State-of-the-art technology: Recent investigations on laser-mediated synthesis of nanocomposites for environmental remediation

In both developing and industrialized/developed countries, various hazardous/toxic environmental pollutants are entering water bodies from organic and inorganic compounds (heavy metals and specifically dyes). The global population is growing whereas the accessibility of clean, potable and safe drinking water is decreasing, leading to world deterioration in human health and limitation of agricultural and/or economic development. Treatment of water/wastewater (mainly industrial water) via catalytic reduction/degradation of environmental pollutants is extremely critical and is a major concern/issue for public health. Light and/or laser ablation induced photocatalytic processes have attracted much attention during recent years for water treatment due to their good (photo)catalytic efficiencies in the reduction/degradation of organic/inorganic pollutants. Pulsed laser ablation (PLA) is a rather novel catalyst fabrication approach for the generation of nanostructures with special morphologies (nanoparticles (NPs), nanocrystals, nanocomposites, nanowires, etc.) and different compositions (metals, alloys, oxides, core-shell, etc.). Laser ablation in liquid (LAL) is generally considered a quickly growing approach for the synthesis and modification of nanomaterials for practical applications in diverse fields. LAL-synthesized nanomaterials have been identified as attractive nanocatalysts or valuable photocatalysts in (photo)catalytic reduction/degradation reactions. In this review, the laser ablation/irradiation strategies based on LAL are systematically described and the applications of LAL synthesized metal/metal oxide nanocatalysts with highly controlled nanostructures in the degradation/reduction of organic/inorganic water pollutants are highlighted along with their degradation/reduction mechanisms.     

Effect of nanostructured grains in co-sputtered Ni-GDC thin-film anode on methane conversion kinetics for low temperature solid oxide fuel cells operating on nearly dry methane

Direct-methane solid oxide fuel cells (DMSOFCs) have recently attracted substantial attention due to their simplified system, reduced cost, and the direct availability of methane fuel obtained from natural gas. Among oxygen-ion conductive materials, doped-ceria such as gadolinium-doped ceria (GDC) or samarium-doped ceria can be incorporated into Ni-based anodes to reinforce their coking resistance, enlarge their electrochemical reaction area, and improve the kinetics of the internal reforming/electrochemical oxidation of methane. To reduce the range of operating temperatures of DMSOFCs while maintaining their performance, the thin film deposition technique of magnetron sputtering was adopted in this work. An Ni-GDC thin-film anode and a Pt thin-film cathode were deposited on scandia-stabilized zirconia (ScSZ) electrolyte supports. This fuel cell was tested with directly supplied methane fuel (3% H₂O) at 500 °C. The results demonstrated the effects of the GDC volume fraction in the anode—which was controlled by co-sputtering power—on open circuit voltage and electrochemical performance. The co-sputtered Ni-GDC anode was able to survive through 36-h operation, although there was some performance degradation. Field-emission scanning electron microscopy results revealed no formation of filamentous carbon on the Ni catalysts, despite the fact that both X-ray photoelectron spectroscopy and Raman spectroscopy analyses detected carbon coking. The relatively high performance and resistance to carbon coking of co-sputtered thin-film anode were attributed to its intrinsic small grain size.     

Co-precipitation of nano Mg–Y/ZrO2 ternary oxide eutectic system: Effects of calcination temperature

In the family of inorganic nanomaterials, zirconia is a highly promising functional ceramic with a high refractive index, hardness, and dielectric constant, as well as excellent chemical inertness and thermal stability. These properties are enhanced in nano-zirconia ceramics, because nanopowders have a small particle size, good morphology, and uniform and dispersive distribution. In this study, a co-precipitation process was proposed to synthesise highly dispersed MgO–Y₂O₃ co-stabilized ZrO₂ nanopowders. The effects of different calcination temperatures on the crystallisation degree and particle dispersion of zirconia nanopowders were characterised by X-ray diffraction (XRD), thermogravimetry-differential scanning calorimetry (TG-DSC), Raman spectroscopy, Fourier transform infrared spectroscopy (FTIR), nitrogen adsorption using the Brunauer–Emmett–Teller (BET) theory, transmission electron microscopy (TEM), and field emission scanning electron microscopy (FESEM). The optimum synthesis conditions were obtained as follows: 6 h of high-energy planetary grinding and calcination at 800 °C in an electric furnace. Under these optimum conditions, the average particle size of the prepared powder was 28.7 nm. This process enriches the literature on the controllable preparation of Mg–Y/ZrO₂ nanopowders obtained by the co-precipitation method.     

