Rapid preparation of binary mixtures of sodium carboxylates as anodes in sodium-ion batteries.

Sodium-ion batteries are emerging as a sustainable solution to tackle the growing global energy demands. In this context, organic electrode materials complement such technologies as they are composed of earth-abundant elements. As organic anodes, sodium carboxylates exhibit promising applicability in a wide range of molecules. To harness the advantages of individual systems and to minimise their limitations, in this work, an approach to form binary mixtures of sodium carboxylates using one-pot, microwave-assisted synthesis is presented. The target mixtures were synthesised in 30 min with disodium naphthalene-2,6-dicarboxylate (Na-NDC) as a common constituent in all. Both components in all mixtures were shown to participate in the charge storage and had a considerable effect on the performance characteristics, such as specific capacity and working voltage, in half and full cell formats. This approach opens a new avenue for enabling organic materials to be considered as more competitive candidates in sodium-ion batteries and promote their use in other material classes to overcome their limitations.

Controlling Crystal Morphology of Anisotropic Zeolites with Elemental Composition.

The morphology of zeolite crystals strongly affects their textural, catalytic, and mechanical attributes. However, controlling zeolite crystal morphology without using modifiers or structure-directing agents remains a challenging task because of our limited understanding of the relationships between zeolite crystal shape, crystallization mechanism, and composition of the starting synthesis mixture. In this study, we aimed at developing a general method for controlling the morphology of zeolites by assessing the impact of the Si/T molar ratio of the synthesis gel on the growth rate of zeolite crystals in various crystallographic directions and on the final crystal morphology of the UTL germanosilicate with a 2D system of intersecting 14- and 12-ring pores. Our results showed that flat UTL crystals progressively thicken with the Si/Ge molar ratio, demonstrating that Ge concentration controls the relative rate of crystal growth in the perpendicular direction to the pore system. The morphology of other zeolites and zeotypes with an anisotropic structure, including AFI (12R), IFR (12R), MWW (10-10R), and IWW (12-10-8R), can also be predicted based on their Si/T ratio, suggesting a systematic pattern across zeolite structures and in a wide range of zeolite framework elements. Combined, these findings introduce a facile and cost-efficient method for directly controlling crystal morphology of zeolites with anisotropic structures with a high potential for scale-up while providing further insights into the role of elemental composition in zeolite crystal growth.

ADOR zeolite with 12 × 8 × 8-ring pores derived from IWR germanosilicate.

Zeolites have been well known for decades as catalytic materials and adsorbents and are traditionally prepared using the bottom-up synthesis method. Although it was productive for more than 250 zeolite frameworks, the conventional solvothermal synthesis approach provided limited control over the structural characteristics of the formed materials. In turn, the discovery and development of the Assembly-Disassembly-Organization-Reassembly (ADOR) strategy for the regioselective manipulation of germanosilicates enabled the synthesis of previously unattainable zeolites with predefined structures. To date, the family tree of ADOR materials has included the topological branches of UTL, UOV, IWW, *CTH, and IWV zeolites. Herein, we report on the expansion of ADOR zeolites with a new branch related to the IWR topology, which is yet unattainable experimentally but theoretically predicted as highly promising adsorbents for CO2 separation applications. The optimization of not only the chemical composition but also the dimensions of the crystalline domain in the parent IWR zeolite in the Assembly step was found to be the key to the success of its ADOR transformation into previously unknown IPC-17 zeolite with an intersecting 12 × 8 × 8-ring pore system. The structure of the as-prepared IPC-17 zeolite was verified by a combination of microscopic and diffraction techniques, while the results on the epichlorohydrin ring-opening with alcohols of variable sizes proved the molecular sieving ability of IPC-17 with potential application in heterogeneous catalysis. The proposed synthesis strategy may facilitate the discovery of zeolite materials that are difficult or yet impossible to achieve using a traditional bottom-up synthesis approach.

In Situ Single-crystal X-ray Diffraction Studies of Physisorption and Chemisorption of SO2 within a Metal-Organic Framework and Its Competitive Adsorption with Water.

Living on an increasingly polluted planet, the removal of toxic pollutants such as sulfur dioxide (SO2) from the troposphere and power station flue gas is becoming more and more important. The CPO-27/MOF-74 family of metal-organic frameworks (MOFs) with their high densities of open metal sites is well suited for the selective adsorption of gases that, like SO2, bind well to metals and have been extensively researched both practically and through computer simulations. However, until now, focus has centered upon the binding of SO2 to the open metal sites in this MOF (called chemisorption, where the adsorbent-adsorbate interaction is through a chemical bond). The possibility of physisorption (where the adsorbent-adsorbate interaction is only through weak intermolecular forces) has not been identified experimentally. This work presents an in situ single-crystal X-ray diffraction (scXRD) study that identifies discrete adsorption sites within Ni-MOF-74/Ni-CPO-27, where SO2 is both chemisorbed and physisorbed while also probing competitive adsorption of SO2 of these sites when water is present. Further features of this site have been confirmed by variable SO2 pressure scXRD studies, DFT calculations, and IR studies.

