Effects of particle size and polymorph type of TiO2 on the properties of BaTiO3 nanopowder prepared by solid-state reaction.

Barium titanate (BaTiO3) has attracted considerable attention as a perovskite ferroelectric ceramic material for electronic multilayer ceramic capacitors (MLCCs). Fine BaTiO3 nanopowders with a considerably high tetragonality directly influence the typical properties of nanopowders; however, their synthesis has remained challenging. In this study, we analyzed the effect of two different TiO2 powders with anatase and rutile phases in a solid-state reaction with barium carbonate (BaCO3). The effect of the particle size ratio (TiO2/BaCO3) of the raw materials on the tetragonality and particle size of the as-synthesized BaTiO3 powders was also determined through extensive characterization of the powders by X-ray diffraction, field-emission scanning electron microscopy, and Raman spectroscopy. The present investigation reveals that the design BaTiO3 structure is expected to advance the development of efficient catalytic and sensor materials for sustainable environmental applications.

Solvent-mediated synthesis of BiOI with a tunable surface structure for effective visible light active photocatalytic removal of Cr(VI) from wastewater.

The present study investigated the effect of various solvents on the tunable surface morphology and photocatalytic activity (PCA) of bismuth oxyiodide (BiOI), which could be used for the reduction of Cr(VI) under visible light irradiation (VLI). BiOI samples exhibiting different morphologies, i.e., two-dimensional square-like nanosheet and three-dimensional hierarchical flower-like morphology, were synthesized by a hydro/solvothermal process using different solvents, namely H2O, MeOH, EtOH, and ethylene glycol (EG). The crystal structure, surface morphology, surface area, light-absorption capability, and recombination rate of the photogenerated charge carriers were examined by X-ray diffraction, scanning electron microscopy, Brunauer-Emmett-Teller analysis, UV-vis diffuse reflectance spectroscopy, photoluminescence, and transient photocurrent analyses, respectively. The BiOI sample fabricated in EG showed excellent photocatalytic efficiency (~99%) for the reduction of Cr(VI) after 90 min under VLI. The enhanced PCA demonstrated that the high surface area and well-structured surface characteristics of flower-like 3D BiOI microspheres played important roles in the photoreduction process. Moreover, a plausible mechanism for the reduction of Cr(VI) over the EG-BiOI photocatalyst was proposed. The results of the PCA evaluation and recycle test revealed that 3D EG-BiOI microspheres could serve as promising materials for the efficient removal of Cr(VI) from wastewater. Additionally, EG-BiOI could be utilized in other environmental remediation processes.

Colorimetric Detection of UO2+2 Using Gold Nanoparticles Immobilized with Pillar[5]arene Complexes with Nitrophenyldiacetic Acids as a Chemoprobe.

Uranium is a crucial raw material in the nuclear energy industry; however, its radioactive nature makes it a critically damaging component to both the atmosphere and human health. In this study, we report a simple and cost-effective selective colorimetric detection technique for UO2+2 using nitrophenyldiacetic acids (NPD)-functionalized gold nanoparticles (Au NPs 1). The hybrid Au NPs 1 can be induced to aggregate in the presence of UO2+2 ions. UO2+2 can be recognized by the colorimetric response of hybrid Au NPs 1, which can be observed by a UV-Vis spectrophotometer and it is easily detectable by the naked eye. The hybrid Au NPs 1 bound by UO2+2 possess a good selective response compared to other metal ions (Li+, Na+, K+, Rb+, Cs+, Ca2+, Mg2+, Ba2+, Ni2+, Zn2+, and Co2+), which can be observed by a prominent color change. The color of the hybrid Au NPs 1 changed from red to dark red upon addition of UO2+2 in the presence of other metal ions. Job's plot demonstrates that one NPD moiety attached onto the surface of Au NPs 1 forms 1:1 stoichiometry with UO2+2, hence providing a simple and effective colorimetric sensor for the real-time detection of UO2+2.

Enhanced photocatalytic degradation of lindane using metal-semiconductor Zn@ZnO and ZnO/Ag nanostructures.

