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Transforming permanently porous but electrically insulating metal–organic frameworks (MOFs) into electrically conducting materials is key to expanding their utility beyond traditional guest storage, separation, and delivery applications into the realms of modern electronics and energy technologies. To this end, herein, we have converted a highly porous but intrinsically insulating NU-1000 MOF into semiconducting NU-1000/gold nanoparticle (AuNP) and NU-1000/polydopamine/AuNP composites via MOF- and polymer-induced reduction of infiltrated Au3+ ions into metallic AuNPs. The NU-1000/AuNP and NU-1000/PDA/AuNP composites not only gained significant room temperature electrical conductivity (∼10–7 S/cm), which was ca. 104 times greater than any MOF/metal nanoparticle (MNP) composites exhibited thus far under the same conditions, i.e., without photoinduction and thermal induction, but also retained sizable porosity and surface areas (1527 and 715 m2/g, respectively), which were also larger than most intrinsically conducting 3D MOFs developed to date. The markedly higher conductivities of the NU-1000/AuNP and NU-1000/PDA/AuNP composites can be attributed to more efficient charge hopping or tunneling through well-dispersed AuNPs embedded inside the crystalline MOF matrix, which pristine NU-1000 lacked. Thus, this work presented an effective new strategy to transform porous but nonconducting MOFs into electrically conducting MOF/MNP composites with considerable porosity, which could be useful in future electronics, electrocatalysis, and energy storage devices. [ABSTRACT FROM AUTHOR]

The versatility of metal-organic frameworks (MOFs) has led to groundbreaking applications in a wide variety of fields, especially in the areas of energy, environment, and sustainability. For example, MOFs can be designed for high uptake of toxic gases and pollutants, such as CO 2 , NH 3 , and SO 2 , but designing a single MOF that shows tangible uptake for all of these gases is challenging due to the differences in the chemical and physical properties of these molecules. To this end, integrating multiple MOFs onto textile fibers and crafting various structures have emerged as pivotal developments, enhancing framework durability and usability. MOF composites prepared on readily available textile fibers offer the flexibility essential for critical applications, including heterogeneous catalysis, chemical sensing, toxic gas adsorption, and drug delivery, while preserving the unique characteristics of MOFs. This study introduces a scalable and adaptable method for seamlessly embedding multiple high-performing MOFs onto a single textile fiber using a dip-coating method. We explored the uptake capacity of these multi-MOF composites for CO 2 , NH 3 , and SO 2 and observed a performance similar to that of traditional powdered materials. Along with harmful gas adsorption, we also have evaluated the permeation and reactivity of these MOF/textile composites toward chemical warfare agents (CWAs) like GD (soman), HD (mustard gas), and VX. In combination, these results demonstrate a fundamental advancement toward establishing a consistent strategy for the hydrolysis of nerve agents in real-world scenarios. This approach can substantially increase the protection toward CWAs and enhance the effectiveness of protective equipment such as fabrics for protective garments. This dip-coating method for the integration of multiple MOFs on a single textile fiber unlocks a wealth of possibilities and paves the way for future innovations in the deployment of MOF-based composites.

The world is currently suffering socially, economically, and politically from the recent pandemic outbreak due to the coronavirus disease 2019 (COVID-19), and those in hospitals, schools, and elderly nursing homes face enhanced threats. Healthcare textiles, such as masks and medical staff gowns, are susceptible to contamination of various pathogenic microorganisms, including bacteria and viruses. Metal-organic frameworks (MOFs) can potentially address these challenges due to their tunable reactivity and ability to be incorporated as porous coatings on textile materials. Here, we report how incorporating titanium into the zirconium-pyrene-based MOF NU-1000, denoted as NU-1012 , generates a highly reactive biocidal photocatalyst. This MOF features a rare ligand migration phenomenon, and both the Ti/Zr center and the pyrene linker act synergistically as dual active centers and widen the absorption band for this material, which results in enhanced reactive oxygen species generation upon visible light irradiation. Additionally, we found that the ligand migration process is generally applicable to other csq topology Zr-MOFs. Importantly, NU-1012 can be easily incorporated onto cotton textile cloths as a coating, and the resulting composite material demonstrates fast and potent biocidal activity against Gram-negative bacteria ( Escherichia coli ), Gram-positive bacteria ( Staphylococcus epidermidis ), and T7 bacteriophage virus with up to a 7-log(99.99999%) reduction within 1 h under simulated daylight.

