Lanthanide-organic-frameworks modified ZnIn2S4 for boosting hydrogen generation under UV–Vis and visible light

Novel Ln-MOF with microrods shape were successfully combined with ZnIn₂S₄ (ZIS) microsphere and used for photocatalytic hydrogen generation under UV–Vis and visible light. The Ln-MOFs/ZIS system comprises lanthanide-carboxylate coordination networks (Tm and Gd as metal ions, and 1,3,5-benzenetricarboxylic acid (BTC) as the organic linker) deposited on ZnIn₂S₄ microspheres. Effect of the amount of ((Tm,Gd)-BTC) (1, 5, 10 wt%) on the optical properties and photocatalytic hydrogen evolution performance was investigated. ZIS microsphere shows the marigold flower-like morphology and hexagonal polytopic crystal form. Our results proved that the combination of ZIS microsphere, Ln-MOF and Pt nanoparticles (NPs) caused significant enhancement in hydrogen generation. Amount of formed hydrogen was raised from 196.3 to 7782.1 μmol g^?1 for pristine ZIS and ZIS decorated with 1% (Tm, Gd)-BTC/Pt under UV–Vis light, respectively.     

Numerical simulation of water and heat transport in the cathode channel of a PEM fuel cell

Cathode channel of a PEM fuel cell is the critical domain for the transport of water and heat. In this study, a mathematical model of water and heat transport in the cathode channel is established by considering two-phase flow of water and air as well as the phase change between water and vapor. The transport process of the species of air is governed by the convection-diffusion equation. The VOSET (coupled volume-of-fluid and level set method) method is used to track the interface between air and water, and the phase equilibrium method of water and vapor is employed to calculate the mass transfer rate on the two-phase interface. The present model is validated against the results in the literature, then applied to investigate the characteristics of two-phase flow and heat transfer in the cathode channel. The results indicate that in the inlet section, water droplets experience three evolution stages: the growing stage, the coalescence stage and the generation stage of dispersed water drops. However, in the middle and outlet sections of the channel, there are only two stages: the growth of water droplets, and the formation of a water film. The mass transfer rate of phase change in the inlet section of the channel varies over time, exhibiting an initial increase, a decrease followed, and a stabilization finally, with the maximum and stable values of 1.78 × 10^?4 kg/s and 1.52 × 10^?4 kg/s for Part 1, respectively. In the middle and outlet sections, the mass transfer rate increase firstly and then keeps stable gradually. Furthermore, regarding the distribution of the temperature and vapor mass fraction in the channel, near the upper surface of the channel, the temperature and vapor mass fraction first change slightly (x < 0.03 m) and then rapidly decrease with fluctuations (x > 0.03 m). In the middle of the channel, the temperature and vapor mass fraction slowly decrease with fluctuation.     

Nanoraspberry-like palladium/spongy nickel oxide for electrooxidation of five light fuels

The spongy nickel oxide (SNO) was synthesized the solution combustion method. The SNO was selected as a promoter to boost the catalytic activity of nanoraspberry-like palladium (NRPd) toward electrooxidation of five light fuels (LFs): methanol, ethanol, formaldehyde, formic acid, and ethylene glycol. The X-ray powder diffraction, Fourier-transform infrared spectroscopy (FT-IR), scanning electron microscopy, and field emission scanning electron microscope techniques were used for the materials characterization. In comparison with nonpromoted Pd, the NRPd-SNO electrocatalyst shown an excellent efficiency in parameters like the electrochemical active surface area and anti-CO poisoning behavior. The turnover data and the parameters, including reaction order, activation energy, and the coefficients of electron transfer and diffusion, were evaluated for the each process of LFs electrooxidation. The outcome for NRPd-SNO activity toward LFs electrooxidation was compared to some reported electrodes. The SNO increases the removal of intermediates created in the oxidation of LFs that can poison the surface of palladium catalyst. This is due to the presence of the lattice oxygens in SNO structure and Ni switching between its high and low valances. The compatibility of the adsorption process of LFs on the surface of the NRPd-SNO catalyst with different isotherms was determined by studying the Tafel polarization and calculating the surface coverage.     