To achieve enhanced photocatalytic activity for the degradation of lindane, we prepared metal-semiconductor composite nanoparticles (NPs). Zn@ZnO core-shell (CS) nanocomposites, calcined ZnO, and Ag-doped ZnO (ZnO/Ag) nanostructures were prepared using pulsed laser ablation in liquid, calcination, and photodeposition methods, respectively, without using surfactants or catalysts. The as-prepared catalysts were characterized by using X-ray diffraction (XRD), field-emission scanning electron microscopy, high-resolution transmission electron microscopy, ultraviolet-visible (UV-vis) spectroscopy, and photoluminescence spectroscopy. In addition, elemental analysis was performed by energy dispersive X-ray spectroscopy. The obtained XRD and morphology results indicated good dispersion of Zn and Ag NPs on the surface of the ZnO nanostructures. Investigation of the photocatalytic degradation of lindane under UV-vis irradiation showed that Zn@ZnO CS nanocomposites exhibit higher photocatalytic activity than the other prepared samples. The maximum degradation rate of lindane was 99.5% in 40min using Zn@ZnO CS nanocomposites. The radical trapping experiments verified that the hydroxyl radical (·OH) was the main reactive species for the degradation of lindane.

Production of size controlled aluminum and alumina nanoparticles via pulsed laser ablation in water.

An Al metal plate was ablated by a pulsed Nd-YAG laser to produce nano-structured Al and gamma-Al2O3 in deionized water in the absence of any surfactants or catalysts. In this study, the mean diameter and the width of size distribution of the nanoparticles was influenced by the laser power, resulting in the production of smaller and larger sizes of nanoparticles with higher and lower laser power, respectively. The influence of laser power on the mean diameter and the width of size distribution of as-prepared nanoparticles generated by the laser ablation process was explained by the space homogeneity of the plasma plume, where the nucleation of nanoparticles has occurred. Further explanations of the influence of laser power on the size distribution are proposed. Furthermore, structural and morphological characterization of aluminum and gamma-Al2O3 nanoparticles was conducted by X-ray diffraction (XRD) and field emission scanning electron microscope (FE-SEM).

Silane-treated BaTiO3 ceramic powders for multilayer ceramic capacitor with enhanced dielectric properties.

Silane/ceramic combination provides the composites with several advantages from the advancements of new ceramic composite materials with good thermal conductivity, high mechanical and dielectric properties have wide significant applications in electrical and electronic industries. In this study, to enhance the dispersibility of dielectric barium titanate (BaTiO3) ceramic powder and additives for the fabrication of multilayer ceramic capacitors (MLCCs), surface treatment of the precursor of ceramic powder was performed using silane coupling agents. Dielectric ceramic sheets fabricated from ceramic powders that had been surface-treated with different amounts of N-[3-(trimethoxysilyl)propyl]aniline (TMSPA) which increased the surface gloss. In particular, the dielectric properties of the multilayer ceramic sheet fabricated by stacking sheets from the TMSPA-treated ceramic powder sintering at 1200 °C, it was confirmed that the dielectric constant increased from 881 to 2382 and the dielectric loss dropped from 1.96 to 1.34% with utilization of the TMSPA treatment. The physical and dielectric properties of the TMSPA-treated multilayer ceramic sheet were also determined by Fourier-transform infrared spectroscopy, X-ray diffraction, field-emission scanning electron microscopy, glossmetry, and electrochemical impedance analysis. The results revealed that the TMSPA-modified BaTiO3 surfaces considerably increased the dielectric property of the fabricated nanocomposite.

Optical Manipulation of Incident Light for Enhanced Photon Absorption in Ultrathin Organic Photovoltaics.

We attempted to improve the photon absorption of the photoactive layer in organic photovoltaic (OPV) devices by device engineering without changing their thickness. Soft nanoimprinting lithography was used to introduce a 1D grating pattern into the photoactive layer. The increase in photocurrent caused by the propagating surface plasmon-polariton mode was quantitatively analyzed by measuring the external quantum efficiency in transverse magnetic and transverse electric modes. In addition, the introduction of an ultrathin substrate with a refractive index of 1.34 improved photon absorption by overcoming the mismatched optical impedance at the air/substrate interface. As a result, the power conversion efficiency (PCE) of an ultrathin OPV with a 400 nm grating period was 8.34%, which was 11.6% higher than that of an unpatterned ultrathin OPV, and the PCE was 3.2 times higher at a low incident light angle of 80°, indicating very low incident light angle dependence.