Investigations of the ADOR Process Using Solid-State NMR Spectroscopy.

The assembly-disassembly-organization-reassembly (ADOR) process for the transformation of zeolite UTL using water has been studied by using 29Si and 17O solid-state NMR spectroscopy. The results show that the intermediate materials that are formed during the reaction are extremely dynamic and that the process involves both irreversible changes in structure that define the overall pathway and reversible lability of the Si-O-Si linkages that have no effect on the overall structure. The combination of processes occurring during the ADOR reaction means that the mechanism is considerably more complex than initially proposed.

Mixed Metal-Organic Framework Mixed-Matrix Membranes: Insights into Simultaneous Moisture-Triggered and Catalytic Delivery of Nitric Oxide using Cryo-scanning Electron Microscopy.

The fundamental chemical and structural diversity of metal-organic frameworks (MOFs) is vast, but there is a lack of industrial adoption of these extremely versatile compounds. To bridge the gap between basic research and industry, MOF powders must be formulated into more application-relevant shapes and/or composites. Successful incorporation of varying ratios of two different MOFs, CPO-27-Ni and CuBTTri, in a thin polymer film represents an important step toward the development of mixed MOF mixed-matrix membranes. To gain insight into the distribution of the two different MOFs in the polymer, we report their investigation by Cryo-scanning electron microscopy (Cryo-SEM) tomography, which minimizes surface charging and electron beam-induced damage. Because the MOFs are based on two different metal ions, Ni and Cu, the elemental maps of the MOF composite cross sections clearly identify the size and location of each MOF in the reconstructed 3D model. The tomography run was about six times faster than conventional focused ion beam (FIB)-SEM and the first insights to image segmentation combined with machine learning could be achieved. To verify that the MOF composites combined the benefits of rapid moisture-triggered release of nitric oxide (NO) from CPO-27-Ni with the continuous catalytic generation of NO from CuBTTri, we characterized their ability to deliver NO individually and simultaneously. These MOF composites show great promise to achieve optimal dual NO delivery in real-world medical applications.

Computational NMR investigation of mixed-metal (Al,Sc)-MIL-53 and its phase transitions.

Compositionally complex metal-organic frameworks (MOFs) have properties that depend on local structure that is often difficult to characterise. In this paper a density functional theory (DFT) computational study of mixed-metal (Al,Sc)-MIL-53, a flexible MOF with several different forms, was used to calculate the relative energetics of these forms and to predict NMR parameters that can be used to evaluate whether solid-state NMR spectroscopy can be used to differentiate, identify and characterise the forms adopted by mixed-metal MOFs of different composition. The NMR parameters can also be correlated with structural features in the different forms, giving fundamental insight into the nature and origin of the interactions that affect nuclear spins. Given the complexity of advanced NMR experiments required, and the potential need for expensive and difficult isotopic enrichment, the computational work is invaluable in predicting which experiments and approaches are likely to give the most information on the disorder, local structure and pore forms of these mixed-metal MOFs.

Pressure-induced postsynthetic cluster anion substitution in a MIL-53 topology scandium metal-organic framework.

Postsynthetic modification of metal-organic frameworks (MOFs) has proven to be a hugely powerful tool to tune physical properties and introduce functionality, by exploiting reactive sites on both the MOF linkers and their inorganic secondary building units (SBUs), and so has facilitated a wide range of applications. Studies into the reactivity of MOF SBUs have focussed solely on removal of neutral coordinating solvents, or direct exchange of linkers such as carboxylates, despite the prevalence of ancillary charge-balancing oxide and hydroxide ligands found in many SBUs. Herein, we show that the µ2-OH ligands in the MIL-53 topology Sc MOF, GUF-1, are labile, and can be substituted for µ2-OCH3 units through reaction with pore-bound methanol molecules in a very rare example of pressure-induced postsynthetic modification. Using comprehensive solid-state NMR spectroscopic analysis, we show an order of magnitude increase in this cluster anion substitution process after exposing bulk samples suspended in methanol to a pressure of 0.8 GPa in a large volume press. Additionally, single crystals compressed in diamond anvil cells with methanol as the pressure-transmitting medium have enabled full structural characterisation of the process across a range of pressures, leading to a quantitative single-crystal to single-crystal conversion at 4.98 GPa. This unexpected SBU reactivity - in this case chemisorption of methanol - has implications across a range of MOF chemistry, from activation of small molecules for heterogeneous catalysis to chemical stability, and we expect cluster anion substitution to be developed into a highly convenient novel method for modifying the internal pore surface and chemistry of a range of porous materials.

