Transient liquid phase sintering of high-purity mullite for high-temperature structural ceramics

High-purity mullite ceramics, promising engineering ceramics for high-temperature applications, were fabricated using transient liquid phase sintering to improve their high-temperature mechanical properties. Small amounts of ultrafine alumina or silica powders were uniformly mixed with the mullite precursor depending on the silica-alumina ratio of the resulting ceramics to allow for the formation of a transient liquid phase during sintering, thus, enhancing densification at the early stage of sintering and mullite formation by the reaction between additional alumina and the residual glassy phase (mullitization) at the final stage of sintering. The addition of alumina powder to the silica-rich mullite precursor resulted in a reaction between the glassy silica and alumina phases during sintering, thereby forming a mullite phase without inhibiting densification. The addition of fine silica powder to the mullite single-phase precursor led to densification with an abnormal grain growth of mullite, whereas some of the added silica remained as a glassy phase after sintering. The resulting mullite ceramics prepared using different powder compositions showed different sintering behaviors, depending on the amount of alumina added. Upon selecting an optimum process and the amount of alumina to be added, the pure mullite ceramics obtained via transient liquid phase sintering exhibited high density (approximately 99%) and excellent high-temperature flexural strength (approximately 320 MPa) at 1500 °C in air. These results clearly demonstrate that pure mullite ceramics fabricated via transient liquid phase sintering with compositions close to those of stoichiometric mullite could be a promising process for the fabrication of high-temperature structural ceramics used in an ambient atmosphere. The transient liquid phase sintering process proposed in this study could be a powerful processing tool that allows for the preparation of superior high-temperature structural ceramics used in the ambient processing atmosphere.     

Optimization of hydrogen enrichment via palladium membrane in vacuum environments using Taguchi method and normalized regression analysis

In this study, the separation of hydrogen from gas mixtures using a palladium membrane coupled with a vacuum environment on the permeate side was studied experimentally. The gas mixtures composed of H₂, N₂, and CO₂ were used as the feed. Hydrogen permeation fluxes were measured with membrane operating temperature in the range of 320–380 °C, pressures on the retentate side in the range of 2–5 atm, and vacuum pressures on the permeate side in the range of 15–51 kPa. The Taguchi method was used to design the operating conditions for the experiments based on an orthogonal array. Using the measured H₂ permeation fluxes from the Taguchi approach, the stepwise regression analysis was also employed for establishing the prediction models of H₂ permeation flux, followed by the analysis of variance (ANOVA) to identify the significance and suitability of operating conditions. Based on both the Taguchi approach and ANOVA, the H₂ permeation flux was mostly affected by the gas mixture composition, followed by the retentate side pressure, the vacuum degree, and the membrane temperature. The predicted optimal operating conditions were the gas mixture with 75% H₂ and 25% N₂, the membrane temperature of 320 °C, the retentate side pressure of 5 atm, and the vacuum degree of 51 kPa. Under these conditions, the H₂ permeation flux was 0.185 mol s^?1 m^?2. A second-order normalized regression model with a relative error of less than 7% was obtained based on the measured H₂ permeation flux.     

Recent progress of electrocatalysts for hydrogen proton exchange membrane fuel cells

Due to stringent environmental regulations and the limited resources of fossil-based fuels, there is an urgent demand for clean and eco-friendly energy conversion devices. These criteria appear to be met by hydrogen proton exchange membrane fuel cells (PEMFCs). PEMFCs have attracted tremendous attention on account of their excellent performance with tunable operability and good portability. Nonetheless, their practical applications are hugely influenced by the scarcity and high cost of platinum (Pt) used as electrocatalysts at both cathode and anode. Pt is also susceptible to easy catalyst poisoning. Herein, this paper reviews the progress of the research regarding the development of electrocatalysts practically used in hydrogen PEMFCs, where the corner-stone reactions are cathodic oxygen reduction reaction (ORR) and anodic hydrogen oxidation reaction (HOR). To reduce the costs of PEMFCs, lessening or eliminating the use of Pt is of prime importance. For current and forthcoming laboratory/large-scale PEMFCs, there is much interest in developing substitute catalysts based on cheaper materials. As such are non-platinum (non-Pt), non-platinum group metals (non-PGMs), metal oxides, and non-metal electrocatalysts. Hence, high-performance, state-of-the-art, and novel structured electrocatalysts as replacements for Pt are needed.     