Production of copper nanoparticles exhibiting various morphologies via pulsed laser ablation in different solvents and their catalytic activity for reduction of toxic nitroaromatic compounds.

Comparative experiments were conducted to determine the effects of various solvents (i.e., deionized water, methanol, ethanol, 1-propanol, butanol, ethylene glycol, hexane, and acetonitrile) on the final compositions, morphologies, and catalytic activities of copper-based nanoparticles (NPs). The NPs were effectively synthesized by pulsed laser ablation (PLA) using a copper plate as the target. The obtained copper NPs were characterized utilizing various analytical techniques. It was established that the developed methodology allows for the production of NPs with different morphologies and compositions in a safe and simple manner. When laser ablation of a solid copper plate was performed in acetonitrile, the formation of copper(I) cyanide cubes was observed. On the other hand, in deionized water and methanol, spherical and rod-like particles of copper(I) and copper(II) oxide were detected, respectively. The catalytic activity of the prepared copper NPs in the reduction of aromatic nitro compounds, such as 4-nitrophenol and nitrobenzene, was also evaluated. A high k value was determined for the reduction over the copper(II) oxide NPs produced in methanol. Moreover, particles with graphitic carbon (GC) layers exhibited superior catalytic performance in the reduction of a hydrophobic substance, i.e., nitrobenzene, over the reduction of 4-nitrophenol. The enhanced catalytic activity of this catalyst may be due its unique surface morphology and the synergistic effects between the copper nanostructure and the GC layer. Lastly, a detailed reduction pathway mechanism for the catalytic reduction of 4-nitrophenol and nitrobenzene has been proposed.

Method development and mechanistic study on direct pulsed laser irradiation process for highly effective dechlorination of persistent organic pollutants.

Chlorine-based compounds are typical persistent organic pollutants (POPs) that are widely generated in industrial production. This paper reports an effective and rapid pulsed laser irradiation technique for the dechlorination of hexachlorobenzene (HCB), a model pollutant, without additional catalysts or supports. The effects of the laser parameters, including the laser wavelength and power, on the dechlorination efficiency, were also investigated. The optimized results showed that a lower laser wavelength of 266 nm with 10 mJ/pulse power exhibited the highest dechlorination efficiency with 95% within 15 min. In addition, the laser beam effect was examined by designing the direct-pulsed laser single and multipath irradiation system. The results showed that improving the laser beam profile resulted in more than 95% dechlorination efficiency within 5 min. Thus, the dechlorination reaction proceeded much faster as the surface area that the laser beam came in contact with increased due to the multipath system than the single pathway. Gas chromatography identified benzene as the final product of HCB with pentachlorobenzene (PCB), tetrachlorobenzene (TeCB), trichlorobenzene (TCB), dichlorobenzene (DCB), and chlorobenzene (CB) as intermediate products. The mechanism of HCB dechlorination was explained by a comparison of theoretical calculations with the experimental results. The present study reports an advanced technique for the complete dechlorination of chlorobenzenes, which holds great application potential in environmental remediation.

Plasmonic ZnO/Au/g-C3N4 nanocomposites as solar light active photocatalysts for degradation of organic contaminants in wastewater.

In the present study, novel ZnO/Au/graphitic carbon nitride (g-C3N4) nanocomposites were fabricated via a facile and eco-friendly liquid phase pulsed laser process followed by calcination. Notably, the approach did not necessitate the use of any capping agents or surfactants. The as-prepared photocatalysts were evaluated by various electron microscopy and spectroscopy techniques. The obtained results confirmed good dispersion of the Au nanoparticles (NPs) on the surface of spherical ZnO particles deposited on the g-C3N4 nanosheets. The ZnO/Au/g-C3N4 nanocomposite exhibited substantially enhanced catalytic activity toward the degradation of methylene blue (MB) under simulated solar light irradiation. In particular, the ZnO/Au15/g-C3N4 composite containing 15 wt% Au displayed a rate constant, which was approximately 3 and 5 times greater than those of pristine g-C3N4 and ZnO, respectively. This improved photocatalytic activity of ZnO/Au15/g-C3N4 was attributed to the surface plasmon resonance of Au NPs and the synergistic effects between ZnO and g-C3N4. The boundary between ZnO/Au and g-C3N4 enabled direct migration of the photogenerated electrons from g-C3N4 to ZnO/Au, which hindered the recombination of electron-hole pairs and enhanced the carrier separation efficiency. Additionally, a plausible MB degradation mechanism over the ZnO/Au/g-C3N4 photocatalyst is proposed based on the results of the conducted scavenger study.

