Double Layer SiO2-Coated Water-Stable Halide Perovskite as a Promising Antimicrobial Photocatalyst under Visible Light.

Halide perovskite nanocrystals (HPNCs) have emerged as promising materials for various light harvesting applications due to their exceptional optical and electronic properties. However, their inherent instability in water and biological fluids has limited their use as photocatalysts in the aqueous phase. In this study, we present highly water-stable SiO2-coated HPNCs as efficient photocatalysts for antimicrobial applications. The double SiO2 layer coating method confers long-term structural and optical stability to HPNCs in water, while the in situ synthesis of lead- and bismuth-based perovskite NCs into the SiO2 shell enhances their versatility and tunability. We demonstrate that the substantial generation of singlet oxygen via energy transfer from HPNCs enables efficient photoinduced antibacterial efficacy under aqueous conditions. More than 90% of Escherichia coli was inactivated under mild visible light irradiation for 6 h. The excellent photocatalytic antibacterial performance suggests that SiO2-coated HPNCs hold great potential for various aqueous phase photocatalytic applications.

An Intrinsic Stable Layered Oxide Cathode for Practical Sodium-Ion Battery: Solid Solution Reaction, Near-Zero-Strain and Marvelous Water Stability.

Non-aqueous solvents, in particular N,N-dimethylaniline (NMP), are widely applied for electrode fabrication since most sodium layered oxide cathode materials are readily damaged by water molecules. However, the expensive price and poisonousness of NMP unquestionably increase the cost of preparation and post-processing. Therefore, developing an intrinsically stable cathode material that can implement the water-soluble binder to fabricate an electrode is urgent. Herein, a stable nanosheet-like Mn-based cathode material is synthesized as a prototype to verify its practical applicability in sodium-ion batteries (SIBs). The as-prepared material displays excellent electrochemical performance and remarkable water stability, and it still maintains a satisfactory performance of 79.6% capacity retention after 500 cycles even after water treatment. The in situ X-ray diffraction (XRD) demonstrates that the synthesized material shows an absolute solid-solution reaction mechanism and near-zero-strain. Moreover, the electrochemical performance of the electrode fabricated with a water-soluble binder shows excellent long-cycling stability (67.9% capacity retention after 500 cycles). This work may offer new insights into the rational design of marvelous water stability cathode materials for practical SIBs.

Accelerating Discovery of Water Stable Metal-Organic Frameworks by Machine Learning.

Metal-organic frameworks (MOFs) provide an extensive design landscape for nanoporous materials that drive innovation across energy and environmental fields. However, their practical applications are often hindered by water stability challenges. In this study, a machine learning (ML) approach is proposed to accelerate the discovery of water stable MOFs and validated through experimental test. First, the largest database currently available that contains water stability information of 1133 synthesized MOFs is constructed and categorized according to experimental stability. Then, structural and chemical descriptors are applied at various fragmental levels to develop ML classifiers for predicting the water stability of MOFs. The ML classifiers achieve high prediction accuracy and excellent transferability on out-of-sample validation. Next, two MOFs are experimentally synthesized with their water stability tested to validate ML predictions. Finally, the ML classifiers are applied to discover water stable MOFs in the ab initio REPEAT charge MOF (ARC-MOF) database. Among ≈280 000 candidates, ≈130 000 (47%) MOFs are predicted to be water stable; furthermore, through multi-stability analysis, 461 (0.16%) MOFs are identified as not only water stable but also thermal and activation stable. The ML approach is anticipated to serve as a prerequisite filtering tool to streamline the exploration of water stable MOFs for important practical applications.

New 2D Metal-Organic Monoacid Framework (MOmAF): Realization of Extreme Water Repellence.

