Applying reticular synthesis to the design of Cu-based MOFs with mechanically interlocked linkers

The concept of“robust dynamics”describes the incorporation of mechanically interlocked molecules(MIMs)into metal-organic framework(MOF)materials such that large amplitude motions(e.g.,rotation or translation of a macrocycle)can occur inside the free volume pore of the MOF.To aid in the preparation of such materials,reticular synthesis was used herein to design rigid molecular building blocks with predetermined ordered structures starting from the well-known MOF NOTT-101.New linkers were synthesized that have a T-shape,based on a triphenylene tetra-carboxylate strut,and their incorporation into Cu(II)-based MOFs was investigated.The single-crystal structures of three new MOFs,UWCM-12(fof),β-UWCM-13(loz),UWCM-14(lil),with naked T-shaped linkers were determined;β-UWCM-13 is the first reported example of the loz topology.A fourth MOF,UWDM-14(lil)is analogous to UWCM-14(lil)but contains a[2]rotaxane linker.Variable-temperature,²H solid-state NMR was used to probe the dynamics of a 24-membered macrocycle threaded onto the MOF skeleton.     

Elastic Aerogels of Cellulose Nanofibers@Metal–Organic Frameworks for Thermal Insulation and Fire Retardancy

Metal–organic frameworks(MOFs)with high microporosity and relatively high thermal stability are potential thermal insulation and flame-retardant materials.However,the difficulties in processing and shaping MOFs have largely hampered their applications in these areas.This study outlines the fabrication of hybrid CNF@MOF aerogels by a stepwise assembly approach involving the coating and cross-linking of cellulose nanofibers(CNFs)with continuous nanolayers of MOFs.The cross-linking gives the aerogels high mechanical strength but superelasticity(80%maximum recoverable strain,high specific compression modulus of^200 MPa cm3 g−1,and specific stress of^100 MPa cm3 g−1).The resultant lightweight aerogels have a cellular network structure and hierarchical porosity,which render the aerogels with relatively low thermal conductivity of^40 mW m−1 K−1.The hydrophobic,thermally stable MOF nanolayers wrapped around the CNFs result in good moisture resistance and fire retardancy.This study demonstrates that MOFs can be used as efficient thermal insulation and flame-retardant materials.It presents a pathway for the design of thermally insulating,superelastic fire-retardant nanocomposites based on MOFs and nanocellulose.     

NiCoLDH nanosheets grown on MOF-derived Co_3O_4 triangle nanosheet arrays for high-performance supercapacitor

Hierarchical Co₃O₄@NiCoLDH nanosheets(NSs)were prepared on carbon cloth through a multistep method,containing Metal-organic frameworks(MOF)-templated thermal annealing and electrodeposition.The triangle-shaped Co₃O_(4 NSs)were firstly obtained by thermal treatment of MOF templates in air.Then,ultrathin NiCoLDH_NSswere in-situ electrodeposited on the surface of Co₃O_4NSs,constructing a core-shell structure.Benefiting the unique hierarchical structure,high conductivity of Co₃O_(4 NSs)core and large surface area of NiCoLDHNSs shell,the Co₃O₄@NiCoLDH_NSsarray served as supercapacitor electrode exhibits excellent electrochemical properties,such as high specific capacitance of 1708 F g^-1(850 C g^-1)at a current density of 1 A g^-1,good rate capability,and excellent cycling stability.Further,the asymmetric supercapacitor assembled by Co₃O₄@NiCoLDH_NSsand activated carbon,also displays superior electrochemical perfo rmance with high energy density and power density.Remarkably,the strategy of constructing core-shell structure based on MOF templates could be extended to other electrochemical fields.     

