Hydrogen, Volume 2, Issue 1 (March 2021) – 9 articles

A systematic study of different ratios of CO, CO₂, N₂ gas components on the hydrogen storage properties of the Na₃AlH₆ complex hydride with 4 mol% TiCl₃, 8 mol% aluminum and 8 mol% activated carbon is presented in this paper. The different concentrations of CO and CO₂ in H₂ and CO, CO₂, N₂ in H₂ mixture were investigated. Both CO and CO₂ gas react with the complex hydride forming Al oxy-compounds, NaOH and Na₂CO₃ that consequently cause serious decline in hydrogen storage capacity. These reactions lead to irreversible damage of complex hydride under the current experimental condition. Thus, after 10 cycles with 0.1 vol % CO + 99.9 vol %H₂ and 1 vol % CO + 99 vol %H₂, the dehydrogenation storage capacity of the composite material decreased by 17.2% and 57.3%, respectively. In the case of investigation of 10 cycles with 1 vol % CO₂ + 99 vol % H₂ gas mixture, the capacity degradation was 53.5%. After 2 cycles with 10 vol % CO +90 vol % H₂, full degradation was observed, whereas after 6 cycles with 10 vol % CO₂ + 90 vol % H₂, degradation of 86.8% was measured. While testing with the gas mixture of 1.5 vol % CO + 10 vol % CO₂ + 27 vol % H₂ + 61.5 vol % N₂, the degradation of 94% after 6 cycles was shown. According to these results, it must be concluded that complex aluminum hydrides cannot be used for the absorption of hydrogen from syngas mixtures without thorough purification. Full article

The engineering correlations for assessment of hazard distance defined by a size of fireball after either liquid hydrogen spill combustion or high-pressure hydrogen tank rupture in a fire in the open atmosphere (both for stand-alone and under-vehicle tanks) are presented. The term “fireball size” is used for the maximum horizontal size of a fireball that is different from the term “fireball diameter” applied to spherical or semi-spherical shape fireballs. There are different reasons for a fireball to deviate from a spherical shape, e.g., in case of tank rupture under a vehicle, the non-instantaneous opening of tank walls, etc. Two conservative correlations are built using theoretical analysis, numerical simulations, and experimental data available in the literature. The theoretical model for hydrogen fireball size assumes complete isobaric combustion of hydrogen in air and presumes its hemispherical shape as observed in the experiments and the simulations for tank rupturing at the ground level. The dependence of the fireball size on hydrogen mass and fireball’s diameter-to-height ratio is discussed. The correlation for liquid hydrogen release fireball is based on the experiments by Zabetakis (1964). The correlations can be applied as engineering tools to access hazard distances for scenarios of liquid or gaseous hydrogen storage tank rupture in a fire in the open atmosphere. Full article

Owing to the high hydrogen content, hydrocarbons are considered as an alternative source for hydrogen energy purposes. Complete decomposition of hydrocarbons results in the formation of gaseous hydrogen and solid carbonaceous by-product. The process is complicated by the methane formation reaction when the released hydrogen interacts with the formed carbon deposits. The present study is focused on the effects of the reaction mixture composition. Variations in the inlet hydrogen and methane concentrations were found to influence the carbon product’s morphology and the hydrogen production efficiency. The catalyst containing NiO (82 wt%), CuO (13 wt%), and Al₂O₃ (5 wt%) was prepared via a mechanochemical activating procedure. Kinetics of the catalytic process of hydrocarbons decomposition was studied using a reactor equipped with McBain balances. The effects of the process parameters were explored in a tubular quartz reactor with chromatographic analysis of the outlet gaseous products. In the latter case, the catalyst was loaded piecemeal. The texture and morphology of the produced carbon deposits were investigated by nitrogen adsorption and electron microscopy techniques. Full article

The storage of hydrogen is the key technology for a sustainable future. We developed an in silico procedure, which is based on the combination of experimental and quantum-chemical methods. This method was used to evaluate energetic parameters for hydrogenation/dehydrogenation reactions of various pyrazine derivatives as a seminal liquid organic hydrogen carriers (LOHC), that are involved in the hydrogen storage technologies. With this in silico tool, the tempo of the reliable search for suitable LOHC candidates will accelerate dramatically, leading to the design and development of efficient materials for various niche applications. Full article

Climate change is one of the major problems that people face in this century, with fossil fuel combustion engines being huge contributors. Currently, the battery powered electric vehicle is considered the predecessor, while hydrogen vehicles only have an insignificant market share. To evaluate if this is justified, different hydrogen power train technologies are analyzed and compared to the battery powered electric vehicle. Even though most research focuses on the hydrogen fuel cells, it is shown that, despite the lower efficiency, the often-neglected hydrogen combustion engine could be the right solution for transitioning away from fossil fuels. This is mainly due to the lower costs and possibility of the use of existing manufacturing infrastructure. To achieve a similar level of refueling comfort as with the battery powered electric vehicle, the economic and technological aspects of the local small-scale hydrogen production are being investigated. Due to the low efficiency and high prices for the required components, this domestically produced hydrogen cannot compete with hydrogen produced from fossil fuels on a larger scale. Full article

