Stress-Induced Martensitic Transformation in Na3YCl6.

Martensitic transformation with volume expansion plays a crucial role in enhancing the mechanical properties of steel and partially stabilized zirconia. We believe that a similar concept could be applied to unexplored nonoxide materials. Herein, we report the stress-induced martensitic transformation of monoclinic Na3YCl6 with an ∼3.4% expansion. In situ synchrotron X-ray diffraction and atomistic simulations showed that anisotropic crystallographic transformation from monoclinic to rhombohedral Na3YCl6 occurs exclusively under uniaxial pressure; no effect is observed under hydrostatic pressure conditions. The uniaxially pressed powder compact of monoclinic Na3YCl6 showed a large indentation impression and low Young's modulus, in contrast to its high bulk modulus, suggesting that these unique mechanical properties are induced by the martensitic transformation.

CdSe nanostructured thin film by electrophoretic deposition for quantum dots sensitized solar cell.

Cadmium selenide (CdSe) quantum dots (QDs) with different size, 2.5 and 3.2 nm, were successfully deposited on mesoporous titanium dioxide (TiO2) (Degussa-P25) nanostructures by electrophoretic deposition method (EPD) at the applied voltage 100 V for 120 s deposition time. In this study, the morphology of CdSe films deposited by EPD and the performance of the film when assembled into a solar cell were investigated. From the field emission scanning electron microscopy cross-section, the thickness of the CdSe nanoparticles with size 2.5 nm films were 3.4 and 3.0µm for CdSe 3.2 nm nanoparticles film. The structure of 2.5 nm is denser than compare of 3.2 nm CdSe nanoparticles. From UV visible spectroscopy, the band gap calculated for 2.5 nm CdSe nanoparticles is 2.28 eV and for 3.2 nm is 2.12 eV. Photovoltaic characterization was performed under an illumination of 100 mW cm-2. A photovoltaic conversion efficiency of 1.81% was obtained for 2.5 nm CdSe and 2.1% was obtained for 3.2 nm CdSe nanoparticles. This result shows that the photovoltaic efficiency is dependent on CdSe nanoparticle size.

Rapid Solution Synthesis of Argyrodite-Type Li6PS5X (X = Cl, Br, and I) Solid Electrolytes Using Excess Sulfur.

All-solid-state lithium-ion batteries (ASSLBs) have the potential to be the next-generation energy storage systems because of their high safety features. However, one of the major challenges to the commercialization of ASSLBs is the development of well-established large-scale manufacturing techniques for solid electrolytes (SEs). Herein, we synthesize Li6PS5X (X = Cl, Br, and I) SEs in a total of 4 h by a rapid solution synthesis method using excess elemental sulfur as a solubilizer and reasonable organic solvents. In the system, trisulfur radical anions stabilized by a highly polar solvent increase the solubility and reactivity of the precursor. Raman and UV-vis spectroscopies reveal the solvation behavior of halide ions in the precursor. This result demonstrates that the solvation structure modified by the halide ions determines the chemical stability, solubility, and reactivity of chemical species in the precursor. The prepared Li6PS5X (X = Cl, Br, and I) SEs show ionic conductivities of 2.1 × 10-3, 1.0 × 10-3, and 3.8 × 10-6 S cm-1 at 30 °C, respectively. Our study provides a rapid synthesis of argyrodite-type SEs with high ionic conductivity.

Influence of Ce3+ Substitution on Antimicrobial and Antibiofilm Properties of ZnCexFe2-xO4 Nanoparticles (X = 0.0, 0.02, 0.04, 0.06, and 0.08) Conjugated with Ebselen and Its Role Subsidised with γ-Radiation in Mitigating Human TNBC and Colorectal Adenocarcinoma Proliferation In Vitro.