Solid-state phase transformations toward a metal-organic framework of 7-connected Zn40 secondary building units

In the development of metal-organic frameworks(MOFs),secondary building units(SBUs)have been utilized as molecular modules for the construction of nanoporous materials with robust structures.Under solvothermal synthetic conditions,dynamic changes in the metal coordination environments and ligand coordination modes of SBUs determine the resultant product structures.Alternatively,MOF phases with new topologies can also be achieved by post-synthetic treatment of as-synthesized MOFs via the introduction of acidic or basic moieties that cause the simultaneous cleavage/reformation of coordination bonds in the solid state.In this sense,we studied the solid-state transformation of two ndc-based Zn-MOFs(ndc=1,4-naphthalene dicarboxylate)with different SBUs but the same pcu topology to another MOF with sev topology.One of the chosen MOFs with pcu nets is[Zn₂(ndc)₂(bpy)]_n(bpy=4,4,-bipyridine),(6C_bpy-MOF)consisting of a 6-connected pillared-paddlewheel SBU,and the other is IRMOF-7 composed of 6-connected Zn40(C 00)6 SBUs and ndc.Upon post-structural modification,these pcu MOFs were converted into the same MOF with sev topology constructed from the uncommon 7-connected Zri₄O(COO)₇SBU(7C-MOF).The appropriate post-synthetic conditions for the transformation of each SBUs were systematically examined.In addition,the effect of the pillar molecules in the pillared-paddlewheel MOFs on the topology conversion was studied in terms of the linker basicity,which determines the inertness during the solid-state phase transformation.This post-synthetic modification approach is expected to expand the available methods for designing and synthesizing MOFs with controlled topologies.     

Piezoresistivity in Carbon Fiber Reinforced Cement Based Composites

The results of some interesting investigation on the piezoresistivity of carbon fiber reinforced cement based composites (CFRC) are presented with the prospect of developing a new nondestructive testing method to assess the integrity of the composite. The addition of short carbon fibers to cement-based mortar or concrete improves the structural performance and at the same time significantly decreases the bulk electrical resistivity. This makes CFRC responsive to the smart behavior by measuring the resistance change with uniaxial pressure. The piezoresistivity of CFRC under different stress was studied, at the same time the damage occurring inner specimens was detected by acoustic emission as well. Test results show that there exists a marking pressure dependence of the conductivity in CFRC, in which the so-called negative pressure coefficient of resistive (NPCR) and positive pressure coefficient of resistive (PPCR) are observed under low and high pressure. Under constant pressures, time-dependent resisti     

High-performance flexible self-powered strain sensor based on carbon nanotube/ZnSe/CoSe2 nanocomposite film electrodes

High-performance energy storage and sensing devices have been undergoing rapid development to meet the demand for portable and wearable electronic products,which require flexibility,extensibility,small volume and lightweight.In this study,we construct a lightweight and flexible self-powered sensing system by integrating a highly stretchable strain sensor with a high-performance asymmetric supercapacitor based on ZnSe/CoSe₂//ECNT(ECNT:electrochemically activated carbon nanotube film).The ZnSe/CoSe₂ two-dimentional nanosheets on carbon nanotube(CNT)films are synthesized through a simple and efficient strategy derived from ZnCo-based metal-organic frameworks(MOFs).The density functional theory(DFT)simulations show the higher conductivity of the ZnSe/CoSe₂/CNT electrode than the CoSe₂/CNT electrode.Due to the synergistic properties of self-supported two-dimentional ZnSe/CoSe₂ nanosheets with high specific surface area and the high pathway of one-dimention CNTs,the nanocomposite electrode provides efficient transmission and short paths for electron/ion diffusion.The asymmetric supercapacitor provides a stable output power supply to the sensors that can precisely respond to strain and pressure changes.The sensor can also be attached to a garment for measuring a variety of joint movements.     

Photothermy-strengthened photocatalytic activity of polydopamine-modified metal-organic frameworks for rapid therapy of bacteria-infected wounds

Herein,a metal-organic framework(MOF)was modified using polydopamine(PDA)to develop the MOFPDA as a photoresponsive bacteria-killing agent under 660 nm light irradiation.The modification using PDA led to the production of not only more heat,but also much more~1O₂.This is because the PDA could interact with the porphyrin ring of the MOF throughπ-πinteraction and the charge transfer between PDA and the MOFs decreases the ene rgy of the band of hybrid nanoparticles.In addition,greater levels of hyperthermia induced by PDA modification accelerated the charge trans fe r,which significantly strengthened the photocatalytic perfo rmance of MO F-PDA.Furthermore,after modification,the light abso rbance and water dispersibility of nanoparticles were both enhanced;both are important for the improvement of photocatalytic and photothermal properties.Consequently,MOF-PDA exhibited the highly effective antibacterial efficacy of 99.62%and 99.97%against Staphylococcus aureus and Escherichia coli,respectively,under 20 min 660 nm light irradiation.     

