Synergistic enhancement of Zn-air battery performance via integration of Ni-doped cobalt sulfide nanoparticles within N, S-doped carbon matrix.

Exploring precious metal-free bifunctional electrocatalysts for both the oxygen reduction reaction (ORR) and the oxygen evolution reaction (OER) is essential for the practical application of rechargeable Zn-air battery (ZAB). Herein, Ni-doped Co9S8 nanoparticles embedded in a defect-rich N, S co-doped carbon matrix (d-NixCo9-xS8@NSC) are synthesized via a facile pyrolysis and acid treatment process. The introduction of abundant defects in both the carbon matrix and metal sulfide provides numerous active sites and significantly enhances the electrocatalytic performances for both the ORR and OER. d-NixCo9-xS8@NSC exhibits a superior half-wave potential of 0.841 V vs. RHE for the ORR and delivers a low overpotential of 0.329 V at 10 mA cm-2 for the OER. Additionally, Zn-air secondary battery using d-NixCo9-xS8@NSC as the air cathode displays a higher specific capacity of 734 mAh gZn-1 and a peak power density of 148.03 mW cm-2 compared to those of state-of-the-art Pt/C-RuO2 (673 mAh gZn-1 and 136.9 mW cm-2, respectively). These findings underscore the potential of d-NixCo9-xS8@NSC as a high-performance electrocatalyst for secondary ZABs, offering new perspectives on the design of efficient noble metal-free electrocatalysts for future energy storage and conversion applications.

Mitigation of Silicon Contamination in Fuel Cell Gasket Materials through Silica Surface Treatment.

Gaskets and seals are essential components in the operation of proton exchange membrane (PEM) fuel cells and are required for keeping hydrogen and air/oxygen within their individual compartments. The durability of these gaskets and seals is necessary, as it influences not only the lifespan but also the electrochemical efficiency of the PEM fuel cell. In this study, the cause of silicon leaching from silicone gaskets under simulated fuel cell conditions was investigated. Additionally, to reduce silicon leaching, the silica surface was treated with methyltrimethoxysilane, vinyltriethoxysilane, and (3,3,3-trifluoropropyl)trimethoxysilane. Changes in the silica surface chemistry were investigated by scanning electron microscopy, energy dispersive X-ray spectroscopy, thermogravimetric analysis, elemental analysis, X-ray photoelectron spectroscopy, and Fourier transform infrared spectroscopy. Inductively coupled plasma-optical emission spectroscopy analysis revealed that surface-treated silica was highly effective in reducing silicon leaching.

Hollow-structured cobalt sulfide electrocatalyst for alkaline oxygen evolution reaction: Rational tuning of electronic structure using iron and fluorine dual-doping strategy.

Utilizing renewable electricity for water electrolysis offers a promising way for generating high-purity hydrogen gases while mitigating the emission of environmental pollutants. To realize the water electrolysis, it is necessary to develop highly active and precious metal-free electrocatalyst for oxygen evolution reaction (OER) which incurs significant overpotential due to its complicated four-electron transfer mechanism. Hence, we propose a facile preparation method for hollow-structured Fe and F dual-doped CoS2 nanosphere (Fe-CoS2-F) as an efficient OER electrocatalyst. The uniform hollow and porous structure of Fe-CoS2-F enlarge the specific surface area and increase the number of exposed active sites. Furthermore, the Fe and F dual-dopants synergistically contributed to the adjustment of electronic structure, thereby promoting the adsorption/desorption of oxygen-containing reaction intermediates on active sites during the alkaline OER procedure. As a result, the prepared Fe-CoS2-F exhibits outstanding OER activity, characterized by a low overpotential of 298 mV to achieve a current density of 10 mA cm-2 and a Tafel slope as small as 46.0 mV dec-1. Based on computational theoretical calculations, the introduction of the dual-dopants into CoS2 structure reduce the excessively strong adsorption energy of reaction intermediate in the rate determining step, leading to effectively promoted electrocatalytic cycle for OER in alkaline environment. This study presents an effective strategy for preparing noble metal-free OER electrocatalysts with promising potential for large-scale industrial water electrolysis.

Regulating the electronic structure of Ni2P by one-step Co, N dual-doping for boosting electrocatalytic performance toward oxygen evolution reaction and urea oxidation reaction.

