MoS2/Mayenite Electride Hybrid as a Cathode Host for Suppressing Polysulfide Shuttling and Promoting Kinetics in Lithium-Sulfur Batteries.

The commercial viability of emerging lithium-sulfur batteries (LSBs) remains greatly hindered by short lifespans caused by electrically insulating sulfur, lithium polysulfides (Li2Sn; 1 ≤ n ≤ 8) shuttling, and sluggish sulfur reduction reactions (SRRs). This work proposes the utilization of a hybrid composed of sulfiphilic MoS2 and mayenite electride (C12A7:e-) as a cathode host to address these challenges. Specifically, abundant cement-based C12A7:e- is the most stable inorganic electride, possessing the ultimate electrical conductivity and low work function. Through density functional theory simulations, the key aspects of the MoS2/C12A7:e- hybrid including electronic properties, interfacial binding with Li2Sn, Li+ diffusion, and SRR have been unraveled. Our findings reveal the rational rules for MoS2 as an efficient cathode host by enhancing its mutual electrical conductivity and surface polarity via MoS2/C12A7:e-. The improved electrical conductivity of MoS2 is attributed to the electron donation from C12A7:e- to MoS2, yielding a semiconductor-to-metal transition. The resultant band positions of MoS2/C12A7:e- are well matched with those of conventional current-collecting materials (i.e., Cu and Ni), electrochemically enhancing the electronic transport. The accepted charge also intensifies MoS2 surface polarity for attracting polar Li2Sn by forming stronger bonds with Li2Sn via ionic Li-S bonds than electrolytes with Li2Sn, thereby preventing polysulfide shuttling. Importantly, MoS2/C12A7:e- not only promotes rapid reaction kinetics by reducing ionic diffusion barriers but also lowers the Gibbs free energies of the SRR for effective S8-to-Li2S conversion. Beyond the reported applications of C12A7:e-, this work highlights its functionality as an electrode material to boost the efficiency of LSBs.

Antiproliferative polyketides from fungus Xylaria cf. Longipes SWUF08-81 in different culture media.

Bioactive compounds from the wood-decay fungus Xylaria cf. longipes SWUF08-81, cultivated in three different culture media (GM, YM and PDB), were isolated. Their structures and stereochemistry were deduced from spectroscopic and MS data analysis, together with quantum chemical calculations of 13C NMR chemical shifts and electronic circular dichroism (ECD) spectra. Five undescribed polyketides including dibenzofuran (1), mellein (2), dihydroisocoumarin (15), and two pyrans (16, 17), together with twenty-three compounds were determined. Compounds 18 and 20 were significantly toxic against cancer cell lines (HCT116, HT29, MCF-7 and HeLa) based on the MTT assay. Quantification by HPLC showed that 18 was produced three-fold higher in the broth of PDB than YM. These studies showed that the production of different compounds were primarily dependent on nutrition sources and it has given a starting point for the growth optimization conditions for the scaling up of bioactive compounds production.

Influence of Co doping on phase, structure and electrochemical properties of hydrothermally obtained CoxZn1-xFe2O4 (x = 0.0-0.4) nanoparticles.

In this work, CoxZn1-xFe2O4 (x = 0.0-0.4) nanoparticles (NPs) were successfully synthesized by a hydrothermal method at 200 °C for 12 h. X-ray diffraction revealed a pure cubic spinel phase of all samples with space group Fd-3m. Fourier transform infrared spectrometry disclosed the vibrational modes of metal oxides in the spinel structure. Scanning electron microscopy and transmission electron microscopy disclosed a uniform distribution of cuboidal shape NPs with a decreased average NPs size from 22.72 ± 0.62 to 20.85 ± 0.47 nm as the Co content increased. X-ray absorption near edge spectroscopy results confirmed the presence of Zn2+, Co2+ and Fe2+/Fe3+ in Co-doped samples. The pore volume, pore size and specific surface area were determined using N2 gas adsorption/desorption isotherms by the Brunauer-Emmett-Teller (BET) and Barrett-Joyner-Halenda (BJH) techniques. Electrochemical properties of supercapacitors, having active CoxZn1-xFe2O4 (x = 0.0-0.4) NPs as working electrodes, indicated pseudo-capacitor performance related to the Faradaic redox reaction. Interestingly, the highest specific capacitance (Csc), 855.33 F/g at 1 A/g, with a capacity retention of 90.41% after 1000 GCD cycle testing was achieved in the Co0.3Zn0.7Fe2O4 electrode.