Electrolyte-mediated dense integration of graphene-MXene films for high volumetric capacitance flexible supercapacitors

High conductivity two-dimensional(2D)materials have been proved to be potential electrode materials for flexible supercapacitors because of its outstanding chemical and physical properties.However,electrodes based on 2D materials always suffer from limited electrolyte-accessible surface due to the restacking of the 2D sheets,hindering the full utilization of their surface area.In this regard,an electrolyte-mediated method is used to integrate dense structure reduced graphene oxide/MXene(RGM)-electrolyte composite films.In such composite films,reduced graphene oxide(RGO)and MXene sheets are controllable assembly in compact layered structure with electrolyte filled between the layers.The electrolyte layer between RGO and MXene sheets forms continuous ion transport channels in the composite films.Therefore,the RGM-electrolyte composite films can be used directly as self-supporting electrodes for supercapacitors without additional conductive agents and binders.As a result,the composite films demonstrate enhanced volumetric specific capacity,improved volumetric energy density and higher power density compared with both pure RGO electrode and porous composite electrode prepared by traditional methods.Specifically,when the mass ratio of MXene is 30%,the electrode delivers a volumetric specific capacity of 454.9 F·cm^?3 with a high energy density of 39.4 Wh·L^?1.More importantly,supercapacitors based on the composite films exhibit good flexibility electrochemical performance.The investigation provides a new approach to synthesize dense structure films based on 2D materials for application in high volumetric capacitance flexible supercapacitors.     

Metallic Graphene Nanoribbons

Isolated graphene nanoribbons(GNRs)usually have energy gaps,which scale with their widths,owing to the lateral quantum confinement effect of GNRs.The absence of metallic GNRs limits their applications in device interconnects or being one-dimensional physics platform to research amazing properties based on metallicity.A recent study published in Science provided a novel method to produce metallic GNRs by inserting a symmetric superlattice into other semiconductive GNRs.This finding will broader the applications of GNRs both in nanoelectronics and fundamental science.     

Hierarchical assemblies of molecular frameworks—MOF-on-MOF epitaxial heterostructures

Functional,porous metal-organic frameworks(MOFs)have attracted much attention as a very flexible class of crystalline,porous materials.For more advanced applications that exploit photophysical properties,the fabrication of hierarchical assemblies,including the creation of MOF/MOF heterointerfaces,is important.For the manufacturing of superstructures with length scales well beyond that of the MOF pore size,layer-by-layer(Ibl)methods are particularly attractive.These allow the isoreticular approach to be extended to superstructures with micrometer length scales,a range that is not accessible using conventional MOF design.The Ibl approach further substantially extends the compositional diversity in MOFs.At the same time,the favorable elastic properties of MOFs allow for heteroepitaxial growth,even in the case of lattice misfits as large as 20%.While the MOF-on-MOF approach to designing multicomponent superstructures with synergistic multifunctionality can also be realized with sophisticated solvothermal synthesis schemes,the Ibl(or liquid-phase epitaxy)approach carries substantial advantages,in particular when it comes to the integration of such MOF superstructures into optical or electronic devices.While the structure vertical to the substrate can be adjusted using the Ibl method,photolithographic methods can be used for lateral structuring.In this review,we will discuss the Ibl liquid-phase epitaxy approach to growing surface-anchored MOF thins films(SURMOFs)as well as other relevant one-pot synthesis methods for constructing such hierarchically designed structures and their emerging applications.     

Ternary MOF‑Based Redox Active Sites Enabled 3D‑on‑2D Nanoarchitectured Battery‑Type Electrodes for High‑Energy‑Density Supercapatteries

