacitor was verified in non-aqueous electrolytes.The initial capacitance retention was 78%after 100000 charge/discharge cycles at 10 A g^(−1).Crucially,the high capacitance of CZMOF2 arises from pore generation during carbonization.Below 1000℃,pore generation is dominated by the Zn/C ratio of ZMOFs,as carbon atoms reduce the zinc oxides formed during carbonization.Above 1000℃,a high O/C ratio becomes essential for pore generation because the oxygen functional groups are pyrolyzed.These findings will provide insightful information for other metal-based MOFderived multifunctional carbons.
基金financial support from Ministry of Science and Technology of China(MoST,2016YFA0200200)the National Natural Science Foundation of China(NSFC,21875114,51373078,and 51422304)NSF of Tianjin City(15JCYBJC17700)。
文摘The development of microwave absorption materials(MAMs) is a considerable important topic because our living space is crowed with electromagnetic wave which threatens human’s health.And MAMs are also used in radar stealth for protecting the weapons from being detected.Many nanomaterials were studied as MAMs,but not all of them have the satisfactory performance.Recently,metal-organic frameworks(MOFs) have attracted tremendous attention owing to their tunable chemical structures,diverse properties,large specific surface area and uniform pore distribution.MOF can transform to porous carbon(PC) which is decorated with metal species at appropriate pyrolysis temperature.However,the loss mechanism of pure MOF-derived PC is often relatively simple.In order to further improve the MA performance,the MOFs coupled with other loss materials are a widely studied method.In this review,we summarize the theories of MA,the progress of different MOF-derived PC-based MAMs,tunable chemical structures incorporated with dielectric loss or magnetic loss materials.The different MA performance and mechanisms are discussed in detail.Finally,the shortcomings,challenges and perspectives of MOF-derived PC-based MAMs are also presented.We hope this review could provide a new insight to design and fabricate MOF-derived PC-based MAMs with better fundamental understanding and practical application.
基金the financial support from the National Natural Science Foundation of China(22008032,22108034,and 22102026)the Guangdong Basic and Applied Basic Research Foundation(2019A1515110706)+2 种基金the Guangdong Provincial Key Lab of Green Chemical Product Technology(GC202111)the Medical Science and Technology Research Foundation of Guangdong Province(A2021189)the Shandong Provincial Natural Science Foundation(ZR2018ZC1458)。
文摘Nanoscale hierarchically porous metal–organic frameworks(NHP-MOFs)have received unprecedented attention in many fields owing to their integration of the strengths of nanoscale size(<1μm)and hierarchical porous structure(micro-,meso-and/or macro-pores)of MOFs.This review focuses on recent advances in the main synthetic strategies for NHP-MOFs based on different metal ions(e.g.,Cu,Fe,Co,Zn,Al,Zr,and Cr),including the template method,composite technology,post-synthetic modification,in situ growth and the grind method.In addition,the mechanisms of synthesis,regulation techniques and the advantages and disadvantages of various methods are discussed.Finally,the challenges and prospects of the commercialisation of promising NHP-MOFs are also presented.The purpose of this review is to provide a road map for future design and development of NHP-MOFs for practical application.
基金supported by JSPS KAKENHI Grant Number15K00597Takahashi Industrial and Economic Research Foundation Japan Grant Number 06-003-154
文摘Hierarchical porous TiOnanopills were synthesized using a titanium metal-organic framework MIL-125(Ti) as precursor. The as-synthesized TiOnanopills owned a large specific surface area of 102 m/g and unique porous structure. Furthermore, the obtained TiOnanopills were applied as anode materials for Na-ion batteries for the first time. The as-synthesized TiOnanopills achieved a high discharge capacity of 196.4 m Ah/g at a current density of 0.1 A/g. A discharge capacity of 115.9 m Ah/g was obtained at a high current density of 0.5 A/g and the capacity retention was remained as high as 90% even after 3000 cycles. The excellent electrochemical performance can be attributed to its unique hierarchical porous feature.
基金support from the National Natural Science Foundation of China (grant Nos.22090062,21922810,21908155).
