Investigating the mechanism of phosphorene nanoribbon synthesis by discharging black phosphorus intercalation compounds.

Phosphorene nanoribbons (PNRs) can be synthesised in intrinsically scalable methods from intercalation of black phosphorus (BP), however, the mechanism of ribbonisation remains unclear. Herein, to investigate the point at which nanoribbons form, we decouple the two key synthesis steps: first, the formation of the BP intercalation compound, and second, the dissolution into a polar aprotic solvent. We find that both the lithium intercalant and the negative charge on the phosphorus host framework can be effectively removed by addition of phenyl cyanide to return BP and investigate whether fracturing to ribbons occurred after the first step.

Amphoteric dissolution of two-dimensional polytriazine imide carbon nitrides in water.

Crystalline two-dimensional carbon nitrides with polytriazine imide (PTI) structure are shown to act amphoterically, buffering both HCl and NaOH aqueous solutions, resulting in charged PTI layers that dissolve spontaneously in their aqueous media, particularly for the alkaline solutions. This provides a low energy, green route to their scalable solution processing. Protonation in acid is shown to occur at pyridinic nitrogens, stabilized by adjacent triazines, whereas deprotonation in base occurs primarily at basal plane NH bridges, although NH edge deprotonation is competitive.

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.

Production of Magnetic Arsenic-Phosphorus Alloy Nanoribbons with Small Band Gaps and High Hole Conductivities.

Quasi-1D nanoribbons provide a unique route to diversifying the properties of their parent 2D nanomaterial, introducing lateral quantum confinement and an abundance of edge sites. Here, a new family of nanomaterials is opened with the creation of arsenic-phosphorus alloy nanoribbons (AsPNRs). By ionically etching the layered crystal black arsenic-phosphorus using lithium electride followed by dissolution in amidic solvents, solutions of AsPNRs are formed.

Influence of Dispersion Interactions on the Polymorphic Stability of Crystalline Oxides.

The accurate determination of relative phase stabilities using DFT methods is a significant challenge when some of these can vary by only a few kJ/mol. Here, we demonstrate that for a selection of oxides (TiO, MnO, and ZnO) the inclusion of dispersion interactions, accomplished using the DFT-D3 correction scheme, allows for the correct ordering and an improved calculation of the energy differences between polymorphic phases. The energetic correction provided is of the same order of magnitude as the energy difference between phases.

Approaching Theoretical Performances of Electrocatalytic Hydrogen Peroxide Generation by Cobalt-Nitrogen Moieties.

Electrocatalytic oxygen reduction reaction (ORR) has been intensively studied for environmentally benign applications. However, insufficient understanding of ORR 2 e -pathway mechanism at the atomic level inhibits rational design of catalysts with both high activity and selectivity, causing concerns including catalyst degradation due to Fenton reaction or poor efficiency of H O electrosynthesis. Herein we show that the generally accepted ORR electrocatalyst design based on a Sabatier volcano plot argument optimises activity but is unable to account for the 2 e -pathway selectivity.

Band Structure Engineering of BiOSeCl for Thermoelectric Applications.

The mixed anion material BiOSeCl has an ultralow thermal conductivity of 0.1 W m K along its stacking axis ( axis) at room temperature, which makes it an ideal candidate for electronic band structure optimization via doping to improve its thermoelectric performance. Here, we design and realize an optimal doping strategy for BiOSeCl from first principles and predict an enhancement in the density of states at the Fermi level of the material upon Sn and Ge doping.

Shock-formed carbon materials with intergrown sp- and sp-bonded nanostructured units.

Studies of dense carbon materials formed by bolide impacts or produced by laboratory compression provide key information on the high-pressure behavior of carbon and for identifying and designing unique structures for technological applications. However, a major obstacle to studying and designing these materials is an incomplete understanding of their fundamental structures. Here, we report the remarkable structural diversity of cubic/hexagonally (/) stacked diamond and their association with diamond-graphite nanocomposites containing sp-/sp-bonding patterns, i.