Designing rationally combined metal-organic frameworks(MOFs)with multifunctional nanogeometries is of significant research interest to enable the electrochemical properties in advanced energy storage devices.Herein,we explored a new class of binderfree dual-layered Ni-Co-Mn-based MOFs(NCM-based MOFs)with three-dimensional(3D)-on-2D nanoarchitectures through a polarityinduced solution-phase method for high-performance supercapatteries.The hierarchical NCM-based MOFs having grown on nickel foam exhibit a battery-type charge storage mechanism with superior areal capacity(1311.4μAh cm^−2 at 5 mA cm^−2),good rate capability(61.8%;811.67μAh cm^−2 at 50 mA cm^−2),and an excellent cycling durability.The superior charge storage properties are ascribed to the synergistic features,higher accessible active sites of dual-layered nanogeometries,and exalted redox chemistry of multi metallic guest species,respectively.The bilayered NCM-based MOFs are further employed as a battery-type electrode for the fabrication of supercapattery paradigm with biomass-derived nitrogen/oxygen doped porous carbon as a negative electrode,which demonstrates excellent capacity of 1.6 mAh cm^−2 along with high energy and power densities of 1.21 mWh cm^−2 and 32.49 mW cm^−2,respectively.Following,the MOF-based supercapattery was further assembled with a renewable solar power harvester to use as a self-charging station for various portable electronic applications.     

Nanoparticles@nanoscale metal-organic framework composites as highly efficient heterogeneous catalysts for size-and shape-selective reactions

Composites incorporating nanoparticles (NPs) within metal-organic frameworks (MOFs) find applications in many different fields.In particular,using MOF layers as molecular sieves built on the NPs could enable selectivity in heterogeneous catalysis.However,such composites typically exhibit low catalytic efficiency,due to the slow diffusion of the reactants in the long and narrow channels of the MOF shell.In order to improve the catalytic efficiency of these systems,here we report the fabrication of NPs incorporated in nanosized MOFs (NPs@nano-MOFs),obtained by reducing the size of the MOF crystals grown around the NPs.The crystal size of the composites was controlled by modulating the nucleation rate of the MOFs during the encapsulation of pre-synthesized and catalytically active NPs;in this way,NPs@MOF crystals smaller than 50 nm were synthesized and subsequently used as highly efficient catalysts.Due to the shorter path from the MOF surface to the active sites,the obtained Pt@nano-MOFs composites showed a higher conversion rate than their larger-sized counterparts in the synthesis of imines via cascade reaction of nitrobenzene and in the hydrogenation of olefins,while retaining the excellent size and shape selectivity associated with the molecular sieving effect of the MOF layer.The present strategy can also be applied to prepare other encapsulated nanostructures combining various types of NPs and nano-MOFs,thus highlighting the broad potential of this approach for developing optimized catalysts with high reactivity and selectivity.     

Controllable photodynamic performance via an acidic microenvironment based on two-dimensional metal-organic frameworks for photodynamic therapy

Photodynamic therapy(PDT)is a widely-used technology for cancer therapy,but conventional photosensitizers still face some drawbacks,such as hydrophobicity,inadequate pharmacokinetics,low cell/tissue specificity,and uncontrollable photodynamic performance during the therapeutic process.Herein,we present a controllable photodynamic performance based on two-dimensional metal-organic frameworks(2D Zn-TCPP MOF)that displayed a week PDT effect under a neutral environment upon exposure to a 660 nm laser due to the degeneracy of Q bands of TCPP.However,the 2D Zn-TCPP MOF showed a significantly enhanced PDT effect in an acidic environment under irradiation with a 660 nm laser due to the released TCPP from decomposed MOF structure.From the in vitro outcomes,the 2D Zn-TCPP MOF showed controllable photodynamic performance from neutral to acidic environments.Due to the acidic tumor microenvironment,the 2D Zn-TCPP MOF presented the strongest antitumor effect in vivo under irradiation with a 660 nm laser.This work offers a promising strategy to develop a next-generation photosensitizer.     

Ultra-small MoS_2 nanodots-incorporated mesoporous silica nanospheres for pH-sensitive drug delivery and CT imaging

Functionalization of mesoporous silica spheres with well-dispersed and ultra-small nanodots to exert their synergistic effects for biomedical applications has been considered to be an urgent challenge.Herein,homogeneously incorporation of ultra-small and monodispersed MoS₂ nanodots in the mesoporous silica nanospheres(MSN)was achieved by a facile one-step solvothermal reaction.The as-synthesized UsMSND@MSN possessed uniform size(~115 nm)and favorable biocompatibility inherited from MSN.The dispersed UsMSND within MSN could act as anchoring sites for aromatic anti-cancer drug DOX loading,and consequently achieved pH-responsive release based on the specialπ-π/electrostatic interactions with the DOX molecules.More importantly,the well-dispersed UsMSND in MSN could function as the non-toxic contrast agent for the sensitive in vivo CT imaging in various tumors including breast cancer and glioma with different sections.This work promises a good strategy for dispersed incorporation of UsMSND into MSN as an excellent pH-responsive platform for simultaneous cancer imaging and therapy.     