Fabrication of barium titanate ceramics via digital light processing 3D printing by using high refractive index monomer

A digital light processing (DLP) technology has been developed for 3D printing lead-free barium titanate (BTO) piezoelectric ceramics. By comparing the curing and rheological properties of slurries with different photosensitive monomer, a high refractive index monomer acryloyl morpholine (ACMO) was chosen, and a design and preparation method of BTO slurry with high solid content, low viscosity and high curing ability was proposed. By further selecting the printing parameters, the single-layer exposure time was reduced and the forming efficiency has been greatly improved. Sintered specimens were obtained after a nitrogen-air double-step debinding and furnace sintering process, and the BTO ceramics fabricated with 80 wt% slurry shows the highest relative density (95.32 %) and piezoelectric constant (168.1 pC/N). Furthermore, complex-structured BTO ceramics were prepared, impregnated by epoxy resin and finally assembly made into hydrophones, which has significance for the future design and manufacture of piezoelectric ceramic-based composites that used in functional devices.     

Increasing the photocatalytic and fungicide activities of Ag3PO4 microcrystals under visible-light irradiation

The present study reports for the first time the performance of silver phosphate (Ag₃PO₄) microcrystals as photocatalyst (degradation of Rodamine B-RhB) and antifungal agent (against Candida albicans–C. albicans) under visible-light irradiation (455 nm). Ag₃PO₄ microcrystals were synthesized by a simple co-precipitation (CP) method at room temperature. The structural and electronic properties of the as-synthetized Ag₃PO₄ have been investigated before and after 4 cycles of RhB degradation under visible light using X-ray diffraction (XRD), micro-Raman spectroscopy, UV–Vis spectrophotometer and field emission scanning electron microscopy (FE-SEM) images. The antifungal activity was analyzed in planktonic cells and 48h-biofilm of C. albicans by colony forming units (CFU) counting, confocal laser and FE-SE microscopies. Statistical analysis was carried out using SPSS software. Morphological and structural modifications of Ag₃PO₄ were observed upon recycling. After 4 recycles, the material maintained its photodegradation property; an eightfold increase in the efficiency of Ag₃PO₄ was observed in planktonic cells and a two fold increase in biofilm when irradiated under visible light. Thus, higher antifungal effectiveness against C. albicans was obtained when associated with visible-light irradiation.     

一种家用手持式红外偏振光治疗仪的设计与实现

红外偏振光治疗仪是一种将红外技术与电子技术应用到医学领域的康复理疗设备,主要用于软组织损伤和慢性疼痛的康复治疗,已在医院得到了推广使用。然而,现有医院使用的台式治疗仪由于体积大、售价高等特点,不方便居家使用。为了开发体积小、售价低、家庭可用的红外偏振光治疗仪,满足家用市场的潜在需求,本文提出了一种新的便携手持式红外偏振光治疗仪,并开发了该智能控制系统。本文首先介绍了一种新的家用手持式治疗仪应具备的特点和关键技术指标,在此基础上设计了手持式治疗仪的硬件总体方案和软件架构,简要介绍了该治疗仪的一些关键技术,最终实现了治疗仪样机的研制。为了验证该样机的性能,本文通过大量的测试,结果表明,研制的手持式红外偏振光治疗仪在关键参数指标上达到了医院同类产品的水平,能够很好地满足家用的需求,具有良好的市场前景。     

Mg0.5NixZn0.5-xFe2O4 spinel as a sustainable magnetic nano-photocatalyst with dopant driven band shifting and reduced recombination for visible and solar degradation of Reactive Blue-19

Focussing on visible light active ferrites for high performance removal of noxious pollutants, we report the synthesis of Mg_0.5Ni_xZn_0.5-xFe₂O₄ (x = 0.1, 0.2, 0.3, 0.4, & 0.5) ferrite nanoparticle for degradation of reactive blue-19 (RB-19). Lattice parameters calculated using intense X-ray diffraction (XRD) peaks and Nelson-Riley plots (N-R plot) are in well agreement with each other. The sample Mg_0.5Ni_0.4Zn_0.1Fe₂O₄ (M5N4) exhibits best performance with 99.5% RB-19 degradation in 90 min under visible light. Photoluminescence (PL) results confirm that recombination of charge carriers is highly reduced in the photocatalyst. Scavenging experiments suggest that O₂⁻ radicals were the dominant species responsible for photocatalytic performance. The photocatalytic mechanism was explained in terms of dopant driven shifting of conduction bands and valence bands (calculated by Mott-Schottky plots). The thermodynamic probability of radical generation along with role of redox cycles of metal ions has been discussed in the mechanism. The dye degradation was ascertained by detection of intermediates via mass spectrometry analysis and a possible degradation route was also predicted. The findings in this work provide intriguing opportunities to modify the electronic band structure of spinel ferrites for visible and solar light photocatalytic activity for environmental detoxification.     

