High adsorption of ammonia in a titanium-based metal-organic framework.

We report the high adsorption of NH3 in a titanium-based metal-organic framework, MFM-300(Ti), comprising extended [TiO6]∞ chains linked by biphenyl-3,3',5,5'-tetracarboxylate ligands. At 273 K and 1 bar, MFM-300(Ti) shows an exceptional NH3 uptake of 23.4 mmol g-1 with a record-high packing density of 0.84 g cm-3. Dynamic breakthrough experiments confirm the excellent uptake and separation of NH3 at low concentration (1000 ppm). The combination of in situ neutron powder diffraction and spectroscopic studies reveal strong, yet reversible binding interactions of NH3 to the framework oxygen sites.

Comprehensive Analysis of Methyl-ß-D-ribofuranoside: A Multifaceted Spectroscopic and Theoretical Approach.

This study presents a comprehensive analysis of the vibrational spectra of methyl-ß-D-ribofuranoside. Employing a combination of inelastic neutron scattering, Raman, and infrared spectroscopy allows for the observation of all modes regardless of the selection rules. The experimental techniques were complemented by density functional theory computational methods using both gas-phase (Gaussian) and solid-state (CRYSTAL, CASTEP) approaches to provide an unambiguous assignment of the defining vibrational features. Two distinct structures of the molecule were identified in the unit cell, differentiated mainly by the orientation of the furanose ring O-H bonds. The low-energy region of the spectrum (<400 cm-1) is dominated by lattice vibrations and functional group rotation, while the midenergy region is dominated by out-of-plane bending motions of the furanose ring (400-900 cm-1) and by C-H bending in the methyl and methylene groups (1400-1600 cm-1). The high-energy region (>2800 cm-1) encompasses the C-H and O-H stretching modes and offers convincing evidence of at least one H-bonding interaction between the two structures of methyl-ß-D-ribofuranoside.

Exploring asymmetry induced entropy in tetraalkylammonium-urea DES systems: what can be learned from inelastic neutron scattering?

In this work, inelastic neutron scattering (INS) spectroscopy is used to investigate the impact of entropic factors on the behaviour of deep eutectic solvents (DES). Periodic density functional theory calculations (DFT) provide a reliable assignment of the vibrational modes of pure compounds. This assignment guides the analysis of INS spectra of binary mixtures - with particular attention to methyl torsional modes. Deviations from ideality in the mixtures of tetraalkylammonium salts with urea are readily determined through a simplified thermodynamic approach. This study reports and discusses the relationship between the cation's asymmetry, the INS spectra of the eutectic mixture and its deviation from ideality. Contrary to the majority of systems studied so far, the deep eutectic system comprised of [N2,2,2,1]Cl and urea appears to owe its deviation from ideality to entropic rather than enthalpic factors.

Control of H-Related Defects in γ-MnO2 in a Hydrothermal Synthesis.

Manganese dioxide is a good candidate for effective energy storage and conversion as it possesses rich electrochemistry. The compound also shows a wide polymorphism. The γ-variety, an intergrowth of ß- and R-MnO2, has been extensively studied in several types of batteries (e.g., Zn/MnO2, Li-ion) and is a common electrode material for commercial batteries. It is well known that the insertion of protons thermodynamically stabilizes γ-MnO2 with respect to ß-MnO2. Protons can enter the structure either by forming groups of 4 hydroxyls around a Mn4+ vacancy, called a Ruetschi defect, or by forming a hydroxyl group near a Mn3+ ion, called a Coleman defect. These defects differently affect the electrochemistry of manganese oxide, and tailoring their amount in the structure can be used to tune the material properties. Previous studies have addressed the proton insertion process, but the role of the synthesis pathway on the amount of defects created is not well understood. We here investigate how the parameters in a hydrothermal synthesis of γ-MnO2 nanoparticles influence the amount and type of H-related defects. Structural investigations are carried out using Pair Distribution Function analysis, X-ray absorption spectroscopy, thermogravimetric analysis, and inelastic neutron scattering. We demonstrate the possibility to control the amount and type of defects introduced during the synthesis. While the amount of Ruetschi defects increases with synthesis temperature, it decreases with extended synthesis time, along with the amount of Coleman defects. Moreover, we discuss the arrangement of the defects in the γ-MnO2 nanoparticles.

