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This study presents in situ detection of Zn2+ using a novel two-step square-wave anodic stripping voltammetry (SWASV)-based needle-type microsensor for citrus plant applications. A double-barrel bismuth/platinum (Bi/Pt) microelectrode was fabricated with a solid metal tip (~110 µm), which was durable enough to penetrate the thick skin of the citrus leaves and sensitive enough to detect ppb changes in Zn2+ concentration using SWASV. The microelectrode tip size was also determined to reduce mass transport limitation and improve limit of detection. Overall, the developed Bi/Pt microelectrode successfully measured Zn2+ concentrations within the vascular bundle of citrus plants.
Binder-free three-dimensional Co3O4 electrodes are fabricated by an economical and scalable one-step flame combustion method, namely Reactive Spray Deposition Technology. The electrodes are composed of porous nanostructured Co3O4 uniformly distributed throughout the conductive substrate. In the absence of any further optimization on the processing conditions, the as-synthesized electrodes demonstrate high capacitance of 567 F g−1 at 1.5 A g−1, excellent rate capability, and stable cycling performance with a capacity retention ratio of 96.7% after 1000 charge/discharge cycles from the three-electrode half-cell testing. This study presents the pathway to a significantly simplified manufacturing process of three-dimensional electrodes with the desirable porous nanostructure.
Porphyrins are photosensitisers used in photodynamic therapy (PDT) due to their tumor localization and in situ singlet oxygen generation. However, their limited absorption, insolubility, and aggregation in an aqueous medium limited their effective application in PDT. To overcome these limitations, we herein, report a large-scale aqueous synthesis of CuInS2/ZnS ternary quantum dots, and its conjugation to 5, 10, 15, 20-meso(4-hydroxyphenyl) porphyrin. The singlet oxygen generation of this highly aqueous soluble novel conjugate shows its potential for PDT applications.
The TiCxN1−x(001)/TiC(001) interface was studied by the first-principles method to provide the theoretical basis for developing TiCxN1−x/TiC coatings. The partial density of state (PDOS), charge density, charge density difference, and Mulliken population analysis were utilized to investigate the bonding nature and the electronic characteristic of the TiC0.25N0.75/TiC interface. The corresponding results indicate that the bonding nature at the interface is ionic and covalent characteristics, which also exist in bulk materials. The extreme similarity of PDOS among interfacial C, N, and Ti atoms and their bulk counterparts reveals that the electronic structure transition at the interface is smooth. The results of Mulliken population analysis and plots of charge density and charge density difference demonstrate that the charge increased for C in the TiC side is less than that for N in the TiC0.25N0.75 side, which reveals that the ionic bond in TiC0.25N0.75 is stronger than that in TiC. Therefore, TiC0.25N0.75 coating can be an alternative choice to combine with TiC coating in the actual production process of multilayer coatings.
This work focuses on the syntheses of Zn-enriched PtZn nanoparticle electrocatalysts by solution combustion for ethanol oxidation reaction (EOR). Analytical techniques of x-ray diffraction, transmission electron microscopy (TEM), scanning electron microscopy, TEM/scanning TEM-energy dispersive x-ray spectroscopy, and x-ray photoelectron spectroscopy are used for the characterization of electrocatalysts. Cyclic voltammetry and chronoamperometry are applied for the electrocatalysis of C2H5OH and stability test in an alkaline medium, respectively. Electrochemical data show that PtZn/C has improved electrocatalytic activity by ~2.3 times compared with commercial Pt/C, in addition to having earlier onset potential and better stability for EOR. The variation of fuel amount in the synthesis has affected crystallite sizes, electronic, and electrochemical properties in electrocatalysts.
Direct polycondensation of L-lactic acid with a comonomer allows tailoring the properties of the product from the very first step. The viscous L-lactic acid co-oligomers with star-shaped architectures obtained were modified with three different acrylate monomers. Regardless the functionalization agent, UV curing was fast and all materials were cell compatible and promoted cell adhesion. The physical properties of the three star-shaped films exhibited a consistent trend as swelling capacity, hydrolytic instability, and gel content decreased simultaneously. A higher network density increased crosslinking degree and gel content among the films with an isocyanate group. The methacrylic end group functionalized material, lowest molecular weight, consistently exhibited the higher hydrolytic instability. Comparison of physical properties of these films with the corresponding linear materials reported previously confirmed the influence of precursor molecular architecture on the final material. The methodology developed herein is prone to scale-up and lead to the industrial production of new bioadhesives.
In this work, we present a solvothermal method to prepare bismuth (Bi)-doped CuGaS2 chalcopyrite nanocrystals ink and apply it to an all-solution-processed approach for the preparation of films with a thickness of approximately 730 nm and with enhanced optical properties and lower band gap energy than the undoped semiconductor films. The low-cost deposition method is comprised by spray deposition of the chalcogenide nanocrystals ink onto the molybdenum substrates, producing microcrystalline films with grains larger than 400 nm originated from coalescence of Bi-doped nanocrystals. Bi-doped CuGaS2 microcrystalline films are a good candidate to be applied as an absorber layer in thin-film solar cells.
Perovskite materials are sensitive to environmental conditions. Here we report the synthesis and characterization of a hydrophobic alkylammonium lead(II) iodide perovskite with enhanced stability in water. Water stability was achieved by growing a shell of 4-[(N-3-butyne)carboxyamido]anilinium lead(II) iodide over methylammonium lead(II) iodide. As a proof of concept, the water-splitting reaction was performed using our new material coated on TiO2, and a 7-fold increase in applied bias photon-to-current efficiency was observed as compared with standard p25-TiO2. Such simple and versatile chemical modification to induce high water stability is useful toward exploring new applications for the perovskite materials.