Cancers are a major challenge to health worldwide. Spinel ferrites have attracted attention due to their broad theranostic applications. This study aimed at investigating the antimicrobial, antibiofilm, and anticancer activities of ebselen (Eb) and cerium-nanoparticles (Ce-NPs) in the form of ZnCexFe2-XO4 on human breast and colon cancer cell lines. Bioassays of the cytotoxic concentrations of Eb and ZnCexFe2-XO4, oxidative stress and inflammatory milieu, autophagy, apoptosis, related signalling effectors, the distribution of cells through the cell-cycle phases, and the percentage of cells with apoptosis were evaluated in cancer cell lines. Additionally, the antimicrobial and antibiofilm potential have been investigated against different pathogenic microbes. The ZOI, and MIC results indicated that ZnCexFe2-XO4; X = 0.06 specimen reduced the activity of a wide range of bacteria and unicellular fungi at low concentration including P. aeruginosa (9.5 mm; 6.250 µg/mL), S. aureus (13.2 mm; 0.390 µg/mL), and Candida albicans (13.5 mm; 0.195 µg/mL). Reaction mechanism determination indicated that after ZnCexFe2-xO4; X = 0.06 treatment, morphological differences in S.aureus were apparent with complete lysis of bacterial cells, a concomitant decrease in the viable number, and the growth of biofilm was inhibited. The combination of Eb with ZFO or ZnCexFe2-XO4 with γ-radiation exposure showed marked anti-proliferative efficacy in both cell lines, through modulating the oxidant/antioxidant machinery imbalance, restoring the fine-tuning of redox status, and promoting an anti-inflammatory milieu to prevent cancer progression, which may be a valuable therapeutic approach to cancer therapy and as a promising antimicrobial agent to reduce the pathogenic potential of the invading microbes.

Formation of grassy TiO2 nanotube thin film by anodisation in peroxide electrolyte for Cr(VI) removal under ultraviolet radiation.

Arrays of TiO2 nanotubes (TiO2 NTs) with grassy surfaces were observed on titanium foil anodised at 60 V in fluorinated ethylene glycol (EG) with added hydrogen peroxide (H2O2). The grassy surface was generated by the chemical etching and dissolution of the surface of the TiO2 NTs walls, which was accelerated by the temperature increase on the addition of H2O2 . Upon annealing at 600 °C, the grassy part of the TiO2 NTs was found to consist of mostly anatase TiO2 whereas the bottom part of the anodic oxide comprised a mixture of anatase and rutile TiO2. The TiO2 NTs were then used to reduce hexavalent chromium (Cr(VI)) under ultraviolet radiation. They exhibited a rather efficient photocatalytic effect, with 100% removal of Cr(VI) after 30 min of irradiation. The fast removal of Cr(VI) was due to the anatase dominance at the grassy part of the TiO2 NTs as well as the higher surface area the structure may have. This work provides a novel insight into the photocatalytic reduction of Cr(VI) on grassy anatase TiO2 NTs.

Sunlight activated anodic freestanding ZrO2 nanotube arrays for Cr(VI) photoreduction.

Visible-light-active freestanding zirconia (ZrO2) nanotube (FSZNT) arrays were fabricated by a facile electrochemical anodization method in fluoride containing ethylene glycol electrolyte added to it was 1 vol% of potassium carbonate (K2CO3) at 60 V for 1 h. Poor adhesion at the metal∣oxide interface was induced by K2CO3 leading to the formation of FSZNT flakes. The effect of the crystal structures of the FSZNTs e.g., amorphous, amorphous/tetragonal, and tetragonal/monoclinic was investigated towards the photocatalytic reduction of 10 ppm hexavalent chromium, Cr(VI) at pH 2 under sunlight. The results demonstrate the amorphous FSZNTs exhibited the highest Cr(VI) removal efficiency than the crystalline FSZNTs (95% versus 33% after 5 h). The high photocatalytic activity of the amorphous FSZNTs can be attributed to enhanced Cr(VI) adsorption, high visible light absorption, and better charge carrier separation. The low photocatalytic activity of the crystalline FSZNTs annealed at 500 °C was mainly attributed to poor Cr(VI) adsorption, low visible light absorption, and less photoactive monoclinic-ZrO2.

Multiferroic nanocomposite fabrication via liquid phase using anodic alumina template.

We report a novel and inexpensive fabrication process of multiferroic nanocomposite via liquid phase using an anodic alumina template. The sol-gel spin-coating technique was used to coat the template with ferrimagnetic CoFe2O4. By dissolving the template with NaOH aqueous solution, a unique nanotube array structure of CoFe2O4 was obtained. The CoFe2O4 nanotube arrays were filled with, and sandwiched in, ferroelectric BaTiO3 layers by a sol-gel spin-coating method to obtain the composite. Its multiferroicity was confirmed by measuring the magnetic and dielectric hysteresis loops.

Ag nanoparticle-filled TiO2 nanotube arrays prepared by anodization and electrophoretic deposition for dye-sensitized solar cells.