Solid supports are crucial in heterogeneous catalysis due to their profound effects on catalytic activity and selectivity. However, elucidating the specific effects arising from such supports remains challenging. We selected a series of metal-organic frameworks (MOFs) with 8-connected Zr 6 nodes as supports to deposit molybdenum(VI) onto to study the effects of pore environment and topology on the resulting Mo-supported catalysts. As characterized by X-ray absorption spectroscopy (XAS) and single-crystal X-ray diffraction (SCXRD), we modulated the chemical environments of the deposited Mo species. For Mo-NU-1000, the Mo species monodentately bound to the Zr 6 nodes were anchored in the microporous c -pore, but for Mo-NU-1008 they were bound in the mesopore of Mo-NU-1008. Both monodentate and bidentate modes were found in the mesopore of Mo-NU-1200. Cyclohexene epoxidation with H 2 O 2 was probed to evaluate the support effect on catalytic activity and to unveil the resulting structure-activity relationships. SCXRD and XAS studies demonstrated the atomically precise structural differences of the Mo binding motifs over the course of cyclohexene epoxidation. No apparent structural change was observed for Mo-NU-1000, whereas the monodentate mode of Mo species in Mo-NU-1008 and the monodentate and bidentate Mo species in Mo-NU-1200 evolved to a new bidentate mode bound between two adjacent oxygen atoms from the Zr 6 node. This work demonstrates the great advantage of using MOF supports for constructing heterogeneous catalysts with modulated chemical environments of an active species and elucidating structure-activity relationships in the resulting reactions.

Electrochemically active hydrogen-bonded organic frameworks (HOFs) offer opportunities to study charge transport in supramolecular systems where the rate of movement of charges is dependent on weak electronic coupling between individual components. Here, we used potential-step chronoamperometric measurements on electrochemically active, drop-cast HOF-102 films to estimate both redox-hopping-based apparent diffusion coefficients for charge transport and rate constants for linker-to-linker charge transfer (hole transfer) in the mesoporous two-dimensional (2D) plane created by interlinker hydrogen bonding. Also present are one-dimensional columns formed by stacking pyrene units. However, because the HOF-102 crystallites containing these columns are oriented parallel to an underlying electrode, dynamics of charge transport (hole-transport) along the column axis, in contrast to the plane, are not directly probed by the electrochemical measurements. Furthermore, we employed electrochemical impedance spectroscopy to measure the electrical conductivity of the as-deposited films biased at various potentials. We found that both the neutral/singly oxidized and the singly oxidized/doubly oxidized pyrene linker redox couples of HOF-102 can engender hopping-based film conductivity within the 2D plane of HOF-102. Consistent with the radical cation and radical dication nature of the singly and doubly oxidized linkers, respectively, HOF-102 films are electrochromic. The measured values of in-plane charge-diffusion coefficients (∼10 -10 to 10 -11 cm 2 s -1 ) and electrical conductivity (∼10 -6 to 10 -8 S cm -1 ) compare favorably with those for related redox-conductive MOFs and suggest that the transport and conductivity parameters for HOF-102 are sufficiently large to support electrocatalysis by subsequently installed catalysts in films─specifically, films of micron or greater thickness, corresponding to the equivalent hundreds of monolayers of closely packed ( i.e., face-to-face-packed) pyrene-derivatives, but with solution access (solvent, ion, and reactant access) still readily provided by channels oriented parallel to an underlying planar electrode.

Heterometallic Ce IV /M oxo clusters are underexplored yet and can benefit from synergistic properties from combining cerium and other metal cations to produce efficient redox catalysts. Herein, we designed and synthesized a series of new Ce 12 V 6 oxo clusters with different capping ligands: Ce 12 V 6 -SO 4 , Ce 12 V 6 -OTs (OTs: toluenesulfonic acid), and Ce 12 V 6 -NBSA (NBSA: nitrobenzenesulfonic acid). Single crystal X-ray diffraction (SCXRD) for all three structures reveals a Ce 12 V 6 cubane core formulated [Ce 12 (VO) 6 O 24 ] 18+ with cerium on the edges of the cube, vanadyl capping the faces, and sulfate on the corners. While infrared spectroscopy (IR), ultraviolet-visible spectroscopy (UV-vis), electrospray ionization mass spectrometry (ESI-MS), and proton nuclear magnetic resonance ( 1 H NMR) proved the successful coordination of the organic ligands to the Ce 12 V 6 core, liquid phase 51 V NMR and small-angle X-ray scattering (SAXS) confirmed the integrity of the clusters in the organic solutions. Furthermore, functionalization of the Ce 12 V 6 core with organic ligands both provides increased solubility in term of homogeneous application and introduces porosity to the assemblies of Ce 12 V 6 -OTs and Ce 12 V 6 -NBSA in term of heterogeneous application, thus allowing more catalytic sites to be accessible and improving reactivity as compared to the nonporous and less soluble Ce 12 V 6 -SO 4 . Meanwhile, the coordinated ligands also influenced the electronic environment of the catalytic sites, in turn affecting the reactivity of the cluster, which we probed by the selective oxidation of 2-chloroethyl ethyl sulfide (CEES). This work provides a strategy to make full use of the catalytic sites within a class of inorganic sulfate capped clusters via organic ligand introduction.