Metal-organic frameworks (MOFs) are normally moisture-sensitive and unstable in aqueous environments, which has considerably limited their practical applications because water/moisture is ubiquitous in many industrial processes. New materials with superior water stability are, therefore, in great demand and vital to their practical applications. Here, a novel oil/water interfacial assembly strategy is demonstrated for the synthesis of a new class of metal-organic monoacid framework (MOmAF) with exceptional water stability and chemical stability. Superhydrophobic 2D sheets are synthesized at room temperature, while 1D nanotubes are obtained via the self-scrolling of their 2D sheets for the first time. In addition, a simple sequential drop-casting method is developed to coat as-synthesized MOmAF structures onto porous membranes. This can potentially open up new avenues in the design of superhydrophobic self-cleaning MOmAF materials without tedious post-synthetic modifications and usher in a new class of materials meeting industrial needs.

Mn(III) O

Polyurethanes are synthesized on industrial scale by the reaction of diisocyanates with diols in the presence of catalysts which are commonly based on tin complexes and amines. However, due to the toxicity and volatility of these tin catalysts and amines, there is the need to develop new catalysts that are more environmentally benign. Herein, we report the synthesis of O^N^O pincer-ligated Mn(III) and Fe(III) complexes that serve as suitable catalysts for urethane formation and are stable to hydrolysis as predicted by computations and observed experimentally. The O^N^O pincer scaffold is vital to the activity of these catalysts, simultaneously ensuring increased solubility in the reaction medium as well as providing a stable framework upon dissociation of co-ligands in the catalytic cycle. In silico mechanistic investigations for urethane formation show that the stabilization of active species in square-planar geometries enabled by these O^N^O ligands permit the simultaneous coordination of alcohol and isocyanate in suitable configuration at the metal center.

Selective CO2 Photoreduction Enabled by Water-stable Cu-based Metal-organic Framework Nanoribbons.

The goal of photocatalytic CO2 reduction system is to achieve near 100 % selectivity for the desirable product with reasonably high yield and stability. Here, two-dimensional metal-organic frameworks are constructed with abundant and uniform monometallic active sites, aiming to be an emerged platform for efficient and selective CO2 reduction. As an example, water-stable Cu-based metal-organic framework nanoribbons with coordinatively unsaturated single CuII sites are first fabricated, evidenced by X-ray diffraction patterns and X-ray absorption spectroscopy. In situ Fourier-transform infrared spectra and Gibbs free energy calculations unravel the formation of the key intermediate COOH* and CO* is an exothermic and spontaneous process, whereas the competitive hydrogen evolution reaction is endothermic and non-spontaneous, which accounts for the selective CO2 reduction. As a result, in an aqueous solution containing 1 mol L-1 KHCO3 and without any sacrifice reagent, the water-stable Cu-based metal-organic framework nanoribbons exhibited an average CO yield of 82 µmol g-1 h-1 with the selectivity up to 97 % during 72 h cycling test, which is comparable to other reported photocatalysts under similar conditions.

Chemical characteristics and water stability evaluation of groundwater in the CKDu Zone of Sri Lanka.

Groundwater is the main source of drinking water for the rural population in the chronic kidney disease of unknown etiology (CKDu) zone of the North Central Province (NCP) in Sri Lanka. In this study, a total of 334 groundwater samples (311 dug wells, 21 tube wells and 2 springs) during the wet season from two aquifers in the NCP were collected, and investigated their chemical characteristics and evaluate their water quality, including groundwater chemistry, main ion sources, the corrosion and scaling potential of groundwater. The results showed that the two hydrochemical types of groundwater in the NCP were mainly of the Ca-HCO3, Na·Ca-HCO3 types, with the main HCO3-, Na+ and Ca2+ ions in both types of groundwater originating from silicate and evaporite salt dissolution and influenced by alternating cation adsorption, while the presence of NO3- was mainly anthropogenic. Evaluation of water stability using namely Langelier saturation index (LSI), Ryznar stability index (RSI), Puckorius scaling index (PSI) and Larson-Skold index (LS), indicated that most groundwater presents corrosion potential and has corrosion behavior tendency of metals to some degrees. The water quality of Polonnaruwa was better than that of Anuradhapura in the NCP, and when the groundwater was worse than the "good" grade, which must be properly treated before it is used as drinking water.

