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.     

Effect of mass transfer on the deactivation model and GPLE parameters of Co/γ-Al2O3 catalysts in the Fischer Tropsch synthesis

The activity of catalysts with various sizes was compared in a fixed-bed Fischer–Tropsch reactor under similar operating conditions by determining the deactivation model. Catalyst size had no impact on the type of deactivation model. The smaller catalyst showed a smaller deactivation constant of catalyst (k_d) and a lower deactivation rate in the initial stage. The decline in the activities of the catalyst with a mesh size of 40 was lower than the other catalysts, suggesting its higher long-term stability (a_ss). Larger catalyst sizes led to the fouling of carbon and heavy hydrocarbons, decreasing the specific surface of the catalyst, thus increasing the pore diffusion resistance and further decrementing the catalyst activities.     

Polyaniline encapsulated Ti-MOF/CoS for efficient photocatalytic hydrogen evolution

We report the study of conductive polyaniline (PANI) chain embedded Ti-MOF functionalized with CoS as a cocatalyst for hydrogen evolution reaction (HER) application. The post synthetically modified hybrid photocatalyst PANI/Ti-MOF/CoS greatly influences the redox and e^? ? h⁺ separation process and exhibits an impressive rate of HER (～1322 μmol h^?1g^?1), suppressing the pristine Ti-MOF (～62 μmol h^?1g^?1) with apparent quantum yield (AQY) of ～3.2 and transient current response of ～46.4 μA cm^?2. In this system, Ti-MOF provides the circulation of Ti³⁺ and Ti⁴⁺ to the reaction of photocatalytic H₂ generation, where the additional PANI and CoS amended the performance of H₂ production through electron enrichment and thereby improving the stability and integrity of Ti-MOF. The Electrochemical studies demonstrated increased photocurrent by interweaving Ti-MOF crystal with PANI through cation-π interaction thereby enhancing interface connection and then promoting electron transfers. The charge dynamics revealed the initial charge transfer from photoexcited PANI to encapsulated MOF framework to boost the photocatalytic performance of the system. Further, the electron movement at the Ti-MOF/CoS interface is investigated through work function and electrochemical potential of electrons (Fermi level). DFT results demonstrate the importance of CoS in improving the photocatalytic performance of hybrid Ti-MOF catalyst, which leads to superior catalytic behaviour. These results establish that the encapsulation of catalytic active sites inside MOFs with desirable energy band gaps would be an ideal choice for the production of solar fuels.     

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.     

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.     

Generation,validation and application of dynamic load profiles in flow measurement using cavitating Herschel–Venturi nozzles

Today, utility meters for water are tested for measurement behavior at stable operating conditions at specified flow rates as part of the approval process. The measurement error that occurs during start and stop or when changing between flow rates may not be taken into account. In addition, there are new technologies whose measuring behavior under real-world conditions is only known to a limited extend. To take these facts into account, a new method has been developed and tested to determine the measurement behavior of water meters under dynamic load profiles as they occur in the real application. For this purpose, a test rig for flow rate measurement was extended by a cavitation nozzle apparatus and the generation of dynamic load profiles was validated. For the cavitation nozzles used, possible factors influencing the flow rate, such as temperature and purity of the water as well as the upstream pressure were investigated. Using different types of domestic water meters, the applicability of the dynamic test procedure was demonstrated and the measurement behavior of the meters was characterised.     

Cation and polyhedron substitution strategies: Effects on local crystal structure and on Bi3+ and Eu3+ co-doped inverse garnet phosphors’ luminescence property

Following the rapid growth of lightning technology, the development of red-emitting phosphors is effective for improving color temperature and color rendering index for w-LEDs devices. Herein, a single phased garnet phosphor with cation and polyhedron substitution modification was firstly prepared. For Mg₃Gd₂Ge₃O₁₂: Bi³⁺, Eu³⁺, the intensity has been remarkably improved by about 16% compared to the one without Bi³⁺ sensitization. The energy transfer mechanism is identified in this work. Based on cation and polyhedron substitution strategies, novel phosphors with different compositions were obtained and further modified the PL properties. With Lu³⁺ substitution, the bond lengths between Bi³⁺ ion and anion ligands are decreased and the site symmetry has been strengthened, which leads to a 21 nm blue shift when Lu³⁺ totally replaced Gd³⁺ ions. In addition, Lu³⁺ and [SiO₄] substitution strategies both effectively increased symmetric rigid structure, which leads to a significant improvement in thermal stability, indicating the samples own great potential in optical applications This work provides a new insight to synthesis red-emitting phosphors for warm white-LEDs.     

High performance asymmetric supercapacitor based on 3D microsphere-like 1T-MoS2 with high 1T phase content

1T phase molybdenum disulfide (1T-MoS₂) has aroused extensive concern in energy storage devices such as supercapacitors due to its large interlayer spacing, high conductivity and good hydrophilicity. However, it is struggle to synthesize 1T-MoS₂ with stable 1T phase with high content. Herein, Ammonium ion intercalation molybdenum disulfide (A-MoS₂) with high 1T content and stable 3D microsphere structure was successfully synthesized using a facile hydrothermal method. We explained the feasibility of ammonium ion (NH₄⁺) intercalation through density functional theory (DFT) calculations and proved the successful intercalation of NH₄⁺ by XRD and XPS. Through XPS fitting, the 1T phase content is calculated as high as 83.1%. The as-prepared A-MoS₂ presents a stable 3D microsphere structure with the interlayer spacing expanded to 0.93 nm, which provides a wide ion diffusion channel that allows ions to pass through quickly. Moreover, the high 1T content increases the hydrophilicity of MoS₂, thereby improving the wettability of the electrode, which contributes to the interaction between the electrolyte and electrode. In 1 M Na₂SO₄, A-MoS₂ electrode material displays high specific capacitance of 228 F g^?1 at 5 mV s^?1 and retains 127 F g^?1 at 80 mV s^?1, which proves the good rate capability. Furthermore, the assembled α-MnO₂//A-MoS₂ asymmetric supercapacitor (ASC) displayed a wide operating voltage of 2.1 V. The assembled ASC displays a high energy density of 35.8 Wh?kg^?1 at a power density of 525.0 W kg^?1, which indicates excellent energy storage performance.