Electron beam and thermal stabilities of MFM-300(M) metal-organic frameworks.

This work reports the thermal and electron beam stabilities of a series of isostructural metal-organic frameworks (MOFs) of type MFM-300(M) (M = Al, Ga, In, Cr). MFM-300(Cr) was most stable under the electron beam, having an unusually high critical electron fluence of 1111 e Å while the Group 13 element MOFs were found to be less stable. Within Group 13, MFM-300(Al) had the highest critical electron fluence of 330 e Å, compared to 189 e Å and 147 e Å for the Ga and In MOFs, respectively.

Diet and the risk of inflammatory bowel disease: A retrospective cohort study in Taiwan.

Background/purpose: The incidence of inflammatory bowel disease (IBD) rapidly increases in Asia, and western dietary pattern is suspected to be the major risk factor. Despite this, there has been a lack of studies analyzing the relationship between dietary patterns and IBD in Taiwan. This study examines the dietary habits of Taiwanese individuals with and without IBD to inform clinical dietary recommendations for IBD patients.

Monitoring the Formation of Nickel-Poor and Nickel-Rich Oxide Cathode Materials for Lithium-Ion Batteries with Synchrotron Radiation.

The syntheses of Ni-poor (NCM111, LiNiCoMnO) and Ni-rich (NCM811 LiNiCoMnO) lithium transition-metal oxides (space group 3̅m) from hydroxide precursors (NiCoMn(OH), NiCoMn(OH)) are investigated using synchrotron powder diffraction and near-edge X-ray absorption fine structure spectroscopy. The development of the layered structure of these two cathode materials proceeds two utterly different reaction mechanisms. While the synthesis of NCM811 involves a rock salt-type intermediate phase, NCM111 reveals a layered structure throughout the entire synthesis.

Direct Visualization of Supramolecular Binding and Separation of Light Hydrocarbons in MFM-300(In).

The purification of light olefins is one of the most important chemical separations globally and consumes large amounts of energy. Porous materials have the capability to improve the efficiency of this process by acting as solid, regenerable adsorbents. However, to develop translational systems, the underlying mechanisms of adsorption in porous materials must be fully understood.

Ultrawide Temperature Range Super-Invar Behavior of R_{2}(Fe,Co)_{17} Materials (R = Rare Earth).

Super Invar (SIV), i.e., zero thermal expansion of metallic materials underpinned by magnetic ordering, is of great practical merit for a wide range of high precision engineering.

Structural Features in Some Layered Hybrid Copper Chloride Perovskites: ACuCl or ACuCl.

We present three new hybrid copper(II) chloride layered perovskites of generic composition ACuCl or ACuCl, which exhibit three distinct structure types. (-PdH)CuCl (-PdH = protonated -phenylenediamine) adopts a Dion-Jacobson (DJ)-like layered perovskite structure type and exhibits a very large axial thermal contraction effect upon heating, as revealed via variable-temperature synchrotron X-ray powder diffraction (SXRD). This can be attributed to the contraction of an interlayer block, via a slight repositioning of the -PdH moiety.

Construction of C-C bonds via photoreductive coupling of ketones and aldehydes in the metal-organic-framework MFM-300(Cr).

Construction of C-C bonds via reductive coupling of aldehydes and ketones is hindered by the highly negative reduction potential of these carbonyl substrates, particularly ketones, and this renders the formation of ketyl radicals extremely endergonic. Here, we report the efficient activation of carbonyl compounds by the formation of specific host-guest interactions in a hydroxyl-decorated porous photocatalyst. MFM-300(Cr) exhibits a band gap of 1.

Induced Active Sites by Adsorbate in Zeotype Materials.

There has been a long debate on how and where active sites are created for molecular adsorption and catalysis in zeolites, which underpin many important industrial applications. It is well accepted that Lewis acidic sites (LASs) and basic sites (LBSs) as active sites in pristine zeolites are generally believed to be the extra-framework Al species and residue anion (OH) species formed at fixed crystallographic positions after their synthesis. However, the dynamic interactions of adsorbates/reactants with pristine zeotype materials to "create" sites during real conditions remain largely unexplored.

The Origin of Catalytic Benzylic C-H Oxidation over a Redox-Active Metal-Organic Framework.

Selective oxidation of benzylic C-H compounds to ketones is important for the production of a wide range of fine chemicals, and is often achieved using toxic or precious metal catalysts. Herein, we report the efficient oxidation of benzylic C-H groups in a broad range of substrates under mild conditions over a robust metal-organic framework material, MFM-170, incorporating redox-active [Cu (O CR) ] paddlewheel nodes. A comprehensive investigation employing electron paramagnetic resonance (EPR) spectroscopy and synchrotron X-ray diffraction has identified the critical role of the paddlewheel moiety in activating the oxidant BuOOH (tert-butyl hydroperoxide) via partial reduction to [Cu Cu (O CR) ] species.

