Dihydrogen: Vs. hydrogen bonding in the solvation of ammonia borane by tetrahydrofuran and liquid ammonia

The solvation structures of two systems rich in hydrogen and dihydrogen bonding interactions have been studied in detail experimentally through neutron diffraction with hydrogen/deuterium isotopic substitution. The results were analysed by an atomistic Monte Carlo simulation employing refinement to the experimental scattering data. The systems studied were the hydrogen storage material ammonia borane (NH 3 BH 3 , AB) dissolved in tetrahydrofuran (THF), and liquid ammonia (NH 3 ), the latter in which AB shows unusually high solubility (260 g AB per 100 g NH 3 ) and potential regeneration properties. The full orientational and positional manner in which AB-AB, AB-THF and AB-NH 3 pairs interact with each other were successfully deciphered from the wide Q-range total neutro n scattering data. This provided an unprecedented level of detail into such highly (di)hydrogen bonding solute-solvent interactions. In particular this allowed insight into the way in which H-B acts as a hydrogen bond acceptor. The (di)hydrogen bonding was naturally determined to dictate the intermolecular interactions, at times negating the otherwise expected tendency for polar molecules to align themselves with anti-parallel dipole moments. Several causes for the extreme solubility of AB in ammonia were determined, including the ability of ammonia to (di)hydrogen bond to both ends of the AB molecule and the small size of the ammonia molecule relative to AB and THF. The AB B-H to ammonia H dihydrogen bond was found to dominate the intermolecular interactions, occurring almost three times more often than any other hydrogen or dihydrogen bond in the system. The favourability of this interaction was seen on the bulk scale by a large decrease in AB clustering in ammonia compared to in the dihydrogen bond-less THF

Catalogue of Plausible Molecular Models for the Molecular Dynamics of Asphaltenes and Resins Obtained from Quantitative Molecular Representation

Computer simulation studies aimed at elucidating the phase behavior of crude oils inevitably require atomistically-detailed models of representative molecules. For the lighter fractions of crudes, such molecules are readily available, as the chemical composition can be resolved experimentally. Heavier fractions pose a challenge, on one hand due to their polydispersity and on the other due to poor description of the morphology of the molecules involved. The Quantitative Molecular Representation (QMR) approach is used here to generate a catalogue of 100 plausible asphaltene and resin structures based on elemental analysis and 1H – 13C NMR spectroscopy experimental data. The computer-generated models are compared in the context of a review of previously proposed literature structures and categorized by employing their molecular weights, double bond equivalents (DBE) and hydrogen to carbon (H/C) ratios. Sample atomistic molecular dynamics simulations were carried out for two of the proposed asphaltene structures with contrasting morphologies, one island-type and one archipelago-type, at 7 wt% in either toluene or heptane. Both asphaltene models, which shared many characteristics in terms of average molecular weight, chemical composition and solubility parameters showed marked differences in their aggregation behavior. The example showcases the importance of considering diversity and polydispersity when considering molecular models of heavy fractions

Intermediate Range Order in Metal-Ammonia Solutions: Pure and Na-Doped Ca-NH_{3}

The local and intermediate range ordering in Ca–NH3 solutions in their metallic phase is determined through H/D isotopically differenced neutron diffraction in combination with empirical potential structure refinements. For both low and high relative Ca concentrations, the Ca ions are found to be octahedrally coordinated by the NH3 solvent, and these hexammine units are spatially correlated out to lengthscales of ∼7.4–10.3 Å depending on the concentration, leading to pronounced ordering in the bulk liquid. We further demonstrate that this liquid order can be progressively disrupted by the substitution of Ca for Na, whereby a distortion of the average ion primary solvation occurs and the intermediate range ion–ion correlations are disrupted

Local structure and polar order in liquid N-Methyl-2-pyrrolidone (NMP)

N-Methyl-2-pyrrolidone (NMP) is an exceptional solvent, widely used in industry and for nanomaterials processing. Yet despite its ubiquity, its liquid structure, which ultimately dictates its solvation properties, is not fully known. Here, neutron scattering is used to determine NMP’s structure in unprecedented detail. Two dominant nearest-neighbor arrangements are found, where rings are parallel or perpendicular. However, compared with related solvents, NMP has a relatively large population of parallel approaches, similar only to benzene, despite its nonaromaticity and the presence of the normally structure-reducing methyl group. This arrangement is underpinned by NMP’s dipole moment, which has a profound effect on its structure: nearest-neighbor molecules arrange in an antiparallel but offset fashion. This polar-induced order extends beyond the first solvation shell, resulting in ordered trimers that reach the nanometer range. The degree of order and balance of interactions rationalize NMP’s high boiling point and versatile capabilities to solvate both charged and uncharged species

