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.     

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.     

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.     

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.     

Two-dimensional d-πconjugated metal-organic framework based on hexahydroxytrinaphthylene

The development of new two-dimensional(2D)d-πconjugated metal-organic frameworks(MOFs)holds great promise for the construction of a new generation of porous and semiconductive materials.This paper describes the synthesis,structural characterization,and electronic properties of a new d-πconjugated 2D MOF based on the use of a new ligand 2,3,8,9,14,15-hexahydroxytrinaphthylene.The reticular self-assembly of this largeπ-conjugated organic building block with Cu(II)ions in a mixed solvent system of 1,3-dimethyl-2-imidazolidinone(DMI)and H2 O with the addition of ammonia water or ethylenediamine leads to a highly crystalline MOF Cu3(HHTN)2,which possesses pore aperture of 2.5 nm.Cu3(HHTN)2 MOF shows moderate electrical conductivity of 9.01×10^-8S·cm^-1at 385 K and temperature-dependent band gap ranging from 0.75 to 1.65 eV.After chemical oxidation by l2,the conductivity of Cu3(HHTN)2 can be increased by 360 times.This access to HHTN based MOF adds an important member to previously reported MOF systems with hexagonal lattice,paving the way towards systematic studies of structure-property relationships of semiconductive MOFs.     

Glass-like energy and property landscape of Pt nanoclusters

Pt nanoclusters play an important role in catalysis-related applications.Essential to their activities are their geometries and energy landscapes.In this work,we studied the energy landscapes of Pt clusters using a parallel differential evolution optimization algorithm and an accelerated ab initio atomic relaxation method,which allowed us to explore unprecedentedly large numbers of geometry local minima at ab initio level.We found many lower-energy isomers with low symmetry in their geometry.The energy landscapes were demonstrated to be glass-like with a large number of local minimum structures close to the global minimum.The electronic and magnetic properties of most glass-like local minima were dramatically different from the global minimum,and they should be observed in the experimental measurements.The connections between these local minima were further analyzed using data mining techniques.     

Spiral fractal patterns via hierarchical assembly

Chirality is ubiquitous in nature and manifested at various scale from subatom to galaxy.Fractal geometry is also very popular and active in the world.However,there are few reports on the concept of combining fractal patterns and chiral structures in self-assembled systems.It was found that tree-shaped fractal patterns could be self-assembled from the N-[(9H-fluoren-9-ylmethoxy)carbonyl]protected glutamic acid(Fmoc-Glu)and zinc-porphyrin(ZnTPyP).The fractal pattern was composed of nanorod aggregate arranged in a spiral fractal way,in which the nanorods were stacked one-by-one in a single direction.The patterns started with the formation of initial nucleon and growing,during which the diffusion limited aggregation(DLA)mechanism led to the fractal patterns.Interestingly,the spiral packing and their branches were closely related to the absolute configuration of Fmoc-Glu that anticlockwise and clockwise arrangement for L-Fmoc-Glu/ZnTPyP and D-Fmoc-Glu/ZnTPyP,respectively.Our work provides a new finding on the spiral fractal pattern via hierarchical self-assembly.     

Epitaxially aligned single-crystal gold nanoplates formed in large-area arrays at high yield

Well-tailored nanomaterials with a single-crystal character provide ideal building blocks for on-chip plasmonic devices.Although colloidal methods have demonstrated mastery over the synthesis of such structures,it has proven quite difficult to deploy these same nanomaterials on substrate surfaces in a highly deterministic manner where precise control over position and orientation is ensured.Herein,we demonstrate a room-temperature two-reagent liquid-phase seed-mediated synthesis of gold nanoplates directly on substrate surfaces in arrays over a square-centimeter area.The synthesis is reliant on benchtop lithographic and directed-assembly processes that give rise to single-crystal seeds of gold that express both an epitaxial relationship with the underlying substrate and the internal defect structure required to promote a two-dimensional growth mode.The resulting structures are highly faceted and,because seed-substrate epitaxy is imposed upon the growing nanoplates,are identically aligned on the substrate surface.Nanoplate yields are increased to values as high as 95%using a post-processing sonication procedure that selectively removes a small population of irregularly shaped nanostructures from the substrate surface,and in doing so,gives rise to an uncompromised plasmonic response.The work,therefore,advances the techniques needed to integrate single-crystal nanomaterials with wafer-based technologies and provides leading-edge capabilities in terms of defining large-area arrays of plasmonic structures with the nanoplate geometry.     

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.     

