Porous Salts Containing Cationic Al24-Hydroxide-Acetate Clusters from Scalable, Green and Aqueous Synthesis Routes

The solution chemistry of aluminum is highly complex and various polyoxocations are known. Here we report on the facile synthesis of a cationic Al24 cluster that forms porous salts of composition [Al24 (OH)56 (CH3 COO)12 ]X4 , denoted CAU-55-X, with X=Cl- , Br- , I- , HSO4 - . Three-dimensional electron diffraction was employed to determine the crystal structures. Various robust and mild synthesis routes for the chloride salt [Al24 (OH)56 (CH3 COO)12 ]Cl4 in water were established resulting in high yields (>95 %, 215 g per batch) within minutes. Specific surface areas and H2 O capacities with maximum values of up to 930 m2  g-1 and 430 mg g-1 are observed. The particle size of CAU-55-X can be tuned between 140 nm and 1250 nm, permitting its synthesis as stable dispersions or as highly crystalline powders. The positive surface charge of the particles, allow fast and effective adsorption of anionic dye molecules and adsorption of poly- and perfluoroalkyl substances (PFAS)

A Novel Porous Ti-Squarate as Efficient Photocatalyst in the Overall Water Splitting Reaction under Simulated Sunlight Irradiation

A new porous titanium(IV) squarate metal–organic framework (MOF), denoted as IEF-11, having a never reported titanium secondary building unit, is successfully synthesized and fully characterized. IEF-11 not only exhibits a permanent porosity but also an outstanding chemical stability. Further, as a consequence of combining the photoactive Ti(IV) and the electroactive squarate, IEF-11 presents relevant optoelectronic properties, applied here to the photocatalytic overall water splitting reaction. Remarkably, IEF-11 as a photocatalyst is able to produce record H amounts for MOF-based materials under simulated sunlight (up to 672 µmol g in 22 h) without any activity loss during at least 10 d.P.S.-A. and A.A.B. contributed equally to this work. The authors acknowledge the Ramón Areces Foundation project H+MOFs, the M-ERA-NET C-MOF-cell (grant PCI2020-111998 funded by MCIN/AEI /10.13039/501100011033 and European Union NextGenerationEU/PRTR) project, and Retos Investigación MOFSEIDON (grant PID2019-104228RB-I00 funded by MCIN/AEI/10.13039/501100011033) project. S.N. thanks financial support by Ministerio de Ciencia, Innovatión y Universidades RTI2018-099482-A-I00 project and Agència Valenciana de la Innovació (AVI, INNEST/2020/111) project. H.G. thanks financial support to the Spanish Ministry of Science and Innovation (Severo Ochoa and RTI2018-098237-CO21) and Generalitat Valenciana (Prometeo2017/083). T.W. acknowledges financial support from the Swedish Research Council (VR, 2019-05465). Parts of this research were carried out at “CRISTAL” at SOLEIL. P.S. and A.A.B. sincerely thank to the project CALIPSOplus under the Grant Agreement 730872 from the EU Framework Programme for Research and Innovation HORIZON 2020 for the support of the synchrotron experiment

Metal-Dependent and Selective Crystallization of CAU-10 and MIL-53 Frameworks through Linker Nitration