A layer of TiO2 nanotube (TNT) arrays with a thickness of 13 µm is synthesized by a two-step anodic oxidation from Ti metal foil. Surface charged Ag nanoparticles (NPs) are prepared by chemical reduction. After a pretreatment of the TNT arrays by acetone vapor, Ag NP filled TNT arrays can be achieved by electrophoretic deposition (EPD). Effects of the applied voltage during EPD such as DC-AC difference, frequency and waveform are investigated by quantitative analysis using atomic absorption spectroscopy. The results show that the best EPD condition is using DC 2 V + AC 4 V and a square wave of 1 Hz as the applied voltage. Back illuminated dye-sensitized solar cells are fabricated from TNT arrays with and without Ag NPs. The efficiency increased from 3.70% to 5.01% by the deposition of Ag NPs.

Photocatalytic performance of freestanding tetragonal zirconia nanotubes formed in H2O2/NH4F/ethylene glycol electrolyte by anodisation of zirconium.

ZrO2 nanotubes (ZrNTs) were produced by anodisation of zirconium foil in H2O2/NH4F/ethylene glycol electrolyte. The as-anodised foils were then soaked in the anodising electrolyte for 12 h. Soaking weakens the adherence of the anodic layer from the substrate resulting in freestanding ZrNTs (FS-ZrNTs). Moreover, the presence of H2O2 in the electrolyte also aids in weakening the adhesion of the film from the foil, as foil anodised in electrolyte without H2O2 has good film adherence. The as-anodised FS-ZrNTs film was amorphous and crystallised to predominantly tetragonal phase upon annealing at >300 °C. Annealing must, however, be done at <500 °C to avoid monoclinic ZrO2 formation and nanotubes disintegration. FS-ZrNTs annealed at 450 °C exhibited the highest photocatalytic ability to degrade methyl orange (MO), whereby 82% MO degradation was observed after 5 h, whereas FS-ZrNTs with a mixture of monoclinic and tetragonal degraded 70% of MO after 5 h.

Visible-light-induced photocatalysis of 2D-hexagonal mesoporous SiO2-TiO2 deposited with Au nanoparticles.

Au nanoparticles (NPs) are deposited using a couple of methods onto a sol-gel-derived mesoporous SiO2-TiO2 template. A modification of the template with 3-aminopropyltriethoxysilane (APTES) before the deposition of Au leads to the formation of Au nanorods instead of Au nanospheres in the tubular mesopores. The modification also causes a deterioration of visible-light-induced photocatalytic activity. Heat treatment of this sample to remove APTES results in an amelioration of the photocatalytic activity. The detailed mechanism of the deterioration and amelioration of the activity is discussed on the accessibility of the reactant to the sample and the easiness of the charge carrier transfer between TiO2 and Au NPs.

Formation of two-dimensional ZnO nanosheets by rapid thermal oxidation in oxygenated environment.

Crystalline 2-D (dimensional) ZnO nanosheets were formed by rapid thermal oxidation of etched Zn foil in oxygen at 300 degrees C and 400 degrees C. Short oxidation time was varied from 10, 20 and 30 min. The morphologies and optical properties of the ZnO nanosheets evolved with the oxidation temperature and time. At 300 degrees C, ZnO nanosheets with thickness ranging from 32 nm to 80 nm were obtained while at 400 degrees C, the thickness of the nanosheets increased from 88 nm to approximately 200 nm after 10 and 30 min of oxidation, respectively. The surface roughness of the ZnO nanosheets and grain size increased with oxidation time and temperature. Photoluminescence of the oxidized samples shows ultraviolet (UV) and visible emissions indicating good crystallinity of ZnO which was further confirmed by high-resolution transmission electron microscope observation of ZnO wurtzite interplanar spacing. Photocatalytic activity of ZnO was also investigated by using degradation of methyl orange (MO) and all the samples exhibit photocatalytic activity. The sample oxidized at 400 degrees C for 10 min show better MO degradation after 2 h of exposure due to higher surface area and better crystallinity of the ZnO nanosheets obtained.

Polybenzimidazole dispersed polymer coated nanowires as efficient electrolytes for proton exchange membrane fuel cells.

