Nanotrap Grafted Anionic MOF for Superior Uranium Extraction from Seawater.

On-demand uranium extraction from seawater (UES) can mitigate growing sustainable energy needs, while high salinity and low concentration hinder its recovery. A novel anionic metal-organic framework (iMOF-1A) is demonstrated adorned with rare Lewis basic pyrazinic sites as uranyl-specific nanotrap serving as robust ion exchange material for selective uranium extraction, rendering its intrinsic ionic characteristics to minimize leaching. Ionic adsorbents sequestrate 99.8% of the uranium in 120 mins (from 20,000 ppb to 24 ppb) and adsorb large amounts of 1336.8 mg g-1 and 625.6 mg g-1 from uranium-spiked deionized water and artificial seawater, respectively, with high distribution coefficient, Kd U ≥ 0.97 × 106  mL g-1 . The material offers a very high enrichment index of ≈5754 and it achieves the UES standard of 6.0 mg g-1 in 16 days, and harvests 9.42 mg g-1 in 30 days from natural seawater. Isothermal titration calorimetry (ITC) studies quantify thermodynamic parameters, previously uncharted in uranium sorption experiments. Infrared nearfield nanospectroscopy (nano-FTIR) and tip-force microscopy (TFM) enable chemical and mechanical elucidation of host-guest interaction at atomic level in sub-micron crystals revealing extant capture events throughout the crystal rather than surface solely. Comprehensive experimentally guided computational studies reveal ultrahigh-selectivity for uranium from seawater, marking mechanistic insight.

Ionic metal-organic frameworks (iMOFs): progress and prospects as ionic functional materials.

Metal-organic frameworks (MOFs) have been a research hotspot for the last two decades, witnessing an extraordinary upsurge across various domains in materials chemistry. Ionic MOFs (both anionic and cationic MOFs) have emerged as next-generation ionic functional materials and are an important subclass of MOFs owing to their ability to generate strong electrostatic interactions between their charged framework and guest molecules. Furthermore, the presence of extra-framework counter-ions in their confined nanospaces can serve as additional functionality in these materials, which endows them a significant advantage in specific host-guest interactions and ion-exchange-based applications. In the present review, we summarize the progress and future prospects of iMOFs both in terms of fundamental developments and potential applications. Furthermore, the design principles of ionic MOFs and their state-of-the-art ion exchange performances are discussed in detail and the future perspectives of these promising ionic materials are proposed.

Unveiling the Impact of Diverse Morphology of Ionic Porous Organic Polymers with Mechanistic Insight on the Ultrafast and Selective Removal of Toxic Pollutants from Water.

In recent years, detoxification of contaminated water by different types of materials has received a great deal of attention. However, lack of methodical in-depth understanding of the role of various physical properties of such materials toward improved sorption performance limits their applicable efficiencies. In perspective, decontamination of oxoanion-polluted water by porous materials with different morphologies are unexplored due to a shortfall of proper synthetic strategies. Herein, systematic optimization of sequestration performance toward efficient decontamination of toxic oxoanion-polluted water has been demonstrated by varying the morphologies of an imidazolium-based cationic polymeric network [ionic porous organic polymers (iPOP-5)]. Detailed morphological evolution showed that the chemically stable ionic polymer exhibited several morphologies such as spherical, nanotube, and flakes. Among them, the flakelike material [iPOP-5(F)] showed ultrafast capture efficiency (up to ∼99 and >85% removal within less than 1 min) with high saturation capacities (301 and 610 mg g-1) toward chromate [Cr(VI)] and perrhenate [Re(VII)] oxoanions, respectively, in water. On the other hand, the spherical-shaped polymer [iPOP-5(S)] exhibited relatively slow removal kinetics (>5 min for complete removal) toward both Cr(VI) and Re(VII) oxoanions. Notably, iPOP-5(F) eliminated Cr(VI) and Re(VII) selectively even in the presence of excessive (∼100-fold) competing anions from both high- and low-concentration contaminated water. Further, the compound demonstrated efficient separation of those oxoanions in a wide pH range as well as in various water systems (such as potable, lake, river, sea, and tannery water) with superior regeneration ability. Moreover, as a proof of concept, a column exchange-based water treatment experiment by iPOP-5(F) has been performed to reduce the concentration of Cr(VI) and Re(VII) below the WHO permitted level. Mechanistic investigation suggested that the rare in situ exfoliation of flakes into thin nanosheets helps to achieve ultrafast capture efficiency. In addition, detailed theoretical binding energy calculations were executed in order to understand such rapid, selective binding of chromate and perrhenate oxoanions with iPOP-5(F) over other nonmetal-based anions.

Unfolding the Role of Building Units of MOFs with Mechanistic Insight Towards Selective Metal Ions Detection in Water.

The potential emergence of fluorescence-based techniques has propelled research towards developing probes that can sense trace metal ions specifically. Although luminescent metal-organic frameworks (MOFs) are well suited for this application, the role of building blocks towards detection is not fully understood. In this work, a systematic screening by varying number of Lewis basic (pyridyl-N atoms) sites is carried out in a series of isostructural, robust UiO-67 MOFs, and targeting a model metal ion-Fe3+ . All the three fluorescent MOFs are seen to present quenching response towards Fe3+ ions in water. However, UiO-67@N exhibits highly selective and sensitive response, whereas emission of both UiO-67 and UiO-67@NN is quenched by several metal ions. Detailed experimental and theoretical mechanistic investigation is carried out in addition to demonstration of UiO-67@N being able to sense trace amount of Fe3+ ions in synthetic biological water sample. Further, UiO-67@N based mixed-matrix membrane (MMM) has been prepared and employed to mimic the real time Fe3+ ions detection in water.

