A Drop-and-Drain Method for Convenient and Efficient Fabrication of MOF/Fiber Composites.

The fabrication of flexible composites by integrating metal-organic frameworks (MOFs) with flexible substrates is a critical strategy for developing advanced materials with excellent feasibility and processability. These flexible MOF-based composites play a particularly important role in the separation and purification processes. However, several drawbacks remain challenge to overcome such as long processing time, high-cost, complicated processes, or harsh reaction conditions. In this paper, a convenient and efficient method is reported for fabricating MOF/fiber composites using a simple drop-and-drain (D&D) process. By exploiting the electrostatic interactions between the positively charged MOF particles and negatively charged fiber-based flexible substrates, a uniform coating of MOF on flexible fibers are achieved. This is accomplished by allowing the MOF ink to drop and drain through a substrate using a custom-made Teflon cell. Additionally, the D&D method enables the production of multiple layers of composites in a single-step process. UiO-66 and ZIF-8 submicroparticles and various substrates such as cotton-pad, cotton-fabric, nylon-fabric, PET-fabric, and filter-paper are employed to create flexible MOF/fiber composites. These composites demonstrate outstanding capacities for capturing negatively charged organic dyes, including methyl orange and indigo carmine. Furthermore, the MOF/fiber composites can be reused for dye capture after a simple washing process.

Au Octahedral Nanosponges: 3D Plasmonic Nanolenses for Near-Field Focusing.

Here, we report the synthesis of three-dimensional plasmonic nanolenses for strong near-field focusing. The nanolens exhibits a distinctive structural arrangement composed of nanoporous sponge-like networks within their interior. We denote these novel nanoparticles as "Au octahedral nanosponges" (Au Oh NSs). Employing a carefully planned multistep synthetic approach with Au octahedra serving as sacrificial templates, we successfully synthesized Au Oh NSs in solution. The porous domains resembling sponges contributed to enhanced scattering and absorption of incident light within metal ligaments. This optical energy was subsequently transferred to the nanospheres at the vertex, where near-field focusing was maximized. We named this observed enhancement a "lightning-sphere effect". Using single particle-by-particle surface-enhanced Raman scattering (SERS), we optimized the morphological dimensions of the spheres and porous domains to achieve the most effective near-field focusing. In the context of bulk SERS measurements targeting weakly adsorbing analytes (2-chloroethyl phenyl sulfide) in the gas phase, we achieved a low detection limit of 10 ppb. For nonadsorbing species (dimethyl methyl phosphonate), utilization of hybrid SERS substrates consisting of Au Oh NSs and metal-organic frameworks as gas-adsorbing intermediate layers was highly effective for successful SERS detection.

Induced Production of Atypical Naturally Nonpreferred Metal-Organic Frameworks and Their Detachment via Provoking Post-Mismatching.

The structures of metal-organic frameworks (MOFs) are typically determined by the building blocks that compose them and the conditions under which they are formed. MOFs tend to adopt a thermodynamically and/or kinetically stable structure (naturally preferred form). Thus, constructing MOFs with naturally nonpreferred structures is a challenging task, as it requires avoiding the easier pathway toward a naturally preferred MOF. Herein, an approach to construct naturally nonpreferred dicarboxylate-linked MOFs employing reaction templates is reported. This strategy relies on the registry between the surface of the template and the cell lattice of a target MOF, which reduces the effort required to form naturally nonpreferred MOFs. Reactions of p-block trivalent metal ions (Ga3+ and In3+ ) with dicarboxylic acids typically produce preferred MIL-53 or MIL-68. However, the surface of UiO-67 (and UiO-66) template exhibits the well-defined hexagonal lattice, which induce the selective formation of a naturally nonpreferred MIL-88 structure. Inductively grown MIL-88s are purely isolated from the template via provoking a post-mismatch in their lattices and weakening the interfacial interaction between product and template. It is also discovered that an appropriate template for effective induced production of naturally nonpreferred MOFs shall be properly selected based on the cell lattice of a target MOF.

Surface Charge-Directed Efficient and Selective Catalytic Activities of Porous M@UiO-66 Composites (M = Pt or Ag) for Reduction of Organic Pollutants.