Highly Fluorinated Nanospace in Porous Organic Salts with High Water Stability/Capability and Proton Conductivity.

Water in hydrophobic nanospaces shows specific dynamic properties different from bulk water. The investigation of these properties is important in various research fields, including materials science, chemistry, and biology. The elucidation of the correlation between properties of water and hydrophobic nanospaces requires nanospaces covered only with simple hydrophobic group (e.g., fluorine) without impurities such as metals. This work successfully fabricated all-organic diamondoid porous organic salts (d-POSs) with highly fluorinated nanospaces, wherein hydrophobic fluorine atoms are densely exposed on the void surfaces, by combining fluorine substituted triphenylmethylamine (TPMA) derivatives with tetrahedral tetrasulfonic acid. This d-POSs with a highly fluorinated nanospace significantly improved their water stability, retaining their crystal structure even when immersed in water over one week. Moreover, this highly hydrophobic and fluorinated nanospace adsorbs 160 mL(STP)/g of water vapor at Pe/P0=0.90; this is the first hydrophobic nanospace, which water molecules can enter, in an all-organic porous material. Furthermore, this highly fluorinated nanospace exhibits very high proton conductivity (1.34×10-2 S/cm) at 90 °C and 95 % RH. POSs with tailorable nanospaces may significantly advance the elucidation of the properties of specific "water" in pure hydrophobic environments.

Developing Water-Stable Pore-Partitioned Metal-Organic Frameworks with Multi-Level Symmetry for High-Performance Sorption Applications.

A new perspective is proposed in the design of pore-space-partitioned MOFs that is focused on ligand symmetry properties sub-divided here into three hierarchical levels: 1) overall ligand, 2) ligand substructure such as backbone or core, and 3) the substituent groups. Different combinations of the above symmetry properties exist. Given the close correlation between nature of chemical moiety and its symmetry, such a unique perspective into ligand symmetry and sub-symmetry in MOF design translates into the influences on MOF properties. Five new MOFs have been prepared that exhibit excellent hydrothermal stability and high-performance adsorption properties with potential applications such as C3 H6 /C2 H4 and C2 H2 /CO2 selective adsorption. The combination of high stability with high benzene/cyclohexane selectivity of ≈13.7 is also of particular interest.

Water-Stabilized Vanadyl Phosphate Monohydrate Ultrathin Nanosheets toward High Voltage Al-Ion Batteries.

Al ion batteries (AIBs) are attracting considerable attention owing to high volumetric capacity, low cost, and high safety. However, the strong electrostatic interaction between Al3+ and host lattice leads to discontented cycling life and inferior rate capability. Herein, a new strategy of employing water molecules contained VOPO4 ·H2 O to boost Al3+ migration via the charge shielding effect of water is reported. It is revealed that VOPO4 ·H2 O with water lubrication effect and smaller steric hindrance owns high capacity and fast Al3+ diffusion, while the loss of unstable water upon cycling leads to a rapid performance degradation. To address this problem, ultrathin VOPO4 ·H2 O@MXene nanosheets are fabricated via the formed TiOV bond between VOPO4 ·H2 O and MXene. The MXene aided exfoliation results in enhanced VOwater bond strength between H2 O and VOPO4 that endows the obtained composite with strong water holding ability, contributing to the extraordinary cycling stability. Consequently, the VOPO4 ·H2 O@MXene delivers a high discharge potential of 1.8 V and maintains discharge capacities of 410 and 374.8 mAh g-1 after 420 and 2000 cycles at the current densities of 0.5 and 1.0 A g-1 , respectively. This work provides a new understanding of water-contained AIBs cathodes and vital guidance for developing high-performance AIBs.