The reaction of the V-shaped linker molecule 5-hydroxyisophthalic acid (H2 L0 ), with Al or Ga nitrate under almost identical reaction conditions leads to the nitration of the linker and subsequent formation of metal-organic frameworks (MOFs) with CAU-10 or MIL-53 type structure of composition [Al(OH)(L)], denoted as Al-CAU-10-L0, 2, 4, 6 or [Ga(OH)(L)], denoted as Ga-MIL-53-L2 . The Al-MOF contains the original linker L0 as well as three different nitration products (L2 , L4 and L4/6 ), whereas the Ga-MOF mainly incorporates the linker L2 . The compositions were deduced by 1 H NMR spectroscopy and confirmed by Rietveld refinement. In situ and ex situ studies were carried out to follow the nitration and crystallization, as well as the composition of the MOFs. The crystal structures were refined against powder X-ray diffraction (PXRD) data. As anticipated, the use of the V-shaped linker results in the formation of the CAU-10 type structure in the Al-MOF. Unexpectedly, the Ga-MOF crystallizes in a MIL-53 type structure, which is usually observed with linear or slightly bent linker molecules. To study the structure directing effect of the in situ nitrated linker, pure 2-nitrobenzene-1,3-dicarboxylic acid (m-H2 BDC-NO2 ) was employed which exclusively led to the formation of [Ga(OH)(C8 H3 NO6 )] (Ga-MIL-53-m-BDC-NO2 ), which is isoreticular to Ga-MIL-53-L2 . Density Functional Theory (DFT) calculations confirmed the higher stability of Ga-MIL-53-L2 compared to Ga-CAU-10-L2 and grand canonical Monte Carlo simulations (GCMC) are in agreement with the observed water adsorption isotherms of Ga-MIL-53-L2

A Robust and Biocompatible Bismuth Ellagate MOF Synthesized Under Green Ambient Conditions

The first bioinspired microporous metal-organic framework (MOF) synthesized using ellagic acid, a common natural antioxidant and polyphenol building unit, is presented. Bi2O(H2O)2(C14H2O8)\ub7nH2O (SU-101) was inspired by bismuth phenolate metallodrugs, and could be synthesized entirely from nonhazardous or edible reagents under ambient aqueous conditions, enabling simple scale-up. Reagent-grade and affordable dietary supplement-grade ellagic acid was sourced from tree bark and pomegranate hulls, respectively. Biocompatibility and colloidal stability were confirmed by in vitro assays. The material exhibits remarkable chemical stability for a bioinspired MOF (pH = 2-14, hydrothermal conditions, heated organic solvents, biological media, SO2 and H2S), attributed to the strongly chelating phenolates. A total H2S uptake of 15.95 mmol g-1 was recorded, representing one of the highest H2S capacities for a MOF, where polysulfides are formed inside the pores of the material. Phenolic phytochemicals remain largely unexplored as linkers for MOF synthesis, opening new avenues to design stable, eco-friendly, scalable, and low-cost MOFs for diverse applications, including drug delivery

Crystalline Porous Materials Inspired by Metallodrugs

Inspiration for developing robust porous materials from sustainable reagents was acquired by determining the crystal structures of bismuth subsalicylate and bibrocathol, two long-used and commonly available bismuth-based pharmaceuticals. From these insights, a number of coordination polymers and metal-organic frameworks (MOFs) were developed, facilitating the synthesis of robust porous materials from sustainably sourced reagents. The structural investigations were carried out using advanced transmission electron microscopy techniques, including three-dimensional electron diffraction. Using Bi3+ to synthesize MOFs, a previously unreported type of the so-called ‘breathing effect’ was observed in two materials. The breathing originates in the inorganic part of the obtained metal-organic structures and was thoroughly investigated for the bismuth-carboxylate framework SU-100. Taking further inspiration from bismuth-based metallodrugs, pseudo-polymorphs of the metallodrug bismuth subgallate were prepared, yielding coordination networks of varying periodicities. Following this line of work, a bismuth-phenolate MOF was prepared using ellagic acid—a phenolic molecule isolated from plant-based waste. The resulting material, SU-101, can be synthesized in water under ambient conditions and exhibits excellent chemical robustness, remaining crystalline upon exposure to harsh aqueous solutions and toxic gases. A second metal-ellagate framework, SU-102, was prepared using zirconium, yielding an equally robust framework. The material was evaluated for the capture and degradation of pharmaceutical pollutants from the effluent of a wastewater treatment plant, showing a selectivity towards cationic pharmaceuticals. This work highlights the potential of using natural products to create high-performing and chemically robust porous materials, for use in applications such as water remediation and the adsorption of toxic gases

