Magnetically Recyclable Fe3O4@TMU-32 Metal-Organic Framework Photocatalyst for Tetracycline Degradation Under Visible Light.

Metal-organic frameworks (MOFs) are a new class of porous crystalline materials being used as photocatalysts for efficient pollutant removal and environmental remediation. In this study, the TMU-32 MOF was synthesized as an effective photocatalyst for the photodegradation of tetracycline (TC) with 96% efficiency in 60 min under visible light. The high photocatalytic activity of the TMU-32 MOF is mainly due to its large specific surface area, which is beneficial for promoting both the adsorption of TC and the separation of the photoinduced charges. Moreover, its desired crystallinity makes it a semiconductor with an appropriate band gap energy. Next, a composite of the TMU-32 MOF with Fe3O4 nanoparticles (as Fe3O4@TMU-32) was prepared as a magnetically recyclable photocatalyst. The results showed that the photocatalytic activity of the Fe3O4@TMU-32 nanocomposite is slightly lower (68% degradation of TC within 60 min) than that of TMU-32 toward TC degradation since Fe3O4 nanoparticles are not acting as a photocatalyst and are used only to make the host photocatalyst (here, TMU-32) magnetically separable. The effects of the photocatalyst concentration and recyclability on the photodegradation of TC were studied under similar conditions. We found that the Fe3O4@TMU-32 composite is easily recycled without a significant loss of photocatalytic activity after being used several times, indicating the stability of the photocatalyst. Finally, a density functional theory study was also conducted to investigate the structural and electronic properties such as the band gap energy and density of states of the TMU-32 MOF and the Fe3O4@TMU-32 composite. Our computational results are in good agreement with the experimental ones. A photocatalytic degradation mechanism was finally proposed under visible-light photoirradiation.

Band alignment tuning of heptazine-g-C3N4/g-ZnO vdW heterostructure as a promising water-splitting photocatalyst.

Van der Waals (vdW) heterostructures of two-dimensional monolayers are a relatively new class of materials with highly tunable band alignment, bandgap energy, and bandgap transition type. In this study, we performed density functional theory calculations to investigate how a vdW heterostructure of heptazine-based graphitic carbon nitride (hg-C3N4) and graphitic zinc oxide (g-ZnO) monolayers is formed (hg-C3N4/g-ZnO). This heterostructure is a potential solar-driven photocatalyst for the water-splitting reaction. Upon the formation of the heterostructure, a type-I indirect bandgap (Eg = 2.08 eV) is created with appropriate conduction band minimum and valence band maximum levels relative to the oxidation/reduction potentials for the water-splitting reaction. In addition, a very large electrostatic potential difference of 11.18 eV is generated across the heterostructure, leading to a large, naturally-formed, built-in electric field directing from hg-C3N4 to g-ZnO. The produced electric field forces photogenerated electrons in g-ZnO to transfer toward hg-C3N4, leading to a decrease in the electron-hole recombination rate. We also found that both g-ZnO and hg-C3N4 synergistically lead to higher light absorption of the heterostructure (λmax = 387 nm). Furthermore, band alignment, bandgap energy, and transition type of the heterostructure can be tuned by applying external perpendicular electric fields and biaxial strains. It was found that a strain of +2% leads to a Z-scheme band alignment (Eg = 2.34 eV, direct) and an electric field of 1 V Å-1 leads to a type-II heterostructure (Eg = 2.29 eV, indirect), which are both beneficial for efficient water-splitting photocatalysis.

Highly improved supercapacitance properties of MnFe2O4 nanoparticles by MoS2 nanosheets.

