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 (TiO2, MnO2, 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. D3-corrected hybrid functionals systematically yield results closest to experiment. We propose that the inclusion of dispersion interactions makes a significant contribution to the relative energetics of polymorphic phases, especially those with different densities, and should therefore be included for calculations of relative energies using DFT methods

Identification of new pillared-layered carbon nitride materials at high pressure

The compression of the layered carbon nitride C6N9H3·HCl was studied experimentally and with density functional theory (DFT) methods. This material has a polytriazine imide structure with Cl− ions contained within C12N12 voids in the layers. The data indicate the onset of layer buckling accompanied by movement of the Cl− ions out of the planes beginning above 10–20 GPa followed by an abrupt change in the diffraction pattern and c axis spacing associated with formation of a new interlayer bonded phase. The transition pressure is calculated to be 47 GPa for the ideal structures. The new material has mixed sp2–sp3 hybridization among the C and N atoms and it provides the first example of a pillared-layered carbon nitride material that combines the functional properties of the graphitic-like form with improved mechanical strength. Similar behavior is predicted to occur for Cl-free structures at lower pressures

New functionalisation reactions of graphitic carbon nitrides: Computational and experimental studies

The functionalisation of two-dimensional materials is key to modify their properties and facilitate assembly into functional devices. Here, new reactions have been proposed to modify crystalline two-dimensional carbon nitrides of polytriazine imide structure. Both amine alkylation and aryl-nitrene-based reactions have been explored computationally and with exploratory synthetic trials. The approach illustrates that alkylation is unfavourable, particularly at basal-plane sites. In contrast, while initial trial reactions were inconclusive, the radical-addition of nitrenes is shown to be energetically favourable, with a preference for functionalising sheet edges to minimise steric effects

The importance of anisotropic Coulomb interaction in LaMnO3

In low-temperature anti-ferromagnetic LaMnO3, strong and localized electronic interactions among Mn 3d electrons prevent a satisfactory description from standard local density and generalized gradient approximations in density functional theory calculations. Here we show that the strong on-site electronic interactions are described well only by using direct and exchange corrections to the intra-orbital Coulomb potential. Only DFT+U calculations with explicit exchange corrections produce a balanced picture of electronic, magnetic and structural observables in agreement with experiment. To understand the reason, a rewriting of the functional form of the +U corrections is presented that leads to a more physical and transparent understanding of the effect of these correction terms. The approach highlights the importance of Hund’s coupling (intra-orbital exchange) in providing anisotropy across the occupation and energy eigenvalues of the Mn d states. This intra-orbital exchange is the key to fully activating the Jahn-Teller distortion, reproducing the experimental band gap and stabilizing the correct magnetic ground state in LaMnO3. The best parameter values for LaMnO3 within the DFT(PBEsol)+U framework are determined to be U = 8 eV and J = 1.9 eV

Impact-formed complex diamond-graphite nanostructures

Shock waves resulting from asteroidal and laboratory impacts convert sp 2 -bonded graphitic material to sp 3 -bonded diamond. Depending on the shock pressure and temperature conditions, complex nano- structures can form that are neither graphite nor diamond but belong to the diaphite material group, which are characterized by structurally intergrown layered sp 2 - and sp 3 -bonded carbon domains. Our ultrahigh-resolution transmission electron microscopy images combined with density functional theory calculations demonstrate that diaphites have two related but distinct structural families. Here, we describe diaphite nanostructures from natural and laboratory shocked samples, provide a framework for classifying the members of these materials, and draw attention to their excellent mechanical and electronic material properties

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 2 edge deprotonation is competitive. We conclude that mildly acidic or basic pHs are necessary to provide sufficient net charge on the nanosheets to promote dissolution, while avoiding high ion concentrations which screen the repulsion of like-charged PTI sheets in solution. This article is part of the theme issue 'Exploring the length scales, timescales and chemistry of challenging materials (Part 2)'

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)'

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 H2O2 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. Through electrochemical and operando spectroscopic studies on a series of CoN x /carbon nanotube hybrids, a construction‐driven approach based on an extended “dynamic active site saturation” model that aims to create the maximum number of 2 e− ORR sites by directing the secondary ORR electron transfer towards the 2 e− intermediate is proven to be attainable by manipulating O2 hydrogenation kinetics

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. The ribbons are typically few-layered, several micrometers long with widths tens of nanometers across, and both highly flexible and crystalline. The AsPNRs are highly electrically conducting above 130 K due to their small band gap (ca. 0.035 eV), paramagnetic in nature, and have high hole mobilities, as measured with the first generation of AsP devices, directly highlighting their properties and utility in electronic devices such as near-infrared detectors, quantum computing, and charge carrier layers in solar cells

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)'