文摘Increasing the mass diffusion efficiency is a major challenge in the realm of metal-organic frameworks(MOFs).Construction of hierarchically porous,typically microporous MOF adsorbents or catalysts is crucial for enhancing both mass transfer and molecular accessibility.Many strategies have been proposed for the synthesis of hierarchically porous MOFs(HP-MOFs),with some striking results.In this paper,we proposed a facile and versatile strategy,termed the MOF-Template strategy,for fabricating hierarchical pores in MOF particle.The highly controlled crystalline sizes and morphologies of the unstable Cu-MOFs Cu_(3)(BTC)_(2) and Cu(Qc)_(2) have been exploited in their utilization as sacrificial agents by uniformly dispersing them during the shaping process of ZIF-8.Through a facile treatment with alkaline solution,tunable mesopores and macropores could be easily introduced in the shaped ZIF-8 spheres.This strategy could effectively improve the adsorption kinetics and separation productivity of MOF materials while maintaining high mechanical stability,offering promising prospects for industrial application.
基金EPSRC CDT in Metamaterials at University of Exeter and Leverhulme Trust(RPG-2018-320) for financial support。
文摘Surface-functionalized nitrogen/carbon co-doped polymorphic TiO_(2) phase junction nanoparticles uniformly distributed in porous carbon matrix were synthesized by a simple one-step pyrolysis of titanium based metal-organic framework(MOF),NH_(2)-MIL^(-1)25(Ti) at 700℃ under water vapour atmosphere.Introducing water vapour during the pyrolysis of NH_(2)-MIL^(-1)25(Ti) not only functionalizes the derived porous carbon matrix with carboxyl groups but also forms additional oxygen-rich N like interstitial/intraband states lying above the valence band of TiO2 along with the self-doped carbo n,which further narrows the energy band gaps of polymorphic TiO2 nanoparticles that enhance photocatalytic charge transfer efficiency.Without co-catalyst,sample N-C-TiO2/CArW demonstrates H_(2) evolution activity of 426 μmol gcat-1h^(-1),which remarkably outperforms commercial TiO_(2)(P-25) and N-C-TiO_(2)/CAr with a 5-fold and 3-fold H_(2) generation,respectively.This study clearly shows that water vapour atmosphere during the pyrolysis increases the hydrophilicity of the Ti-MOF derived composites by functionalizing porous carbon matrix with carboxylic groups,as well as enhancing the electrical conductivity and charge transfer efficiency due to the formation of additional localized oxygen-rich N like interstitial/intraband states.This work also demonstrates that by optimizing the anatase-rutile phase composition of the TiO2 polymorphs,tuning the energy band gaps by N/C co-doping and functionalizing the porous carbon matrix in the N-C-TiO2/C nanocomposites,the photocatalytic H_(2) generation activity can be further enhanced.
基金supported by the National Postdoctoral Program(2020M672782)National Natural Science Foundation of China(No.U1663225)+2 种基金Changjiang Scholars and Innovative Research Team in University(No.IRT15R52)National 111 project from the Ministry of Science and Technologythe Ministry of Education of China and the National Key R&D Program of China(No.2016YFA0202602)。
文摘Lithium-selenium(Li-Se)battery has attracted growing attention.Nevertheless,its practical application is still impeded by the shuttle effect of the formed polyselenides.Herein,we report in-situ hydrothermal weaving the three-dimensional(3 D)highly conductive hierarchically interconnected nanoporous web by threading microporous metal organic framework MIL-68(Al)crystals onto multi-walled carbon nanotubes(MWCNTs).Such 3 D hierarchically nanoporous web(3 D MIL-68(Al)@MWCNTs web)with a very high surface area,a large amount of micropores,electrical conductivity and elasticity strongly traps the soluble polyselenides during the electrochemical reaction and significantly facilitates lithium ion diffusion and electron transportation.Molecular dynamic calculation confirmed the strong affinity of MIL-68(Al)for the adsorption of polyselenides,quite suitable for Li-Se battery.Their hexahedral channels(1.56 nm)are more efficient for the confinement of polyselenides and for the diffusion of electrolytes compared to their smaller triangular channels(0.63 nm).All these excellent characteristics of 3 D MIL-68(Al)@MWCNTs web with suitable confinement of a large amount of selenium and the conductive linkage between MIL-68(Al)host by MWCNTs result in a high capacity of 453 m Ah/g at 0.2 C with 99.5%coulombic efficiency after 200 cycles with significantly improved cycle stability and rate performance.The 3 D MIL-68(Al)@MWCNTs web presents a good performance in Li-Se battery in term of the specific capacity and cycling stability and also in terms of rate performance compared with all the metal-organic framework(MOF)based or MOF derived porous carbons used in Li-Se battery.
