Chemical exfoliation of MAX phases into two-dimensional (2D) MXenes can be considered as a major breakthrough in the synthesis of novel 2D systems. To gain insight into the exfoliation possibility of MAX phases and to identify which MAX phases are promising candidates for successful exfoliation into 2D MXenes, we perform extensive electronic structure and phonon calculations, and determine the force constants, bond strengths, and static exfoliation energies of MAX phases to MXenes for 82 different experimentally synthesized crystalline MAX phases. Our results show a clear correlation between the force constants and the bond strengths. As the total force constant of an "A" atom contributed from the neighboring atoms is smaller, the exfoliation energy becomes smaller, thus making exfoliation easier. We propose 37 MAX phases for successful exfoliation into 2D Ti2C, Ti3C2, Ti4C3, Ti5C4, Ti2N, Zr2C, Hf2C, V2C, V3C2, V4C3, Nb2C, Nb5C4, Ta2C, Ta5C4, Cr2C, Cr2N, and Mo2C MXenes. In addition, we explore the effect of charge injection on MAX phases. We find that the injected charges, both electrons and holes, are mainly received by the transition metals. This is due to the electronic property of MAX phases that the states near the Fermi energy are mainly dominated by d orbitals of the transition metals. For negatively charged MAX phases, the electrons injected cause swelling of the structure and elongation of the bond distances along the c axis, which hence weakens the binding. For positively charged MAX phases, on the other hand, the bonds become shorter and stronger. Therefore, we predict that the electron injection by electrochemistry or gating techniques can significantly facilitate the exfoliation possibility of MAX phases to 2D MXenes.

Solid-state lanthanide (Ln) borides of the simple LnB6 composition not only exhibit exciting physical behavior, in particular magnetic properties, but their electronic structure and chemical bonding are particularly intriguing as well. To shed more light on the latter, we have performed quantum-chemical (DFT+U) electronic-structure calculations and bonding analyses of the entire LnB6 series with Ln from La to Lu. Trivially, the boron framework is held together by the B 2sp orbitals, and this framework bonds to the Ln atoms via covalent–ionic interactions. The Ln 4f electrons, however, are decisive for the magnetic properties. In more detail, the effective charges of the Ln atoms as calculated by (Mulliken or Löwdin) occupation numbers of the 6s/5d/4f orbitals are compatible with experimentally assigned oxidation numbers. The shorter inter-octahedral B–B bonds, dominated by 2s–2p interactions, turn out to be stronger than the intra-octahedral B–B bonding with a more 2p–2p-like character. Interestingly, there are strong structural similarities between the LnB6 motif studied here and gas-phase Ln2B8 species showing inverse sandwich structures, and these similarities are also reflected in the electronic structure. In particular, Ln2B8 is predicted to have a large electron affinity. Hence, this work aims at providing an intrinsic link between gas-phase complexes and solid-state crystal structures in order to better understand the former species.

Binary diblock copolymers and corresponding ternary miktoarm stars are studied at oil-water interfaces. All polymers contain oil-soluble poly(propylene oxide) PPO, water-soluble poly(dimethylaminoethyl methacrylate) PDMAEMA and/or poly(ethylene oxide) PEO. The features of their Langmuir compression isotherms are well related to the ones of the corresponding homopolymers. Within the Langmuir-trough, PEO-b-PPO acts as the most effective amphiphile compared to the other PPO-containing copolymers. In contrast, the compression isotherms show a complexation of PPO and PDMAEMA for PPO-b-PDMAEMA and the star, reducing their overall amphiphilicity. Such complex formation between the blocks of PPO-b-PDMAEMA is prevented in bulk water but facilitated at the interface. The weakly-interacting blocks of PPO-b-PDMAEMA form a complex due to their enhanced proximity in such confined environments. Scanning force microscopy and Monte Carlo simulations with varying confinement support our results, which are regarded as compliant with the mathematical random walk theorem by Pólya. Finally, the results are expected to be of relevance for e.g. emulsion formulation and macromolecular engineering.

For the Ti/O system, three titanium monoxide (TiO) phases (α, β, and γ) with defective NaCl-type structures and a high-temperature hexagonal phase (H) have been known for decades. In this work, single crystals of a novel polymorph, ɛ-TiO, were synthesized by using a bismuth flux. X-ray diffraction (XRD) revealed a hexagonal crystal structure (a=4.9936(3) Å, c=2.8773(2) Å, P6‾ 2m) that is isotypic with ɛ-TaN. While the Ti atoms are surrounded by trigonal prismatic (sixfold coordination) and trigonal planar (threefold coordination) arrangements of O atoms, the O atoms are found in a pseudo-square-pyramidal arrangement of Ti atoms. First-principles calculations of the formation enthalpy and the electron and phonon density of states and crystal orbital Hamilton population (COHP) analysis revealed that ɛ-TiO is more stable than α-TiO, which had previously been regarded as the most stable phase at low temperatures.

Two-dimensional (2D) inorganic transition metal boride nanosheets are emerging as promising post-graphene materials in energy research due to their unique properties. State-of-the-art processing strategies are based on chemical etching of...

Layered bismuth oxides exhibit a broad range of tunable physical properties as a result of their excellent structural versatility which facilitates compositional substitutions at both cationic and anionic positions. Here we expand this family in a new direction through the preparation of the first example of a bismuth-containing oxide carbodiimide, Bi2O2NCN, which assumes an extended variant of the anti-ThCr2Si2 structure-type adopted by Bi2O2 Ch (Ch = Se or Te) oxide chalcogenides. Electronic structure calculations reveal the title compound to be an indirect band gap semiconductor with a band gap of approximately 1.4 eV, in good agreement with the measured value of 1.8 eV, and intermediate between that of structurally related Bi2O2S (1.12 eV) and β-Bi2O3 (2.48 eV). Mott–Schottky experiments demonstrate Bi2O2NCN to be an n-type semiconductor with a conduction band edge position of −0.37 V vs reversible hydrogen electrode. This study highlights the pseudochalcogenide nature of the –NCN– carbodiimide anion, which may be substituted in place of oxide or chalcogenide anions in this and potentially other structural classes as an effective means of electronic tuning.

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Abstract:Since the addition of Al to high-Mn steels is known to reduce their sensitivity to hydrogen-induced delayed fracture, we investigate possible trapping effects connected to the presence of Al in the grain interior employing density-functional theory (DFT). The role of Al-based precipitates is also investigated to understand the relevance of short-range ordering effects. So-called E2 1 -Fe 3 AlC κ-carbides are frequently observed in Fe-Mn-Al-C alloys. Since H tends to occupy the same positions as C in these precipitates, the interaction and competition between both interstitials is also investigated via DFT-based simulations. While the individual H-H/C-H chemical interactions are generally repulsive, the tendency of interstitials to increase the lattice parameter can yield a net increase of the trapping capability. An increased Mn content is shown to enhance H trapping due to attractive short-range interactions. Favorable short-range ordering is expected to occur at the interface between an Fe matrix and the E2 1 -Fe 3 AlC κ-carbides, which is identified as a particularly attractive trapping site for H. At the same time, accumulation of H at sites of this type is observed to yield decohesion of this interface, thereby promoting fracture formation. The interplay of these effects, evident in the trapping energies at various locations and dependent on the H concentration, can be expressed mathematically, resulting in a term that describes the hydrogen embrittlement.