Non‑Magnetic Bimetallic MOF‑Derived Porous Carbon‑Wrapped TiO2/ ZrTiO4 Composites for Efficient Electromagnetic Wave Absorption

Modern communication technologies put forward higher requirements for electromagnetic wave(EMW)absorption materials.Metal-organic framework(MOF)derivatives have been widely concerned with its diverse advantages.To break the mindset of magneticderivative design,and make up the shortage of monometallic non-magnetic derivatives,we first try non-magnetic bimetallic MOFs derivatives to achieve efficient EMW absorption.The porous carbon-wrapped TiO2/ZrTiO4 composites derived from PCN-415(TiZr-MOFs)are qualified with a minimum reflection loss of?67.8 dB(2.16 mm,13.0 GHz),and a maximum effective absorption bandwidth of 5.9 GHz(2.70 mm).Through in-depth discussions,the synergy of enhanced interfacial polarization and other attenuation mechanisms in the composites is revealed.Therefore,this work confirms the huge potentials of nonmagnetic bimetallic MOFs derivatives in EMW absorption applications.     

Interfacially stable MOF nanosheet membrane with tailored nanochannels for ultrafast and thermo-responsive nanofiltration

Two-dimensional nanosheet membranes with responsive nanochannels are appealing for controlled mass transfer/separation, but limited by everchanging thicknesses arising from unstable interfaces. Herein, an interfacially stable, thermo-responsive nanosheet membrane is assembled from twin-chain stabilized metal-organic framework (MOF) nanosheets, which function via two cyclic amide-bearing polymers, thermo-responsive poly(N-vinyl caprolactam) (PVCL) for adjusting channel size, and non-responsive polyvinylpyrrolidone for supporting constant interlayer distance. Owing to the microporosity of MOF nanosheets and controllable interface wettability, the hybrid membrane demonstrates both superior separation performance and stable thermo-responsiveness. Scattering and correlation spectroscopic analyses further corroborate the respective roles of the two polymers and reveal the microenvironment changes of nanochannels are motivated by the dehydration of PVCL chains.

     

Quantum-confined ion superfluid in nerve signal transmission

We propose a process of quantum-confined ion superfluid (QISF), which is enthalpy-driven confined ordered fluid, to explain the transmission of nerve signals. The ultrafast Na⁺ and K⁺ ions transportation through all sodium-potassium pump nanochannels simultaneously in the membrane is without energy loss, and leads to QISF wave along the neuronal axon, which acts as an information medium in the ultrafast nerve signal transmission. The QISF process will not only provide a new view point for a reasonable explanation of ultrafast signal transmission in the nerves and brain, but also challenge the theory of matter wave for ions, molecules and particles.

     

Doping modulated in-plane anisotropic Raman enhancement on layered ReS2

Anisotropic two-dimensional (2D) materials exhibit lattice-orientation dependent optical and electrical properties. Carriers doping of such materials has been used to modulate their energy band structures for opto-electronic applications. Herein, we show that by stacking monolayer rhenium disulfide (ReS₂) on a flat gold film, the electrons doping in ReS₂ can affect the in-plane anisotropic Raman enhancement of molecules adsorbed on ReS₂. The change of enhancement factor and the degree of anisotropy in enhancement with layer number are sensitively dependent on the doping level of ReS₂ by gold, which is further confirmed by Kelvin probe force microscopy (KPFM) measurements. These findings could open an avenue for probing anisotropic electronic interactions between molecules and 2D materials with low symmetry using Raman enhancement effect.

     

The fabrication and application of Ni-DNA nanowire-based nanoelectronic devices

DNA is a self-assembled, double stranded natural molecule that can chelate and align nickel ions between its base pairs. The fabrication of a DNA-guided nickel ion chain (Ni-DNA) device was successful, as indicated by the conducting currents exhibiting a Ni ion redox reaction-driven negative differential resistance effect, a property unique to mem-elements (1). The redox state of nickel ions in the Ni-DNA device is programmable by applying an external bias with different polarities and writing times (2). The multiple states of Ni-DNA-based memristive and memcapacitive systems were characterized (3). As such, the development of Ni-DNA nanowire device-based circuits in the near future is proposed.

     

Mimicking peroxidase active site microenvironment by functionalized graphene quantum dots

The development of high-efficiency peroxidase mimetics is highly desirable in view of high cost and low stability of natural enzymes. From the perspective of mimicking active site microenvironment at low cost, we herein report a novel histidine-functionalized graphene quantum dot (His-GQD)/hemin complex, which exhibits the highest catalytic rate for the peroxidase-based chromogenic reaction among the hemin-containing mimetics reported so far. Also, our peroxidase mimetic shows excellent tolerance to strongly acidic conditions and can function in a wide temperature range. Lineweaver-Burk plots and comprehensive electron paramagnetic resonance analysis reveal a ping-pong type catalytic mechanism for this mimetic. In addition, His-GQD/hemin demonstrates high efficiency and accuracy in detecting H₂O₂ and blood glucose. Our work provides an effective design of artificial enzymes for practical applications.