Efficient recovery of palladium nanoparticles from industrial wastewater and their catalytic activity toward reduction of 4-nitrophenol.

Discharge of heavy metals from various sources of industrial wastewater poses significant environmental and health concerns. Thus, efficient recovery of precious metals from wastewater employing sustainable, rapid, and cost-effective treatment methods is highly desirable. In this work, palladium nanoparticles (Pd NPs) were successfully recovered from industrial wastewater using a pulsed laser process in the absence of additives or reducing agents. Notably, the developed approach is faster and more environmentally friendly than other conventional recovery methods. The recovered Pd NPs were characterized by X-ray powder diffraction (XRD), field emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM), and inductively coupled plasma optical emission spectroscopy (ICP-OES). Various pulsed laser parameters (i.e., laser wavelength, power, and irradiation time) were optimized to obtain ideal conditions for the pulsed laser ablation process. Effective recovery of the Pd metal from industrial wastewater was achieved at a laser wavelength of 355 nm, power of 40 mJ/pulse, and irradiation time of 30 min. The Pd NPs exhibited excellent catalytic activity toward the reduction of 4-nitrophenol. Thus, the recovered materials showed remarkable potential for application in degradation of toxic aromatic nitro compounds in the environment.

In-situ thermal phase transition and structural investigation of ferroelectric tetragonal barium titanate nanopowders with pseudo-cubic phase.

Optimization and miniaturization of existing electronic devices require the development of advanced nanostructured materials with high phase and structural purity. Over the past decade, barium titanate (BaTiO3) has attracted considerable attention due to its outstanding ferroelectric and dielectric properties. The present study involved the investigation of the phase transition and structural stability of tetragonal BaTiO3 nanopowders with pseudo-cubic phase using an in-situ high resolution and high temperature X-ray diffraction method. Under ambient conditions, the coexistence the tetragonal and cubic phases with weight fractions of 75.7% and 24.3%, respectively, was determined in BaTiO3. In the temperature range of 25 °C-300 °C, phase boundaries of BaTiO3 (180 nm in size) exhibiting several phases were detected. The phase transformation behavior, relative crystal phase content, lattice parameters, crystallite size, and tetragonality of the BaTiO3 nanopowders were established by the Rietveld refinement method at the onset temperature from 25 °C to 300 °C. Up to 150 °C, the nanopowders exhibited a complete transition of the cubic phase. Additionally, a complete tetragonal to cubic transformation was accomplished by a decrease of tetragonality at 125 °C and an increase in the crystallite size at 300 °C.

Enhanced dechlorination of m-DCB using iron@graphite/palladium (Fe@C/Pd) nanoparticles produced by pulsed laser ablation in liquid.

In this work, the zero valent Fe (ZVI) and graphite-encapsulated Fe (Fe@C) nanoparticles (NPs) were easily and selectively prepared by a pulsed laser ablation (PLA) method in an aqueous sodium borohydride solution and ascorbic acid dissolved in methanol, respectively. Here, the Fe@C NPs were uniquely synthesized by PLA in methanol, where the solvent is used as both a carbon source for the graphitic layers and solvent, which is very unique. Furthermore, Pd NPs were loaded onto the surface of the Fe@C NPs to prepare bimetallic (Fe@C/Pd) NPs for the enhancement of the degradation efficiency of m-dichlorobenzene (m-DCB). The morphology, crystallinity, and surface composition of the prepared NPs were carefully characterized by high-resolution transmission electron microscopy (HRTEM), energy dispersive x-ray spectrometer (EDS), X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS). The degradation rate of m-DCB using single (Fe and Pd) or bimetallic (Fe/Pd and Fe@C/Pd) NPs were compared by using gas chromatography. Among these NPs produced in this work, the Fe@C/Pd NPs with 1.71 wt % of Pd showed an excellent dechlorination efficiency for m-DCB with 100% degradation within 75 min. The graphitic layer on the Fe NPs played as not only an oxidation resistant for the Fe NPs to surroundings, but also a supporter of the Pd NPs for the enhanced degradation efficiency of m-DCB.