Prediction of single-layer antimony oxyselenide (Sb2O2Se2): metal-to-semiconductor transition via hydrogenation.

In this study, the structural, electronic, vibrational, and mechanical properties of single-layer Antimony Oxyselenide (Sb2O2Se2) and its hydrogenated structure (Sb2O2Se2H2) are investigated by performing density functional theory-based first principles calculations. Geometry optimizations reveal that single-layer Sb2O2Se2crystallizes in tetragonal structure which is shown to possess dynamical stability by means of phonon band dispersions. In addition, the mechanical stability of the predicted single layer is satisfied via the linear-elastic parameters. Electronically, it is revealed that single-layer Sb2O2Se2exhibits metallic behavior whose highest occupied states are found to arise from the surface Se atoms, may be an indication for tuning the electronic features via surface functionalization. For the surface modification of Sb2O2Se2, top of each Se atom is saturated with a H atom and fully hydrogenated single-layer Sb2O2Se2H2is shown to be an in-plane anisotropic structure. Phonon band dispersion calculations indicate the dynamical stability of Sb2O2Se2H2. Mechanically stable Sb2O2Se2H2is found to possess anisotropic linear-elastic behavior, which is much softer than its pristine structure. Moreover, electronically a metallic-to-semiconducting transition is shown to occur as the unoccupied Se-orbitals are saturated via H atoms. Our work offers insights into prediction of a novel single-layer material, namely Sb2O2Se2, and reports the chemically-driven semiconducting behavior via hydrogenation, which may lead to the use of hydrogenated structure in solar cell, photoelectrode, or photocatalyst applications owing to its suitable band gap.

Anisotropic structural, vibrational, electronic, optical, and elastic properties of single-layer hafnium pentatelluride: an ab initio study.

Motivated by the highly anisotropic nature of bulk hafnium pentatelluride (HfTe5), the structural, vibrational, electronic, optical, and elastic properties of single-layer two-dimensional (2D) HfTe5 were investigated by performing density functional theory (DFT)-based first-principles calculations. Total energy and geometry optimizations reveal that the 2D single-layer form of HfTe5 exhibits in-plane anisotropy. The phonon band structure shows dynamic stability of the free-standing layer and the predicted Raman spectrum displays seven characteristic Raman-active phonon peaks. In addition to its dynamic stability, HfTe5 is shown to exhibit thermal stability at room temperature, as confirmed by quantum molecular dynamics simulations. Moreover, the obtained elastic stiffness tensor elements indicate the mechanical stability of HfTe5 with its orientation-dependent soft nature. The electronic band structure calculations show the indirect-gap semiconducting behavior of HfTe5 with a narrow electronic band gap energy. The optical properties of HfTe5, in terms of its imaginary dielectric function, absorption coefficient, reflectance, and transmittance, are shown to exhibit strong in-plane anisotropy. Furthermore, structural analysis of several point defects and their oxidized structures was performed by means of simulated STM images. Among the considered vacancy defects, namely , , VTeout, VTein, , and VHf, the formation of VTeout is revealed to be the most favorable defect. While and VHf defects lead to local magnetism, only the oxygen-substituted VHf structure possesses magnetism among the oxidized defects. Moreover, it is found that all the bare and oxidized vacant sites can be distinguished from each other through the STM images. Overall, our study indicates not only the fundamental anisotropic features of single-layer HfTe5, but also shows the signatures of feasible point defects and their oxidized structures, which may be useful for future experiments on 2D HfTe5.

Ion and Molecule Sieving through Highly Stable Graphene-Based Laminar Membranes.

Biological ion channels use both their sizes and residual groups to reject large ions and molecules and allow highly selective permeation of small species with similar sizes. To realize these properties in artificial membranes, the main challenge is the precise control of both the channel size and the interior at the nanoscale. Here we report the permeation of ions and molecules through interlayer channels in graphene-based laminar membranes. The amino groups decorated on channel walls are found to form hydrogen bond networks with intercalated water molecules, thus providing a highly stable laminate structure and a controlled channel size. Solutes with hydration diameters of >10 Å are precisely sieved out. Small species permeate through with selectivities of up to a few thousand, governed by their distinct electrical interactions with channels depending on the atomistic distance from the charged species to the channel walls. Our work offers important insights into manipulating channel structures for enhanced separation performance at the nanoscale.

High-throughput analysis of tetragonal transition metal Xenes.

We report a high-throughput first-principles characterization of the structural, mechanical, electronic, and vibrational properties of tetragonal single-layer transition metal Xenes (t-TMXs). Our calculations revealed 22 dynamically, mechanically and chemically stable structures among the 96 possible free-standing layers present in the t-TMX family. As a fingerprint for their structural identification, we identified four characteristic Raman active phonon modes, namely three in-plane and one out-of-plane optical branches, with various intensities and frequencies depending on the material in question. Spin-polarized electronic calculations demonstrated that anti-ferromagnetic (AFM) metals, ferromagnetic (FM) metals, AFM semiconductors, and non-magnetic semiconductor materials exist within this family, evidencing the potential of t-TMXs for further use in multifunctional heterostructures.

Gas permeation through graphdiyne-based nanoporous membranes.

Nanoporous membranes based on two dimensional materials are predicted to provide highly selective gas transport in combination with extreme permeance. Here we investigate membranes made from multilayer graphdiyne, a graphene-like crystal with a larger unit cell. Despite being nearly a hundred of nanometers thick, the membranes allow fast, Knudsen-type permeation of light gases such as helium and hydrogen whereas heavy noble gases like xenon exhibit strongly suppressed flows. Using isotope and cryogenic temperature measurements, the seemingly conflicting characteristics are explained by a high density of straight-through holes (direct porosity of ∼0.1%), in which heavy atoms are adsorbed on the walls, partially blocking Knudsen flows. Our work offers important insights into intricate transport mechanisms playing a role at nanoscale.