Low thermal conductivity in a modular inorganic material with bonding anisotropy and mismatch.

The thermal conductivity of crystalline materials cannot be arbitrarily low, as the intrinsic limit depends on the phonon dispersion. We used complementary strategies to suppress the contribution of the longitudinal and transverse phonons to heat transport in layered materials that contain different types of intrinsic chemical interfaces. BiOCl and BiOSe encapsulate these design principles for longitudinal and transverse modes, respectively, and the bulk superlattice material BiOSeCl combines these effects by ordering both interface types within its unit cell to reach an extremely low thermal conductivity of 0.

Aquaporin-like water transport in nanoporous crystalline layered carbon nitride.

Designing next-generation fuel cell and filtration devices requires the development of nanoporous materials that allow rapid and reversible uptake and directed transport of water molecules. Here, we combine neutron spectroscopy and first-principles calculations to demonstrate rapid transport of molecular HO through nanometer-sized voids ordered within the layers of crystalline carbon nitride with a polytriazine imide structure. The transport mechanism involves a sequence of molecular orientation reversals directed by hydrogen-bonding interactions as the neutral molecules traverse the interlayer gap and pass through the intralayer voids that show similarities with the transport of water through transmembrane aquaporin channels in biological systems.

Probing Mg Intercalation in the Tetragonal Tungsten Bronze Framework VNbO.

While commercial Li-ion batteries offer the highest energy densities of current rechargeable battery technologies, their energy storage limit has almost been achieved. Therefore, there is considerable interest in Mg batteries, which could offer increased energy densities in comparison to Li-ion batteries if a high-voltage electrode material, such as a transition-metal oxide, can be developed. However, there are currently very few oxide materials which have demonstrated reversible and efficient Mg insertion and extraction at high voltages; this is thought to be due to poor Mg diffusion kinetics within the oxide structural framework.

The Role of Phosphate Group in Doped Cobalt Molybdate: Improved Electrocatalytic Hydrogen Evolution Performance.

The hydrogen evolution reaction (HER) is a critical process in the electrolysis of water. Recently, much effort has been dedicated to developing low-cost, highly efficient, and stable electrocatalysts. Transition metal phosphides are investigated intensively due to their high electronic conductivity and optimized absorption energy of intermediates in acid electrolytes.

Diamond-Graphene Composite Nanostructures.

The search for new nanostructural topologies composed of elemental carbon is driven by technological opportunities as well as the need to understand the structure and evolution of carbon materials formed by planetary shock impact events and in laboratory syntheses. We describe two new families of diamond-graphene (diaphite) phases constructed from layered and bonded sp and sp nanostructural units and provide a framework for classifying the members of this new class of materials. The nanocomposite structures are identified within both natural impact diamonds and laboratory-shocked samples and possess diffraction features that have previously been assigned to lonsdaleite and postgraphite phases.

Modular Design via Multiple Anion Chemistry of the High Mobility van der Waals Semiconductor BiOSeCl.

Making new van der Waals materials with electronic or magnetic functionality is a chemical design challenge for the development of two-dimensional nanoelectronic and energy conversion devices. We present the synthesis and properties of the van der Waals material BiOSeCl, which is a 1:1 superlattice of the structural units present in the van der Waals insulator BiOCl and the three-dimensionally connected semiconductor BiOSe. The presence of three anions gives the new structure both the bridging selenide anion sites that connect pairs of BiO layers in BiOSe and the terminal chloride sites that produce the van der Waals gap in BiOCl.

Phytostabilization of Pb and Cd polluted soils using as pioneer aromatic plant species.

The area of soils polluted with heavy metals is increasing due to industrialization and globalization. Aromatic plant species can be a suitable alternative way for agricultural valorization and phytomanagement of such soils by the commercialization of essential oils avoiding risks for the food chain. The potential of growing in heavy metal polluted soils was assessed in pot experiments using spiked soils and soils from a shooting range.

Quantifying hexagonal stacking in diamond.

