Effect of Vacancy Behavior on Precipitate Formation in a Reduced-Activation V-Cr-Mn Medium-Entropy Alloy.

In this work, we studied the evolution of vacancy-like defects and the formation of brittle precipitates in a reduced-activation V-Cr-Mn medium-entropy alloy. The evolution of local electronic circumstances around Cr and Mn enrichments, the vacancy defects, and the CrMn3 precipitates were characterized by using scanning electron microscopy with energy-dispersive spectroscopy, X-ray diffraction, and positron annihilation spectroscopy. The microstructure measurements showed that the Mn and Cr enrichments in the as-cast sample significantly evolved with temperature, i.e., from 400 °C, the Cr/Mn-segregated regions gradually dissolved into the matrix and then disappeared, and from 900 °C to 1000 °C, they existed as CrMn3 precipitates. The crystallite size of the phase corresponding to CrMn3 precipitates was about 29.4 nm at 900 °C and 43.7 nm at 1000 °C. The positron annihilation lifetime results demonstrated that the vacancies mediated the migration of Cr and Mn, and Cr and Mn segregation finally led to the formation of CrMn3 precipitates. The coincidence Doppler broadening results showed that the characteristic peak moved to the low-momentum direction, due to an increase in the size of the vacancy defects at the interface and the formation of CrMn3 precipitates.

Magnetism arising from Mexican-hat-like band dispersion in the WSe2/SnS2 heterostructure via interlayer strain.

Mexican-hat-like band dispersion is extremely critical to the realization of hole-doping-induced magnetism in monolayer metal monochalcogenides. However, it is absent from transition-metal dichalcogenides (TMDCs), i.e., WSe2. Herein, using first-principles calculations, we show that Mexican-hat-like band dispersion can be achieved by applying interlayer strain (ε) in the WSe2/SnS2 van der Waals (vdW) heterostructure when ε exceeds 15%. This is because in the strain-induced distorted trigonal prismatic crystal field, at the valence band edge, the W_dz2 orbitals shift upward around the Γ point, while the double-degenerate W_dxy/dx2-y2 orbitals shift downward at the K point, resulting in Mexican-hat-like band dispersion near the Γ point when the energy level of the Γ point surpasses that of the K point. On account of the appearance of the Mexican-hat-like band edge (MHBE), hole-doping in the strained WSe2/SnS2 heterostructure induces magnetization readily from the nonmagnetized phase. Our findings may provide a new strategy for the realization of magnetized TMDC-based vdW heterostructures.

Two-dimensional carbon dioxide with high stability, a negative Poisson's ratio and a huge band gap.

Carbon dioxide (CO2) normally exists in a gaseous molecular state under ambient conditions, while two-dimensional (2D) crystals of CO2 have not been reported yet. In this work, based on density functional theory and the particle swarm optimization method, we unveil two CO2 2D crystals with space groups of P4[combining macron]M2 and Amm2. Our results show that these structures have excellent thermal, dynamic, and mechanical stability. The new structures are insulators with an indirect or direct band gap, while the indirect band gap can be tuned to be direct with small uniaxial strains. More importantly, the P4[combining macron]M2 structure has an in-plane negative Poisson's ratio, which is due to the interaction of the lattice symmetry and the local CO4 tetrahedron symmetry. In addition, the Amm2 sheet has a very large electronic band gap (>9 eV), which is the largest in all known 2D materials. Enthalpy curves indicate that these 2D structures may be obtained from the ambient phase of CO2 under high pressure. This work presents new structures of CO2, and because of their excellent performance in terms of stability, mechanical and electronic properties, they potentially have broad applications.

Synthesis of TiO2@g-C3N4 core-shell nanorod arrays with Z-scheme enhanced photocatalytic activity under visible light.

Novel rutile TiO2@g-C3N4 core-shell photocatalysts were synthesized by a facile saturated aqueous solution method. The composites were further characterized by using X-ray diffraction (XRD), high-resolution transmission microscopy (HRTEM), UV-visible light diffusion reflectance spectrometry (DRS), X-ray photoelectron spectroscopy (XPS) and so on. The results indicated that an ultrathin layer of g-C3N4 was in-situ fabricated over the surface of rutile TiO2 nanorod. The rutile TiO2@ g-C3N4 core-shell structures showed much higher photo-current and photocatalytic activity for Rhodamine B (RhB) degradation under visible irradiation. The enhanced performance was attributed to the high separation efficiency of photo-induced carriers via a Z-scheme form.

In silico construction of HK2-VDAC1 complex and investigating the HK2 binding-induced molecular gating mechanism of VDAC1.

Hexokinase 2 (HK2) binds to Voltage-Dependent Anion Channel 1 (VDAC1) on mitochondrial outer membrane (MOM) to facilitate a preferential access of ATP to HK2 for glycolysis, in order to maintain a constant energy source for cell proliferation in cancer especially. While previous studies have discovered that the VDAC1 N-terminal helix is responsible for regulating molecules from within mitochondria to cytoplasm, the molecular mechanism of how HK2 is able to regulate the ATP access remains elusive. We hereby propose a model for the HK2-VDAC1 association. The model is then subjected to molecular dynamics (MD) simulations, where we probe the effect of HK2 binding on the mobility of the VDAC1 N-terminal helix. Results from the simulations show that HK2 binding restricts the movement of the VDAC1 N-terminal helix. As a result, VDAC1 is kept in the open state most of the time and probably allows a constant supply of ATP to HK2 for glycolysis.

Van der Waals Effects on semiconductor clusters.

Van der Waals (vdW) interactions play an important role on semiconductors in nanoscale. Here, we utilized first-principles calculations based on density functional theory to demonstrate the growth mode transition from prolate to multiunit configurations for Gen (n = 10-50) clusters. In agreement with the injected ion drift tube techniques that "clusters with n < 70 can be thought of as loosely bound assemblies of small strongly bound fragments (such as Ge7 and Ge10 )," we found these stable fragments are connected by Ge6 , Ge9 , or Ge10 unit (from bulk diamond), via strong covalent bonds. Our calculated cations usually fragment to Ge7 and Ge10 clusters, in accordance with the experiment results that the spectra Ge7 and Ge10 correspond to the mass abundance spectra. By controlling a germanium cluster with vdW interactions parameters in the program or not, we found that the vdW effects strengthen the covalent bond from different units more strikingly than that in a single unit. With more bonds between units than the threadlike structures, the multiunit structures have larger vdW energies, explaining why the isolated nanowires are harder to produce. © 2015 Wiley Periodicals, Inc.