Increased hydroxyl concentration by tungsten oxide modified h-BN promoted catalytic performance in partial oxidation of methane

Hexagonal boron nitride (h-BN) as a layered inorganic nonmetallic material has been widely used. Hydrogen peroxide (H₂O₂) modification can trigger exfoliation and afford abundant B–OH active sites at edge of h-BN, which can enhance methane activation ability. Introducing tungsten oxide (WO₃) to h-BN produces a similar effect, because doping WO₃ into h-BN resulted in electron transfer to N, inducing fracture of B–N bond, resulting in N vacancy (triboron center), exposing more B sites and promoting the generation of B–OH. Significantly, the introduction of WO₃ on the modified h-BN dramatically increased the concentration of B–OH compared with the unmodified h-BN, because H₂O₂ modification weakened B–N bond. By means of XRD, TEM, XPS,EPR, FT-IR, it is proved that the high concentration of B–OH active sites contributed to activating C–H bond, thus methane conversion and CO and H₂ selectivity were significantly improved.     

Co2FeO4@rGO composite: Towards trifunctional water splitting in alkaline media

Development of efficient, low cost and multifunctional electrocatalysts for water splitting to harvest hydrogen fuels is a challenging task, but the combination of carbon materials with transition metal-based compounds is providing a unique and attractive strategy. Herein, composite systems based on cobalt ferrite oxide-reduced graphene oxide (Co₂FeO₄) @(rGO) using simultaneous hydrothermal and chemical reduction methods have been prepared. The proposed study eliminates one step associated with the conversion of GO into rGO as it uses direct GO during the synthesis of cobalt ferrite oxide, consequently rGO based hybrid system is achieved in-situ significantly, the optimized Co₂FeO₄@rGO composite has revealed an outstanding multifunctional applications related to both oxygen evolution reaction (OER) and hydrogen counterpart (HER). Various metal oxidation states and oxygen vacancies at the surface of Co₂FeO₄@rGO composites guided the multifunctional surface properties. The optimized Co₂FeO₄@rGO composite presents excellent multifunctional properties with onset potential of 0.60 V for ORR, an overpotential of 240 mV at a 20 mAcm^?2 for OER and 320 mV at a 10 mAcm^?2 for HER respectively. Results revealed that these multifunctional properties of the optimized Co₂FeO₄@ rGO composite are associated with high electrical conductivity, high density of active sites, crystal defects, oxygen vacancies, and favorable electronic structure arisinng from the substitution of Fe for Co atoms in binary spinel oxide phase. These surface features synergistically uplifted the electrocatalytic properties of Co₂FeO₄@rGO composites. The multifunctional properties of the Co₂FeO₄@ rGO composite could be of high interest for its use in a wide range of applications in sustainable and renewable energy fields.     

Effect of micro-cracks on the in-plane electronic conductivity of proton exchange membrane fuel cell catalyst layers based on lattice Boltzmann method

Micro-cracks commonly occur on the catalyst layers (CLs) during the manufacturing of catalyst coated membranes (CCMs). However, the crack shape parameters effect on CLs in-plane (IP) electronic conductivity λ_s is not clear. In this work, the relationship between crack parameters and the λ_s is obtained based on the two-dimensional (2D) multiple-relaxation time (MRT) lattice Boltzmann method (LBM). The LBM numerical model is validated by the normalized λ_s experiment applied on three different home-made cracked CLs, and the parameter study focus on crack width, length, quantity and phase angle are carried out. The results show that the decrease of λ_s has different sensitivity |k| to the parameters above. The crack width has little effect on λ_s decrease, and the |k_w| is 0.038. However, crack arm length and quantity show more significant impact, which |k_l| and |k_N| are 0.753 and 0.725, respectively. The CLs with different crack propagation directions show significant anisotropy on λ_s, and a 53.53% decrease in λ_s is observed between 0° and 90° crack phase angle change. To manufacture a high electronic conductivity CL, crack initiation and migration mitigation are highly encouraged.     

