Controlled Synthesis of Large Single Crystals of Metal-Organic Framework CPO-27-Ni Prepared by a Modulation Approach: In situ Single-Crystal X-ray Diffraction Studies.

The size of single crystals of the metal-organic framework CPO-27-Ni was incrementally increased through a series of modulated syntheses. A novel linker modulated synthesis using 2,5-dihydroxyterephthalic acid and the isomeric ligand 4,6-dihydroxyisophthalic acid yielded large single crystals of CPO-27-Ni (∼70 µm). All materials were shown to have high crystallinity and phase purity through powder X-ray diffraction, electron microscopy methods, thermogravimetry, and compositional analysis. For the first time single-crystal structure analyses were carried out on CPO-27-Ni. High BET surface areas and nitric oxide (NO) release efficiencies were recorded for all materials. Large single crystals of CPO-27-Ni showed a prolonged NO release and proved suitable for in situ single-crystal diffraction experiments to follow the NO adsorption. An efficient activation protocol was developed, leading to a dehydrated structure after just 4 h, which subsequently was NO-loaded, leading to a first NO loaded single-crystal structural model of CPO-27-Ni.

Size dependence of the surface spin disorder and surface anisotropy constant in ferrite nanoparticles.

The magnetic properties of nanoscale magnets are greatly influenced by surface anisotropy. So far, its quantification is based on the examination of the blocking temperature shift within a series of nanoparticles of varying sizes. In this scenario, the surface anisotropy is assumed to be a particle size-independent quantity. However, there is no solid experimental proof to support this simplified picture. On the contrary, our work unravels the size-dependent magnetic morphology and surface anisotropy in highly uniform magnetic nanoparticles using small-angle polarized neutron scattering. We observed that the surface anisotropy constant does not depend on the nanoparticle's size in the range of 3-9 nm. Furthermore, our results demonstrate that the surface spins are less prone to polarization with increasing nanoparticle size. Our study thus proves the size dependence of the surface spin disorder and the surface anisotropy constant in fine nanomagnets. These findings open new routes in materials based on a controlled surface spin disorder, which is essential for future applications of nanomagnets in biomedicine and magnonics.

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.

From crystal phase mixture to pure metal-organic frameworks - Tuning pore and structure properties.

In this study, a sonochemical route for the preparation of a new Hf-MIL-140A metal-organic framework from a mixture of UiO-66/MIL-140A is presented. The sonochemical synthesis route not only allows the phase-pure MIL-140A structure to be obtained but also induces structural defects in the MIL-140A structure. The synergic effect between the sonochemical irradiation and the presence of a highly acidic environment results in the generation of slit-like defects in the crystal structure, which increases specific surface area and pore volume. The BET-specific surface area in the case of sonochemically derived Zr-MIL-140A reaches 653.3 m2/g, which is 1.5 times higher than that obtained during conventional synthesis. The developed Hf-MIL-140A structure is isostructural to Zr-MIL-140A, which was confirmed by synchrotron X-ray powder diffraction (SR-XRD) and by continuous rotation electron diffraction (cRED) analysis. The obtained MOF materials have high thermal and chemical stability, which makes them promising candidates for applications such as gas adsorption, radioactive waste removal, catalysis, and drug delivery.

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.

Confining Gold Nanoparticles in Preformed Zeolites by Post-Synthetic Modification Enhances Stability and Catalytic Reactivity and Selectivity.

