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.     

Thermomechanical stability and inelastic energy dissipation as durability criteria for fuel cell gas diffusion media with pre-assembly effects

In this article, pre-assembly hot-press pressure and thermal expansion effects in gas-diffusion layers (GDLs) are addressed to explore the practicalities of the constitutive model reported in the companion article. A facile technique is proposed to include deformation history dependent residual strain effects. The model is implemented in the numerical environment and compared with widely followed conventional models such as isotropic and orthotropic material models. With the normal and accelerated thermal expansion effects no significant variation in stresses or strains is reported with the compressible GDL model in contrast to the conventional incompressible form of the GDL model. The present work identifies the critical differences with advanced and extended variants of the model along with conventional GDL material models in terms of planar stress/strain distribution and the membrane response. Finally, the model is simulated for micro-cyclic stress loads of varying amplitudes that imitate the real working conditions of fuel cell. The inelastic energy dissipation in GDLs is predicted using the proposed model, which is utilized further to distinguish the safe (elastic) and unsafe (inelastic shakedown) operating limits. The inelastic collapse of GDLs is shown to be a active function of high amplitude micro-cyclic load with high initial clamping load.     

Enhanced electrocatalytic oxygen reduction reaction from organic-inorganic heterostructure

Herein, molybdenum disulfide nanoflakes decorated copper phthalocyanine microrods (CuPc-MoS₂) are synthesized via two step simple hydrothermal method. The as synthesized hybrid along with pure molybdenum disulfide (MoS₂) nanoflower and pure copper phthalocyanine (CuPc) microrods are well characterized by various techniques that confirm phase, morphology, elemental compositions etc. Next, electrocatalytic oxygen reduction reaction towards fuel cell is investigated in alkaline medium and obtained results proclaim that our CuPc-MoS₂ heterostructure outperforms the other two constituent materials. Efficient oxygen reduction is achieved following four electron pathway by CuPc-MoS₂ whereas partial reduction is done through two electron process by CuPc and MoS₂ separately. Long-time durability test reveals almost 97.6% retention after 8000s that eventually dictate us that CuPc-MoS₂ heterostructure can be the efficient cathode electrocatalyst for future generation fuel cell.     

Amorphous-crystalline cobalt-molybdenum bimetallic phosphide heterostructured nanosheets as Janus electrocatalyst for efficient water splitting

Efficient and sustainable Janus catalysts toward hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) are highly desirable for future hydrogen production via water electrolysis. Herein we report an active Janus electrocatalyst of amorphous-crystalline cobalt-molybdenum bimetallic phosphide heterostructured nanosheets on nickel foam (CoMoP/CoP/NF) for efficient electrolysis of alkaline water. As-reported CoMoP/CoP/NF consists of amorphous bimetal phosphide nanosheets doped with crystalline CoMoP/CoP heterostructured nanoparticles on NF. It can efficiently catalyze both HER (η = 127 mV@100 mA cm^?2) and OER (η = 308 mV@100 mA cm^?2) in alkaline electrolyte with long-term durability. Serving as anode and cathode of water electrolyzer, CoMoP/CoP/NF generates electrolytic current of 10, 50 and 100 mA cm^?2 at low voltage of 1.50, 1.59, and 1.67 V, respectively.     

Zeolitic-imidazolate frameworks-derived Co3S4/NiS@Ni foam heterostructure as highly efficient electrocatalyst for oxygen evolution reaction

Transition metals sulfide-based nanomaterials have recently received significant attention as a promising cathode electrode for the oxygen evolution reaction (OER) due to their easily tunable electronic, chemical, and physical properties. However, the poor electrical conductivity of metal-sulfide materials impedes their practical application in energy devices. Herein, firstly nano-sized crystals of cobalt-based zeolitic-imidazolate framework (Co-ZIF) arrays were fabricated on nickel-form (NF) as the sacrificial template by a facile solution method to enhance the electrical conductivity of the electrocatalyst. Then, the Co₃S₄/NiS@NF heterostructured arrays were synthesized by a simple hydrothermal route. The Co-ZIFs derived Co₃S₄ nanosheets are grown successfully on NiS nanorods during the hydrothermal sulfurization process. The bimetallic sulfide-based Co₃S₄/NiS@NF-12 electrocatalyst demonstrated a very low overpotential of 119 mV at 10 mA cm^?2 for OER, which is much lower than that of mono-metal sulfide NiS@NF (201 mV) and ruthenium-oxide (RuO₂) on NF (440 mV) electrocatalysts. Furthermore, the Co₃S₄/NiS@NF-12 electrocatalyst showed high stability during cyclic voltammetry and chronoamperometry measurements. This research work offers an effective strategy for fabricating high-performance non-precious OER electrocatalysts.     