First-principles investigation of electronic, mechanical and thermoelectric properties of graphene-like XBi (X = Si, Ge, Sn) monolayers.

Research progress on single layer group III monochalcogenides has been increasing rapidly owing to their interesting physics. Herein, we investigate the dynamically stable single layer forms of XBi (X = Ge, Si or Sn) using density functional theory calculations. Phonon band dispersion calculations and ab initio molecular dynamics simulations reveal the dynamical and thermal stability of the considered monolayers. Raman spectra calculations indicate the existence of 5 Raman active phonon modes, 3 of which are prominent and can be observed in possible Raman measurements. The electronic band structures of the XBi single layers were investigated with and without the effects of spin-orbit coupling (SOC). Our results show that XBi single layers show semiconducting properties with narrow band gap values without SOC. However, only single layer SiBi is an indirect band gap semiconductor, while GeBi and SnBi exhibit metallic behaviors when adding spin-orbit coupling effects. In addition, the calculated linear elastic parameters indicate the soft nature of the predicted monolayers. Moreover, our predictions for the thermoelectric properties of single layer XBi reveal that SiBi is a good thermoelectric material with increasing temperature. Overall, it is proposed that single layer XBi structures can be alternative, stable 2D single layers with varying electronic and thermoelectric properties.

Aluminum and lithium sulfur batteries: a review of recent progress and future directions.

Advanced materials with various micro-/nanostructures have attracted plenty of attention for decades in energy storage devices such as rechargeable batteries (ion- or sulfur based batteries) and supercapacitors. To improve the electrochemical performance of batteries, it is uttermost important to develop advanced electrode materials. Moreover, the cathode material is also important that it restricts the efficiency and practical application of aluminum-ion batteries. Among the potential cathode materials, sulfur has become an important candidate material for aluminum-ion batteries cause of its considerable specific capacity. Two-dimensional materials are currently potential candidates as electrodes from lab-scale experiments to possible pragmatic theoretical studies. In this review, the fundamental principles, historical progress, latest developments, and major problems in Li-S and Al-S batteries are reviewed. Finally, future directions in terms of the experimental and theoretical applications have prospected.

Blue Energy Conversion from Holey-Graphene-like Membranes with a High Density of Subnanometer Pores.

Blue energy converts the chemical potential difference from salinity gradients into electricity via reverse electrodialysis and provides a renewable source of clean energy. To achieve high energy conversion efficiency and power density, nanoporous membrane materials with both high ionic conductivity and ion selectivity are required. Here, we report ion transport through a network of holey-graphene-like sheets made by bottom-up polymerization. The resulting ultrathin membranes provide controlled pores of <10 Å in diameter with an estimated density of about 1012 cm-2. The pores' interior contains NH2 groups that become electrically charged with varying pH and allow tunable ion selectivity. Using the holey-graphene-like membranes, we demonstrate power outputs reaching hundreds of watts per square meter. The work shows a viable route toward creating membranes with high-density angstrom-scale pores, which can be used for energy generation, ion separation, and related technologies.

Two-Dimensional Covalent Crystals by Chemical Conversion of Thin van der Waals Materials.

Most of the studied two-dimensional (2D) materials have been obtained by exfoliation of van der Waals crystals. Recently, there has been growing interest in fabricating synthetic 2D crystals which have no layered bulk analogues. These efforts have been focused mainly on the surface growth of molecules in high vacuum. Here, we report an approach to making 2D crystals of covalent solids by chemical conversion of van der Waals layers. As an example, we used 2D indium selenide (InSe) obtained by exfoliation and converted it by direct fluorination into indium fluoride (InF3), which has a nonlayered, rhombohedral structure and therefore cannot  possibly be obtained by exfoliation. The conversion of InSe into InF3 is found to be feasible for thicknesses down to three layers of InSe, and the obtained stable InF3 layers are doped with selenium. We study this new 2D material by optical, electron transport, and Raman measurements and show that it is a semiconductor with a direct bandgap of 2.2 eV, exhibiting high optical transparency across the visible and infrared spectral ranges. We also demonstrate the scalability of our approach by chemical conversion of large-area, thin InSe laminates obtained by liquid exfoliation, into InF3 films. The concept of chemical conversion of cleavable thin van der Waals crystals into covalently bonded noncleavable ones opens exciting prospects for synthesizing a wide variety of novel atomically thin covalent crystals.

Nitrogenated, phosphorated and arsenicated monolayer holey graphenes.

Motivated by a recent experiment that reported the synthesis of a new 2D material nitrogenated holey graphene (C2N) [Mahmood et al., Nat. Commun., 2015, 6, 6486], the electronic, magnetic, and mechanical properties of nitrogenated (C2N), phosphorated (C2P) and arsenicated (C2As) monolayer holey graphene structures are investigated using first-principles calculations. Our total energy calculations indicate that, similar to the C2N monolayer, the formation of the other two holey structures are also energetically feasible. Calculated cohesive energies for each monolayer show a decreasing trend going from the C2N to C2As structure. Remarkably, all the holey monolayers considered are direct band gap semiconductors. Regarding the mechanical properties (in-plane stiffness and Poisson ratio), we find that C2N has the highest in-plane stiffness and the largest Poisson ratio among the three monolayers. In addition, our calculations reveal that for the C2N, C2P and C2As monolayers, creation of N and P defects changes the semiconducting behavior to a metallic ground state while the inclusion of double H impurities in all holey structures results in magnetic ground states. As an alternative to the experimentally synthesized C2N, C2P and C2As are mechanically stable and flexible semiconductors which are important for potential applications in optoelectronics.