From PEF to PBF: What difference does the longer alkyl chain make a computational spectroscopy study of poly(butylene 2,5-furandicarboxylate).

This work explores the conformational preferences and the structure-property correlations of poly(butylene 2,5-furandicarboxylate) (PBF), a longer chain analogue of the most well-known biobased polyester from the furan family, poly(ethylene 2,5-furandicarboxylate) (PEF). A thorough computational spectroscopic study-including infrared, Raman and inelastic neutron scattering spectroscopy, combined with discrete and periodic density functional theory calculations-allowed the identification of dominant structural motifs in the amorphous and crystalline regions. Discrete calculations and vibrational spectroscopy of semi-crystalline and amorphous samples strongly support the predominance of gauche, trans, gauche conformations of the butylene glycol fragment in both the crystalline and amorphous domains. In what concerns the furandicarboxylate fragment, amorphous domains are dominated by syn,syn conformations, while in the crystalline domains the anti,anti forms prevail. A possible crystalline structure-built from these conformational preferences and including a network of C-H···O hydrogen bond contacts-was optimized using periodic density functional theory. This proposed crystal structure avoids the unrealistic structural features of the previously proposed X-ray structure, provides an excellent description of the inelastic neutron scattering spectrum of the semi-crystalline form, and allows the correlation between microscopic structure and macroscopic properties of the polymer.

Controlling Amyloid Fibril Properties Via Ionic Liquids: The Representative Case of Ethylammonium Nitrate and Tetramethylguanidinium Acetate on the Amyloidogenesis of Lysozyme.

Protein aggregation into amyloid fibrils has been observed in several pathological conditions and exploited in nanotechnology. It is also key in several biochemical processes. In this work, we show that ionic liquids (ILs), a vast class of organic electrolytes, can finely tune amyloid properties, opening a new landscape in basic science and applications. The representative case of ethylammonium nitrate (EAN) and tetramethyl-guanidinium acetate (TMGA) ILs on lysozyme is considered. First, atomic force microscopy has shown that the addition of EAN and TMGA leads to thicker and thinner amyloid fibrils of greater and lower electric potential, respectively, with diameters finely tunable by IL concentration. Optical tweezers and neutron scattering have shed light on their mechanism of action. TMGA interacts with the protein hydration layer only, making the relaxation dynamics of these water molecules faster. EAN interacts directly with the protein instead, making it mechanically unstable and slowing down its relaxation dynamics.

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. Herein, we report the adsorption and dynamic separation of C2 and C3 hydrocarbons in the metal-organic framework MFM-300(In), which exhibits excellent performance in the separation of mixtures of ethane/ethylene and propyne/propylene. Unusually selective adsorption of ethane over ethylene at low pressure is observed, resulting in selective retention of ethane from a mixture of ethylene/ethane, thus demonstrating its potential for a one-step purification of ethylene (purity > 99.9%). In situ neutron powder diffraction and inelastic neutron scattering reveal the preferred adsorption domains and host-guest binding dynamics of adsorption of C2 and C3 hydrocarbons in MFM-300(In).

Direct Observation of Ammonia Storage in UiO-66 Incorporating Cu(II) Binding Sites.

The presence of active sites in metal-organic framework (MOF) materials can control and affect their performance significantly in adsorption and catalysis. However, revealing the interactions between the substrate and active sites in MOFs at atomic precision remains a challenging task. Here, we report the direct observation of binding of NH3 in a series of UiO-66 materials containing atomically dispersed defects and open Cu(I) and Cu(II) sites. While all MOFs in this series exhibit similar surface areas (1111-1135 m2 g-1), decoration of the -OH site in UiO-66-defect with Cu(II) results in a 43% enhancement of the isothermal uptake of NH3 at 273 K and 1.0 bar from 11.8 in UiO-66-defect to 16.9 mmol g-1 in UiO-66-CuII. A 100% enhancement of dynamic adsorption of NH3 at a concentration level of 630 ppm from 2.07 mmol g-1 in UiO-66-defect to 4.15 mmol g-1 in UiO-66-CuII at 298 K is observed. In situ neutron powder diffraction, inelastic neutron scattering, and electron paramagnetic resonance, solid-state nuclear magnetic resonance, and infrared spectroscopies, coupled with modeling reveal that the enhanced NH3 uptake in UiO-66-CuII originates from a {Cu(II)···NH3} interaction, with a reversible change in geometry at Cu(II) from near-linear to trigonal coordination. This work represents the first example of structural elucidation of NH3 binding in MOFs containing open metal sites and will inform the design of new efficient MOF sorbents by targeted control of active sites for NH3 capture and storage.