Cracking behavior and delamination mechanism of lamellar structured TBC with localized mixed oxides

Mixed oxide (MO) with localized growth feature and high growth rate remarkably affects the lifetime of thermal barrier coatings (TBCs), which indicates that clarifying the ceramic cracking mechanism induced by MO is critical for developing new coatings with high durability. Two kinds of TBC models involving spherical and layered mixed oxides are created to explore the influence of MO growth on the local stress state and crack evolution during thermal cycle. The growth of α-Al₂O₃ is also included in the model. The undulating interface between ceramic coat and bond coat is approximated using a cosine curve. Dynamic ceramic cracking is realized by a surface-based cohesive interaction. The ceramic delamination by simulation agrees with the experimental observation. The effects of MO coverage ratio and growth rate on the TBC failure are also discussed. The results show that the MO growth causes the local ceramic coat to bear the normal tensile stress. The failure mode of coating is turned from α-Al₂O₃ thickness control to MO growth control. Once the mixed oxide appears, local ceramic cracking is easy to occur. When multiple cracks connect, ceramic delamination happens. Suppressing MO formation or decreasing MO growth can evidently improve the coating durability. These results in this work can provide important theoretical guidance for the development of anti-cracking TBCs.     

Fabrication and characterization of In doped Li13.9Sr0.1Zn(GeO4+δ)4 electrolytes for proton-conducting solid oxide fuel cells

Li_13.9Sr_0.1Zn(GeO_4+δ)₄ (LSZG) materials can exhibit proton conduction by Li⁺/H⁺ ion exchange in hydrogen atmosphere. It can be used in solid oxide fuel cells (SOFCs) as an electrolyte. In this study, In³⁺ doped LSZG powders are synthesized by sol-gel method. X-ray diffraction, scanning electron microscopy, thermal gravimetric analyzer, and electrochemical impedance spectroscopy are used to investigate the effects of In doping on LSZG. All Li_13.9-xIn_xSr_0.1Zn(GeO_4+δ)₄ (LISZG, 0 ≤ x ≤ 0.3) ceramics exhibit the same phase with LSZG. The dopant of In promotes the sintering activity and Li⁺/H⁺ ion exchange rate of LSZG. The optimum doping of In is x = 0.2. At 600 °C, Li_13.7In_0.2Sr_0.1Zn(GeO_4+δ)₄ (0.2LISZG) shows a proton conductivity of 0.094 S/cm under 0.9 V direct current bias voltage. In addition, the single cell based on 0.2LISZG electrolyte is prepared, and it has been demonstrated that the practical utilization of 0.2LISZG in IT-SOFCs is feasible.     

Growth mechanism and gas-sensing characteristics of organic-additive-free zinc oxide of various shapes

Zinc oxide is widely used in gas sensors, solar cells, and photocatalysts because of its wide bandgap and exciton binding energy of 60 meV in various metal oxides. To use ZnO as a gas sensor, it is necessary to synthesize it with surface defects and a large specific surface area. In this study, hydrothermal synthesis without surfactants was employed to obtain organic-additive-free ZnO. For morphology control, we varied the ratio of the hydroxide ion concentration to the zinc ion concentration. To confirm the growth mechanism of ZnO, we performed X-ray diffraction, scanning electron microscopy, and transmission electron microscopy analyses. Raman spectroscopy and photoluminescence measurements were performed to analyze the surface properties. The Brunauer–Emmett–Teller method and probe stations were used to measure the specific surface area and sensitivity of the gas sensor, respectively. The results confirmed that flower-shaped ZnO is the most suitable gas-sensing material.     

High ultraviolet transparent conducting electrodes formed using tantalum oxide/Ag multilayer

We investigated the optical and electrical properties of Ta₂O₅/Ag/Ta₂O₅ films as functions of the thicknesses of the Ta₂O₅ and Ag layers. It was found that with an increase in the thicknesses of the Ta₂O₅ and Ag layers from 10 to 40 nm and from 12 to 24 nm, respectively, the sheet resistance, carrier concentration, electron mobility, and resistivity of the Ta₂O₅/Ag/Ta₂O₅ film varied from 2.02 to 8.95 Ω/sq, 5.74 × 10²¹ to 2.92 × 10²² cm^–3, from 13.21 to 24.07 cm²/V·s, and from 8.89 × 10^-6 to 8.24 × 10^-5 Ω cm, respectively. The average transmittance (T_av) of the multilayer samples ranged from 57.18% to 93.99%, and it depended on the Ta₂O₅ and Ag layer thicknesses. The highest T_av of 93.99% was observed for the film with 35 nm thick Ta₂O₅ and 18 nm thick Ag layers, and the peak Haacke's figure of merit (157.04 × 10^–3 Ω^–1) was obtained for 20 nm thick Ta₂O₅ and 21 nm thick Ag layers. Ta₂O₅ (100 nm) and Ta₂O₅/Ag/Ta₂O₅ (20 nm/21 nm/20 nm) samples had optical bandgaps of 4.70 and 4.45 eV, respectively. Film Wizard simulations were conducted to understand the dependence of the transmittance of the multilayer on the thicknesses of the Ta₂O₅ and Ag layers, and phasor analyses were performed to determine how the transmittance of the Ta₂O₅/Ag/Ta₂O₅ (20 nm/21 nm/20 nm) film depended on the Ta₂O₅ layer's thickness.     