The Electrophilicity of Surface Carbon Species in the Redox Reactions of CuO-CeO Catalysts.

Electronic metal-support interactions (EMSI) describe the electron flow between metal sites and a metal oxide support. It is generally used to follow the mechanism of redox reactions. In this study of CuO-CeO redox, an additional flow of electrons from metallic Cu to surface carbon species is observed via a combination of operando X-ray absorption spectroscopy, synchrotron X-ray powder diffraction, near ambient pressure near edge X-ray absorption fine structure spectroscopy, and diffuse reflectance infrared Fourier transform spectroscopy.

Responses of Defect-Rich Zr-Based Metal-Organic Frameworks toward NH Adsorption.

Understanding structural responses of metal-organic frameworks (MOFs) to external stimuli such as the inclusion of guest molecules and temperature/pressure has gained increasing attention in many applications, for example, manipulation and manifesto smart materials for gas storage, energy storage, controlled drug delivery, tunable mechanical properties, and molecular sensing, to name but a few. Herein, neutron and synchrotron diffractions along with Rietveld refinement and density functional theory calculations have been used to elucidate the responsive adsorption behaviors of defect-rich Zr-based MOFs upon the progressive incorporation of ammonia (NH) and variable temperature. UiO-67 and UiO-bpydc containing biphenyl dicarboxylate and bipyridine dicarboxylate linkers, respectively, were selected, and the results establish the paramount influence of the functional linkers on their NH affinity, which leads to stimulus-tailoring properties such as gate-controlled porosity by dynamic linker flipping, disorder, and structural rigidity.

Control of zeolite microenvironment for propene synthesis from methanol.

Optimising the balance between propene selectivity, propene/ethene ratio and catalytic stability and unravelling the explicit mechanism on formation of the first carbon-carbon bond are challenging goals of great importance in state-of-the-art methanol-to-olefin (MTO) research. We report a strategy to finely control the nature of active sites within the pores of commercial MFI-zeolites by incorporating tantalum(V) and aluminium(III) centres into the framework. The resultant TaAlS-1 zeolite exhibits simultaneously remarkable propene selectivity (51%), propene/ethene ratio (8.

Enhanced proton conductivity in a flexible metal-organic framework promoted by single-crystal-to-single-crystal transformation.

MFM-722(Pb)-DMA undergoes a single-crystal-to-single-crystal (SCSC) transformation to give MFM-722(Pb)-H2O via ligand substitution upon exposure to water vapour. In situ single crystal impedance spectroscopy reveals an increase in proton conductivity due to this structural transition, with MFM-722(Pb)-H2O showing a proton conductivity of 6.61 × 10-4 S cm-1 at 50 °C and 98% RH.

A rational study on the geometric and electronic properties of single-atom catalysts for enhanced catalytic performance.

We investigate the geometric and electronic properties of single-atom catalysts (SACs) within metal-organic frameworks (MOFs) with respect to electrocatalytic CO2 reduction as a model reaction. A series of mid-to-late 3d transition metals have been immobilised within the microporous cavity of UiO-66-NH2. By employing Rietveld refinement of new-generation synchrotron diffraction, we not only identified the crystallographic and atomic parameters of the SACs that are stabilised with a robust MN(MOF) bonding of ca.

Porous Metal-Organic Polyhedra: Morphology, Porosity, and Guest Binding.

Designing porous materials which can selectively adsorb CO or CH is an important environmental and industrial goal which requires an understanding of the host-guest interactions involved at the atomic scale. Metal-organic polyhedra (MOPs) showing permanent porosity upon desolvation are rarely observed. We report a family of MOPs , , ), which derive their permanent porosity from cavities between packed cages rather than from within the polyhedra.

Refinement of pore size at sub-angstrom precision in robust metal-organic frameworks for separation of xylenes.

The demand for xylenes is projected to increase over the coming decades. The separation of xylene isomers, particularly p- and m-xylenes, is vital for the production of numerous polymers and materials. However, current state-of-the-art separation is based upon fractional crystallisation at 220 K which is highly energy intensive.

Bulk fatigue induced by surface reconstruction in layered Ni-rich cathodes for Li-ion batteries.