High capacity ammonia adsorption in a robust metal-organic framework mediated by reversible host-guest interactions.

To understand the exceptional adsorption of ammonia (NH3) in MFM-300(Sc) (19.5 mmol g-1 at 273 K and 1 bar without hysteresis), we report a systematic investigation of the mechanism of adsorption by a combination of in situ neutron powder diffraction, inelastic neutron scattering, synchrotron infrared microspectroscopy, and solid-state 45Sc NMR spectroscopy. These complementary techniques reveal the formation of reversible host-guest supramolecular interactions, which explains directly the observed excellent reversibility of this material over 90 adsorption-desorption cycles.

Hydrogen Detection Limits and Instrument Sensitivity of High-Resolution Broadband Neutron Spectrometers.

The limits of detection (LOD) and quantitation (LOQ) in the mass domain, for broadband vibrational spectroscopy with neutrons on the TOSCA spectrometer at the ISIS Pulsed Neutron and Muon Source (UK), have been studied. The well-known 3σ and 10σ approaches are used through a specifically developed analytical procedure that is based on the calculation of the integrated spectral intensities in selected energy-transfer ranges, as a function of mass of standard reference materials and calibrants, such as ZrH2, 2,5-diiodothiophene, and low-density polyethylene. The analysis shows that the blank, that is, the instrument setup without the analyte, plays a critical role in the measurement performance, especially for small specimen quantities. The results point that TOSCA enables detection of 128 µmol (LODH) and quantitation of 428 µmol (LOQH) of elemental hydrogen analytes in ZrH2. The determined values for this and other standards allow for the assessment of the calibration curve design and instrument sensitivity and define a method to be used for inelastic neutron scattering spectrometers such as TOSCA, or VESPA, the new beamline under construction at the European Spallation Source in Lund (Sweden).

Understanding the ZIF-L to ZIF-8 transformation from fundamentals to fully costed kilogram-scale production.

The production of MOFs at large scale in a sustainable way is key if these materials are to be exploited for their promised widespread application. Much of the published literature has focused on demonstrations of preparation routes using difficult or expensive methodologies to scale. One such MOF is nano-zeolitic imidazolate framework-8 (ZIF-8) - a material of interest for a range of possible applications. Work presented here shows how the synthesis of ZIF-8 can be tracked by a range of methods including X-ray diffraction, thermo gravimetric analysis and inelastic neutron scattering - which offer the prospect of in-line monitoring of the synthesis reaction. Herein we disclose how the production of nano-ZIF-8 can be conducted at scale using the intermediate phase ZIF-L. By understanding the economics and demonstrating the production of 1 kg of nano-ZIF-8 at pilot scale we have shown how this once difficult to make material can be produced to specification in a scalable and cost-efficient fashion.

Spectroscopic Signatures of Hydrogen-Bonding Motifs in Protonic Ionic Liquid Systems: Insights from Diethylammonium Nitrate in the Solid State.

Diethylammonium nitrate, [N0 0 2 2][NO3], and its perdeuterated analogue, [N D D 2 2] [NO3], were structurally characterized and studied by infrared, Raman, and inelastic neutron scattering (INS) spectroscopy. Using these experimental data along with state-of-the-art computational materials modeling, we report unambiguous spectroscopic signatures of hydrogen-bonding interactions between the two counterions. An exhaustive assignment of the spectral features observed with each technique has been provided, and a number of distinct modes related to NH···O dynamics have been identified. We put a particular emphasis on a detailed interpretation of the high-resolution, broadband INS experiments. In particular, the INS data highlight the importance of conformational degrees of freedom within the alkyl chains, a ubiquitous feature of ionic liquid (IL) systems. These findings also enable an in-depth physicochemical understanding of protonic IL systems, a first and necessary step to the tailoring of hydrogen-bonding networks in this important class of materials.