Precisely constructed porous composites containing catalytically active nanoparticles can stabilize unstable nanoparticles, thus improving catalytic activity and longevity while preventing agglomeration of active nanoparticles. Herein, we report the confined incorporation of highly active metal nanoparticles within a metal-organic framework support and efficient catalytic performances in the reduction of organic pollutants, such as methylene blue (MB) and 4-nitrophenol (4-NP). UiO-66-based porous composites (M@UiO-66, M = Pt or Ag) containing well-dispersed metal nanoparticles are constructed via the one-step thermal treatment of UiO-66 implanted with metal ions (UiO-66/Mn+, Mn+ = Pt2+ or Ag+). The comprehensive features of M@UiO-66s, such as well-dispersed nanocatalysts, well-developed pores, and characteristic surface charges, expedite not only efficient but also selective catalytic activities in the reduction of MB or 4-NP, along with impressive recyclability.

Tip-To-Middle Anisotropic MOF-On-MOF Growth with a Structural Adjustment.

Well-organized construction of hybrid metal-organic frameworks (MOFs) with complicated structures or components is a great importance because of their potential usefulness. In this regard, the conjugation of more than two MOFs, which have dissimilar components and/or structures, is a smart strategy for the production of hybrid MOFs. MOF-on-MOF growth is fundamental for the conjugation of two MOFs and should be deeply understood for the finely controlled conjugation and for the formation of well-organized hybrid MOFs. Herein, we report an interesting MOF growth process for the construction of hybrid MOF particles containing heterogeneous components and cell lattices. Interestingly, even though a newly grown MOF and an MOF template have mismatched cell lattices, the anisotropic growth results in unexpectedly well-defined core-shell-type hybrid MOFs. Comprehensive monitoring of the growth process revealed a tip-to-middle MOF-on-MOF growth, which elucidates the uncommon formation of a well-defined core-shell hybrid despite the anisotropic growth. A tip-to-middle anisotropic growth process is accompanied by self-adjustment of MOF cell lattices to anchor on the template surface having mismatched cell lattices in the early reaction stage and self-reversion of cell lattices to the original comfortable configuration in the middle stage of the reaction.

Atypical Hybrid Metal-Organic Frameworks (MOFs): A Combinative Process for MOF-on-MOF Growth, Etching, and Structure Transformation.

The structural, compositional, and morphological features of metal-organic frameworks (MOFs) govern their properties and applications. Construction of hybrid MOFs with complicated structures, components, or morphologies is significant for the development of well-organized MOFs. An advanced route is reported for construction of atypical hybrid MOFs with unique morphologies and complicated components: 1) MOF-on-MOF growth of a 3D zeolitic imidazolate framework (ZIF) on a ZIF-L template, 2) etching of a part of the 2D ZIF-L template, and 3) structural transformation of 2D ZIF-L into 3D ZIF. The formation of core-shell-type MOF rings and plates is controlled by regulating the three processes. The formation route for the core-shell-type MOF rings and plates was monitored by tracking changes in morphology, structure, and composition. Carbon materials prepared from the pyrolysis of the core-shell-type hybrid MOFs displayed enhanced oxygen reduction reaction activities compared to their monomeric counterparts.

Synthesis of Bimetallic Conductive 2D Metal-Organic Framework (Cox Niy -CAT) and Its Mass Production: Enhanced Electrochemical Oxygen Reduction Activity.

The development of new electrocatalysts for electrochemical oxygen reduction to replace expensive and rare platinum-based catalysts is an important issue in energy storage and conversion research. In this context, conductive and porous metal-organic frameworks (MOFs) are considered promising materials for the oxygen reduction reaction (ORR) due to not only their high surface area and well-developed pores but also versatile structural features and chemical compositions. Herein, the preparation of bimetallic conductive 2D MOFs (Cox Niy -CATs) are reported for use as catalysts in the ORR. The ratio of the two metal ions (Co2+ and Ni2+ ) in the bimetallic Cox Niy -CATs is rationally controlled to determine the optimal composition of Cox Niy -CAT for efficient performance in the ORR. Indeed, bimetallic MOFs display enhanced ORR activity compared to their monometallic counterparts (Co-CAT or Ni-CAT). During the ORR, bimetallic Cox Niy -CATs retain an advantageous characteristic of Co-CAT in relation to its high diffusion-limiting current density, as well as a key advantage of Ni-CAT in relation to its high onset potential. Moreover, the ORR-active bimetallic Cox Niy -CAT with excellent ORR activity is prepared at a large scale via a convenient method using a ball-mill reactor.