The development of efficient bifunctional electrocatalysts for oxygen evolution reaction (OER) and urea oxidation reaction (UOR) is critical for hydrogen production and wastewater purification. In this work, we propose a facile synthetic method for Co and N dual-doped Ni2P directly grown on Ni foam (Co-Ni2P-N/NF) using hydrothermal and annealing process. Simultaneous Co and N dual-doping into Ni2P not only modifies the surface electronic structure, but also generates a multitude of active sites with high valence states, which are beneficial for improving electrocatalytic kinetics for both OER and UOR. As a result, the Co-Ni2P-N/NF catalyst exhibits a low overpotential of 329 mV to deliver a current density of 100 mA cm-2 for OER in alkaline solution, which is much lower than that of the state-of-the-art RuO2 electrocatalyst. In addition, the urea-assisted water oxidation process exhibits a significant reduction of approximately 163 mV in the required potential at 100 mA cm-2 compared to that of the OER, which highlights the remarkable potential of the prepared Co-Ni2P-N/NF electrocatalyst in facilitating the purification of wastewater and hydrogen production with significantly lower energy consumption.

Improvement of Heat Resistance of Fluorosilicone Rubber Employing Vinyl-Functionalized POSS as a Chemical Crosslinking Agent.

Fluorosilicone rubber (F-LSR) is a promising material that can be applied in various cutting-edge industries. However, the slightly lower thermal resistance of F-LSR compared with that of conventional PDMS is difficult to overcome by applying nonreactive conventional fillers that readily agglomerate owing to their incompatible structure. Polyhedral oligomeric silsesquioxane with vinyl groups (POSS-V) is a suitable material that may satisfy this requirement. Herein, F-LSR-POSS was prepared using POSS-V as a chemical crosslinking agent chemically bonded with F-LSR through hydrosilylation. All F-LSR-POSSs were successfully prepared and most of the POSS-Vs were uniformly dispersed in the F-LSR-POSSs, as confirmed by Fourier transform infrared spectroscopy (FT-IR), proton nuclear magnetic resonance spectroscopy (1H-NMR), scanning electron microscopy (SEM), and X-ray diffraction (XRD) measurements. The mechanical strength and crosslinking density of the F-LSR-POSSs were determined using a universal testing machine (UTM) and dynamic mechanical analysis (DMA), respectively. Finally, differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA) measurements confirmed that the low-temperature thermal properties were maintained, and the heat resistance was significantly improved compared with conventional F-LSR. Eventually, the poor heat resistance of the F-LSR was overcome with three-dimensional high-density crosslinking by introducing POSS-V as a chemical crosslinking agent, thereby expanding the potential fluorosilicone applications.

Lipase-based MIL-100(Fe) biocomposites as chiral stationary phase for high-efficiency capillary electrochromatographic enantioseparation.

A novel chiral porous column was fabricated by lipase immobilized MIL-100(Fe) biocomposites as chiral stationary phase through covalent coupling and applied to capillary electrochromatographic enantioseparation. MOF-based lipase biocomposites not only enhance stereoselective activities but also improve the stability and applicability of the enzyme. The functionalized porous columns were characterized by Fourier transform infrared spectroscopy, scanning electron microscopy, and powder X-ray diffraction. The performance of the porous column was evaluated by enantioseparating amino acid enantiomers, affording high resolution over 2.0. Besides, the enantio-resolutions of phenylephrine, phenylsuccinic acid, chloroquine, and zopiclone were also greater than 2.0. The relative standard deviations of run-to-run, intra-, and inter-day repeatability were within 4.0% in terms of resolution and retention time, exhibiting excellent stability of the column. Conceivably, the results show that MOF-based lipase composites as chiral stationary phase offer a highly efficient means for enantioseparation in capillary electrochromatography, attributing to the enhanced enantioselective activities of lipase by highly ordered frameworks.

Effect of the Particle Size and Layer Thickness of GNP Fillers on the Dielectric Properties and Actuated Strain of GNP-PDMS Composites.