     

Superbroad-band actively tunable acoustic metamaterials driven from poly(ethylene terephthalate)/carbon nanotube nanocomposite membranes

Actively tunable acoustic metamaterials have attracted ever increasing attention.However,their tunable frequency range is quite narrow(tens of Hz)even under ultrahigh applied voltage(about 1,000 V).Here,we report a superbroad-band actively tunable acoustic metamaterials with the bandwidth over 400 Hz under a low voltage.In the actively tunable acoustic metamaterials,the acoustic membrane is a laminated nanocomposite consisting of a poly(ethylene terephthalate)(PET)and super-aligned carbon nanotube(CNT)drawn from CN T forest array.The laminated nanocomposite membrane exhibits adjustable acoustic properties,whose modulus can be adjusted by applying external electric field.The maximum frequency bandwidth of PET/CN T nanocomposite membrane reaches 419 Hz when applying an external DC voltage of 60 V.Our actively tunable acoustic metamaterials with superbroad-band and lightweight show very promising foreground in noise reduction applications.     

Bioengineering of nano metal-organic frameworks for cancer immunotherapy

Immunotherapy techniques,such as immune checkpoint inhibitors,chimeric antigen receptor(CAR)T cell therapies and cancer vaccines,have been burgeoning with great success,particularly for specific cancer types.However,side effects with fatal risks,dysfunction in tumor microenvironment and low immune response rates remain the bottlenecks in immunotherapy.Nano metal-organic frameworks(nMOFs),with an accurate structure and a narrow size distribution,are emerging as a solution to these problems.In addition to their function of temporospatial delivery,a large library of their compositions,together with flexibility in chemical interaction and inherent immune efficacy,offers opportunities for various designs of nMOFs for immunotherapy.In this review,we overview state-of-the-art research on nMOFs-based immunotherapies as well as their combination with other therapies.We demonstrate that nMOFs are predominantly customized for vaccine delivery or tumor-microenvironment modulation.Finally,a prospect of nMOFs in cancer immunotherapy will be discussed.     

FeOOH quantum dots decorated graphene sheet: An efficient electrocatalyst for ambient N2 reduction

Electrochemical N₂ reduction offers a promising alternative to the Haber-Bosch process for sustainable NH₃ synthesis at ambient conditions, but it needs efficient catalysts for the N₂ reduction reaction (NRR). Here, we report that FeOOH quantum dots decorated graphene sheet acts as a superior catalyst toward enhanced electrocatalytic N₂ reduction to NH₃ under ambient conditions. In 0.1 M LiClO₄, this hybrid attains a large NH₃ yield rate and a high Faradaic efficiency of 27.3 µg·h⁻¹·mg⁻¹_cat. and 14.6% at −0.4 V vs. reversible hydrogen electrode, respectively, rivalling the current efficiency of all Fe-based NRR electrocatalysts in aqueous media. It also shows strong durability during the electrolytic process.

     

All-inorganic dual-phase halide perovskite nanorings

In the present work, we report the growth of all-inorganic perovskite nanorings with dual compositional phases of CsPbBr₃ and CsPb₂Br₅ via a facile hot injection process. The self-coiling of CsPbBr₃-CsPb₂Br₅ nanorings is driven by the axial stress generated on the outside surface of the as-synthesized nanobelts, which results from the lattice mismatch during the transformation of CsPbBr₃ to CsPb₂Br₅. The tailored growth of nanorings could be achieved by adjusting the key experimental parameters such as reaction temperature, reaction time and stirring speed during the cooling process. The photoluminescence intensity and quantum yield of nanorings are higher than those of CsPbBr₃ nanobelts, accompanied by a narrower full width at half maximum (FWHM), suggesting their high potential for constructing self-assembled optoelectronic nanodevices.

     

Vacuum-tuned-atmosphere induced assembly of Au@Ag core/shell nanocubes into multi-dimensional superstructures and the ultrasensitive IAPP proteins SERS detection

Utilizing vacuum-tuned-atmosphere induced dip coating method, we achieve the cross-dimensional macroscopic diverse self-assemblies by using one building block with one chemical functionality. Coordinated modulating the vacuum degree, colloid concentration and evaporation atmosphere, Au@Ag core/shell NCs can controllably assemble into diverse multi-dimensional superstructures. Under 0.08 MPa, we obtained the two-dimensional (2D) stepped superstructures with continuously tunable step width. In addition, we generated a series of tailorable nanoscale-roughened 2D Au@Ag NCs superstructures at 0.04 MPa, which exhibited the label-free ultrasensitive SERS detection for the different mutants of IAPP8-37 proteins. Under 0.01 MPa, we obtained the cross-dimensional tailorable Au@Ag NCs assemblies from random to macroscale 2D and three-dimensional (3D) densest superstructures by adjusting the capping ligand-environmental molecule interactions. This is a flexible method to generate as-prepared Au@Ag core/shell NCs into well-defined macroscopic diverse superstructures and to promote the exploitation into biological applications.