The Bi4Te3 films with well-ordered orientation and microstructure were successfully prepared on SiO2 substrate by a vacuum thermal evaporation deposition technique for the first time. We discussed the effects of evaporation temperature and substrate temperature on the phase and its well-ordered growth of Bi4Te3 films. The formation of Bi4Te3 phase is owing to the differences of the saturated vapor pressure. The thermoelectric transport properties of the Bi4Te3 films were investigated and the (00l)-oriented nanopillars array film has a better electrical transport performance, whose value of PF is 0.032 mWm−1 K−2 at 339 K, approaching twice that of the non-oriented ordinary film. The enhanced electrical properties of Bi4Te3 films could be achieved via the high-crystallinity well-controlled (00l)-oriented nanopillars array.
Metal–air batteries promise higher energy densities than state-of-the-art Li-ion batteries and have, therefore, received significant research attention lately. The most distinguishing feature of this technology is that it takes advantage of reversible conversion reactions of O2 or other air components (such as N2 or CO2) at the cathode. To promote these reactions, catalysts are often needed. A large number of materials have been studied for this purpose. In the present paper, we discuss the roles played by catalysts in metal–air battery systems. In particular, we choose to focus the discussions on the Li–O2 batteries as they are most intensely studied in the literature. Within this context, catalysts are often shown effective to facilitate the oxygen (O2) reduction reactions and/or O2 evolution reactions. The overall cell performance as measured by the round-trip efficiencies and charge/discharge rates can be significantly improved by the incorporation of catalysts. However, the presence of catalysts is also found to complicate the chemical reactions as they often exhibit activities toward parasitic chemical reactions such as electrolyte and electrode decompositions. The issue is especially acute in aprotic Li–O2 batteries, where organic electrolytes and reactive O2 species are mixed. In addition to heterogeneous catalysts, we also discuss the roles played by homogeneous catalysts as redox mediators, which are effective to promote redox reactions that are critical to energy storage applications.
Millions of micro electro mechanical system sensors are fabricated each year using an ultra-clean process that allows for a vacuum-encapsulated cavity. These devices have a multi-layer structure that contains hidden layers with highly doped silicon, which makes common imaging techniques ineffective. Thus, examining device features post-fabrication, and testing, is a significant challenge. Here, we use a combination of micro- and nano-scale x-ray computed tomography to study device features and assess failure mechanisms in such devices without destroying the ultra-clean cavity. This provides a unique opportunity to examine surfaces and trace failure mechanisms to specific steps in the fabrication process.
We report fabrication of 200 mm silicon (Si)-wafer mold structure for polydimethylsiloxane (PDMS) microfluidic devices to demonstrate a real-time fluorescence imaging of single DNA molecules. Conventional photolithography with deep reactive ion etching process allows us to build a “mesa”-type Si mold with a nanoscallop sidewall geometry aiding PDMS residue-free process. By optimizing fluorescence microscopy with the fabricated PDMS chamber, we obtain a protocol to visualize the motions of single DNA molecules. This integrative PDMS-based single-molecule imaging system can, in principle, be used as a platform to study biochemical reactions occurring in proteins, nucleotides, and vesicles.
Ag deposition-based multicolor electrochromic (EC) device we reported can switch various optical states among transparent, black, silver, cyan, magenta, and yellow by only using electrochemical deposition of Ag. However, the EC device had poor color retention property under open-circuit state because of dissolution of deposited Ag metal by Cu2+ ions, which is essential because it acts as redox material at counter electrode. Here, we introduced an anion exchange membrane to separate Cu2+ from the Ag deposit. The improved device achieved longer retention time of colored state. It is effective to maintain the coloring state without electric power for practical application.
We present classical potential molecular dynamics simulations of nanoporous gold (np-Au) impacted by a spherical indenter. The atomic structure was generated using a phase field model as a template. In agreement with previous experiments, we observe densification in the region under the indenter. The hardness values obtained from our simulations exhibit a transition from an initially perfect-plastic plateau to hardening behavior in the later stages of indentation. This transition occurs when the relative density beneath the indenter exceeds ∼0.9. Hardness values obtained from the nanoindentation simulations reach 0.6 GPa, due to the densification of the material under the indenter. Elevated dislocation densities are observed in the densified region. The mechanism of pore collapse in the densified layer under the indenter is seen to switch from uniaxial to triaxial, consistent with a change in deformation mechanism from one based on shearing of individual ligaments in np-Au to one involving dislocation-mediated plasticity around voids in a Au single crystal undergoing uniaxial compression.
Coupling oxidation type semiconductors is a feasible strategy to improve the photocatalytic activity of reduction type g-C3N4 photocatalysts. In this work, Bi2O3 was used as an oxidation type semiconductor to construct direct Z-scheme Bi2O3/g-C3N4 photocatalysts by a one-step calcination method. The obtained Bi2O3/g-C3N4 composites exhibited excellent photocatalytic activity and stability toward methylene blue degradation under visible light irradiation. The composite with 1% weight content of Bi2O3 to g-C3N4 exhibited the highest photocatalytic activity with an apparent rate constant of 0.063 min−1, which was 3.0 and 3.7 times higher than that of pure Bi2O3 and g-C3N4, respectively. The enhanced photocatalytic activity of the Bi2O3/g-C3N4 composite was mainly attributed to the improved charge separation efficiency and stronger redox ability. This work gave a new insight in developing g-C3N4-based Z-scheme heterojunction photocatalysts with enhanced photocatalytic activity.