The structure of liquid thiophene from total neutron scattering

The structure of pure liquid thiophene is revealed by using a combination of total neutron scattering experiments with isotopic substitution and molecular simulations via the next generation empirical potential refinement software, Dissolve. In the liquid, thiophene presents three principle local structural motifs within the first solvation shell, in plane and out of the plane of the thiophene ring. Firstly, above/below the ring plane thiophenes present a single H towards the π cloud, due to a combination of electrostatic and dispersion interactions. Secondly, around the ring plane, perpendicular thiophene molecules find 5 preferred sites driven by bifurcated C-H⋯S interactions, showing that hydrogen-sulfur bonding prevails over the charge asymmetry created by the heteroatom. Finally, parallel thiophenes sit above and below the ring, excluded from directly above the ring center and above the sulfur

Weak Interactions in Dimethyl Sulfoxide (DMSO)-Tertiary Amide Solutions: The Versatility of DMSO as a Solvent

The structures of equimolar mixtures of the commonly used polar aprotic solvents dimethylformamide (DMF) and dimethylacetamide (DMAc) in dimethyl sulfoxide (DMSO) have been investigated via neutron diffraction augmented by extensive hydrogen/deuterium isotopic substitution. Detailed 3-dimensional structural models of these solutions have been derived from the neutron data via Empirical Potential Structure Refinement (EPSR). The intermolecular center-of-mass (CoM) distributions show that the first coordination shell of the amides comprises ∼13-14 neighbors, of which approximately half are DMSO. In spite of this near ideal coordination shell mixing, the changes to the amide-amide structure are found to be relatively subtle when compared to the pure liquids. Analysis of specific intermolecular atom-atom correlations allows quantitative interpretation of the competition between weak interactions in the solution. We find a hierarchy of formic and methyl C-H···O hydrogen bonds forms the dominant local motifs, with peak positions in the range of 2.5-3.0 Å. We also observe a rich variety of steric and dispersion interactions, including those involving the O═C-N amide π-backbones. This detailed insight into the structural landscape of these important liquids demonstrates the versatility of DMSO as a solvent and the remarkable sensitivity of neutron diffraction, which is critical for understanding weak intermolecular interactions at the nanoscale and thereby tailoring solvent properties to specific applications

Strong structuring arising from weak cooperative O-H···π and C-H···O hydrogen bonding in benzene-methanol solution

Weak hydrogen bonds, such as O-H···π and C-H···O, are thought to direct biochemical assembly, molecular recognition, and chemical selectivity but are seldom observed in solution. We have used neutron diffraction combined with H/D isotopic substitution to obtain a detailed spatial and orientational picture of the structure of benzene-methanol mixtures. Our analysis reveals that methanol fully solvates and surrounds each benzene molecule. The expected O-H···π interaction is highly localised and directional, with the methanol hydroxyl bond aligned normal to the aromatic plane and the hydrogen at a distance of 2.30 Å from the ring centroid. Simultaneously, the tendency of methanol to form chain and cyclic motifs in the bulk liquid is manifest in a highly templated solvation structure in the plane of the ring. The methanol molecules surround the benzene so that the O-H bonds are coplanar with the aromatic ring while the oxygens interact with C-H groups through simultaneous bifurcated hydrogen bonds. This demonstrates that weak hydrogen bonding can modulate existing stronger interactions to give rise to highly ordered cooperative structural motifs that persist in the liquid phase

Advancing fluoride-ion batteries with a Pb-PbF2 counter electrode and a diluted liquid electrolyte

Fluoride ion batteries (FIB) are a promising post lithium-ion technology thanks to their high theoretical energy densities and Earth-abundant materials. However, the flooded cells commonly used to test liquid electrolyte FIBs severely affect the overall performance and impede comparability across different studies, hindering FIB progress. Here, we report a reliable Pb-PbF2 counter electrode that enables the use of two-electrode coin cells. To test this setup, we first introduce a liquid electrolyte that combines the advantages of a highly concentrated electrolyte (tetramethylammonium fluoride in methanol) while addressing its transport and high-cost shortcomings by introducing a diluent (propionitrile). We then demonstrate the viability of this system by reporting a BiF3–Pb-PbF2 cell with the highest capacity retention to date

The local ordering of polar solvents around crystalline carbon nitride nanosheets in solution

The crystalline graphitic carbon nitride, poly-triazine imide (PTI) is highly unusual among layered materials since it is spontaneously soluble in aprotic, polar solvents including dimethylformamide (DMF). The PTI material consists of layers of carbon nitride intercalated with LiBr. When dissolved, the resulting solutions consist of dissolved, luminescent single to multilayer nanosheets of around 60–125 nm in diameter and Li+ and Br− ions originating from the intercalating salt. To understand this unique solubility, the structure of these solutions has been investigated by high-energy X-ray and neutron diffraction. Although the diffraction patterns are dominated by inter-solvent correlations there are clear differences between the X-ray diffraction data of the PTI solution and the solvent in the 4–6 Å −1 range, with real space differences persisting to at least 10 Å. Structural modelling using both neutron and X-ray datasets as a constraint reveal the formation of distinct, dense solvation shells surrounding the nanoparticles with a layer of Br − close to the PTI-solvent interface. This solvent ordering provides a configuration that is energetically favourable underpinning thermodynamically driven PTI dissolution. This article is part of the theme issue 'Exploring the length scales, timescales and chemistry of challenging materials (Part 2)'