Effects of sintering condition on giant dielectric and nonlinear current-voltage properties of Na1/2Y1/2Cu3Ti3.975Ta0.025O12 ceramics.

The effects of sintering conditions on the microstructure, giant dielectric response, and electrical properties of Na1/2Y1/2Cu3Ti3.975Ta0.025O12 (NYCTTaO) were studied. A single phase of Na1/2Y1/2Cu3Ti4O12 and a high density (>98.5%) were obtained in the sintered NYCTTaO ceramics. First-principles calculations were used to study the structure of the NYCTTaO. Insulating grain boundaries (i-GBs) and semiconducting grains (semi-Gs) were studied at different temperatures using impedance and admittance spectroscopies. The conduction activation energies of the semi-Gs and i-GBs were Eg ≈ 0.1 and Egb ≈ 0.6 eV, respectively. A large dielectric constant (ε' ≈ 2.43-3.89 × 104) and low loss tangent (tanδ ≈ 0.046-0.021) were achieved. When the sintering temperature was increased from 1070 to 1090 °C, the mean grain size slightly increased, while ε' showed the opposite tendency. Furthermore, the breakdown electric field (Eb) increases significantly. As the sintering time increased from 5 to 10 h, the mean grain size did not change, whereas ε' and Eb increased. Variations in the dielectric response and non-linear electrical properties were primarily described by the intrinsic (Egb) and extrinsic (segregation of Na-, Cu-, Ta-, and O-rich phases) properties of the i-GBs based on the internal barrier layer capacitor effect.

Improved Thermoelectric Properties of SrTiO3 via (La, Dy and N) Co-Doping: DFT Approach.

This work considers the enhancement of the thermoelectric figure of merit, ZT, of SrTiO3 (STO) semiconductors by (La, Dy and N) co-doping. We have focused on SrTiO3 because it is a semiconductor with a high Seebeck coefficient compared to that of metals. It is expected that SrTiO3 can provide a high power factor, because the capability of converting heat into electricity is proportional to the Seebeck coefficient squared. This research aims to improve the thermoelectric performance of SrTiO3 by replacing host atoms by La, Dy and N atoms based on a theoretical approach performed with the Vienna Ab Initio Simulation Package (VASP) code. Here, undoped SrTiO3, Sr0.875La0.125TiO3, Sr0.875Dy0.125TiO3, SrTiO2.958N0.042, Sr0.750La0.125Dy0.125TiO3 and Sr0.875La0.125TiO2.958N0.042 are studied to investigate the influence of La, Dy and N doping on the thermoelectric properties of the SrTiO3 semiconductor. The undoped and La-, Dy- and N-doped STO structures are optimized. Next, the density of states (DOS), band structures, Seebeck coefficient, electrical conductivity per relaxation time, thermal conductivity per relaxation time and figure of merit (ZT) of all the doped systems are studied. From first-principles calculations, STO exhibits a high Seebeck coefficient and high figure of merit. However, metal and nonmetal doping, i.e., (La, N) co-doping, can generate a figure of merit higher than that of undoped STO. Interestingly, La, Dy and N doping can significantly shift the Fermi level and change the DOS of SrTiO3 around the Fermi level, leading to very different thermoelectric properties than those of undoped SrTiO3. All doped systems considered here show greater electrical conductivity per relaxation time than undoped STO. In particular, (La, N) co-doped STO exhibits the highest ZT of 0.79 at 300 K, and still a high value of 0.77 at 1000 K, as well as high electrical conductivity per relaxation time. This renders it a viable candidate for high-temperature applications.

Giant Dielectric Properties of W6+-Doped TiO2 Ceramics.

The effects of the sintering temperature and doping level concentration on the microstructures, dielectric response, and electrical properties of W6+-doped TiO2 (WTO) prepared via a solid-state reaction method were investigated. A highly dense microstructure, pure rutile-TiO2, and homogenously dispersed dopant elements were observed in all of the ceramic samples. The mean grain size increased as the doping concentration and sintering temperature increased. The presence of oxygen vacancies was studied. A giant dielectric permittivity (ε' ~ 4 × 104) and low tanδ (~0.04) were obtained in the WTO ceramic sintered at 1500 °C for 5 h. The ε' response at a low temperature was improved by increasing the doping level concentration. The giant ε' response in WTO ceramics can be described by the interfacial polarization at the interface between the semiconducting and insulating parts, which was supported by the impedance spectroscopy.