Warm-white light performance of Dy3+, Eu3+: NaLa(WO4)2 phosphors excited with a 450-nm LED

Dy³⁺, Eu³⁺: NaLa(WO₄)₂ phosphors are successfully synthesized through the solid-state reaction technique. The phase-structure and morphology are measured via X-ray diffraction and energy dispersive spectrometry. The concentrations of Dy³⁺, Eu³⁺, La³⁺, and W⁶⁺ are measured via ICP. The absorption and excited spectra are presented, which indicate that a blue band ranging from 430 to 480 nm is suitable for excitation. Using a commercial blue LED with a wavelength of 450 nm as the excitation light source, emission spectra for samples with varying dopant concentration ratios of Dy³⁺ to Eu³⁺ are obtained, which show good tunable yellow and red emission. For the purpose of investigating white LED performance, CIE spectra and a white light photo are also presented. The results reveal that varying the dopant concentration ratio of Dy³⁺ to Eu³⁺ plays a key role in the warm-white performance. With increasing concentration of Eu³⁺, the correlated color temperature decreases from 4069 to 3172 K, which indicates good warm-white performance.     

High-resolution FIB-TEM-STEM structural characterization of grain boundaries in the high dielectric constant perovskite CaCu3Ti4O12

In this work, the grain boundaries composition of the polycrystalline CaCu₃Ti₄O₁₂ (CCTO) was investigated. A Focused Ion Beam (FIB)/lift-out technique was used to prepare site-specific thin samples of the grain boundaries interface of CCTO ceramics. Scanning transmission electron microscopy (STEM) coupled with energy dispersive X-ray spectrometry (EDXS) and Electron Energy Loss Spectroscopy (EELS) systems were used to characterize the composition and nanostructure of the grain and grain boundaries region. It is known that during conventional sintering, discontinuous grain growth occurs and a Cu-rich phase appears at grain boundaries. This Cu-rich phase may affect the final dielectric properties of CCTO but its structure and chemical composition remained unknown. For the first time, this high-resolution FIB-TEM-STEM study of CCTO interfacial region highlights the composition of the phases segregated at grain boundaries namely CuO, Cu₂O and the metastable phase Cu₃TiO_4.     

Preparation and physical properties of the layered niobate Cu0.5Nb3O8: Application to photocatalytic hydrogen evolution

The new layered niobate Cu_0.5Nb₃O₈ is synthesized by soft chemistry in aqueous electrolyte via Cu²⁺→H⁺ exchange between copper nitrate and HNb₃O₈·H₂O. The characterization of the exchanged product is made by means of thermal gravimetry, chemical analysis, X-ray diffraction and IR spectroscopy. Thermal analysis shows a conversion to anhydrous compound above 500 °C. The oxide displays a semiconductor like behavior; the thermal variation of the conductivity shows that d electrons are strongly localized and the conduction is thermally activated with activation energy of 0.13 eV. The temperature dependence of the thermopower is indicative of an extrinsic conductivity; the electrons are dominant carriers in conformity with an anodic photocurrent. Indeed, the Mott–Schottky plot confirms n-type conduction from which a flat band potential of −0.82 V_SCE, an electronic density of 8.72×10¹⁹ m⁻³ and a depletion width of 4.4 nm are determined. The upper valence band, located at ~5.8 eV below vacuum is made up predominantly of Cu²⁺: 3d with a small admixture of O²⁻: 2p orbitals whereas the conduction band consists of empty Nb⁵⁺: 5s level. The energy band diagram shows the feasibility of the oxide for the photocatalytic hydrogen production upon visible light (29 mW cm⁻²) with a rate evolution of 0.31 mL g⁻¹ min⁻¹.