基金the National Natural Science Foundation of China(No.52004179)the Natural Nat-ural Science Foundation of Guangxi Province,China(No.2020GXNSFAA159015)Shanxi Water and Wood New Carbon Materials Technology Co.,Ltd.,China,and Shanxi Wote Haimer New Materials Technology Co.,Ltd,China.
文摘The development of anode materials with high rate capability and long charge-discharge plateau is the key to improve per-formance of lithium-ion capacitors(LICs).Herein,the porous graphitic carbon(PGC-1300)derived from a new triply interpenetrated co-balt metal-organic framework(Co-MOF)was prepared through the facile and robust carbonization at 1300°C and washing by HCl solu-tion.The as-prepared PGC-1300 featured an optimized graphitization degree and porous framework,which not only contributes to high plateau capacity(105.0 mAh·g^(−1)below 0.2 V at 0.05 A·g^(−1)),but also supplies more convenient pathways for ions and increases the rate capability(128.5 mAh·g^(−1)at 3.2 A·g^(−1)).According to the kinetics analyses,it can be found that diffusion regulated surface induced capa-citive process and Li-ions intercalation process are coexisted for lithium-ion storage.Additionally,LIC PGC-1300//AC constructed with pre-lithiated PGC-1300 anode and activated carbon(AC)cathode exhibited an increased energy density of 102.8 Wh·kg^(−1),a power dens-ity of 6017.1 W·kg^(−1),together with the excellent cyclic stability(91.6%retention after 10000 cycles at 1.0 A·g^(−1)).
基金supported by the National Natural Science Foundation of China(No.22101004)the Natural Science Foundation of Anhui Province(No.2008085QB62)the Shanghai Science and Technology Committee(No.19DZ2270100).
文摘Multiple space from the interior of metal-organic polyhedra(MOPs),the exterior among MOPs,and the inherent nature of big organic molecules makes MOPs as promising platform with hierarchical porous structures,especially when well-elucidated reticular chemistry principles were used.Herein we describe the preparation of a series of isoreticular octahedral MOPs featuring Zn4-p-tert-butylsulfonylcalix[4]arene clusters by the metal-directed assembly of three rigid organic ligands with different lengths.Intercage hydrogen-bonds and hydrophobic interactions between sulfonylcalix[4]arene groups direct the stacking of discrete MOPs into a novel permanent hierarchical porous material.More importantly,the optimal MOP 1-Zn exhibits high adsorption capacity of Xe and excellent Xe/Kr(20/80,v/v)separation performance,as demonstrated by adsorption isotherms,breakthrough experiments,and density functional theory calculations.Additionally,grand canonical Monte Carlo(GCMC)and dispersion-corrected density functional theory(DFT-D)theoretical calculations provide molecular-level insight over the adsorption/separation mechanism.
文摘Metal-organic frameworks(MOFs)have a high specific surface area,adjustable pores and can be used to obtain functional porous materials with diverse and well-ordered structures through coordination and self-assembly,which has intrigued wide interest in a broad range of disciplines.In the arena of biomedical engineering,the functionalized modification of MOFs has produced drug carriers with excellent dispersion and functionalities such as target delivery and response release,with promising applications in bio-detection,disease therapy,tissue healing,and other areas.This review summa-rizes the present state of research on the functionalization of MOFs by physical binding or chemical cross-linking of small molecules.polvmers.bioma romolecules.and hvdrogels and evaluates the role and approach of MOFs functionalization in boosting the reactivity of materials.On this basis,research on the application of functionalized MOFs composites in biomedical engineering fields such as drug delivery,tissue repair,disease treatment,bio-detection and imaging is surveyed,and the development trend and application prospects of functionalized MOFs as an important new class of biomedical materials in the biomedical field are anticipated,which may provide some inspiration and reference for further development of MOF for bio-medical applications.