Exploring cation distribution in ion-exchanged Al,Ga-containing metal-organic frameworks using 17O NMR spectroscopy.

A mixed-metal metal-organic framework, (Al,Ga)-MIL-53, synthesised by post-synthetic ion exchange has been investigated using solid-state nuclear magnetic resonance (NMR) spectroscopy, microscopy and energy dispersive X-ray (EDX) spectroscopy. 17O enrichment during the ion-exchange process enables site specific information on the metal distribution to be obtained. Within this work two ion-exchange processes have been explored. In the first approach (exchange of metals in the framework with dissolved metal salts), 17O NMR spectroscopy reveals the formation of crystallites with a core-shell structure, where the cation exchange takes place on the surface of these materials forming a shell with a roughly equal ratio of Al3+ and Ga3+. For the second approach (exchange of metals between two frameworks), no core-shell structure is observed, and instead crystallites containing a majority of Al3+ are obtained with lower levels of Ga3+. Noticeably, these particles show little variation in the metal cation distribution between crystallites, a result not previously observed for bulk (Al,Ga)-MIL-53 materials. In all cases where ion exchange has taken place NMR spectroscopy reveals a slight preference for clustering of like cations.

In situ single-crystal synchrotron X-ray diffraction studies of biologically active gases in metal-organic frameworks.

Metal-organic frameworks (MOFs) are well known for their ability to adsorb various gases. The use of MOFs for the storage and release of biologically active gases, particularly nitric oxide (NO) and carbon monoxide (CO), has been a subject of interest. To elucidate the binding mechanisms and geometry of these gases, an in situ single crystal X-ray diffraction (scXRD) study using synchrotron radiation at Diamond Light Source has been performed on a set of MOFs that display promising gas adsorption properties. NO and CO, were introduced into activated Ni-CPO-27 and the related Co-4,6-dihydroxyisophthalate (Co-4,6-dhip). Both MOFs show strong binding affinity towards CO and NO, however CO suffers more from competitive co-adsorption of water. Additionally, we show that morphology can play an important role in the ease of dehydration for these two systems.

Surface-Functionalized Metal-Organic Frameworks for Binding Coronavirus Proteins.

Since the outbreak of SARS-CoV-2, a multitude of strategies have been explored for the means of protection and shielding against virus particles: filtration equipment (PPE) has been widely used in daily life. In this work, we explore another approach in the form of deactivating coronavirus particles through selective binding onto the surface of metal-organic frameworks (MOFs) to further the fight against the transmission of respiratory viruses. MOFs are attractive materials in this regard, as their rich pore and surface chemistry can easily be modified on demand. The surfaces of three MOFs, UiO-66(Zr), UiO-66-NH2(Zr), and UiO-66-NO2(Zr), have been functionalized with repurposed antiviral agents, namely, folic acid, nystatin, and tenofovir, to enable specific interactions with the external spike protein of the SARS virus. Protein binding studies revealed that this surface modification significantly improved the binding affinity toward glycosylated and non-glycosylated proteins for all three MOFs. Additionally, the pores for the surface-functionalized MOFs can adsorb water, making them suitable for locally dehydrating microbial aerosols. Our findings highlight the immense potential of MOFs in deactivating respiratory coronaviruses to be better equipped to fight future pandemics.

Azo-functionalised metal-organic framework for charge storage in sodium-ion batteries.

Sodium-ion batteries (NIBs) are emerging as promising devices for energy storage applications. Porous solids, such as metal-organic frameworks (MOFs), are well suited as electrode materials for technologies involving bulkier charge carriers. However, only limited progress has been made using pristine MOFs, primarily due to lack of redox-active organic groups in the materials. In this work a azo-functional MOF, namely UiO-abdc, is presented as an electrode compound for sodium-ion insertion. The MOF delivers a stable capacity (∼100 mA h g-1) over 150 cycles, and post-cycling characterisation validates the stability of the MOF and participation of the azo-group in charge storage. This study can accelerate the realisation of pristine solids, such as MOFs and other porous organic compounds, as battery materials.

Correction: Toxicity of metal-organic framework nanoparticles: from essential analyses to potential applications.