De novo synthesis of bifunctional conjugated microporous polymers for synergistic coordination mediated uranium entrapment

This work reports a de novo synthesis of novel bifunctional conjugated microporous polymers(CMPs)exhibiting a synergistic-effect involved coordination behavior to uranium.It is highlighted that the synthetic strategy enables the engineering of the coordination environment within amidoxime functionalized CMP frameworks by specifically introducing ortho-substituted amino functionalities,enhancing the affinity to uranyl ions via forming synergistic complexes.The CMPs exhibit high Brunauer-Emmett-Teller(BET)surface area,well-developed three-dimensional(3D)networks with hierarchical porosity,and favorable chemical and thermal stability because of the covalently cross-linked structure.Compared with the amino-free counterparts,the adsorption capacity of bifunctional CMPs was increased by almost 70%,from 105 to 174 mg/g,indicating evidently enhanced binding ability to uranium.Moreover,new insights into coordination mechanism were obtained by in-depth X-ray photoelectron spectroscopy(XPS)analysis and density functional theory(DFT)calculation,suggesting a dominant role of the oxime ligands forming a 1:1 metal ions/ligands(M/L)coordination model with uranyl ions while demonstrating the synergistic engagement of the amino functionalities via direct binding to uranium center and hydrogen-bonding involved secondary-sphere interaction.This work sheds light on the underlying principles of ortho-substituted functionalities directed synergistic effect to promote the coordination of amidoxime with uranyl ions.And the synthetic strategy established here would enable the task-specific development of more novel CMP-based functional materials for broadened applications.     

A hierarchical heterostructure of CdS QDs confined on 3D ZnIn2S4 with boosted charge transfer for photocatalytic CO2 reduction

Metal sulfide based materials as photocatalysts for energy conversion are essential to produce value-added chemical fuels,but their intrinsically slow carrier dynamics and low activity are yet to be resolved.Herein,we developed a unique heterogeneously nanostructured ZnIn₂S₄-CdS heterostructure that involves zero-dimensional(0D)CdS quantum dots uniformly confined on three-dimensional(3D)ZnIn₂S₄nanoflowers,which achieves an excellent catalytic performance of CO₂ photoconversion under visible-light irradiation.The obtained hierarchical heterostructure can significantly enhance the light harvesting,shorten the migration distance of carriers,and obviously accelerate the transport of electrons.As evidenced by the ultrafast transient absorption spectroscopy,the formed interface can effectively facilitate charge separation and transport.This work opens up a new avenue to carefully design the elaborate heterostructures for achieving optimal charge separation efficiency by lowering interfacial kinetic barriers and energy losses at the interface.     

Formation of a new intermediate phase and its evolution toward θ' during aging of pre-deformed Al-Cu alloys

The frequent occurrence of hitherto unknown phase Pre-θ'-2 and unusual 1.5 _(cθ') thick θ' precipitate was observed by atomic-resolution scanning transmission electron microscopy in the well-studied Al-Cu alloys. This phenomenon is associated with heterogeneous precipitate nucleation and growth on preexisting dislocations introduced by slight deformation prior to aging. In this study, the precise structure details of Pre-θ'-2 was determined by atomic scale imaging, image simulation based on image forming theories and first principle calculations. Pre-θ'-2 has a well-defined ordered structure sandwiched between two 2 aAl(～1.5 _(cθ')) spaced Cu layers on {200}Alplanes. The strong structural similarities between Pre-θ'-2 and 1.5 _(cθ') thick θ' in terms of interfacial structure and thickness, coupled with energetic calculations and preliminary in-situ observations, lead us to propose a new precipitation path toward key strengthening phase θ'.     