Fabrication of Cellulose-Graphite Foam via Ion Cross-linking and Ambient-Drying.

Conventional plastic foams are usually produced by fossil-fuel-derived polymers, which are difficult to degrade in nature. As an alternative, cellulose is a promising biodegradable polymer that can be used to fabricate greener foams, yet such a process typically relies on methods (e.g., freeze-drying and supercritical-drying) that are hardly scalable and time-consuming. Here, we develop a fast and scalable approach to prepare cellulose-graphite foams via rapidly cross-linking the cellulose fibrils in metal ions-containing solution followed by ambient drying. The prepared foams exhibit low density, high compressive strength, and excellent water stability. Moreover, the cross-linking of the cellulose fibrils can be triggered by various metal ions, indicating good universality. We further use density functional theory to reveal the cross-linking effect of different ions, which shows good agreement with our experimental observation. Our approach presents a sustainable route toward low-cost, environmentally friendly, and scalable foam production for a range of applications.

Strengthening Aqueous Electrolytes without Strengthening Water.

Aqueous electrolytes typically suffer from poor electrochemical stability; however, eutectic aqueous solutions-25 wt.% LiCl and 62 wt.% H3 PO4 -cooled to -78 °C exhibit a significantly widened stability window. Integrated experimental and simulation results reveal that, upon cooling, Li+ ions become less hydrated and pair up with Cl- , ice-like water clusters form, and H⋅⋅⋅Cl- bonding strengthens. Surprisingly, this low-temperature solvation structure does not strengthen water molecules' O-H bond, bucking the conventional wisdom that increasing water's stability requires stiffening the O-H covalent bond. We propose a more general mechanism for water's low temperature inertness in the electrolyte: less favorable solvation of OH- and H+ , the byproducts of hydrogen and oxygen evolution reactions. To showcase this stability, we demonstrate an aqueous Li-ion battery using LiMn2 O4 cathode and CuSe anode with a high energy density of 109 Wh/kg. These results highlight the potential of aqueous batteries for polar and extraterrestrial missions.

Porous and Water Stable 2D Hybrid Metal Halide with Broad Light Emission and Selective H2 O Vapor Sorption.

In this work we report a strategy for generating porosity in hybrid metal halide materials using molecular cages that serve as both structure-directing agents and counter-cations. Reaction of the [2.2.2] cryptand (DHS) linker with PbII in acidic media gave rise to the first porous and water-stable 2D metal halide semiconductor (DHS)2 Pb5 Br14 . The corresponding material is stable in water for a year, while gas and vapor-sorption studies revealed that it can selectively and reversibly adsorb H2 O and D2 O at room temperature (RT). Solid-state NMR measurements and DFT calculations verified the incorporation of H2 O and D2 O in the organic linker cavities and shed light on their molecular configuration. In addition to porosity, the material exhibits broad light emission centered at 617 nm with a full width at half-maximum (FWHM) of 284 nm (0.96 eV). The recorded water stability is unparalleled for hybrid metal halide and perovskite materials, while the generation of porosity opens new pathways towards unexplored applications (e.g. solid-state batteries) for this class of hybrid semiconductors.

Dye adsorption of aluminium- and zirconium-based metal organic frameworks with azobenzene dicarboxylate linkers.