Dielectric Responses of (Zn0.33Nb0.67)xTi1-xO2 Ceramics Prepared by Chemical Combustion Process: DFT and Experimental Approaches.

The (Zn, Nb)-codoped TiO2 (called ZNTO) nanopowder was successfully synthesized by a simple combustion process and then the ceramic from it was sintered with a highly dense microstructure. The doped atoms were consistently distributed, and the existence of oxygen vacancies was verified by a Raman spectrum. It was found that the ZNTO ceramic was a result of thermally activated giant dielectric relaxation, and the outer surface layer had a slight effect on the dielectric properties. The theoretical calculation by using the density functional theory (DFT) revealed that the Zn atoms are energy preferable to place close to the oxygen vacancy (Vo) position to create a triangle shape (called the ZnVoTi defect). This defect cluster was also opposite to the diamond shape (called the 2Nb2Ti defect). However, these two types of defects were not correlated together. Therefore, it theoretically confirms that the electron-pinned defect-dipoles (EPDD) cannot be created in the ZNTO structure. Instead, the giant dielectric property of the (Zn0.33Nb0.67)xTi1-xO2 ceramics could be caused by the interfacial polarization combined with electron hopping between the Zn2+/Zn3+ and Ti3+/Ti4+ ions, rather than due to the EPDD effect. Additionally, it was also proved that the surface barrier-layer capacitor (SBLC) had a slight influence on the giant dielectric properties of the ZNTO ceramics. The annealing process can cause improved dielectric properties, which are properties with a huge advantage to practical applications and devices.

Effects of Sintering Conditions on Giant Dielectric and Nonlinear Current-Voltage Properties of TiO2-Excessive Na1/2Y1/2Cu3Ti4.1O12 Ceramics.

The effects of the sintering conditions on the phase compositions, microstructure, electrical properties, and dielectric responses of TiO2-excessive Na1/2Y1/2Cu3Ti4.1O12 ceramics prepared by a solid-state reaction method were investigated. A pure phase of the Na1/2Y1/2Cu3Ti4.1O12 ceramic was achieved in all sintered ceramics. The mean grain size slightly increased with increasing sintering time (from 1 to 15 h after sintering at 1070 °C) and sintering temperature from 1070 to 1090 °C for 5 h. The primary elements were dispersed in the microstructure. Low dielectric loss tangents (tan δ~0.018-0.022) were obtained. Moreover, the dielectric constant increased from ε'~5396 to 25,565 upon changing the sintering conditions. The lowest tan δ of 0.009 at 1 kHz was obtained. The electrical responses of the semiconducting grain and insulating grain boundary were studied using impedance and admittance spectroscopies. The breakdown voltage and nonlinear coefficient decreased significantly as the sintering temperature and time increased. The presence of Cu+, Cu3+, and Ti3+ was examined using X-ray photoelectron spectroscopy, confirming the formation of semiconducting grains. The dielectric and electrical properties were described using Maxwell-Wagner relaxation, based on the internal barrier layer capacitor model.

The Primary Origin of Excellent Dielectric Properties of (Co, Nb) Co-Doped TiO2 Ceramics: Electron-Pinned Defect Dipoles vs. Internal Barrier Layer Capacitor Effect.

(Co, Nb) co-doped rutile TiO2 (CoNTO) nanoparticles with low dopant concentrations were prepared using a wet chemistry method. A pure rutile TiO2 phase with a dense microstructure and homogeneous dispersion of the dopants was obtained. By co-doping rutile TiO2 with 0.5 at.% (Co, Nb), a very high dielectric permittivity of ε' ≈ 36,105 and a low loss tangent of tanδ ≈ 0.04 were achieved. The sample-electrode contact and resistive outer-surface layer (surface barrier layer capacitor) have a significant impact on the dielectric response in the CoNTO ceramics. The density functional theory calculation shows that the 2Co atoms are located near the oxygen vacancy, creating a triangle-shaped 2CoVoTi complex defect. On the other hand, the substitution of TiO2 with Nb atoms can form a diamond-shaped 2Nb2Ti complex defect. These two types of complex defects are far away from each other. Therefore, the electron-pinned defect dipoles cannot be considered the primary origins of the dielectric response in the CoNTO ceramics. Impedance spectroscopy shows that the CoNTO ceramics are electrically heterogeneous, comprised of insulating and semiconducting regions. Thus, the dielectric properties of the CoNTO ceramics are attributed to the interfacial polarization at the internal insulating layers with very high resistivity, giving rise to a low loss tangent.