Crystalline Porous Materials Inspired by Metallodrugs

Inspiration for developing robust porous materials from sustainable reagents was acquired by determining the crystal structures of bismuth subsalicylate and bibrocathol, two long-used and commonly available bismuth-based pharmaceuticals. From these insights, a number of coordination polymers and metal-organic frameworks (MOFs) were developed, facilitating the synthesis of robust porous materials from sustainably sourced reagents. The structural investigations were carried out using advanced transmission electron microscopy techniques, including three-dimensional electron diffraction. Using Bi3+ to synthesize MOFs, a previously unreported type of the so-called ‘breathing effect’ was observed in two materials. The breathing originates in the inorganic part of the obtained metal-organic structures and was thoroughly investigated for the bismuth-carboxylate framework SU-100. Taking further inspiration from bismuth-based metallodrugs, pseudo-polymorphs of the metallodrug bismuth subgallate were prepared, yielding coordination networks of varying periodicities. Following this line of work, a bismuth-phenolate MOF was prepared using ellagic acid—a phenolic molecule isolated from plant-based waste. The resulting material, SU-101, can be synthesized in water under ambient conditions and exhibits excellent chemical robustness, remaining crystalline upon exposure to harsh aqueous solutions and toxic gases. A second metal-ellagate framework, SU-102, was prepared using zirconium, yielding an equally robust framework. The material was evaluated for the capture and degradation of pharmaceutical pollutants from the effluent of a wastewater treatment plant, showing a selectivity towards cationic pharmaceuticals. This work highlights the potential of using natural products to create high-performing and chemically robust porous materials, for use in applications such as water remediation and the adsorption of toxic gases

Upcycling of Spent NiMH Battery Material—Reconditioned Battery Alloys Show Faster Activation and Reaction Kinetics than Pristine Alloys

During formation and cycling of nickel–metal hydride (NiMH cells), surface corrosion on the metal hydride particles forms a porous outer layer of needle-shaped rare-earth hydroxide crystals. Under this layer, a denser but thinner oxidized layer protects the inner metallic part of the MH electrode powder particles. Nano-sized nickel-containing clusters that are assumed to promote the charge and discharge reaction kinetics are also formed here. In this study, mechanical treatments are tested to recycle hydrogen storage alloys from spent NiMH batteries. This removes the outer corroded surface of the alloy particles, while maintaining the catalytic properties of the surface. Scanning electron microscopy images and powder X-ray diffraction measurements show that the corrosion layer can be partly removed by ball milling or sonication, combined with a simple washing procedure. The reconditioned alloy powders exhibit improved high rate properties and activate more quickly than the pristine alloy. This indicates that the protective interphase layer created on the alloy particle during their earlier cycling is rather stable. The larger active surface that is created by the mechanical impact on the surface by the treatments also improves the kinetic properties. Similarly, the mechanical strain during cycling cracks the alloy particles into finer fragments. However, some of these particles form agglomerates, reducing the accessibility for the electrolyte and rendering them inactive. The mechanical treatment also separates the agglomerates and thus further promotes reaction kinetics in the upcycled material. Altogether, this suggests that the MH electrode material can perform better in its second life in a new battery

Structure of the active pharmaceutical ingredient bismuth subsalicylate

Structure determination of pharmaceutical compounds is invaluable for drug development but is challenging for those that form as small crystals with defects. Bismuth subsalicylate (BSS), among the most commercially significant bismuth compounds, is an active ingredient in over-the-counter medications such as Pepto-Bismol, used to treat dyspepsia and H. pylori infections. Despite its century-long history, the structure has remained unknown. Three-dimensional electron diffraction and hierarchical clustering analysis were applied on select data from ordered crystals, revealing a layered structure. In other less ordered crystals, high-resolution scanning transmission electron microscopy revealed variations in the stacking of layers. Together, these modern electron crystallography techniques provide a new toolbox for structure determination of active pharmaceutical ingredients and drug discovery, demonstrated by this study of BSS