基金supported by the National Natural Science Foundation of China (92061201, 21825106, 22001238)the Program for Innovative Research Team (in Science and Technology) in Universities of Henan Province (19IRTSTHN022)Zhengzhou University。
文摘Multiple enzymes-induced biological cascade catalysis is indispensable in biotechnology and industrial processes. Nevertheless,the drawbacks of most natural enzymes, including poor stability and recyclability and sensitivity to the environment, have hindered their broader application. Here, we report a facile strategy to prepare a biomimetic cascade reaction system by combining the advantages of enzyme immobilization and biomimetic catalysis in a one-pot reaction system based on the hierarchically porous metal-organic frameworks(HP-MOFs). The hierarchically porous zirconium-porphyrin-based MOF(HPPCN-222(Fe)) synthesized by modulator-induced strategy possessed tunable hierarchical porous and peroxidase-like activity,permitting them to act as not only an efficient immobilization matrix for glucose oxidase(GOx) but also peroxidase mimics to catalyze the cascade for glucose detection. A stable, anti-interference and reusable colorimetric biosensor for glucose detection was successfully established through GOx@HP-PCN-222(Fe) on the basis of the artificial tandem catalysis. Moreover, the GOx@HP-PCN-222(Fe)-fabricated electrode was available for glucose detection by electrochemical method. This work provides a potentially universal method to design functional multi-enzymatic cascade reaction systems by integrating the merits of enzyme encapsulation and biomimetic catalysis in HP-MOFs.
基金This work was financially supported by the National Natural Science Foundation of China (21207018, 21273033, 21573042 and 21203024) and the Fujian Science and Technology Department (2014J06003 and 2014H6007). S. X. gratefully acknowledges the support of the Recruitment Program of Global Young Experts, Program for New Century Excellent Talents in University (NCET- 10-0108), and the Award 'MinJiang Scholar Program' in Fujian Province.sity (NCET- 10-0108), and the Award 'MinJiang Scholar Program' in Fujian Province.
文摘Hierarchically porous materials play an important role in facilitating mass transport and improving efficiency of adsorption and separation processes. In this paper, a new strategy is proposed to realize a hierarchically porous metal-organic framework ([Cu2(OH)(L)]'(DMF)0.8 (FJU-11, H3L=3,5-(4-carboxybenzyloxy)benzoic acid, DMF= N,N-dimethylformamide) via using semi-rigid multi-carboxylic acids. Interestingly, FJU-11 possesses the large adsorption capacities and small isosteric heats toward CO2. The column breakthrough experiment for FJU-11 highlights its potential application in the separation of the flue gas.
基金financially supported by the National Natural Science Foundation of China (NSFC,Nos.51978354,52002201,52008223)the major program of Shandong province (No.GG201809170147)+3 种基金Outstanding Youth Foundation of Shandong province (No.ZR2020YQ43)Qingchuang Technology Project (No.2020KJG002)Natural Science Foundation of Shandong Province(No.ZR2020QE055)the fellowship support received from the Tai Shan Scholar Programme。
文摘The exploitation of electromagnetic wave absorption(EMA) materials has attracted ever-increasing attention,not only because electromagnetic wave(EMW) originated from overuse of electronic products has threatened human' health seriously,but also because EMA materials can effectively protect radar stealth from being detected.However,it is still a challenge to obtain broadband and efficient EMA materials to satisfy practical applications.In this work,we developed a series of hierarchical CoFe alloy/porous carbon@carbon nanotubes(CoFe/PC@CNTs) nanocomposites through revising the proportion of Fe^(2+) in the metal-organic frameworks(MOFs)(CoFe-ZIF) precursor and one-step simple pyrolysis process.The cross deposition between CoFe alloy,carbon nanotubes(CNTs),and porous carbon(PC) formed a double conductive network,favoring for achieving excellent EMA property.Surprisingly,when the filler mass ratio is only 10 wt%,the optimized CoFe/PC@CNTs nanocomposites display the best EMA capability,whose minimum reflection loss(RL_(min)) value is-68.94 dB at 13.69 GHz and the effective absorption band(EAB,<-10 dB) reaches up 9.14 GHz with a matching thickness of 2.63 mm.In addition,the largest EAB can achieve up to 11 GHz(3.35-14.35 GHz) during all matching thicknesses.The splendid EMA performance benefits the favorable dielectric loss provided by the double conductive network,the good magnetic loss benefited from the evenly distributed CoFe alloy,the excellent impedance matching,rich transmission paths,and multiple polarization.Therefore,such EMA materials with super broadband absorbing provide desirable candidates for lightweight and high-efficient microwave absorbers.