Manganese ferrite (MnFe2O4) nanoparticles were synthesized via a hydrothermal method and combined with exfoliated MoS2 nanosheets, and the nanocomposite was studied as a supercapacitor. X-ray diffractometry and Raman spectroscopy confirmed the crystalline structures and structural characteristics of the nanocomposite. Transmission electron microscopy images showed the uniform size distribution of MnFe2O4 nanoparticles (~ 13 nm) on few-layer MoS2 nanosheets. UV-visible absorption photospectrometry indicated a decrease in the bandgap of MnFe2O4 by MoS2, resulting in a higher conductivity that is suitable for capacitance. Electrochemical tests showed that the incorporation of MoS2 nanosheets largely increased the specific capacitance of MnFe2O4 from 600 to 2093 F/g (with the corresponding energy density and power density of 46.51 Wh/kg and 213.64 W/kg, respectively) at 1 A/g, and led to better charge-discharge cycling stability. We also demonstrated a real-world application of the MnFe2O4/MoS2 nanocomposite in a two-cell asymmetric supercapacitor setup. A density functional theory study was also performed on the MnFe2O4/MoS2 interface to analyze how a MoS2 monolayer can enhance the electronic properties of MnFe2O4 towards a higher specific capacitance.

Incremental substitution of Ni with Mn in NiFe2O4 to largely enhance its supercapacitance properties.

By using a facile hydrothermal method, we synthesized Ni1-xMnxFe2O4 nanoparticles as supercapacitor electrode materials and studied how the incremental substitution of Ni with Mn would affect their structural, electronic, and electrochemical properties. X-ray diffractometry confirmed the single-phase spinel structure of the nanoparticles. Raman spectroscopy showed the conversion of the inverse structure of NiFe2O4 to the almost normal structure of MnFe2O4. Field-emission scanning electron microscopy showed the spherical shape of the obtained nanoparticles with a size in the range of 20-30 nm. Optical bandgaps were found to decrease as the content of Mn increased. Electrochemical characterizations of the samples indicated the excellent performance and the desirable cycling stability of the prepared nanoparticles for supercapacitors. In particular, the specific capacitance of the prepared Ni1-xMnxFe2O4 nanoparticles was found to increase as the content of Mn increased, reaching the highest specific capacitance of 1,221 F/g for MnFe2O4 nanoparticles at the current density of 0.5 A/g with the corresponding power density of 473.96 W/kg and the energy density of 88.16 Wh/kg. We also demonstrated the real-world application of the prepared MnFe2O4 nanoparticles. We performed also a DFT study to verify the changes in the geometrical and electronic properties that could affect the electrochemical performance.

Tunable electronic properties of the novel g-ZnO/1T-TiS2 vdW heterostructure by electric field and strain: crossovers in bandgap and band alignment types.

A relatively new and promising method to tune properties of monolayers is by forming a heterostructure of them. Here, the van der Waals heterostructure of graphene-like zinc oxide (g-ZnO) and 1-trigonal titanium disulfide (1T-TiS2) was formed and its structural, electronic, and optical properties were studied in the framework of density functional theory. The dynamical stability of the heterostructure was confirmed based on its phonon band structure. An indirect (Γ â†’ M) bandgap of 0.65 eV, a large built-in electric field (or a large potential drop of 3.12 eV), a type-II (staggered) band alignment, and a large conduction band offset of 2.94 eV were found to form across the interface, which are all desirable for potentially efficient separation of charge carriers. We showed also that the formation of the heterostructure largely enhances the almost-zero optical absorption of g-ZnO in visible and near-infrared regions, which is desirable for optoelectronic applications. By applying a perpendicular electric field, we could tune the bandgap value and the band alignment type (type-II → type-I) of the heterostructure. Finally, we showed that by applying compressive strain, one can change the band alignment type (type-II → type-I) and by applying tensile strain, the bandgap value could be tuned and a crossover occurs in the bandgap type (indirect → direct → indirect).

Surgical implications of the potential new tubal pathway for ovarian carcinogenesis.

Since 2001, many studies by different investigators have demonstrated that the fallopian tube might be at the origin of most high-grade ovarian and peritoneal serous carcinomas. Simple changes in surgical practice (ie, prophylactic bilateral salpingectomy instead of salpingo-oophorectomy) could have significant implications for death from ovarian cancer and, on the other hand, for the morbidity caused by ovariectomy (surgical menopause). In this review, we describe the new tubal carcinogenic sequence, the advantages and disadvantages of exclusive use of salpingectomy in the general population, and in cases of hereditary predisposition to ovarian cancer such as for carriers of BRCA mutation.