The most recent global health crisis caused by the SARS-CoV-2 outbreak and the alarming use of chemical warfare agents highlight the necessity to produce efficient protective clothing and masks against biohazard and chemical threats. However, the development of a multifunctional protective textile is still behind to supply adequate protection for the public. To tackle this challenge, we designed multifunctional and regenerable N-chlorine based biocidal and detoxifying textiles using a robust zirconium metal-organic framework (MOF), UiO-66-NH 2 , as a chlorine carrier which can be easily coated on textile fibers. A chlorine bleaching converted the amine groups located on the MOF linker to active N-chlorine structures. The fibrous composite exhibited rapid biocidal activity against both Gram-negative bacteria ( E. coli ) and Gram-positive bacteria ( S. aureus ) with up to a 7 log reduction within 5 min for each strain as well as a 5 log reduction of SARS-CoV-2 within 15 min. Moreover, the active chlorine loaded MOF/fiber composite selectively and rapidly degraded sulfur mustard and its chemical simulant 2-chloroethyl ethyl sulfide (CEES) with half-lives less than 3 minutes. The versatile MOF-based fibrous composite designed here has the potential to serve as protective cloth against both biological and chemical threats.

The understanding of structure-activity relationships at the atomic level has played a profound role in heterogeneous catalysis, providing valuable insights into designing suitable heterogeneous catalysts. However, uncovering the detailed roles of how such active species' structures affect their catalytic performance remains a challenge owing to the lack of direct structural information on a specific active species. Herein, we deposited molybdenum(VI), an active species in oxidation reactions, on the Zr 6 node of a mesoporous zirconium-based metal-organic framework (MOF) NU-1200, using solvothermal deposition in MOFs (SIM). Due to the high crystallinity of the NU-1200 support, the precise structure of the resulting molybdenum catalyst, Mo-NU-1200, was characterized through single-crystal X-ray diffraction (SCXRD). Two distinct anchoring modes of the molybdenum species were observed: one mode (Mo1), displaying an octahedral geometry, coordinated to the node through one terminal oxygen atom and the other mode (Mo2) coordinated to two adjacent Zr 6 node oxygen atoms in a tetrahedral geometry. To investigate the role of base in the catalytic activity of these Mo centers, we assessed the activity of Mo-NU-1200 for the aerobic oxidation of 4-methoxybenzyl alcohol as a model reaction. The results revealed that Mo-NU-1200 exhibited remarkably higher catalytic reactivity under base-free conditions, while the presence of base inhibited the catalytic reactivity of this species. SCXRD studies revealed that the molybdenum binding motifs (structures of the supported metal on the Zr 6 node in the MOF) changed over the course of the reactions. Following the oxidation without base, both pristine coordination modes (Mo1 and Mo2) evolved into a new coordination mode (Mo3), in which the molybdenum atom coordinated to two adjacent oxygen atoms from the Zr 6 node in an octahedral geometry, while in the presence of base, the pristine Mo1 coordination mode evolved entirely into the pristine Mo2. This study demonstrates the direct observation of an active species' structural evolution from metal installation to subsequent catalytic reaction. As a result, these subtle structural changes in catalyst binding motifs led to distinct differences in catalytic activities, providing a compelling strategy for elucidating structure-activity relationships.

A flexible slippery membrane (FSM) with tunable morphology and high elastic deformability has been developed by infusing perfluoropolyether (PFPE) into a fluorinated-copolymer-modified thermoplastic polyurethane (TPU) nanofiberous membrane. To immobilize PFPE in TPU matrix, we synthesized a fluorinated-copolymer poly(DFMA-co-IBOA-co-LMA) with low surface energy, high chemical affinity to PFPE, adequate flexibility, and strong physical adhesion on TPU. Upon external tensile stress, the as-prepared FSM can realize a real-time manipulation of water sliding and coalescence on it. Furthermore, it exhibits the ability to preserve the captured water from being blown away by strong wind, which ensures the water collection efficiency in windy regions.

It is challenging to explore a unified solution for the treatment of oily wastewater from complex sources. Thus, membrane materials with flexible separation schemes are highly desired. Herein, we fabricated a smart membrane by electrospinning TiO2 doped polyvinylidene fluoride (PVDF) nanofibers. The as-formed beads-on-string structure and hierarchical roughness of the nanofibers contribute to its superwetting/resisting property to liquids, which is desirable in oil/water separation. Switched simply by UV (or sunlight) irradiation and heating treatment, the smart membrane can realize reversible separation of oil/water mixtures by selectively allowing water or oil to pass through alone. Most importantly, the as-prepared nanofiber membrane possesses outstanding antifouling and self-cleaning performance resulting from the photocatalytic property of TiO2, which has practical significance in saving solvents and recycling materials. This work provides a route for fabricating cost-effective, easily scaled up, and recyclable membranes for on-demand oil/water separation in versatile situations, which can be of great usage in the new green separation technology.