基金Changjiang Scholars Program of the Ministry of Education,Grant/Award Number:Q2018270Outstanding Youth Funding of Anhui Province,Grant/Award Number:OUFAH 1908085J10+2 种基金Jiangsu Students'Innovation and Entrepreneurship Training Program,Grant/Award Number:202111117079YNatural Science Foundation of Jiangsu Province,Grant/Award Number:BK20200044National Natural Science Foundation of China,Grant/Award Numbers:NSFC 21671004,NSFC 21975001,NSFC U1904215。
文摘The ferrocene(Fc)-based metal-organic frameworks(MOFs)are regarded as compelling platforms for the construction of efficient and robust oxygen evolution reaction(OER)electrocatalysts due to their superior conductivity and flexible electronic structure.Herein,density functional theory simulations were addressed to predict the electronic structure regulations of CoFc-MOF by nickel doping,which demonstrated that the well-proposed CoNiFc-MOFs delivered a small energy barrier,promoted conductivity,and well-regulated d-band center.Inspired by these,a series of sea-urchin-like CoNiFc-MOFs were successfully synthesized via a facile solvothermal method.Moreover,the synchrotron X-ray and X-ray photoelectron spectroscopy measurements manifested that the introduction of nickel could tailor the electronic structure of the catalyst and induce the directional transfer of electrons,thus optimizing the rate-determining step of^(*)O→^(*)OOH during the OER process and yielding decent overpotentials of 209 and 252 mV at 10 and 200 mA cm^(−2),respectively,with a small Tafel slope of 39 mV dec^(−1).This work presents a new paradigm for developing highly efficient and durable MOF-based electrocatalysts for OER.
基金financially supported by the National Natural Science Foundation of China (21825802, 22138003)the Natural Science Foundation of Guangdong Province (2017A030312005)+1 种基金the Guangdong Natural Science Funds for Distinguished Young Scholar (2018B030306050)the Science and Technology Program of Qingyuan City (2021YFJH01002)。
文摘The rational integration of multi-functional components with metal–organic frameworks(MOFs) to form MOF-based catalysts can often afford enhanced catalytic activity for specific reactions. Herein, we propose a novel strategy for the synthesis of hierarchically porous MOFs(e.g., MIL-101)-encapsulated N-doped nanocarbon(CN@MIL) by controlled pyrolysis of ionic liquids@MIL-101 precursors(ILs@MIL). The obtained CN@MIL composites not only possess abundant enlarged mesopores,but also show multi-active sites without the sacrifice of their structure stability. The CN@MIL can efficiently facilitate the mass transfer of substrates, exhibiting excellent catalytic performance in the synthesis of cyclic carbonates from epoxides and CO_(2) under mild and co-catalyst-free conditions(i.e., 90 ℃ and ambient pressure of CO_(2)). Furthermore, the multi-active Lewis acid sites and nucleophilic sites(Br ions) as well as the strong affinity of catalysts toward CO_(2)also contribute to the excellent catalytic activity of the CN@MIL. This study might open a new avenue for the rational design of MOF-based composites by employing ILs@MOF as precursors for advanced heterogeneous catalysis.
基金supported by the National Natural Science Foundation of China(No.32271462)the Young Innovation Promotion Association CAS,National Key R&D Program of China(No.2022YFA1206000)the Strategic Priority Research Program of Chinese Academy of Sciences(No.XDB36000000).
文摘Development of simple methods for controlled integration of DNA molecules with metal-organic frameworks(MOFs)is important for various biomedical applications,yet remains a challenge.Herein,a simple and general approach to load DNA on the surface of MOFs is developed via one-pot self-assembly of DNA and FeII ions on nanoscale MOFs,resulting in hierarchical core-shell nanostructures of metal-organic@metal-DNA coordination polymers.The strategy enables assembly of DNA molecules on MOFs with ultra-high contents and precise controllability.By incorporation of a chemotherapeutic drug into the Fe-DNA shell,the systems allow to integrate chemotherapy and gene therapy with photodynamic therapy for combinational tumor treatment.Moreover,the hybrid nanostructures enable light-triggered production of cytotoxic singlet oxygen,which further boosts the endosomal escape of the system for an enhanced gene silencing efficacy and thus improved therapeutic outcome.This work highlights a robust approach for the construction of coordination-based drug delivery systems to combat tumor.