Modulation of electrical transport in calcium cobaltite ceramics and thick films through microstructure control and doping

Ca₃Co₄O₉ is a promising p-type thermoelectric oxide material having intrinsically low thermal conductivity. With low cost and opportunities for automatic large scale production, thick film technologies offer considerable potential for a new generation of micro-sized thermoelectric coolers or generators. Here, based on the chemical composition optimized by traditional solid state reaction for bulk samples, we present a viable approach to modulating the electrical transport properties of screen-printed calcium cobaltite thick films through control of the microstructural evolution by optimized heat-treatment. XRD and TEM analysis confirmed the formation of high-quality calcium cobaltite grains. By creating 2.0 at% cobalt deficiency in Ca_2.7Bi_0.3Co₄O_9+δ, the pressureless sintered ceramics reached the highest power factor of 98.0 μWm^?1 K^-2 at 823 K, through enhancement of electrical conductivity by reduction of poorly conducting secondary phases. Subsequently, textured thick films of Ca_2.7Bi_0.3Co_3.92O_9+δ were efficiently tailored by controlling the sintering temperature and holding time. Optimized Ca_2.7Bi_0.3Co_3.92O_9+δ thick films sintered at 1203 K for 8 h exhibited the maximum power factor of 55.5 μWm^?1 K^-2 at 673 K through microstructure control.     

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.     

Effect of mesoporous carbon on oxygen reduction reaction activity as cathode catalyst support for proton exchange membrane fuel cell

In this paper, a new carbon support with a large number of mesoporous-structures is selected to prepare Pt/C catalysts. Transmission electron microscope (TEM) results show that the Pt/3# catalyst presents a sponge-like morphology, Pt particles are not only evenly distributed on the surface of carbon support, but also the smaller Pt particles are deposited in the mesoporous inside the support. The average diameter of Pt particles is only 2.8 nm. The membrane electrode assembly (MEA) based on Pt/3# catalyst also shows excellent performance. In conclusion, the 3# support is an idea carbon support for PEMFC, which helps to improve the oxygen reduction reaction (ORR) activity of the catalyst. Based on the “internal-Pt” structure of the support mesoporous, the efficient three-phase boundaries (TPBs) are construct to avoid the poisoning effect of ionomer on the nano-metal particles, reduce the activation impedance and oxygen mass transfer impedance, and improve the reaction efficiency.     

Density functional theory study of the hydrogen evolution reaction in haeckelite boron nitride quantum dots

To satisfy arising energy needs and to handle the forthcoming worldwide climate transformation, the major research attention has been drawn to environmentally friendly, renewable and abundant energy resources. Hydrogen plays an ideal and significant role is such resources, due to its non-carbon based energy and production through clean energy. In this work, we have explored catalytic activity of a newly predicted haeckelite boron nitride quantum dot (haeck-BNQD), constructed from the infinite BN sheet, for its utilization in hydrogen production. Density functional theory calculations are employed to investigate geometry optimization, electronic and adsorption mechanism of haeck-BNQD using Gaussian16 package, employing the hybrid B3LYP and wB97XD functionals, along with 6–31G(d,p) basis set. A number of physical quantities such as HOMO/LUMO energies, density of states, hydrogen atom adsorption energies, Mulliken populations, Gibbs free energy, work functions, overpotentials, etc., have been computed and analysed in the context of the catalytic performance of haeck-BNQD for the hydrogen-evolution reaction (HER). Based on our calculations, we predict that the best catalytic performance will be obtained for H adsorption on top of the squares or the octagons of haeck-BNQD. We hope that our prediction of most active catalytic sites on haeck-BNQD for HER will be put to test in future experiments.     

Porous CoNiOOH nanosheets derived from the well-mixed MOFs as stable and highly efficient electrocatalysts for water oxidation

The development of efficient and stable electrocatalysts is of great significance for improving water splitting. Among them, transition metal oxyhydroxides show excellent performance in oxygen evolution reactions (OER), but there are certain difficulties in direct preparation. Recently, Metal–organic frameworks (MOFs) as precatalysts or precursors have shown promising catalytic performance in OER and can be decomposed under alkaline conditions. Therefore, using a mild and controllable way to convert MOFs into oxyhydroxides and retaining the original structural advantages is crucial for improving the catalytic activity. Herein, a rapid electrochemical strategy is used to activate well-mixed MOFs to prepare Co/Ni oxyhydroxide nanosheets for efficient OER catalysts, and the structural transformation in this process was investigated in detail by using scanning electron microscope, X-ray diffraction, Raman, X-ray photoelectron spectroscopy and electrochemical methods. It is discovered that electrochemical activation can promote ligand substitution of well-mixed MOFs to form porous oxyhydroxide nanosheets and tune the electronic structure of the metal (Co and Ni), which can lead to more active site exposure and accelerate charge transfer. In addition, the change of structure also improves hydrophilicity, as well as benefiting from the strong synergistic effect between multiple species, the optimal a-MCoNi–MOF/NF has excellent OER performance and long-term stability. More obviously, the porous CoNiOOH nanosheets are formed in situ during electrochemical activation process through structural transformation and acts as the active centers. This work provides new insights for mild synthesis of MOFs derivatives and also provides ideas for the preparation of highly efficient catalysts.