In this study, polymer-coated anisotropic inorganic nanowires dispersed in PBI matrix were introduced to construct 1D proton conducting channels within PBI. Ionic-liquid and solvothermal methods were used for the synthesis of ZrO2 and W18O49 NWs, which were coated with PVPA and PDDA polymers to increase their proton conductivity. Our results showed that, prepared membranes have amorphous nature due to the dominating presence of PBI. SEM analysis revealed the average thickness of membrane of about 36 µm. TG/DTA analysis detected lower weight loss of W18O49 NWs (total 2.8%) compared to ZrO2 NWs (18%). Proton conductivity analysis showed that, PDDA/W18O49 NWs possess relatively 4 times higher proton conductivity (4 × 10-4 Scm-1) compared to PDDA/ZrO2 NWs (1 × 10-4 Scm-1) at 80 â„ƒ. In addition, PDDA-coated W18O49 NWs dispersed PBI membranes showed the highest fuel cell current density (1.2 A/cm2) and power density (215 mW/cm2) at 150 â„ƒ after 24 h which is nearly 2.5 times higher than pure PBI membrane. In addition, they exhibited the lowest in-situ proton resistance of about (0.47 Ω) compared with that of pure PBI membrane (0.8 Ω). Our results are introducing new concepts towards the development of thin and efficient polymer electrolyte membranes for PEM fuel cells.

Enhanced Photoelectrochemical Property of TiO2 Nanotube Array Photoanode Deposited with Al,Cr-Codoped SrTiO3 Nanocubes.

There is a demand for the effective utilization of solar energy with highly functional photoelectrodes for photoelectrochemical (PEC) applications, such as water splitting and CO2 reduction. TiO2 nanotube arrays (TNTA) with a large surface area have been studied as potential photoelectrodes mainly due to their strong oxidation potential. However, it has disadvantages of fast charge recombination and little responsivity to visible light. In this study, we prepared TNTA by anodizing a Ti plate and decorated the TNTA with Al,Cr-codoped SrTiO3 (STO) nanocubes through a hydrothermal treatment to enhance the PEC properties. We also prepared pristine and undoped STO-decorated TNTA for comparison. The hydrothermal treatment duration was optimized for the TNTA-STO:Al,Cr sample to achieve the best PEC performance. Finally, the possible PEC reaction mechanism was proposed based on the obtained experimental results.

Electrochemical and microstructural analysis of LiNi1/3Mn1/3Co1/3O2 cathode composites prepared using the SEED method.

Cathode composites were fabricated using the nuclear growth (SEED) method. Compared to mortar mixing, the SEED method demonstrated higher cycle stability, with a 90LiNi1/3Mn1/3Co1/3O2-10Li7P2S8I composite retaining 99.7% discharge capacity after six cycles compared to 66.1%. Cross-sectional SEM-EDX images suggest that the solid electrolyte was more uniformly distributed in the cathode composite prepared using the SEED method. This study opens up the potential for higher cathode-active material loading ratios.

Bottom-up synthesis of ion-pair-bridged metal-organic framework for H+ conduction.

As a novel conceptual synthesis of a metal-organic framework (MOF)-based proton conductor, UiO-66 based on a pyridinedicarboxylic acid phosphate (PyDC-PA) ion pair linker has been developed, in which the phosphoric acid is fixed to the N donor moiety of pyridine via an ionic bond.

Tube length optimization of titania nanotube array for efficient photoelectrochemical water splitting.

Anodic TiO2 nanotube arrays (TNTAs) have attracted much attention due to their excellent photoelectrochemical (PEC) properties. In this work, the tube length of TNTAs was optimized for efficient PEC water splitting under two different conditions, in which very few or a massive amount of gas bubbles were generated on the electrodes. As a result, relatively longer TNTAs were found to be preferable for higher PEC performance when a larger number of bubbles were generated. This suggests that the mass transport in the electrolyte is assisted by the generated bubbles, so that the electrode surfaces are more easily exposed to the fresh electrolyte, leading to the higher PEC performance.

Transition-Metal Sulfides for High-Performance Lithium Sulfide Cathodes in All-Solid-State Lithium-Sulfur Batteries.

All-solid-state lithium-sulfur batteries (ASLSBs) have been attracting attention as next-generation batteries because of their high theoretical energy density, which exceeds that of traditional lithium-ion batteries. However, the performance of ASLSBs is limited by the sluggish redox reaction kinetics of lithium sulfide (Li2S) and S8 cathodes and the electrochemical degradation of cathode materials and solid electrolytes during cycling. Herein, we report a cathode design consisting of Li2S and transition-metal sulfides. This cathode design enhances the redox reaction kinetics of the cathode and suppresses interfacial degradation between the cathodes and solid electrolytes in the composite cathodes. The interface design uses titanium disulfide, molybdenum sulfide (MoS2), and tungsten sulfide to facilitate redox reaction kinetics, which improves the practical performance of ASLSBs. Among the composite cathodes examined in this work, the Li2S-MoS2 composite cathode exhibited the highest discharge capacity of 661 mA h g-1 (2.09 mA h cm-2) after 100 cycles. Electrochemical impedance analysis demonstrated that transition-metal sulfides, particularly MoS2, suppressed the increase in resistance through cycling of the composite cathodes. This finding suggests that transition-metal sulfides in Li2S composite cathodes multifunction as redox mediators and buffer layers, improving practical battery performance. Therefore, the electrode design offered in this study enhances the electrochemical utilization and long-term stability of ASLSBs.