Magnetic properties,phase evolution,hollow structure and biomedical application of hematite (α-Fe2O3) and QUAIPH

We investigate synthesis, phase evolution, hollow and porous structure and magnetic properties of quasi-amorphous intermediate phase (QUAIPH) and hematite (α-Fe₂O₃) nanostructure synthesized by annealing of akaganeite (β-FeOOH) nanorods. It is found that the annealing temperature determines the phase composition of the products, the crystal structure/size dictates the magnetic properties whereas the final nanorod morphology is determined by the starting material. Annealing of β-FeOOH at ～300 °C resulted in the formation of hollow QUAIPH nanorods. The synthesized material shows low-cytotoxicity, superparamagnetism and good transverse relaxivity, which is rarely reported for QUAIPH. The QUAIPH nanorods started to transform to porous hematite nanostructures at ～350 °C and phase transformation was completed at 600 °C. During the annealing, the crystal structure changed from monoclinic (akaganeite) to quasi-amorphous and rhombohedral (hematite). Unusually, the crystallite size first decreased (akaganeite → QUAIPH) and then increased (QUAIPH → hematite) during annealing whereas the nanorods retained particle shape. The magnetic properties of the samples changed from antiferromagnetic (akaganeite) to superparamagnetic with blocking temperature T_B = 84 K (QUAIPH) and finally to weak-ferromagnetic with the Morin transition at T_M = 244 K and high coercivity H_C = 1652 Oe (hematite). The low-cytotoxicity and MRI relaxivity (r₂ = 5.80 mM^?1 s^?1 (akaganeite), r₂ = 4.31 mM^?1 s^?1 (QUAIPH) and r₂ = 5.17 mM^?1 s^?1 (hematite)) reveal potential for biomedical applications.     

A dotted nanowire arrayed by 5 nm sized palladium and nickel composite nanopaticles showing significant electrocatalytic activity towards ethanol oxidation reaction (EOR)

To the best of our knowledge, this is the first time to report the preparation of a dotted nanowire arrayed by 5 nm sized palladium and nickel composite nanoparticles (denoted as Pd_xNi_y NPs) via a hydrothermal method using NU and PdO·H₂O as the starting materials. The samples prepared at the mass ratio of NU to PdO·H₂O 1:1, 1:2 and 2:1 were, respectively, nominated as catalyst c₁, c₂ and c₃. The chemical compositions of all synthesized catalysts were mainly studied by using X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS), revealing that metallic Ni was one main component of all prepared catalysts. Surprisingly, the main diffraction peaks appearing in the XRD patterns of all prepared catalysts were assigned to the metallic Ni rather than the metallic Pd. Very interestingly, as indicated by the TEM images, a large number of dotted nanowires arrayed by numerous equidistant 5 nm sized nanoparticles were distinctly exhibited in catalyst c₁. More importantly, when being used as electrocatalysts for EOR, all prepared catalysts exhibited an evident electrocatalytic activity towards EOR. In the cyclic voltammetry (CV) test, the peak current density of the forward peak of EOR on catalyst c₁ measured at 50 mV s^?1 was as high as 56.1 mA cm^?2, being almost 9 times higher than that of EOR on catalyst c₃ (6.3 mA cm^?2). Particularly, the polarized current density of EOR on catalyst c₁ at 3600 s, as indicated by the chronoamperometry (CA) experiment, was still maintained to be around 1.47 mA cm^?2, a value higher than the latest reported data of 1.3 mA cm^?2 (measured on the pure Pd/C electrode). Presenting a novel method to prepare dotted nanowires arranged by 5 nm sized nanoparticles and showing the significant eletrocatalytic activities of the newly prepared dotted nanowires towards EOR were the major contributions of this preliminary work.     

Silver-substituted (Ag1-xCux)2ZnSnS4 solar cells from aprotic molecular inks

To battle the high open-circuit voltage deficit (V_OC,def) in kesterite (Cu₂ZnSnS₄ or CZTS) solar cells, a current field of research relates to point defect engineering by cation substitution. For example, by partly replacing Cu with an element of a larger ionic radius, such as Ag, the degree of Cu/Zn disorder decreases, and likewise does the associated band tailing. In this paper, solution-processed (Ag_1-xCu_x)₂ZnSnS₄ (ACZTS) samples are prepared through the aprotic molecular ink approach using DMSO as the solvent. The successful incorporation of silver into the CZTS lattice is demonstrated with relatively high silver concentrations, namely Ag/(Ag+Cu) ratios of 13% and 26%. The best device was made with 13% Ag/(Ag+Cu) and had an efficiency of 4.9%. The samples are compared to the pure CZTS sample in terms of microstructure, phase distribution, photoluminescence, and device performance. In the XRD patterns, a decrease in the lattice parameter c/a ratio is observed for ACZTS, as well as significant peak splitting with Ag addition for several of the characteristic kesterite XRD reflections. In addition to the improvement in efficiency, other advantageous effects of Ag-incorporation include enhanced grain growth and an increased band gap. A too high concentration of Ag leads to the formation of secondary phases such as SnS and Ag₂S as detected by XRD.