On the origin of the non-Arrhenius Na-ion conductivity in Na3OBr

The sodium-rich antiperovskites (NaRAPs) with composition Na3OB (B=Br, Cl, I, BH4, etc.) are a family of materials that has recently attracted great interest for application as solid electrolytes in sodium metal batteries. Non-Arrhenius ionic conductivities have been reported for these materials, the origin of which is poorly understood. In this work, we combined temperature-resolved bulk and local characterisation methods to gain an insight into the origin of this unusual behaviour using Na3OBr as a model system. We first excluded crystallographic disorder on the anion sites as the cause of the change in activation energy; then identified the presence of a poorly crystalline impurities, not detectable by XRD, and elucidated their effect on ionic conductivity. These findings improve understanding of the processing-structure-properties relationships pertaining to NaRAPs and highlight the need to determine these relationships in other materials systems, which will accelerate the development of high-performance solid electrolytes

Synthesis of Black Phosphorene Quantum Dots from Red Phosphorus

Phosphorene quantum dots (PQDs) are most commonly derived from high-cost black phosphorus, while previous syntheses from the low-cost red phosphorus (Pred) allotrope are highly oxidised. Herein, we present an intrinsically scalable method to producing high quality PQDs, by first ball-milling Pred to create nanocrystalline Pblack and subsequent reductive etching using lithium electride solvated in liquid ammonia. The resultant ~25 nm PQDs are crystalline with low oxygen content, and spontaneously soluble as individualized monolayers in tertiary amide solvents, as directly imaged by liquid-phase transmission electron microscopy. This new method presents a scalable route to producing quantities of high quality PQDs for academic and industrial applications

On the origin of the non-Arrhenius Na-ion conductivity in Na3OBr

The sodium-rich antiperovskites (NaRAPs) with composition Na3OB (B=Br, Cl, I, BH4, etc.) are a family of materials that has recently attracted great interest for application as solid electrolytes in sodium metal batteries. Non-Arrhenius ionic conductivities have been reported for these materials, the origin of which is poorly understood. In this work, we combined temperature-resolved bulk and local characterisation methods to gain an insight into the origin of this unusual behaviour using Na3OBr as a model system. We first excluded crystallographic disorder on the anion sites as the cause of the change in activation energy; then identified the presence of a poorly crystalline impurities, not detectable by XRD, and elucidated their effect on ionic conductivity. These findings improve understanding of the processing-structure-properties relationships pertaining to NaRAPs and highlight the need to determine these relationships in other materials systems, which will accelerate the development of high-performance solid electrolytes

The local ordering of polar solvents around crystalline carbon nitride nanosheets in solution

The crystalline graphitic carbon nitride, poly-triazine imide (PTI) is highly unusual among layered materials since it is spontaneously soluble in aprotic, polar solvents including dimethylformamide (DMF). The PTI material consists of layers of carbon nitride intercalated with LiBr. When dissolved, the resulting solutions consist of dissolved, luminescent single to multilayer nanosheets of around 60–125 nm in diameter and Li+ and Br− ions originating from the intercalating salt. To understand this unique solubility, the structure of these solutions has been investigated by high-energy X-ray and neutron diffraction. Although the diffraction patterns are dominated by inter-solvent correlations there are clear differences between the X-ray diffraction data of the PTI solution and the solvent in the 4–6 Å−1 range, with real space differences persisting to at least 10 Å. Structural modelling using both neutron and X-ray datasets as a constraint reveal the formation of distinct, dense solvation shells surrounding the nanoparticles with a layer of Br−close to the PTI-solvent interface. This solvent ordering provides a configuration that is energetically favourable underpinning thermodynamically driven PTI dissolution. This article is part of the theme issue 'Exploring the length scales, timescales and chemistry of challenging materials (Part 2)'

Weak Inter-Molecular Interactions in Bulk Liquids and at Liquid/Nanomaterial Interfaces

Liquid systems are the ideal platform to study weak, competitive interactions. While molecular reorganization is inhibited in solids, molecules in liquids can rapidly rearrange. Understanding the average local molecular restructuring, in the presence of energetically comparable interactions, underpins this thesis. Here, hydrogen bonding, dipole-dipole interactions, and dispersion forces have been studied in a variety of bulk liquids and at the interface of a charged surface. The aim is to understand the molecular mechanisms from which macroscopic processes such as dissolution, dispersion, and solution stability are derived. The high hydrogen sensitivity, high spatial resolution, and highly penetrative nature of neutrons make them the ideal probe for studying hydrogen bonding and solution structures. Neutron diffraction combined with H/D isotopic substitution and molecular simulations via the empirical potential structure refinement method allowed the study weak OH···π and CH···O hydrogen bonding in the liquid state, revealing undiscovered cooperative interactions in the benzene-methanol prototypical system. The highly templated structuring found for benzene in methanol evolves when the π system is an alkene C=C bond or a substituted aromatic. In the latter case, due to the higher solubility in water of phenol, aniline, and p-nitrophenol than benzene, the aromatic hydrogen bonding can be tested directly with water, with important implications for our understanding of liquid water interactions. Lastly, the CH···O and the dipole-dipole interactions in tertiary amides play an important role in the dissolution of supercapacitor-like systems such as carbon nanomaterials. Testing these systems with the level of detail reached by neutron diffraction enabled a full characterisation of the restructuring of cyclic and planar amides at a charged π interface