Well-Arranged and Confined Incorporation of PdCo Nanoparticles within a Hollow and Porous Metal-Organic Framework for Superior Catalytic Activity.

A convenient method for the confined incorporation of highly active bimetallic PdCo nanocatalysts within a hollow and porous metal-organic framework (MOF) support is presented. Several chemical conversions occur simultaneously during the one-step low temperature pyrolysis of well-designed polystyrene@ZIF-67/Pd2+ core-shell microspheres, where ZIF (zeolitic imidazolate framework) is a subclass of MOF: the polystyrene core is removed, resulting in a beneficial hollow and porous ZIF support; the ZIF-67 shell acts as a well-defined porous support and as a felicitous Co2+ supplier for metal nanoparticle formation; and Pd2+ and Co2+ are reduced to form catalytically active bimetallic PdCo nanoparticles in the well-defined micropores, inducing the confined growth of PdCo nanoparticles with excellent dispersity.

Improvement in Crystallinity and Porosity of Poorly Crystalline Metal-Organic Frameworks (MOFs) through Their Induced Growth on a Well-Crystalline MOF Template.

Porous metal-organic frameworks (MOFs) are interesting materials owing to their interesting structural features and their many useful properties and applications. In particular, the structural features are greatly important to optimize the MOFs' porosities and so properties. Indeed, the MOFs' well-developed micropore and high surface area are the most important structural features, and as such, many practical applications of MOFs originate from these structural features. We herein demonstrate a strategy for improving the crystallinity of MOFs, and so increasing the porosity and surface area of poorly crystalline MOFs by making them in core-shell-type hybrids through the induced growth on the well-crystalline template. Although poorly crystalline versions of MOFs generate naturally in the absence of the well-crystalline template, well-crystalline versions of MOFs produce inductively in the presence of the well-crystalline template. In addition, the crystallinity enhancement of MOFs brings together the improvement in their porosities and surface areas. The surface areas and pore volumes of the well-crystalline versions of MOFs produced through the induced growth on the template are calculated based on this study, indicating that MOF surface areas increase by up to 7 times compared to the poorly crystalline versions.

Isotropic and Anisotropic Growth of Metal-Organic Framework (MOF) on MOF: Logical Inference on MOF Structure Based on Growth Behavior and Morphological Feature.

The growth of one metal-organic framework (MOF) on another MOF for constructing a heterocompositional hybrid MOF is an interesting research topic because of the curiosity regarding the occurrence of this phenomenon and the value of hybrid MOFs as multifunctional materials or routes for fine-tuning MOF properties. In particular, the anisotropic growth of MOF on MOF is fascinating for the development of MOFs possessing atypical shapes and heterostructures or abnormal properties. Herein, we clarify the understanding of growth behavior of a secondary MOF on an initial MOF template, such as isotropic or anisotropic ways associated with their cell parameters. The isotropic growth of MIL-68-Br on the MIL-68 template results in the formation of core-shell-type MIL-68@MIL-68-Br. However, the unique anisotropic growth of a secondary MOF (MOF-NDC) on the MIL-68 template results in semitubular particles, and structural features of this unknown secondary MOF are successfully speculated for the first time on the basis of its unique growth behavior and morphological characteristics. Finally, the validation of this structural speculation is verified by the powder X-ray diffraction and the selected area electron diffraction studies. The results suggests that the growth behavior and morphological features of MOFs should be considered to be important factors for understanding the MOFs' structures.

Facile Synthesis of Au or Ag Nanoparticles-Embedded Hollow Carbon Microspheres from Metal-Organic Framework Hybrids and Their Efficient Catalytic Activities.