Dielectric elastomer actuators (DEAs), a type of electroactive polymers (EAPs), are smart materials that are used in various fields such as artificial muscles and biomimetic robots. In this study, graphene nanoplatelets (GNPs), which are conductive carbon fillers, were added to a widely used DEA, namely, polydimethylsiloxane (PDMS), to improve its low actuated strain. Four grades of GNPs were used: H5, H25, M5, and M25 (here, the number following the letter indicates the average particle size of the GNPs in µm). The average layer thickness of the H grade is 13−14 nm and that of the M grade is 5−7 nm. PDMS composites were prepared by adding 0.5, 1, 2, and 3 wt% of each GNP, following which the mechanical properties, dielectric properties, and actuated strain of the composites were measured. The mechanical properties were found to increase as the particle size increased. Regarding the dielectric characteristics, it was found that the higher the aspect ratio of the filler, the easier the formation of a micro-capacitor network in the composite­this led to an increase in the dielectric constant. In addition, the higher amounts of GNPs in the composites also led to an increase in the dielectric constant. For the actuated strain analysis, the electromechanical sensitivity was calculated using the ratio of the dielectric constant to the Young's modulus, which is proportional to the strain. However, it was found that when the loss tangent was high, the performance of the actuated strain decreased owing to the conversion of electric energy into thermal energy and leakage current loss. As a result, the highest actuated strain was exhibited by the M25 composite, with an actuated strain value of 3.01% measured at a low electric field (<4 kV/mm). In conclusion, we proved that the GNP−PDMS composites with a thin layer and large particle size exhibited high deformation.

Deciphering van der Waals interaction between polypropylene and carbonated fly ash from experimental and molecular simulation.

Pollution emitted from power plants, including a considerable amount of fly ash (FA) and carbon dioxide (CO2), annually increases and is challenging from an environmentally friendly and sustainable point of view. To date, laboratory-scaled approaches cannot efficiently replace the FA-landfilling and mitigate the stress from CO2 emission. Here, a practically operatable fundamental work by combining carbonated FA (C-FA)-immobilizing CO2 in FA-and polypropylene (PP) matrix is reported and reveals abnormal mechanical and thermal features clarified by calculating van der Waals (vdW) interaction from an atomic scale. This is the first study wherein the interaction between instantaneous dipole moment-induced PP and fillers is simulated and examined. The vdW interactions at the (hetero)interfaces are -59.66, -82.30, and -224.39 kJ mol-1 Å-2 for PP, calcium oxide (CaO; before carbonation), and calcium carbonate (CaCO3; after carbonation), respectively, which provides concrete theoretical support for interesting findings such as the independence of tensile strength on filler loadings and "well-grown" interface-induced higher conductivity characteristics of the composites. Therefore, this work can offer practical solutions to mitigate pollution, provide a new perspective on fundamental physical interactions, and guide the development of practical next-generation composite materials.

Valorization of fly ash as a harmless flame retardant via carbonation treatment for enhanced fire-proofing performance and mechanical properties of silicone composites.

Owing to the environmental and economic problems arising from fly ash (FA), there have been various ongoing efforts over the past decades to find a use for it. Among the various applications of FA, its use as a filler in polymer composites has gained much attention. However, most studies have applied FA as a semi-reinforcing filler, which only marginally improves mechanical properties arising from the poor surface wettability of FA with polymer matrices. To solve this problem and to explore new applications, FA was carbonated by bubbling CO2 in water in this study. The carbonated FA was adopted as a fire-proofing filler in silicone rubber (SR). The surface properties and compositional changes of FA by carbonation were thoroughly examined. Mechanical and thermal properties of carbonated FA-filled SR were evaluated. In particular, the gas torch test confirmed that the carbonation of FA increased the penetration time of SR composites by 11%. In addition, the penetration time of the carbonated FA-filled SR composite was 2-3 times greater than that of the composites filled with commercially available fillers.

A palladium complex confined in a thiadiazole-functionalized porous conjugated polymer for the Suzuki-Miyaura coupling reaction.

Porous organic polymers (POPs) with well-distributed and tunable functional groups acting as ligands for specific reactions are promising supports for confining useful novel metals such as Pd, Au, and Pd. Herein, a thiadiazole-containing POP has been successfully synthesized and used for immobilizing Pd species. Pd immobilized inside the micropores (2.3 nm) of the POP material is easily prepared owing to a large amount of the strong anchoring group, thiadiazole, which is intrinsically distributed in the as-prepared POP. The rigid thiadiazole-containing polymer can stabilize the central metal rather than poisoning it. The as-prepared catalyst shows excellent catalytic activity in Suzuki-Miyaura coupling reactions under mild reaction conditions and low catalyst loading. Importantly, the intrinsically distributed thiadiazole ligands can stabilize the Pd moiety, preventing aggregation and leaching, and afford excellent catalytic lifetimes. Consequently, the catalyst can be reused 10 times without a significant loss of its catalytic activity.

Facile Analytical Methods to Determine the Purity of Titanium Tetrachloride.