Li10GeP2S12 solid electrolytes synthesised via liquid-phase methods.

Li10GeP2S12 solid electrolytes for all-solid-state batteries were synthesised through liquid-phase shaking, which is a suspension synthesis method, in 1 d. Additionally, Li10GeP2S12 solid electrolytes were prepared in 7.5 h, which is the fastest synthesis time, through solution synthesis using excess sulfur and a mixed solvent of acetonitrile, tetrahydrofuran, and ethanol. These Li10GeP2S12 solid electrolytes exhibited an ionic conductivity of 1.6 × 10-3 S cm-1, which is the highest ionic conductivity of previous studies of liquid phase synthesis. Therefore, Li10GeP2S12 solid electrolytes with high ionic conductivity can be rapidly synthesised via liquid-phase methods.

Anodic nanoporous WO3 modified with Bi2S3 quantum dots as a photoanode for photoelectrochemical water splitting.

Although anodic nanoporous (ANP) WO3 has gained a lot of attention for photoelectrochemical water splitting (PEC-WS), there is still a lack of efficient WO3-based photoanodes with sufficient light absorption and good e-/h+ separation and transfer. The decoration of ANP WO3 with narrow bandgap semiconductor quantum dots (QDs) can enhance charge carrier transfer while reducing their recombination, resulting in a high PEC efficiency. In this study, ANP WO3 was synthesized via an anodic oxidation process and then modified with Bi2S3 QDs via successive ionic layer adsorption and reaction (SILAR) process and examined as a photoanode for PEC-WS under ultraviolet-visible illumination. The ANP WO3 photoanode modified with ten cycles of Bi2S3 QDs demonstrated the highest current density of 16.28 mA cm-2 at 0.95 V vs RHE, which is approximately 19 times that of pure ANP WO3 (0.85 mA cm-2). Furthermore, ANP WO3/Bi2S3 QDs (10) photoanode demonstrated the highest photoconversion efficiency of 4.1 % at 0.66 V vs RHE, whereas pure ANP WO3 demonstrated 0.3 % at 0.85 V vs RHE. This can be attributed to the proper number of Bi2S3 QDs significantly enhancing the visible light absorption, construction of type-II band alignment with WO3, and improved charge separation and migration. The modification of ANP WO3 with nontoxic Bi2S3 QDs as a prospective metal chalcogenide for enhancing visible light absorption and PEC-WS performance has not yet been investigated. Consequently, this study paves the path for a facile technique of designing effective photoelectrodes for PEC-WS.

Ternary Triazole-Based Organic-Inorganic Proton-Conducting Hybrids Based on Computational Models for HT-PEMFC Application.

We reported a new ternary hybrid anhydrous proton-conducting material based on triazole (Tz), wherein it interacted with TiO2 and cesium hydrogen sulfate (CHS) constructed based on the acid-base interaction. It exhibited high proton conductivity derived by the two acid-base interactions: between CHS and Tz and between Tz and TiO2. As a starting point of discussion, we attempted to theoretically predict the high/low proton conductivity using the push-pull protonated atomic distance (PAD) law, which makes it possible to predict the proton conductivity in the acid-base part based on density functional theory. The calculations indicate the possibility of achieving higher proton conductivity in the ternary composites (CHS·Tz-TiO2) involving two acid-base interactions than in binary hybrids, such as CHS·Tz and TiO2-Tz composites, suggesting the positive effect of two simultaneous acid-base interactions for achieving high proton conductivity. This result is supported by the experimental result with respect to synthesized materials obtained using the mechanochemical method. Adding TiO2 to the CHS·Tz system causes a change in the CHS·Tz interaction and promotes proton dissociation, producing a new and fast proton-conducting layer through the formation of Tz-TiO2 interaction. Applying CHS·Tz-TiO2 to high-temperature proton exchange membrane fuel cells results in improved membrane conductivity and power-generation properties at 150 °C under anhydrous conditions.