Pore Distortion in a Metal-Organic Framework for Regulated Separation of Propane and Propylene.

The development of porous solids for adsorptive separation of propylene and propane remains an important and challenging line of research. State-of-the-art sorbent materials often suffer from the trade-off between adsorption capacity and selectivity. Here, we report the regulated separation of propylene and propane in a metal-organic framework via designed pore distortion. The distorted pore structure of HIAM-301 successfully excludes propane and thus achieved simultaneously high selectivity (>150) and large capacity (∼3.2 mmol/g) of propylene at 298 K and 1 bar. Dynamic breakthrough measurements validated the excellent separation of propane and propylene. In situ neutron powder diffraction and inelastic neutron scattering revealed the binding domains of adsorbed propylene molecules in HIAM-301 as well as host-guest interaction dynamics. This study presents a new benchmark for the adsorptive separation of propylene and propane.

Predicting the impact sensitivity of a polymorphic high explosive: the curious case of FOX-7.

The impact sensitivity (IS) of FOX-7 polymorphs is predicted by phonon up-pumping to decrease as layers of FOX-7 molecules flatten. Experimental validation proved anomalous owing to a phase transition during testing, raising questions regarding impact sensitivity measurement and highlighting the need for models to predict IS of polymorphic energetic materials.

Metallodrug-protein interaction probed by synchrotron terahertz and neutron scattering spectroscopy.

This experimental work applied coherent synchrotron-radiation terahertz spectroscopy and inelastic neutron scattering to address two processes directly associated with the mode of action of metal-based anticancer agents that can severely undermine chemotherapeutic treatment: drug binding to human serum albumin, occurring during intravenous drug transport, and intracellular coordination to thiol-containing biomolecules (such as metallothioneins) associated with acquired drug resistance. Cisplatin and two dinuclear platinum (Pt)- and palladium (Pd)-polyamine agents developed by this research group, which have yielded promising results toward some types of human cancers, were investigated. Complementary synchrotron-radiation-terahertz and inelastic neutron scattering data revealed protein metalation, through S- and N-donor ligands from cysteine, methionine, and histidine residues. A clear impact of the Pt and Pd agents was evidenced, drug binding to albumin and metallothionein having been responsible for significant changes in the overall protein conformation, as well as for an increased flexibility and possible aggregation.

Atomically Dispersed Copper Sites in a Metal-Organic Framework for Reduction of Nitrogen Dioxide.

Metal-organic framework (MOF) materials provide an excellent platform to fabricate single-atom catalysts due to their structural diversity, intrinsic porosity, and designable functionality. However, the unambiguous identification of atomically dispersed metal sites and the elucidation of their role in catalysis are challenging due to limited methods of characterization and lack of direct structural information. Here, we report a comprehensive investigation of the structure and the role of atomically dispersed copper sites in UiO-66 for the catalytic reduction of NO2 at ambient temperature. The atomic dispersion of copper sites on UiO-66 is confirmed by high-angle annular dark-field scanning transmission electron microscopy, electron paramagnetic resonance spectroscopy, and inelastic neutron scattering, and their location is identified by neutron powder diffraction and solid-state nuclear magnetic resonance spectroscopy. The Cu/UiO-66 catalyst exhibits superior catalytic performance for the reduction of NO2 at 25 °C without the use of reductants. A selectivity of 88% for the formation of N2 at a 97% conversion of NO2 with a lifetime of >50 h and an unprecedented turnover frequency of 6.1 h-1 is achieved under nonthermal plasma activation. In situ and operando infrared, solid-state NMR, and EPR spectroscopy reveal the critical role of copper sites in the adsorption and activation of NO2 molecules, with the formation of {Cu(I)···NO} and {Cu···NO2} adducts promoting the conversion of NO2 to N2. This study will inspire the further design and study of new efficient single-atom catalysts for NO2 abatement via detailed unravelling of their role in catalysis.