Ni-rich layered cathode materials are among the most promising candidates for high-energy-density Li-ion batteries, yet their degradation mechanisms are still poorly understood. We report a structure-driven degradation mechanism for NMC811 (LiNiMnCoO), in which a proportion of the material exhibits a lowered accessible state of charge at the end of charging after repetitive cycling and becomes fatigued. Operando synchrotron long-duration X-ray diffraction enabled by a laser-thinned coin cell shows the emergence and growth in the concentration of this fatigued phase with cycle number.

Long-Term Stability of MFM-300(Al) toward Toxic Air Pollutants.

Temperature- or pressure-swing sorption in porous metal-organic framework (MOF) materials has been proposed for new gas separation technologies. The high tunability of MOFs toward particular adsorbates and the relatively low energy penalty for system regeneration indicate that reversible physisorption in MOFs has the potential to create economic and environmental benefits compared with state-of-the-art chemisorption systems. However, for MOF-based sorbents to be commercialized, they have to show long-term stability under the conditions imposed by the application.

Amino Acid Residues Determine the Response of Flexible Metal-Organic Frameworks to Guests.

Flexible metal-organic frameworks (MOFs) undergo structural transformations in response to physical and chemical stimuli. This is hard to control because of feedback between guest uptake and host structure change. We report a family of flexible MOFs based on derivatized amino acid linkers.

Adsorption and activation of molecular oxygen over atomic copper(I/II) site on ceria.

Supported atomic metal sites have discrete molecular orbitals. Precise control over the energies of these sites is key to achieving novel reaction pathways with superior selectivity. Here, we achieve selective oxygen (O) activation by utilising a framework of cerium (Ce) cations to reduce the energy of 3d orbitals of isolated copper (Cu) sites.

Evaluation of microflow configurations for scale inhibition and serial X-ray diffraction analysis of crystallization processes.

The clean and reproducible conditions provided by microfluidic devices are ideal sample environments for in situ analyses of chemical and biochemical reactions and assembly processes. However, the small size of microchannels makes investigating the crystallization of poorly soluble materials on-chip challenging due to crystal nucleation and growth that result in channel fouling and blockage. Here, we demonstrate a reusable insert-based microfluidic platform for serial X-ray diffraction analysis and examine scale formation in response to continuous and segmented flow configurations across a range of temperatures.

Control of zeolite pore interior for chemoselective alkyne/olefin separations.

The efficient removal of alkyne impurities for the production of polymer-grade lower olefins remains an important and challenging goal for many industries. We report a strategy to control the pore interior of faujasite (FAU) zeolites by the confinement of isolated open nickel(II) sites in their six-membered rings. Under ambient conditions, Ni@FAU showed remarkable adsorption of alkynes and efficient separations of acetylene/ethylene, propyne/propylene, and butyne/1,3-butadiene mixtures, with unprecedented dynamic separation selectivities of 100, 92, and 83, respectively.

Dynamic Crystallization Pathways of Polymorphic Pharmaceuticals Revealed in Segmented Flow with Inline Powder X-ray Diffraction.

Understanding the transitions between polymorphs is essential in the development of strategies for manufacturing and maximizing the efficiency of pharmaceuticals. However, this can be extremely challenging: crystallization can be influenced by subtle changes in environment, such as temperature and mixing intensity or even imperfections in the crystallizer walls. Here, we highlight the importance of in situ measurements in understanding crystallization mechanisms, where a segmented flow crystallizer was used to study the crystallization of the pharmaceuticals urea: barbituric acid (UBA) and carbamazepine (CBZ).

Enantiospecificity in achiral zeolites for asymmetric catalysis.

This article highlights the recent fundamental study in using achiral and chiral porous materials for the potential applications in asymmetric catalysis. Thanks to the new-generation synchrotron X-ray powder diffraction (SXRD) facilities, we reveal the presence of the unique 'chiral region' in achiral zeolites with the MFI topology. Both the inherent site-isolation effect of the active sites and internal confinement restraints in zeolites are critical for creating 'chiral regions' that can aid the design of more enantioselective catalytic reactions.

Quantitative production of butenes from biomass-derived γ-valerolactone catalysed by hetero-atomic MFI zeolite.

The efficient production of light olefins from renewable biomass is a vital and challenging target to achieve future sustainable chemical processes. Here we report a hetero-atomic MFI-type zeolite (NbAlS-1), over which aqueous solutions of γ-valerolactone (GVL), obtained from biomass-derived carbohydrates, can be quantitatively converted into butenes with a yield of >99% at ambient pressure under continuous flow conditions. NbAlS-1 incorporates simultaneously niobium(V) and aluminium(III) centres into the framework and thus has a desirable distribution of Lewis and Brønsted acid sites with optimal strength.