Fabrication of three-dimensional nanoporous nickel films with tunable nanoporosity and their excellent electrocatalytic activities for hydrogen evolution reaction

Three-dimensional (3D) nanoporous nickel films were fabricated by a novel and facile method. The fabrication process involved the heat treatment of the electrodeposited zinc layer on nickel substrate and the subsequent electrochemical dealloying. The mutual diffusion of Ni and Zn during the heat treatment resulted in the formation of the Ni₂Zn₁₁ alloy surface film. The 3D nanoporous nickel films with open pores and interconnected ligaments were obtained by the electrochemical dealloying of relatively active zinc from the alloy surface film. As the electrodeposited zinc amount increased, the thickness, pore diameter and pore density of the nanoporous nickel films became larger. In our experimental range, the thickest nanoporous nickel film presented a thickness of 8 μm and an average pore diameter of 700 nm. The as-prepared 3D nanoporous nickel films exhibited much higher electrocatalytic activity for hydrogen evolution reaction (HER) than smooth nickel foil, and their electrocatalytic activities for HER enhanced with increase in the porosity and thickness. It was concluded that the enhanced electrocatalytic activity and excellent electrochemical stability for HER of the as-prepared 3D nanoporous nickel films can be ascribed to their unique nanostructured characteristics.     

Analysis of operator human errors in hydrogen refuelling stations: Comparison between human rate assessment techniques

The use of hydrogen as an energy carrier for road transport appears to be an optimal solution for the reduction of greenhouse gas emissions. Nevertheless, the development of this technology depends on the growth and diffusion of production, storage and refuelling infrastructures together with accurate risk analyses to appropriately design the safety and management systems used in these plants. Moreover, to improve safety standards, it is also important to focus attention on the estimation of hazards related to human factors, as this is one of the major causes leading to accidental events, especially in complex industrial technology. The paper reports a case study relevant to operator errors that occur during maintenance procedures on safety venting devices in refuelling station hydrogen storage systems performed using first- and second-generation Human Rate Assessment (HRA) techniques. HEART (Human Error Assessment and Reduction Technique) methodology, a first-generation HRA method, which was modified on the basis of the fuzzy set concept, was employed to evaluate the probability of erroneous actions. The obtained results have been compared with results obtained using CREAM (second-generation) methodology. The critical analyses of the obtained results have also allowed to provide procedural recommendations and suggestions regarding safety equipment and procedures which can be adopted to reduce the risk of accidents.     

Genome based metabolic flux analysis of Ethanoligenens harbinense for enhanced hydrogen production

Ethanoligenens harbinense is a promising hydrogen producing microorganism due to its high inherent hydrogen production rate. Even though the effect of media optimization and inhibitory metabolites has been studied in order to improve the hydrogen productivity of these cultures, the identification of the underlying causes of the observed changes in productivity has not been targeted to date. In this work we present a genome based metabolic flux analysis (MFA) framework, for the comprehensive study of E. harbinense in culture, and the effect of inhibitory metabolites and media composition on its metabolic state. A metabolic model was constructed for E. harbinense based on its annotated genome sequence and proteomic evidence. This model was employed to perform MFA and obtain the intracellular flux distribution under different culture conditions. These results allow us to identify key elements in the metabolism that can be associated to the observed production phenotypes, and that can be potential targets for metabolic engineering in order to enhanced hydrogen production in E. harbinense.     

3.5-Year tritium aging effect on isotopic exchange at constant flow rate between gaseous hydrogen and palladium deuteride

Isotopic exchange experiments were performed between gaseous hydrogen flows with constant rate through packed-powder beds of 0-year and 3.5-year tritium aged palladium deuteride. X-ray diffraction (XRD) indicated that the crystal lattice of palladium swelled due to the decayed ³He which existed in the interstitial void of 3.5-year tritium aged palladium. The effluent curves of isotopic exchange reaction were simulated by plate theory of chromatography separation, and the reasons which influenced isotopic exchange performance were analyzed by rate theory of chromatography separation. After 3.5-year tritium aged, the isotopic exchange effluent curve went smooth, and the isotopic exchange efficiency declined. The results of isotopic exchange experiments accorded well with the theory simulated results. After exchange temperature raised, isotopic exchange performance of 3.5-year aged palladium increased, moreover, isotopic exchange performance of 3.5-year aged palladium was sensitive to temperature change.     

Elastic properties of perovskite-type hydride NaMgH3 for hydrogen storage

Mechanical properties of NaMgH₃ were investigated using the norm-conserving pseudopotentials and plane waves (PP–PW) within the general gradient approximation (GGA) in the frame of density functional theory (DFT). The elastic constants of NaMgH₃ were calculated for the first time. The NaMgH₃ compound is found to be mechanically stable at ambient pressure. The linear bulk modulus and the bulk modulus along crystallographic axes of single crystals have been derived using elastic constants. The calculated linear bulk moduli are found to be in good agreement with the theoretical value reported in the literature. Shear and Young's moduli as well as Poisson's ratio for ideal polycrystalline NaMgH₃ are also calculated. According to the obtained results, NaMgH₃ can be classified as brittle material. The shear anisotropic factors and the elastic anisotropy are also discussed. A Debye temperature of 648 K was also determined using theoretical elastic constants.     