Confining Au nanoparticles (NPs) in a restricted space (e.g., zeolite micropores) is a promising way of overcoming their inherent thermal instability and susceptibility to aggregation, which limit catalytic applications. However, such approaches involve complex, multistep encapsulation processes. Here, we describe a successful strategy and its guiding principles for confining small (<2 nm) and monodisperse Au NPs within commercially available beta and MFI zeolites, which can oxidize CO at 40 °C and show size-selective catalysis. This protocol involves post-synthetic modification of the zeolite internal surface with thiol groups, which confines AuCl x species inside microporous frameworks during the activation process whereby Au precursors are converted into Au nanoparticles. The resulting beta and MFI zeolites contain uniformly dispersed Au NPs throughout the void space, indicating that the intrinsic stability of the framework promotes resistance to sintering. By contrast, in situ scanning transmission electron microscopy (STEM) studies evidenced that Au precursors in bare zeolites migrate from the matrix to the external surface during activation, thereby forming large and poorly dispersed agglomerates. Furthermore, the resistance of confined Au NPs against sintering is likely relevant to the intrinsic stability of the framework, supported by extended X-ray absorption fine structure (EXAFS), H2 chemisorption, and CO Fourier transform infrared (FT-IR) studies. The Au NPs supported on commercial MFI maintain their uniform dispersity to a large extent after treatment at 700 °C that sinters Au clusters on mesoporous silicas or beta zeolites. Low-temperature CO oxidation and size-selective reactions highlight that most gold NPs are present inside the zeolite matrix with a diameter smaller than 2 nm. These findings illustrate how confinement favors small, uniquely stable, and monodisperse NPs, even for metals such as Au susceptible to cluster growth under conditions often required for catalytic use. Moreover, this strategy may be readily adapted to other zeolite frameworks that can be functionalized by thiol groups.

New avenues for mechanochemistry in zeolite science.

Zeolites are a class of microporous materials with tremendous value for large scale industrial applications such as catalysis, ion exchange, or gas separation. In addition to naturally ocurring variants, zeolites are made synthetically using hydrothermal synthesis, requiring temperatures beyond 100 °C and long reaction times up to weeks. Furthermore, specific applications may require more sophisticated synthesis conditions, expensive reagents, or post-synthetic modifications. Some of these issues can be tackled by using the reemerged technique of mechanochemistry. In 2014, Majano et al. reviewed the space and outlined several possibilities for the usage of mechanical forces in zeolite chemistry. Since then the field has seen many more publications employing mechanochemical methodology to further and improve the synthesis and properties of zeolite materials. The usage ranges from the activation of raw materials, rendering the synthesis of the widely used catalysts much more economical in terms of duration, atom efficiency, and production of waste, to post-synthetic modification of the materials leading to improved properties for target aplications. We present a short review of the advances that have been reported recently, highlight promising work and important studies, and give a perspective of potential future endeavours.

In situ flow pair distribution function analysis to probe the assembly-disassembly-organisation-reassembly (ADOR) mechanism of zeolite IPC-2 synthesis.

The assembly-disassembly-organisation-reassembly (ADOR) process is an important tool to access zeolite structures that are otherwise unfeasible via hydrothermal methods. In situ flow pair distribution function (PDF) analysis has been used to probe the mechanism of the disassembly and organisation steps, with the disassembly a rapid step that is often difficult to capture. Zeolite UTL was hydrolysed by 6 M hydrochloric acid, with PDF measurements used to monitor framework alterations as the reaction proceeded. The resulting disassembly mechanism shows an initial rapid removal of germanium from the germanium-rich double 4 rings (d4r), followed by silicon rearrangement and gradual silanol condensation to form IPC-2P.

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.

Mechanochemically assisted hydrolysis in the ADOR process.

The ADOR (Assembly-Disassembly-Organisation-Reassembly) process for zeolites has been shown to produce a number of previously unknown frameworks inaccessible through conventional synthesis methods. Here, we present successful mechanochemically assisted hydrolysis of germanosilicate zeolite UTL leading to ADOR products under mild conditions, low amounts of solvent and in short reaction times. The expansion of zeolite synthesis into the realm of mechanochemistry opens up feasible pathways regarding the production of these materials, especially for industrial purposes, as well as an exciting application for economical enrichment of materials with the low natural abundance NMR-active isotope of oxygen, 17O. The results from mechanochemically assisted hydrolysis differ from those seen in the traditional ADOR approach: differences that can be attributed to a change in solvent availability.