Photoanodes comprising a transparent glass substrate coated with a thin conductive film of fluorine-doped tin oxide (FTO) and a thin layer of a photoactive phase have been fabricated and tested with regard to the photo-electro-oxidation of water into molecular oxygen. The photoactive layer was made of a mat of TiO₂ nanorods (TDNRs) of micrometric thickness. Individual nanorods were successfully photosensitized with nanoparticles of a metal–organic framework (MOF) of nickel and 1,2-benzene dicarboxylic acid (BDCA). Detailed microstructural information was obtained from SEM and TEM analysis. The chemical composition of the active layer was determined by XRD, XPS and FTIR analysis. Optical properties were determined by UV–Vis spectroscopy. The water photooxidation activity was evaluated by linear sweep voltammetry and the robustness was assessed by chrono-amperometry. The OER (oxygen evolution reaction) photo-activity of these photoelectrodes was found to be directly related to the amount of MOF deposited on the TiO₂ nanorods, and was therefore maximized by adjusting the MOF content. The microscopic reaction mechanism which controls the photoactivity of these photoelectrodes was analyzed by photo-electrochemical impedance spectroscopy. Microscopic rate parameters are reported. These results contribute to the development and characterization of MOF-sensitized OER photoanodes. Full article

Hydrogen is receiving increasing attention as a versatile energy vector to help accelerate the transition to a decarbonised energy future. Gas turbines will continue to play a critical role in providing grid stability and resilience in future low-carbon power systems; however, it is recognised that this role is contingent upon achieving increased thermal efficiencies and the ability to operate on carbon-neutral fuels such as hydrogen. An important consideration in the development of gas turbine combustors capable of operating with pure hydrogen or hydrogen-enriched natural gas are the significant changes in thermoacoustic instability characteristics associated with burning these fuels. This article provides a review of the effects of burning hydrogen on combustion dynamics with focus on swirl-stabilised lean-premixed combustors. Experimental and numerical evidence suggests hydrogen can have either a stabilising or destabilising impact on the dynamic state of a combustor through its influence particularly on flame structure and flame position. Other operational considerations such as the effect of elevated pressure and piloting on combustion dynamics as well as recent developments in micromix burner technology for 100% hydrogen combustion have also been discussed. The insights provided in this review will aid the development of instability mitigation strategies for high hydrogen combustion. Full article

Among the processes for producing hydrogen and oxygen from water via the use of solar energy, water splitting has the advantage of being carried out in onestep. According to thermodynamics, this process exhibits conversions of practical interest at very high temperatures and needs efficient separation systems in order to separate the reaction products, hydrogen and oxygen. In this conceptual work, the behavior of a membrane reactor that uses two membranes perm-selective to hydrogen and oxygen is investigated in the temperature range 2000–2500 °C of interest for coupling this device with solar receivers. The effect of the reaction pressure has been evaluated at 0.5 and 1 bar while the permeate pressure has been fixed at 100 Pa. As a first result, the use of the membrane perm-selective to oxygen in addition to the hydrogen one has improved significantly the reaction conversion that, for instance, at 0.5 bar and 2000 °C, moves from 9.8% up to 18.8%. Based on these critical data, a preliminary design of a membrane reactor consisting of a Ta tubular membrane separating the hydrogen and a hafnia camera separating the oxygen is presented: optimaloperating temperature of the reactor results in being around 2500 °C, a value making impracticable its coupling with solar receivers even in view of an optimistic development of this technology. The study has verified that at 2000 °C with a water feed flow rate of 1000 kg h⁻¹ about 200 and 100 m³ h⁻¹ of hydrogen and oxygen are produced. In this case, a surface of the hafnia membrane of the order of hundreds m² is required: the design of such a membrane device may be feasible when considering special reactor configurations. Full article

Low-cost, high-performance coatings for hydrogen production via electrolytic water-splitting are of great importance for de-carbonising energy. In this study the Raney2.0 coating was analysed using various electrochemical techniques to assess its absolute performance, and it was confirmed to have an extremely low overpotential for hydrogen evolution of just 28 mV at 10 mA/cm². It was also confirmed to be an acceptable catalyst for oxygen evolution, making it the highest performing simple bifunctional electrocatalyst known. The coating exhibits an extremely high capacitance of up to 1.7 F/cm${}^2$, as well as being able to store 0.61 J/cm${}^2$ in the form of temporary hydride deposits. A new technique is presented that performs a best-fit of a transient simulation of an equivalent circuit containing a constant phase element to cyclic voltammetry measurements. From this the roughness factor of the coating was calculated to be approximately 40,000, which is the highest figure ever reported for this type of material. The coating is therefore an extremely useful improved bifunctional coating for the continued roll-out of alkaline electrolysis for large-scale renewable energy capture via hydrogen production. Full article