The high efficiency of metal-organic-frameworks (MOFs) such as the ZIF, MIL and UiO type species in dye adsorption is well established. Recently, an emerging class of photoresponsive azobenzene-based MOFs has found suitable application in gas adsorption. However, there is a dearth of research on their use in the adsorption of dyes and other water pollutants. In this research, two microporous photoresponsive azobenzene dicarboxylate MOFs of Al3+ (Al-AZB) and Zr4+ (Zr-AZB) were synthesized for the adsorption of congo red (CR) dye. The surface and textural properties of the synthesized MOFs were characterized by FTIR, PXRD, SEM, TGA, BET and pore analysis. Both MOFs were crystalline, thermally stable up to 300 °C and stable in aqueous medium at room temperature. The Al-AZB displayed a higher surface area (2718 m2/g) than the Zr-AZB (1098 m2/g), which significantly impacted the higher adsorption of CR. Besides, pore volumes of 0.86 cm3/g and 0.35 cm3/g were obtained for Al-AZB and Zr-AZB, respectively. The maximum adsorption capacity of Al-AZB and Zr-AZB was 456.6 mg/g and 128.9 mg/g, respectively, with the former superior to other potent adsorbents. The pseudo-second-order and Langmuir models were well correlated with the dye uptake on the MOFs. Thermodynamics revealed random and endothermic sorption of CR dominated by chemisorption, while efficient regeneration and reuse of both MOFs were achieved using dimethylformamide as eluent. The results proved the potency of the synthesized photoresponsive MOFs, as highly efficient and reusable materials for dye adsorption.

Allelotoxicity and Water Stability of Sod-Podzolic Soil after Growing Wheat on It.

It is well-known that soil allelotoxicity and the water stability of soil structure are determined by the entry of plant residues into the soil, but the relationship of these soil properties has not been investigated. Soil samples from the fields of the Federal Research Center "Nemchinovka" after growing 25 cultivars of spring and winter wheat on plots with sod-podzolic soil are selected in this study. The effect of the soil's allelotoxicity of plot samples on the germination of spring wheat seed of the Liza cultivar is studied by the biotesting method. The water stability of the soil structure is determined for the same samples. The existence of a sigmoid dependence between the allelotoxicity of soil samples and their water stability with a correlation greater than 95% is established. The presence of this dependence is apparently related to the increase in the soil's water stability with an increase in the amount of fresh plant residues entering them, which is known from the literature, and the transition of the allelotoxins' effects from stimulation to suppression with a growth in their concentration in soils.

Ultrahigh stable lead halide perovskite nanocrystals as bright fluorescent label for the visualization of latent fingerprints.

Fingerprints formed by the raised papillary ridges are one of the most important markers for individual identification. However, the current visualization methods for latent fingerprints (LFPs) suffer from poor resolution, low contrast, and high toxicity. In this work, the CsPbBr3/Cs4PbBr6nanostructured composite crystal (CsPbBr3/Cs4PbBr6NCC) were synthesized via a simple chemical solvent-assisted method. Compared with conventional perovskites, the as-prepared CsPbBr3/Cs4PbBr6NCC present an outstanding long-term environmental and water stability with 42% and 80% photoluminescence intensity remaining after 28 d under water and air conditions, respectively. Moreover, a special response to biomolecules from fingerprints was observed due to the hydrophobic interactions between the CsPbBr3/Cs4PbBr6NCC surface hydrophobic ligands (oleyl amine and oleic acid) and the hydrophobic groups in the biomolecules from the human fingers. Clear LFPs images were visualized in a bright environment illuminating the prepared CsPbBr3/Cs4PbBr6NCC powder under UV light of wavelength 365 nm. The images were also obtained on porous and non-porous surfaces such as metal, plastic, wood, glass, and paper products. These perovskite nanocrystals are expected a stable and bright luminescent labeling agent for LFPs visualization and have potential application in crime scene and personal identifications.

Adsorptive removal of pharmaceuticals from water using metal-organic frameworks: A review.

Pharmaceutical pollution has emerged as a highly concerned issue due to its adverse effects. Elevated concentrations of pharmaceuticals in water should be regulated to satisfy the requirement for the provision of clean water. Metal-organic frameworks (MOFs) with high specific surface area, controllable porous structure, and facile modification can serve as promising adsorbents for the removal of pharmaceutical contaminants from water. In this review, a selected collection illustrating the reliable strategies and concepts to prepare the MOFs-based materials with superior water stability is described. In addition, recent progress on the adsorptive removal of pharmaceutical pollutant using burgeoning and functional MOFs is also summarized in terms of maximum capacity, equilibrium time, and regenerate ability. Meanwhile, to understand the adsorption mechanism, related interactions including coordination with unsaturated site, pore-filling effect, hydrogen bonding, electrostatic, and π-π stacking are further discussed. Finally, critical perspectives/assessment of future research emphasising on fabricating desirable MOFs and establishing structure-property relationships to facilitate capture performance are identified.