The quantum confined Stark effect in N-doped ZnO/ZnO/N-doped ZnO nanostructures for infrared and terahertz applications.

The terahertz (THz) frequency range is very important in various practical applications, such as terahertz imaging, chemical sensing, biological sensing, high-speed telecommunications, security, and medical applications. Based on the density functional theory (DFT), this work presents electronic and optical properties of N-doped ZnO/ZnO/N-doped ZnO quantum well and quantum wire nanostructures. The density of states (DOS), the band structures, effective masses, and the band offsets of ZnO and N-doped ZnO were calculated as the input parameters for the subsequent modeling of the ZnO/N-doped ZnO heterojunctions. The results show that the energy gaps of the component materials are different, and the conduction and valence band offsets at the ZnO/N-doped ZnO heterojunction give type-II alignment. Furthermore, the optical characteristics of N-doped ZnO/ZnO/N-doped ZnO quantum well were studied by calculating the absorption coefficient from transitions between the confined states in the conduction band under the applied electric field (Stark effect). The results indicate that N-doped ZnO/ZnO/N-doped ZnO quantum wells, quantum wires, and quantum cascade structures could offer the absorption spectrum tunable in the THz range by varying the electric field and the quantum system size. Therefore, our work indicates the possibility of using ZnO as a promising candidate for infrared and terahertz applications.

Fe3+/Nb5+ Co-doped rutile-TiO2 nanocrystalline powders prepared by a combustion process: preparation and characterization and their giant dielectric response.

Fe3+/Nb5+ co-doped TiO2 (FeNb-TO) nanocrystalline powders were prepared by a combustion process. A pure rutile-TiO2 phase of powders and sintered ceramics with a dense microstructure was achieved. Both co-dopants were homogeneously dispersed in the ceramic microstructure. The presence of oxygen vacancies was confirmed by Raman and X-ray photoelectron spectroscopy techniques. The low-frequency dielectric permittivity enhanced as co-doping concentration increased. The thermally activated giant-dielectric relaxation of FeNb-TO ceramics was observed. Removing the outer-surface layer had a slight effect on the dielectric properties of FeNb-TO ceramics. Density functional theory (DFT) calculation showed that, in the energy preferable configuration, the 2Fe atoms are located near the oxygen vacancy, forming a triangle-shaped FeVoTi defect complex. This defect cluster was far away from the diamond-shaped 2Nb2Ti defect complex. Thus, the electron-pinned defect-dipoles (EPDD) cannot be formed. The giant-dielectric relaxation process of the FeNb-TO ceramics might be attributed to the interfacial polarization associated with electron hopping between Ti3+/Ti4+ ions inside the grains, rather than due to the surface barrier layer capacitor (SBLC) or EPDD effect.

Chemical constituents and cytotoxic activity from the wood-decaying fungus Xylaria sp. SWUF08-37.

A new cyclic pentapeptide, pentaminolarin (1), and a new cytochalasin, xylochalasin (2), along with thirteen known compounds (3-15) were isolated from the wood-decaying fungus Xylaria sp. SWUF08-37. The absolute configurations of 1 were determined by a combination of Marfey's method and TDDFT ECD calculation and the absolute configurations of 2 were established by TDDFT ECD calculation. Compound 12 showed moderate cytotoxicity against HeLa (IC50 = 19.60 µg/mL), HT29 (IC50 = 17.31 µg/mL), HCT116 (IC50 = 14.28 µg/mL), MCF-7 (IC50 = 15.38 µg/mL), and Vero (IC50 = 24.97 µg/mL) cell lines by MTT assay. Compounds 1 and 2 showed slight cytotoxicity against all tested cancer cell lines.