Au or Ag nanoparticles-embedded hollow carbon spheres, which display outstanding catalytic activity and excellent recyclability, are prepared by a one-step pyrolysis of metal-organic framework (MOF) hybrids consisting of polystyrene cores and MOF shells loaded with noble metal ions (polystyrene@ZIF-8/M(n+) ; M(n+) = Au(3+) or Ag(+) ).

Morphological and Structural Evolutions of Metal-Organic Framework Particles from Amorphous Spheres to Crystalline Hexagonal Rods.

Compositions as well as morphologies and structures of particles are vital factors that define their properties and applications. However, the morphology and structure changes associated with the composition change of metal-organic frameworks (MOFs) are barely studied. Herein, we report the morphology and structure changes of MOF particles associated with the ratio of two organic linkers incorporated within MOF particles, when they are constructed from the reactions of In(NO3)3 in the presence of isophthalic acid (H2IPA) and/or 1,4-benzenedicarboxylic acid (H2BDC). Two tendencies­the tendency of BDC and In(3+) to form porous crystalline hexagonal rods, and the tendency of IPA and In(3+) to form non-porous amorphous spherical particles­compete during the formation of MOF particles. Eventually, the incorporated ratio of BDC and IPA within the MOF particles, and thus their morphology and porosity, are controlled by altering the relative amounts of H2BDC and H2IPA used during the reactions.

Dual changes in conformation and optical properties of fluorophores within a metal-organic framework during framework construction and associated sensing event.

Microsized chemosensor particle (CPP-16, CPP means coordination polymer particle), which is made from a metal-organic framework (MOF), is synthesized using pyrene-functionalized organic building block. This building block contains three important parts, a framework construction part, a Cu(2+) detection part, and a fluorophore part. PXRD studies have revealed that CPP-16 has a 3D cubic structure of MOF-5. During both MOF formation and sensing event, fluorophores within CPP-16 undergo dual changes in conformation and optical properties. After MOF construction, pyrene moieties experience an unusual complete conversion from monomer to excimer form. This conversion takes place due to a confinement effect induced by space limitations within the MOF structure. The selective sensing ability of CPP-16 on Cu(2+) over many other metal ions is verified by emission spectra and is also visually identified by fluorescence microscopy images. Specific interaction of Cu(2+) with binding sites within CPP-16 causes a second conformational change of the fluorophores, where they change from stacked excimer (CPP-16) to quenched excimer states (CPP-16·Cu(2+)).

Coordination polymer nanobamboos of {Fe(x)In(1-x)}-MIL-88B: induced formation of a virtual In-MIL-88B.

A precise fabrication of nanobamboo structures made from hybrid coordination polymers of the type {Fex In1-x }-MIL-88B is demonstrated. The compositions of the hybrid coordination polymer nanobamboos of {Fex In1-x }-MIL-88B (x=0.06, 0.19, or 0.75) are regulated by altering the amount of metal ions used in the reactions. Interestingly, the formation of a virtual In-MIL-88B (precise structure, {Fe0.06 In0.94 }-MIL-88B), which cannot be created in a typical reaction, is induced by the assistance of a Fe-MIL-88B structure. The a and c cell parameters of {Fe0.06 In0.94 }-MIL-88B are calculated at 10.95 and 19.86 Å, respectively. These values of {Fe0.06 In0.94 }-MIL-88B are larger than those of pure Fe-MIL-88B owing to the large ionic size of In(3+) within the framework.

Synthesis and photoluminescence properties of Eu3+-doped silica@coordination polymer core-shell structures and their calcinated silica@Gd2O3:Eu and hollow Gd2O3:Eu microsphere products.