Influential Factors on Electromagnetic Properties of Selected 3D Reticulated Ceramics

3D reticulated ceramics (3DRCs) with the composition containing SrFe12O19-SiC-TiO2 were prepared by a replication process with polyurethane sponges as the template in ceramic slurry. The electrical conductivity, dielectric and magnetic parameters of 3D reticulated ceramics (3DRCs) were measured with changes in cell size of the sponges, contents in the slurry and sintering temperature in this paper. Discussions about the influential factors of those parameters were focused on their electrical conductivity. The experimental results indicated that the electrical conductivity of 3DRCs raised with the increase of cell size, SiC/SrO.6Fe2O3 with weight ratio and sintering temperature. X-ray diffractions and SEM were used to investigate the relationship between electrical conductivity and sintering temperature. Deoxidizing reactions of SrO.6Fe2O3 caused the increasing electrical conductivity. The real part of permittivity (ε′) and imaginary part of permeability (μ") raised with the increase of electrical conductivity (σ). The imaginary part of permittivity (ε") has a maximum at 10° S/cm with the increase of σ, and the real part of permeability (μ′)changes slightly with the increase of σ. When σ is at the range of 10-4 S/cm to 100 S/cm (a semi conductive state),both the imagine part of permittivity and permeability raises with increasing σ, therefore, the 3DRCs present their high electromagnetic loss properties.     

Tumor-responsive copper-activated disulfiram for synergetic nanocatalytic tumor therapy

Exploring alternative biomedical use of traditional drugs in different disease models is highly important as it can reduce the cost of drug development and overcome several critical issues of traditional chemodrugs such as low chemotherapeutic efficiency,severe side effect,and drug resistance.Disulfiram(DSF),a clinically approved alcohol-aversion drug,was recently demonstrated tofeature tumor-growth suppression effect along with the co-administration of Cu²⁺species,but direct Cu²⁺administration mode might cause severe toxicity originating from low Cu²⁺accumulation into the tumor and nonspecific Cu²⁺distribution-induced cytotoxicity.Based on the intriguing drug-delivery performance of nanoscale metal-organic frameworks(MOFs),we herein construct HKUST nMOFs as the Cu²⁺self-supplying nanocarriers for efficient delivery of the D SF drug.The mildly acidic condition of tumor microenvironment initially triggered the release of Cu ions from HKUST nMOFs,which further reacted with the encapsulated DSF toform toxic Cu(DDTC)2(activation)for tumor chemotherapy.Especially,during the Cu(DDTC)2 complexation,Cu⁺species were formed concomitantly,triggering the intratumoral nanocatalytic therapy for the generation of reactive oxygen species to synergistically destroying the tumor cells/tissue.As a result,synergetic tumor-responsive chemotherapy and nanocatalytic therapy are enabled by DSF@HKU ST nanodrugs,as demonstrated by the dominant anticancer efficacy with satisfied biocompatibility both in vitro and in vivo.The present work offers a sophisticated strategy for tumor-responsive nontoxic-to-toxic therapeutic with high biocompatibility.     

Chiral metal-organic frameworks with tunable catalytic selectivity in asymmetric transfer hydrogenation reactions

Metal-organic frameworks(MOFs)have achieved great success in the field of heterogeneous catalysis,however,ifs still challenging to design MOF catalysts with enhanced selectivity.Here,we demonstrated a combination strategy of metal design and ligand design on the enantioselectivity—that is the enantioselectivities of chiral MOF(CMOF)catalysts could be significantly enhanced by the rational choice of metal ions with higher electronegativities and introducing sterically demanding groups into the ligands.Four isostructural Ca-,Sr-and Zn-based CMOFs were prepared from enantiopure phosphono-carboxylate ligands of 1,V-biphenol that are functionalized with 2,4,6-trimethyl-and 2,4,6-trifluoro-phenyl groups at the Supposition.The uniformly distributed metal phosphonates along the channels could act as Lewis acids and catalyze the asymmetric transfer hydrogenation of heteroaromatic imines(benzoxazines and quinolines).Particularly,the Ca-based MOF 1 with 2,4,6-trimethyl groups at the substituents exhibited enhanced catalytic performance,affording the highest enantioselectivity(up to 97%).It is also the first report of the heterogeneous catalyst with chiral non-noble metal phosphonate active sites for asymmetric transfer hydrogenation reactions with Hantzsch ester as the hydrogen source.The catalyst design strategy demonstrated here is expected to develop new types of chiral materials for asymmetric catalysis and other chiral applications.