Correction for 'Toxicity of metal-organic framework nanoparticles: from essential analyses to potential applications' by Romy Ettlinger et al., Chem. Soc. Rev., 2022, 51, 464-484, https://doi.org/10.1039/D1CS00918D.

Clicking zeolites together.

A new mechanism to synthesize catalytic zeolites gives a previously unknown topology.

Pair distribution function analysis of the reassembly step of the assembly-disassembly-organisation-reassembly (ADOR) process.

An in situ pair distribution function study assessing the reassembly of three IM-12 (UTL) intermediate materials to the corresponding fully connected materials. A greater level of atomic change is observed at higher temperatures for the reassembly of the fully disconnected intermediate, IPC-1P, compared to the two partially connected intermediates of IPC-2P and IPC-6P.

Synthesis of FeAPO-34 Molecular Sieve under Ionothermal Condition.

FeAPO-34 with a chabazite (CHA) topology structure was successfully synthesized under ionothermal conditions using 1-ethyl-3-methylimidazoliumchloride (EMIMCl) ionic liquid in the presence of ethylenediamine (EDA). The material was characterized using powder X-ray diffraction (XRD), thermogravimetric analysis (TGA), elemental analyses, and solid-state NMR spectroscopy. Incorporation of iron within the covalent framework of the material was confirmed by the presence of broad signals between 1000 and 14,000 ppm in the 31P NMR spectrum, corresponding to the P(OFe)x(OAl)4-x species.

A structural investigation of organic battery anode materials by NMR crystallography.

Conjugated alkali metal dicarboxylates have recently received attention for applications as organic anode materials in lithium- and sodium-ion batteries. In order to understand and optimise these materials, it is important to be able to characterise both the long-range and local aspects of the crystal structure, which may change during battery cycling. Furthermore, some materials can display polymorphism or hydration behaviour. NMR crystallography, which combines long-range crystallographic information from diffraction with local information from solid-state NMR via interpretation aided by DFT calculations, is one such approach, but this has not yet been widely applied to conjugated dicarboxylates. In this work, we evaluate the application of NMR crystallography for a set of model lithium and sodium dicarboxylate salts. We investigate the effect of different DFT geometry optimisation strategies and find that the calculated NMR parameters are not systematically affected by the choice of optimisation method, although the inclusion of dispersion correction schemes is important to accurately reproduce the experimental unit cell parameters. We also observe hydration behaviour for two of the sodium salts and provide insight into the structure of an as-yet uncharacterised structure of sodium naphthalenedicarboxylate. This highlights the importance of sample preparation and characterisation for organic sodium-ion battery anode materials in particular.

Toxicity of metal-organic framework nanoparticles: from essential analyses to potential applications.

In the last two decades, the field of metal-organic frameworks (MOFs) has exploded, and MOF nanoparticles in particular are being investigated with increasing interest for various applications, including gas storage and separation, water harvesting, catalysis, energy conversion and storage, sensing, diagnosis, therapy, and theranostics. To further pave their way into real-world applications, and to push the synthesis of MOF nanoparticles that are 'safe-and-sustainable-by-design', this tutorial review aims to shed light on the importance of a systematic toxicity assessment. After clarifying and working out the most important terms and aspects from the field of nanotoxicity, the current state-of-the-art of in vitro and in vivo toxicity studies of MOF nanoparticles is evaluated. Moreover, the key aspects affecting the toxicity of MOF nanoparticles such as their chemical composition, their physico-chemical properties, including their colloidal and chemical stability, are discussed. We highlight the need of more targeted synthesis of MOF nanoparticles that are 'safe-and-sustainable-by-design', and their tailored hazard assessment in the context of their potential applications in order to tap the full potential of this versatile material class in the future.

Rapid Microwave-Assisted Synthesis and Electrode Optimization of Organic Anode Materials in Sodium-Ion Batteries.

Sodium-ion batteries are commanding increasing attention owing to their promising electrochemical performance and sustainability. Organic electrode materials (OEMs) complement such technologies as they can be sourced from biomass and recycling them is environmentally friendly. Organic anodes based on sodium carboxylates have exhibited immense potential, except the limitation of current synthesis methods concerning upscaling and energy costs. In this work, a rapid and energy efficient microwave-assisted synthesis for organic anodes is presented using sodium naphthalene-2,6-dicarboxylate as a model compound. Optimizing the synthesis and electrode composition enables the compound to deliver a reversible initial capacity of ≈250 mAh g-1 at a current density of 25 mA g-1 with a high initial Coulombic efficiency (≈78%). The capacity is stable over 400 cycles and the compound also exhibits good rate performance. The successful demonstration of this rapid synthesis may facilitate the transition to preparing organic battery materials by scalable, efficient methods.