Efficient composite bipolar plate reinforced with carbon fiber and graphene for proton exchange membrane fuel cell

The composite bipolar plates are developed using natural graphite, carbon black, and carbon fiber, along with 1% graphene with phenol formaldehyde (resole) resin. The graphene is developed by thermo-chemical exfoliation of natural graphite and characterized by XRD, Raman, FESEM, and AFM analyses. The synthesized graphene is monolayer graphene with a minimum thickness of 1 Å. The bipolar plates are developed using compression molding technique and thoroughly characterized considering stringent benchmarks (US-DOE and Plug Power Inc.) for PEMFC viz., electrical conductivity, flexural strength, deflection at mid-point, and corrosion current density. The composite bipolar plate showed excellent corrosion resistance to the rigorous fuel cell environment. All the required properties are achieved by the developed composite bipolar plate for PEMFC application. The fuel cell is fabricated with the developed bipolar plate and the performance of the fuel cell is studied. The incorporation of graphene has improved the fuel cell performance significantly.     

Facile synthesis of triangular shaped palladium nanoparticles decorated nitrogen doped graphene and their catalytic study for renewable energy applications

We report a novel method for the synthesis of triangular shaped palladium nanoparticles (Pd NPs) decorated nitrogen doped graphene. Nitrogen doped graphene (N-G) is synthesized by uniform coating of polyelectrolyte modified graphene surface with a nitrogen containing polymer followed by their pyrolysis. The triangular shaped Pd NPs are decorated over nitrogen doped graphene (Pd/N-G) by kinetically controlling the polyol reduction process. The kinetic control of the growth of the nanoparticles and nitrogen doping of the supporting material leads to the formation of highly dispersed anisotropic nanoparticles over the graphene support. Hydrogen storage study of N-G and Pd/N-G give a storage capacity of 1.1 wt% and 1.9 wt%, respectively at 25 °C and 2 MPa hydrogen equilibrium pressure. Electrocatalytic study of Pd/N-G shows that it is a very good electrocatalyst for oxygen reduction reaction and highly stable in acidic media due to the strong binding between Pd NPs and graphene support as a result of nitrogen doping besides has high methanol tolerance in acidic media. The present synthesis procedure highlights a new pathway for the highly dispersed and different morphological metal nanoparticles decorated graphene composites for energy related applications.     

Mechanochemical synthesis of NaBH4 starting from NaH–MgB2 reactive hydride composite system

The present investigation focuses on a new synthesis route of NaBH₄ starting from the 2NaH + MgB₂ system subjected to mechanochemical activation under reactive hydrogen atmosphere. The milling process was carried out under two different hydrogen pressures (1 and 120 bar) with two different rotation speeds (300 and 550 rpm). The reaction products were characterized by ex-situ solid state magic angle spinning (MAS) nuclear magnetic resonance (NMR), ex-situ X-ray powder diffraction (XRPD) and Infrared Spectroscopy (IR). From the results of these analyses, it can be concluded that milling in all the considered conditions led to the formation of NaBH₄ (cubic-Fm-3m). In particular, a reaction yield of 5 and 14 wt% is obtained after 20 h of milling at 120 bar of H₂ for the tests performed at 300 rpm and 550 rpm, respectively. The presence of MgH₂ is also detected among the final products on the as milled powders. The influence of the milling conditions and the evaluation of the parameters related the mechanochemical process are here discussed.     

H2 sensors based on WO3 thin films activated by platinum nanoparticles synthesized by electroless process

Platinum (Pt) nanoparticles were successfully synthesized on tungsten oxide (WO₃) thin films by electroless process without any further post-treatment. The prepared Pt nanoparticles were characterized by X-ray diffraction, X-ray photoelectron spectroscopy and field-emission scanning electron microscopy. Gas sensors based on the Pt–WO₃ films were found to provide repeatable and significant responses to ppm-level H₂. The size of Pt nanoparticles increases with the deposition time and has improved the sensing characteristics of the sensors. The work in this paper paves a facile way to the fabrication of Pt nanoparticles on metal oxide surface at a low temperature (68 °C).     

Application of artificial neural networks for modeling of biohydrogen production

In this study, an artificial neural network (ANN) model was developed to estimate the hydrogen production profile with time in batch studies. A back propagation artificial neural network ANN configuration of 5–6–4–1 layers was developed. The ANN inputs were the initial pH, initial substrate and biomass concentrations, temperature, and time. The model training was done using 313 data points from 26 published experiments. The correlation coefficient between the experimental and estimated hydrogen production was 0.989 for training, validating, and testing the model. Results showed that the trained ANN successfully predicted the hydrogen production profile with time for new data with a correlation coefficient of 0.976.