Low-temperature constrained sintering of YSZ electrolyte with Bi2O3 sintering sacrificial layer for anode-supported solid oxide fuel cells

Solid oxide fuel cells (SOFCs) have strong potential for next-generation energy conversion systems. However, their high processing temperature due to multi-layer ceramic components has been a major challenge for commercialization. In particular, the constrained sintering effect due to the rigid substrate in the fabrication process is a main reason to increase the sintering temperature of ceramic electrolyte. Herein, we develop a bi-layer sintering method composed of a Bi₂O₃ sintering sacrificial layer and YSZ main electrolyte layer to effectively lower the sintering temperature of the YSZ electrolyte even under the constrained sintering conditions. The Bi₂O₃ sintering functional layer applied on the YSZ electrolyte is designed to facilitate the densification of YSZ electrolyte at the significantly lowered sintering temperature and is removed after the sintering process to prevent the detrimental effects of residual sintering aids. Subsequent sublimation of Bi₂O₃ was confirmed after the sintering process and a dense YSZ monolayer was formed as a result of the sintering functional layer-assisted sintering process. The sintering behavior of the Bi₂O₃/YSZ bi-layer system was systematically analyzed, and material properties including the microstructure, crystallinity, and ionic conductivity were analyzed. The developed bi-layer sintered YSZ electrolyte was employed to fabricate anode-supported SOFCs, and a cell performance comparable to a conventional high temperature sintered (1400 °C) YSZ electrolyte was successfully demonstrated with significantly reduced sintering temperature (<1200 °C).     

Recycling spent lead acid batteries into aqueous zinc-ion battery material with ultra-flat voltage platforms

The harmless disposal of lead paste in the spent lead-acid batteries (LABs) remains an enormous challenge in traditional pyrometallurgical recycling. Here, we introduced a hydrometallurgical method for the recycling of the spent LABs’ waste to obtain the β-PbO as a novel zinc ion batteries (ZIBs) active material. The obtained β-PbO exhibits ultra-flat charge/discharge voltage platforms (0.21 mV/(mAh g^?1)) and stable specific capacity. During the charge/discharge, the β-PbO spontaneously triggers the formation of (ZnSO₄)[Zn(OH)₂]₃·5H₂O (ZHS) micro-sheets as a surface passivation layer. Moreover, the ex-situ X-ray spectra reveal that the reversible phase transformation occurs between PbSO₄ and Pb with the assistance of ZHS by adjusting the PH value on the electrode-electrolyte interface. The synergistic two-phase-reaction mechanism generates ultra-flat voltage platforms upon the charge/discharge. This “energy-saving and environment-friendly” recycling route eliminates the major source of emission of pollution particulates/gases compared to the traditional pyrometallurgical recycling, while at the same time replacing energy-consuming and environmentally detrimental processes of synthesis of current ZIBs cathodes.     

Novel rhombus-shaped cerium oxide sheets as a highly durable methanol oxidation electrocatalyst and high-performance supercapacitor electrode material

In this work, novel rhombus-shaped cerium oxide sheets (RCOS) were prepared using a facile, soft-chemical approach that was low cost, scalable, eco-friendly, and industrially viable. The structural and surface chemical properties were studied using spectroscopic and electron microscopic techniques. The synthesized RCOSs were used for the methanol oxidation reaction and supercapacitor studies. The RCOSs showed a current density of ～227 mA cm^–2 with an onset potential of ～0.37 V. The electrocatalyst activity retention was 92% of the initial activity after 500 CV cycles. A specific capacitance of 481 F g^–1 at a scan rate of 5 mV s^–1 was observed for supercapacitor application. The specific capacitance retention was ～83% after 500 cycles. The huge specific surface area and conductivity associated with cerium oxide sheets were responsible for the enhanced electrochemical properties. This is the first report on the synthesis of rhombus-shaped cerium oxide sheets, which leads to new avenues for synthesizing novel cerium-based electrode materials.