Diamond is a material of immense technological importance and an ancient signifier for wealth and societal status. In geology, diamond forms as part of the deep carbon cycle and typically displays a highly ordered cubic crystal structure. Impact diamonds, however, often exhibit structural disorder in the form of complex combinations of cubic and hexagonal stacking motifs.

The effect of management models on thromboembolic and bleeding rates in anticoagulated patients: an ecological study.

The primary study objective is to compare the outcomes of patients taking oral anticoagulant medications in two distinct populations treated according to different management models (comprehensive vs. usual care). (Design: regional prospective cohort study; setting: hospital admission data from two regions).

Formation of an ion-free crystalline carbon nitride and its reversible intercalation with ionic species and molecular water.

The development of processes to tune the properties of materials is essential for the progression of next-generation technologies for catalysis, optoelectronics and sustainability including energy harvesting and conversion. Layered carbon nitrides have also been identified as of significant interest within these fields of application. However, most carbon nitride materials studied to date have poor crystallinity and therefore their properties cannot be readily controlled or easily related to their molecular level or nanoscale structures.

Phase stability of intercalated VO battery cathodes elucidated through the Goldschmidt tolerance factor.

Orthorhombic VO is a promising Mg battery cathode material, and reversible intercalation in the layered α-phase has been claimed experimentally. However, these results, based on electrochemistry and XRD, are controversial. Previous computational studies have predicted high activation barriers (∼1 eV) for ionic migration in α-VO, although improved Mg mobility is expected in the δ-phase.

Fast Exfoliation and Functionalisation of Two-Dimensional Crystalline Carbon Nitride by Framework Charging.

Two-dimensional (2D) layered graphitic carbon nitride (gCN) nanosheets offer intriguing electronic and chemical properties. However, the exfoliation and functionalisation of gCN for specific applications remain challenging. We report a scalable one-pot reductive method to produce solutions of single- and few-layer 2D gCN nanosheets with excellent stability in a high mass yield (35 %) from polytriazine imide.

Thermodynamics and defect chemistry of substitutional and interstitial cation doping in layered α-VO.

A systematic study of the location and energetics of cation dopants in α-V2O5 has been conducted using pair-potential methods, supplemented by first-principles calculations. The consequences of doping on intrinsic defect equilibria have been discussed and the effects of selected dopants on Li+ and Mg2+ diffusion energy barriers have been investigated.

Carbon nitrides: synthesis and characterization of a new class of functional materials.

Carbon nitride compounds with high N : C ratios and graphitic to polymeric structures are being investigated as potential next-generation materials for incorporation in devices for energy conversion and storage as well as for optoelectronic and catalysis applications. The materials are built from C- and N-containing heterocycles with heptazine or triazine rings linked via sp-bonded N atoms (N(C) units) or -NH- groups. The electronic, chemical and optical functionalities are determined by the nature of the local to extended structures as well as the chemical composition of the materials.

Impact of residual pulmonary obstruction on the long-term outcome of patients with pulmonary embolism.

The impact of residual pulmonary obstruction on the outcome of patients with pulmonary embolism is uncertain.We recruited 647 consecutive symptomatic patients with a first episode of pulmonary embolism, with or without concomitant deep venous thrombosis. They received conventional anticoagulation, were assessed for residual pulmonary obstruction through perfusion lung scanning after 6 months and then were followed up for up to 3 years.

Room Temperature Magnetically Ordered Polar Corundum GaFeO Displaying Magnetoelectric Coupling.

The polar corundum structure type offers a route to new room temperature multiferroic materials, as the partial LiNbO-type cation ordering that breaks inversion symmetry may be combined with long-range magnetic ordering of high spin d cations above room temperature in the AFeO system. We report the synthesis of a polar corundum GaFeO by a high-pressure, high-temperature route and demonstrate that its polarity arises from partial LiNbO-type cation ordering by complementary use of neutron, X-ray, and electron diffraction methods. In situ neutron diffraction shows that the polar corundum forms directly from AlFeO-type GaFeO under the synthesis conditions.