Purification of Propylene and Ethylene by a Robust Metal-Organic Framework Mediated by Host-Guest Interactions.

Industrial purification of propylene and ethylene requires cryogenic distillation and selective hydrogenation over palladium catalysts to remove propane, ethane and/or trace amounts of acetylene. Here, we report the excellent separation of equimolar mixtures of propylene/propane and ethylene/ethane, and of a 1/100 mixture of acetylene/ethylene by a highly robust microporous material, MFM-520, under dynamic conditions. In situ synchrotron single crystal X-ray diffraction, inelastic neutron scattering and analysis of adsorption thermodynamic parameters reveal that a series of synergistic host-guest interactions involving hydrogen bonding and π⋅⋅⋅π stacking interactions underpin the cooperative binding of alkenes within the pore. Notably, the optimal pore geometry of the material enables selective accommodation of acetylene. The practical potential of this porous material has been demonstrated by fabricating mixed-matrix membranes comprising MFM-520, Matrimid and PIM-1, and these exhibit not only a high permeability for propylene (≈1984 Barrer), but also a separation factor of 7.8 for an equimolar mixture of propylene/propane at 298 K.

High Ammonia Adsorption in MFM-300 Materials: Dynamics and Charge Transfer in Host-Guest Binding.

Ammonia (NH3) is a promising energy resource owing to its high hydrogen density. However, its widespread application is restricted by the lack of efficient and corrosion-resistant storage materials. Here, we report high NH3 adsorption in a series of robust metal-organic framework (MOF) materials, MFM-300(M) (M = Fe, V, Cr, In). MFM-300(M) (M = Fe, VIII, Cr) show fully reversible capacity for >20 cycles, reaching capacities of 16.1, 15.6, and 14.0 mmol g-1, respectively, at 273 K and 1 bar. Under the same conditions, MFM-300(VIV) exhibits the highest uptake among this series of MOFs of 17.3 mmol g-1. In situ neutron powder diffraction, single-crystal X-ray diffraction, and electron paramagnetic resonance spectroscopy confirm that the redox-active V center enables host-guest charge transfer, with VIV being reduced to VIII and NH3 being oxidized to hydrazine (N2H4). A combination of in situ inelastic neutron scattering and DFT modeling has revealed the binding dynamics of adsorbed NH3 within these MOFs to afford a comprehensive insight into the application of MOF materials to the adsorption and conversion of NH3.

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 (8.3) and catalytic stability (>50 h) at full methanol conversion. In situ synchrotron X-ray powder diffraction, X-ray absorption spectroscopy and inelastic neutron scattering coupled with DFT calculations reveal that the first carbon-carbon bond is formed between an activated methanol molecule and a trimethyloxonium intermediate. The unprecedented cooperativity between tantalum(V) and Brønsted acid sites creates an optimal microenvironment for efficient conversion of methanol and thus greatly promotes the application of zeolites in the sustainable manufacturing of light olefins.

Ammonia Storage in Hydrogen Bond-Rich Microporous Polymers.

The fascinating structural flexibility of porous polymers is highly attractive because it can result in optimized materials with specific host-guest interactions. Nevertheless, the fundamental mechanisms responsible for controlling the weak interactions of these hydrogen bond-rich networks-essential for developing smart task-specific materials used in recognition, capture, and sequestration processes-remain unexplored. Herein, by systematically comparing performance changes between poly(amic acid) (PAA)- and polycyclic imide (PI)-based porous polymers before and after NH3 adsorption, the role of hydrogen bonds in conformational lability and responsiveness toward guest molecules is highlighted. By combining thermal gravimetric analysis with neutron spectroscopy supported by DFT calculations, we demonstrate that PAA's chemical and physical stability is enhanced by the presence of stronger host-guest interactions. This observation also emphasizes the idea that efficient adsorption relies on having a high number of sites, upon which gas molecules can adsorb with greater affinity via strong hydrogen bonding interactions.