Neutron studies of Na-ion battery materials

The relative vast abundance and more equitable global distribution of terrestrial sodium makes sodium-ion batteries (NIBs) potentially cheaper and more sustainable alternatives to commercial lithium-ion batteries (LIBs). However, the practical capacities and cycle lives of NIBs at present do not match those of LIBs and have therefore hindered their progress to commercialisation. The present drawback of NIB technology stems largely from the electrode materials and their associated Na+ion storage mechanisms. Increased understanding of the electrochemical storage mechanisms and kinetics is therefore vital for the development of current and novel materials to realise the commercial NIB. In contrast to x-ray techniques, the non-dependency of neutron scattering on the atomic number of elements (Z) can substantially increase the scattering contrast of small elements such as sodium and carbon, making neutron techniques powerful for the investigation of NIB electrode materials. Moreover, neutrons are far more penetrating which enables more complex sample environments including in situ and operando studies. Here, we introduce the theory of, and review the use of, neutron diffraction and quasi-elastic neutron scattering, to investigate the structural and dynamic properties of electrode and electrolyte materials for NIBs. To improve our understanding of the actual sodium storage mechanisms and identify intermediate stages during charge/discharge, ex situ, in situ, and operando neutron experiments are required. However, to date there are few studies where operando experiments are conducted during electrochemical cycling. This highlights an opportunity for research to elucidate the operating mechanisms within NIB materials that are under much debate at present

Neutron studies of Na-ion battery materials

The relative vast abundance and more equitable global distribution of terrestrial sodium makes sodium-ion batteries (NIBs) potentially cheaper and more sustainable alternatives to commercial lithium-ion batteries (LIBs). However, the practical capacities and cycle lives of NIBs at present do not match those of LIBs and have therefore hindered their progress to commercialisation. The present drawback of NIB technology stems largely from the electrode materials and their associated Na+ion storage mechanisms. Increased understanding of the electrochemical storage mechanisms and kinetics is therefore vital for the development of current and novel materials to realise the commercial NIB. In contrast to x-ray techniques, the non-dependency of neutron scattering on the atomic number of elements (Z) can substantially increase the scattering contrast of small elements such as sodium and carbon, making neutron techniques powerful for the investigation of NIB electrode materials. Moreover, neutrons are far more penetrating which enables more complex sample environments including in situ and operando studies. Here, we introduce the theory of, and review the use of, neutron diffraction and quasi-elastic neutron scattering, to investigate the structural and dynamic properties of electrode and electrolyte materials for NIBs. To improve our understanding of the actual sodium storage mechanisms and identify intermediate stages during charge/discharge, ex situ, in situ, and operando neutron experiments are required. However, to date there are few studies where operando experiments are conducted during electrochemical cycling. This highlights an opportunity for research to elucidate the operating mechanisms within NIB materials that are under much debate at present

Bulk and Confined Benzene-Cyclohexane Mixtures Studied by an Integrated Total Neutron Scattering and NMR Method

AbstractHerein mixtures of cyclohexane and benzene have been investigated in both the bulk liquid phase and when confined in MCM-41 mesopores. The bulk mixtures have been studied using total neutron scattering (TNS), and the confined mixtures have been studied by a new flow-utilising, integrated TNS and NMR system (Flow NeuNMR), all systems have been analysed using empirical potential structure refinement (EPSR). The Flow NeuNMR setup provided precise time-resolved chemical sample composition through NMR, overcoming the difficulties of ensuring compositional consistency for computational simulation of data ordinarily found in TNS experiments of changing chemical composition—such as chemical reactions. Unique to the liquid mixtures, perpendicularly oriented benzene molecules have been found at short distances from the cyclohexane rings in the regions perpendicular to the carbon–carbon bonds. Upon confinement of the hydrocarbon mixtures, a stronger parallel orientational preference of unlike molecular dimers, at short distances, has been found. At longer first coordination shell distances, the like benzene molecular spatial organisation within the mixture has also found to be altered upon confinement.</jats:p

Publisher Correction: Liquid phase blending of metal-organic frameworks

The original version of this Article contained an error in Figure 1b, where the blue ‘(ZIF-4-Zn)0.5 (ZIF-62)0.5 blend’ data curve was omitted from the enthalpy response plot. This has now been corrected in both the PDF and HTML versions of the Article