We propose a simple method to investigate both the qualitative and quantitative properties of titanium tetrachloride. The selection and concentration of the employed solvent were found to be very important in the analysis of highly reactive titanium tetrachloride (TiCl4). Herein, we employed various concentrations of an acid solution to serve as a stabilizing medium. Qualitative analysis was performed via Fourier transform-infrared spectroscopy (FT-IR) and scanning electron microscope-energy dispersive spectroscopy (SEM-EDS). Additionally, the quantitative analysis was performed via inductively coupled plasma optical emission spectroscopy (ICP-OES). We concluded that both the qualitative and quantitative properties of titanium tetrachloride could be easily measured using a specific acidic solvent as a medium.

Electro-Catalytic Activity of RuO2-IrO2-Ta2O5 Mixed Metal Oxide Prepared by Spray Thermal Decomposition for Alkaline Water Electrolysis.

Oxygen evolution reaction for alkaline water electrolysis was studied using various mixed metal oxide catalysts. Mixed metal oxide electrodes consisting of RuO2, IrO2, and Ta2O5 with various ratios on a titanium substrate were prepared by spray thermal decomposition. The crystallinity of the synthesized catalyst was investigated via X-ray diffraction, and the oxidation state of each component was determined using X-ray photoelectron spectroscopy (XPS). Surface morphology was investigated by scanning electron microscopy, and the roughness factor was determined by cyclic voltammetry (CV) in 1 M H2SO4. Electo-catalytic activity for oxygen evolution reaction was measured by cyclic voltammetry (CV) in 1 M KOH at room temperature, and it was found to be strongly dependent.on composition of catalyst. Among all electrodes tested, catalyst with a composition of Ru:Ir:Ta = 1:2:2.5 exhibited the highest current density of 100 mA cm(-2) at 1.67 V, corresponding to an overpotential of 0.44 V.

Preparation and Characterization of Nanostructured Manganese Oxide for Supercapacitors.

Nanostructured manganese oxides were synthesized by a sol-gel method using manganese acetate (MnAc2) and citric acid (C6H8O7,) as precursors, and characterized by Brunauer-Emmett-Teller (BET) analysis, Barrett-Joyner-Halenda (BJH), X-ray diffraction (XRD), scanning electron microscopy (SEM), and transmission electron microscopy (TEM) techniques. The nano-rod structure of MnO2 developed gradually when the calcination temperature varied from 380 to 580 degrees C. As the pH increased, the pore size increased, while the specific surface area decreased. The effects of the pH and calcination temperature on the electrochemical properties of the nano-MnO2 electrode, including the supercapacitive behavior, were investigated by cyclic voltammetry (CV) tests. The tests were performed between 0 and 0.8 V versus Ag/AgCl in 1 M Na2SO4 electrolyte at various scan rates (10-200 mVs(-1)). The specific capacitance of the SP-380 sample, prepared at pH 6, was equal to 269.3 Fg(-1). After 300 cycles, approximately a 3.4% increase of the specific capacitance was measured, confirming the excellent cyclability.

Fabrication and Characterization of Amorphous Cobalt-Doped Molybdenum Sulfide for Hydrogen Evolution Reaction.

In the present study, hydrogen evolution reaction (HER) by alkaline water electrolysis was conducted without using a precious metal catalyst. We synthesized an amorphous cobalt-doped molybdenum sulfide by electrodeposition using different cobalt loadings. The amorphous Co-MoSx produced was characterized by scanning electron microscopy, transmission electron microscopy, and X-ray photoelectron spectroscopy. The cobalt doping and sulfidation procedure resulted in the successful fabrication of a candidate catalyst for the catalytic hydrogen evolution in alkaline solution with high intrinsic activity. Cobalt incorporated amorphous MoSx exhibited 3 times higher HER activity than non-promoted MoSx.

Synthesis and Electrochemical Analyses of Manganese Oxides for Super-Capacitors.

δ-Phase and α-phase manganese oxides were prepared using a hydrothermal method and their electrochemical properties were characterized. The influence of calcination temperature on the properties of manganese oxides was studied. Crystallinities were studied by X-ray diffraction, and scanning and transmission electron microscopy were utilized to examine morphologies. Average pore sizes and specific surface areas of samples were analyzed using the Barret-Joyner-Halenda and Brunauer-Emmett-Teller methods, respectively. After calcination in the range 300 degrees C to 600 degrees C, changes in morphology and crystallinity were observed. The flower-like shape of as synthesized samples became nanorod-like and the δ-phase changed to the α-phase. These changes may have been due to the removal of water during calcination. Furthermore, a transition stage in which the two phases coexisted was observed. Synthesized manganese oxides were mixed with carbon by sonification, to increase electric conductivity and to induce a synergistic effect between pseudo-capacitor and electric double layer capacitor (EDLC). Specific capacitances and rate durability of each composite were investigated by cyclic voltammetry in 1 M Na2SO4 electrolyte at different scan rates. MnO2 calcined at 400 degrees C exhibited the highest capacitance, probably due to its high surface area and more porous structure.