The conjugation of Eu(3+)-doped coordination polymers constructed from Gd(3+) and isophthalic acid (H(2)IPA) with silica particles is investigated for the production of luminescent microspheres. A series of doping ratio-controlled silica@coordination polymer core-shell spheres is easily synthesized by altering the amounts of metal nodes used in the reactions, where the ratios of Gd(3+) and Eu(3+) are 10:0 (1a), 9:1 (1b), 8:2 (1c), 7:3 (1d), 5:5 (1e), and 0:10 (1f). The formation of monodisperse uniform core-shell structures is achieved throughout the entirety of a series. Investigations of the photoluminescence property of the resulting series of silica@coordination polymer core-shell spheres reveal that 20% Eu(3+)-doped product (1c) has the strongest emission intensity. The subsequent calcination process on the silica@coordination polymer core-shell structures (1a-f) results in the formation of a series of doping ratio-controlled silica@Gd(2)O(3):Eu core-shell microspheres (2a-f) with uniform shell thickness. During the calcination step, the coordination polymers within silica@coordination polymer core-shells are transformed into metal oxides, resulting in silica@Gd(2)O(3):Eu core-shell structures. The final etching process on the silica@Gd(2)O(3):Eu core-shell microspheres (2a-f) produces a series of hollow Gd(2)O(3):Eu microspheres (3a-f) as a result of the elimination of silica cores. The luminescence intensities of silica@Gd(2)O(3):Eu core-shell (2a-f) and hollow Gd(2) O(3):Eu microspheres (3a-f) also vary depending upon the doping ratio of Eu(3+) ions.

The "Texas-sized" molecular box: a versatile building block for the construction of anion-directed mechanically interlocked structures.

Over the last two decades, researchers have focused on the synthesis and development of mechanically interlocked molecules (MIMs). The intramolecular motion of mechanical bonds and the ability to induce this effect with the choice of the proper external stimuli has prompted the development of macromolecular systems that possess the ability to "perform work" at the molecular level. Currently, researchers are working to incorporate interlocked species into complex structural systems, such as molecular frameworks and nanoparticles, and to create ever more elegant noncovalent architectures. This effort provides an incentive to generate new building blocks for the construction of MIMs. In this Account, we describe progress in the development of a new cationic building block inspired by the "blue box" of Stoddart and collaborators. The blue box (cylcobis(paraquat-p-phenylene) or CBPQT(4+)) is a tetracationic, electron-deficient macrocycle widely recognized for its role in the construction of MIMs. This venerable receptor displays a high affinity for a variety of π-donor guests, and researchers have used them to construct a wide range of molecular and supramolecular structures, including rotaxanes, catenanes, pseudorotaxanes, polypseudorotaxanes, pseudo[n]polyrotaxanes, and electrochemically switchable molecules. To date, several synthetic analogues of the basic CBPQT(4+) structure have been reported, including systems containing biphenylene linkers and chiral tetracationic cyclophanes. However, researchers have not yet fully generalized the promise of the blue box. In this Account, we chronicle the development of a larger, more flexible tetracationic macrocycle, referred to as the "Texas-sized" molecular box. To highlight its relatively increased size and to distinguish it from CBPQT(4+), we have chosen to color this new receptor burnt orange. The Texas-sized box (cyclo[2](2,6-di(1H-imidazol-1-yl)pyridine)[2](1,4-dimethylenebenzene), 1(4+)·4PF(6)(-)) acts as a dynamic molecular receptor that displays an ability to adjust its shape and conformation to accommodate anionic guests of different size and charge within its central core. The use of different guests can favor different binding modes and promote the formation of different macromolecular aggregates. Furthermore, the proper selection of the guest allows for the "turning on" or "turning off" of molecular threading and can be used to produce new kinds of threaded species. This dynamic behavior is a special feature of the Texas-sized molecular box, as is its ability to stabilize a range of polypseudorotaxanes, rotaxane-containing metal-organic frameworks (MORFs), and rotaxane-based supramolecular organic frameworks (RSOFs).

Systematic formation of multilayered core-shell microspheres through the multistep growth of coordination polymers.

Hybrid materials: The multistep growth of various coordination polymers has been demonstrated to induce formation of well-defined multilayered core-shell structures. Composition of these structures can be fine-tuned by altering the sequence of the multistep-growth process (see scheme).

Structural Compromise Between Conflicted Spatial-Arrangements of Two Linkers in Metal-Organic Frameworks.