Effect mechanism of biochar application on soil structure and organic matter in semi-arid areas.

There are global concerns regarding soil remediation and water conservation in arid and semi-arid areas. Studying the mechanism and factors influencing soil structure and organic matter content is very important for soil remediation and the rational utilization of water resources. We tracked the changes in soil aggregates and organic matter content during the growth period of maize using different application rates of straw biochar (10, 20, 30, and 50 t/ha) to investigate the effects of biochar on the structure of weakly alkaline soil. The results were as follows: 1) Biochar significantly increased the content of water-stable soil aggregates. The content of water-stable macroaggregates (≥0.25 mm) increased by 8.3-35.0%, and the increase was the highest (35%) when biochar was applied at a rate of 30 t/ha 2) After applying biochar, the content of air-dried aggregates on the surface layer increased by 112.6-168.5%. 3). Biochar increased the organic matter content to varying degrees from the spatiotemporal aspect. In terms of soil depth, organic matter content increased by 2.15-5.88 g/kg. The jointing stage, which the time demand for organic matter is the highest, organic matter content increased by 35.4% when biochar was applied at 50 t/ha 4) We established a three-dimensional surface correlation equation based on the synergistic relationships among biochar, water-stable aggregates, and organic matter content. The particle size of soil aggregates was the highest when the biochar application rate was 29.38 t/ha and the organic matter content increased by 25.7%. It provided evidence that applies to biochar has good potential for water-saving irrigation and soil remediation.

Silica Monolith for the Removal of Pollutants from Gas and Aqueous Phases.

This study focused on the application of mesoporous silica monoliths for the removal of organic pollutants. The physico-chemical textural and surface properties of the monoliths were investigated. The homogeneity of the textural properties along the entire length of the monoliths was assessed, as well as the reproducibility of the synthesis method. The adsorption properties of the monoliths for gaseous toluene, as a model of Volatile Organic Compounds (VOCs), were evaluated and compared to those of a reference meso-structured silica powder (MCM-41) of commercial origin. Silica monoliths adsorbed comparable amounts of toluene with respect to MCM-41, with better performances at low pressure. Finally, considering their potential application in water phase, the adsorption properties of monoliths toward Rhodamine B, selected as a model molecule of water soluble pollutants, were studied together with their stability in water. After 24 h of contact, the silica monoliths were able to adsorb up to the 70% of 1.5 × 10-2 mM Rhodamine B in water solution.

Water-Stable DMASnBr3 Lead-Free Perovskite for Effective Solar-Driven Photocatalysis.

Water-stable metal halide perovskites could foster tremendous progresses in several research fields where their superior optical properties can make differences. In this work we report clear evidence of water stability in a lead-free metal halide perovskite, namely DMASnBr3 , obtained by means of diffraction, optical and X-ray photoelectron spectroscopy. Such unprecedented water-stability has been applied to promote photocatalysis in aqueous medium, in particular by devising a novel composite material by coupling DMASnBr3 to g-C3 N4 , taking advantage from the combination of their optimal photophysical properties. The prepared composites provide an impressive hydrogen evolution rate >1700 µmol g-1 h-1 generated by the synergistic activity of the two composite costituents. DFT calculations provide insight into this enhancement deriving it from the favorable alignment of interfacial energy levels of DMASnBr3 and g-C3 N4 . The demonstration of an efficient photocatalytic activity for a composite based on lead-free metal halide perovskite in water paves the way to a new class of light-driven catalysts working in aqueous environments.