Performance Evaluation of Activated Carbon Nanofiber as Carbon Supports to Improve the Cyclability of Li-Air Batteries.

This study addresses the effects of the pore structures of carbon materials used as cathodes for non-aqueous lithium-air batteries on cycle life. Carbon Nanofibers (CNFs) were synthesized by electrospinning polyacrylonitrile (PAN) and carbonization. The synthesized CNF was then converted to activated carbon nanofibers (ACNFs) under flowing CO2. The specific surface areas CNFs were increased on activation. ACNFs were arranged randomly to form a web-like structure providing both oxygen pathways and a means of discharging products. To examine the electrochemical properties of ACNF, charge-discharge tests were conducted using a Swagelok-type cell at a constant current density of 0.2 mA/cm2; impedance tests were also conducted. ACNF sheet electrodes had cycle lives of up to 50 cycles, which was attributed to high surface area and porosity, although overpotentials for both charge and discharge were high. This cycling performance showed that the pore structure of sheet ACNF is more suitable for the transport of oxygen and for the storage of discharge products than carbon powders.

Synthesis and characterizations of MnO2/multi-wall carbon nanotubes nanocomposites for lithium-air battery.

In this work, rechargeable lithium-air battery using MnO2/MWNTs nanocomposites as a catalyst was studied. MnO2/MWNTs nanocomposites were synthesized by a hydrothermal method, and their physical and chemical properties were investigated. X-ray diffraction (XRD) was used to examine crystallinity and morphology was investigated by transmission electron microscopy (TEM). Charge-discharge behavior and cell impedance with electrolyte replacement were investigated, and charge-discharge capacity decreased with cycles mainly due to the decomposition of carbonate-based electrolyte.

Growth of Pt nanowires by atomic layer deposition on highly ordered pyrolytic graphite.

The formation of Pt nanowires (NWs) by atomic layer deposition on highly ordered pyrolytic graphite (HOPG) is investigated. Pt is deposited only at the step edges of HOPG and not on the basal planes, leading to the formation of laterally aligned Pt NWs. A growth model involving a morphological transition from 0-D to 1-D structures via coalescence is presented. The width of the NWs grows at a rate greater than twice the vertical growth rate. This asymmetry is ascribed to the wetting properties of Pt on HOPG as influenced by the formation of graphene oxide. A difference in Pt growth kinetics based on crystallographic orientation may also contribute.

Self-assembly of colloidal gamma-Fe2O3 and FePt nanoparticles on carbon nanotubes by dip-coating process.

The chemically synthesized colloidal gamma-Fe2O3 and FePt nanoparticles (NPs), with the diameter of approximately 10 nm and approximately 4 nm, respectively, adsorbed and assembled on the surface of carbon nanotubes (CNTs) by dip-coating process, through van der Waals interaction between NP and CNT. Repeating the steps of dip-coating and removing the surfactants from NPs significantly increased the amount of NPs as forming multilayers on the CNT. In addition, the electrochemical activities of FePt/CNTs for methanol oxidation were investigated for the potential application as catalysts of direct methanol fuel cells.

Nano-sized Ni-doped carbon aerogel for supercapacitor.

Carbon aerogel was prepared by polycondensation of resorcinol with formaldehyde using sodium carbonate as a catalyst in ambient conditions. Nano-sized Ni-doped carbon aerogel was then prepared by a precipitation method in an ethanol solvent. In order to elucidate the effect of nickel content on electrochemical properties, Ni-doped carbon aerogels (21, 35, 60, and 82 wt%) were prepared and their performance for supercapacitor electrode was investigated. Electrochemical properties of Ni-doped carbon aerogel electrodes were measured by cyclic voltammetry at a scan rate of 10 mV/sec and charge/discharge test at constant current of 1 A/g in 6 M KOH electrolyte. Among the samples prepared, 35 wt% Ni-doped carbon aerogel (Ni/CA-35) showed the highest capacitance (110 F/g) and excellent charge/discharge behavior. The enhanced capacitance of Ni-doped carbon aerogel was attributed to the faradaic redox reactions of nano-sized nickel oxide. Moreover, Ni-doped carbon aerogel exhibited quite stable cyclability, indicating long-term electrochemical stability.