The structural control of metal-organic frameworks (MOFs) is essential for the development of superlative MOFs because the structural features of MOFs and their components play a critical role in determining their properties, and ultimately, their applications. The best components to endow the desired properties for MOFs are available via the appropriate choice from many existing chemicals or synthesizing new ones. However, to date, considerably less information exists regarding fine-tuning the MOF structures. Herein, a strategy for tuning MOF structures by merging two MOF structures into a single MOF, is demonstrated. Depending on the incorporated amounts and relative contributions of the two coexisting organic linkers, benzene-1,4-dicarboxylate (BDC2- ) and naphthalene-1,4-dicarboxylate (NDC2- ), which have conflicting spatial-arrangement preferences within an MOF structure, MOFs are rationally designed to have a Kagomé or rhombic lattice. In particular, MOFs with rhombic lattices are constructed to have specific lattice angles by compromising the optimal structural arrangements between the two mixed linkers. The relative contributions of the two linkers during MOF construction determine the final MOF structures, and the competitive influence between BDC2- and NDC2- is effectively regulated to produce specific MOF structures with controlled lattices.

Defective MOF-74 with ancillary open metal sites for the enhanced adsorption of chemical warfare agent simulants.

The development of effective porous adsorbents plays a vital role in eliminating hazardous substances from the environment. Toxic chemicals, including chemical warfare agents (CWAs), pose significant risks to both humans and ecosystems, highlighting the urgency to create efficient porous adsorbents. Therefore, substantial attention has been directed towards advancing adsorption techniques for the successful eradication of CWAs from the environment. Herein, we demonstrate a rational approach for enhancing the adsorption capability of a porous metal-organic framework (MOF) by employing ancillary open metal sites within the MOF structure. To generate defective MOF-74 (D-MOF-74) with ancillary open metal sites, some of the 2,5-dihydroxy-1,4-bezenedicarboxylic acid (DHBDC) linkers originally present in the MOF-74 structure were replaced with 1,4-benzenedicarboxylic acid (BDC) linkers. The absence of hydroxyl groups in the BDC linkers compared to the original DHBDC linkers creates ancillary open metal sites, which enhance the adsorption ability of D-MOF-74 for CWA simulants such as dimethyl methyl phosphonate, 2-chloroethyl ethyl sulfide, and methyl salicylate by providing effective interaction sites for the targeted molecules. However, excessive creation of open metal sites causes the collapse of the originally well-developed MOF-74 structure, resulting in a substantial reduction in its empty space and a subsequent decline in adsorption efficiency. Thus, to produce a defective MOF with the best performance, it is necessary to replace an appropriate amount of organic linker and create suitable open metal sites. Moreover, D-MOF-74 displays excellent recyclability during consecutive adsorption cycles without losing its original structure and morphology, suggesting that D-MOF-74 is an effective and stable material for the removal of CWA simulants.

Enhanced adsorption capacity of ZIF-8 for chemical warfare agent simulants caused by its morphology and surface charge.

The effective separation of toxic chemicals, including chemical warfare agents (CWAs), from the environment via adsorption is of great importance because such chemicals pose a significant threat to humans and ecosystems. To this end, the development of effective porous adsorbents for CWA removal has received significant attention. Understanding the specific interactions between adsorbents and CWAs must precede for the development of effective adsorbents. Herein, we report the relationship between the adsorption capacity of porous ZIF-8 and its morphological and surface characteristics. Four types of ZIF-8, which have different morphologies (such as cubic, rhombic dodecahedron, and leaf- and plate-shaped samples), were selectively prepared. The four types of ZIF-8 were found to have different surface charges owing to dissimilarly exposed components on the surfaces and additionally incorporated components. The specific surface charges of ZIF-8 were found to be closely related to their adsorption capacities for CWA simulants such as 2-chloroethyl ethyl sulfide (CEES) and dimethyl methyl phosphonate (DMMP). Cubic ZIF-8, with the most positive surface charge among four ZIF-8 samples, exhibited the highest adsorption capacity for CEES and DMMP via the effective polar interaction. Moreover, ZIF-8 exhibited excellent recyclability without losing its adsorption capacity and without critical morphological or structural changes.