Post-synthetically modified metal-organic frameworks for sensing and capture of water pollutants.

Thanks to a bottom-up design of metals and organic ligands, the library of metal-organic frameworks (MOFs) has seen a conspicuous growth. Post-synthetically modified MOFs comprise a relatively smaller subset of this library. Whereas the approach of post-synthetic modification was seminally introduced for MOFs in the early 1990s, the earliest examples of post-synthetically modified MOFs are only congruous with adsorption and catalysis. The utility of PSM-derived MOFs for the sensing and capture of water contaminants is relatively niche. Arguably though, an increasing number of post-synthetically modified MOFs are finding relevance in the context of water pollutant remediation. In this article, we review the recent advances in this area and propose a structure-function relationship-guided blueprint for the future outlook.

A luminescent cationic MOF for bimodal recognition of chromium and arsenic based oxo-anions in water.

Water pollution from heavy metals and their toxic oxo-anionic derivatives such as CrO42-, Cr2O72-, HAsO42-, and HAsO32- has become one of the most critical environmental issues. To address this, herein, we report a new hydrolytically stable luminescent Zn(ii) based cationic metal organic framework (MOF), iMOF-4C, which further successfully exhibited a rare dual "turn off/on" fluorescence response toward Cr(vi), As(v) and As(iii) based oxo-anions respectively in water medium. In addition, iMOF-4C was found to maintain its superior selectivity in the presence of other concurrent anions (e.g. SO42-, Cl-, Br-, ClO4-, NO3-, SCN- and CO32-). More importantly, iMOF-4C exhibited an excellent selective and sensitive luminescence "turn-off" response towards CrO42- and Cr2O72- anions in water medium with the quenching constant (Ksv) values as high as 1.31 × 105 M-1 (CrO42-) and 4.85 × 105 M-1 (Cr2O72-), which are found to be the highest among the values reported in the regime of MOFs. Interestingly, iMOF-4C showed fluorescence "turn-on" response toward HAsO42- and HAsO32- with an enhancement coefficient (Kec) of 1.98 × 104 M-1 and 3.56 × 103 M-1 respectively. The high sensitivity and low detection limits make iMOF-4C more feasible for real-time sensing of such toxic oxo-anions in an aqueous medium. Furthermore, the probable sensing mechanism has been investigated by DFT calculation studies and discussed in detail.

Seed Power: Natural Seed and Electrospun Poly(vinyl difluoride) (PVDF) Nanofiber Based Triboelectric Nanogenerators with High Output Power Density.

A triboelectric nanogenerator (TENG) based on natural seeds and electrospun poly(vinyl difluoride) (PVDF) fibers is reported. The nanofibers are specifically used to enhance the triboelectric effects. A mustard (flax) seed based TENG renders an impressively high electrical output with an average open circuit voltage of 84 V (126 V) and maximum power density 334 mW m-2 (324 mW m-2) under an impact force of 40 N at 25 Hz. Basil seeds are relatively weaker in power delivery. By comparing the seed crust properties and TENG performances, we analyze the powering capability in terms of the cellulose content in the crust, dielectric constant, and surface morphological features.

Hydrophobic Shielding of Outer Surface: Enhancing the Chemical Stability of Metal-Organic Polyhedra.

Metal-organic polyhedra (MOP) are a promising class of crystalline porous materials with multifarious potential applications. Although MOPs and metal-organic frameworks (MOFs) have similar potential in terms of their intrinsic porosities and physicochemical properties, the exploitation of carboxylate MOPs is still rudimentary because of the lack of systematic development addressing their chemical stability. Herein we describe the fabrication of chemically robust carboxylate MOPs via outer-surface functionalization as an a priori methodology, to stabilize those MOPs system where metal-ligand bond is not so strong. Fine-tuning of hydrophobic shielding is key to attaining chemical inertness with retention of the framework integrity over a wide range of pH values, in strong acidic conditions, and in oxidizing and reducing media. These results are further corroborated by molecular modelling studies. Owing to the unprecedented transition from instability to a chemically ultra-stable regime using a rapid ambient-temperature gram-scale synthesis (within seconds), a prototype strategy towards chemically stable MOPs is reported.

A Bifunctional Metal-Organic Framework: Striking CO2 -Selective Sorption Features along with Guest-Induced Tuning of Luminescence.

A phenanthroline-functionalized CdII aminoterephthalate [Cd(NH2 -bdc)(phen)]n (NH2 -bdc=2-aminobenzenedicarboxylic acid, phen=1,10-phenanthroline) metal-organic framework (MOF) displays CO2 -selective adsorption properties and photoluminescence induced by phenolic guests. The inherently guest-free, rigid amine-rich framework exhibits substantial CO2 -selective adsorption at ambient temperatures (both at 273 and 298 K) over other flue gases like N2 , CH4 , O2 , Ar and H2 , with a high isosteric heat of adsorption at zero coverage (ΔHads ≈34 KJmol-1 ). Moreover, the fluorescent phenanthroline guest introduced to the MOF results in an excellent photoluminescence signature, which can serve as a marker for tuning phenolic-guest-induced luminescence. This marks the first report of observing distinct fluorescence responses to differentially functionalized phenolic analytes, in the domain of coordination polymer materials.