Hydrogen

Molecular cobaloxime-based heterogeneous systems have attracted great interest during the last decades in light-driven hydrogen production. Here, we present a novel cobaloxime-tethered periodic mesoporous organosilica (PMO) hybrid (Im-EtPMO-Co) prepared through the immobilization of a molecular cobaloxime complex on the imidazole groups present in ethylene-bridged PMO. The successful assembly of a molecular cobaloxime catalyst via cobalt-imidazole axial ligation has been evidenced by several techniques, such as ¹³C NMR, Raman spectroscopy, ICP-MS, and XPS. The catalytic performance of Im-EtPMO-Co catalyst was essayed on the hydrogen evolution reaction (HER) under visible light in presence of a photosensitizer (Eosin Y) and an electron donor (TEOA). It showed an excellent hydrogen production of 95 mmol hydrogen at 2.5 h, which corresponded to a TON of 138. These results reflect an improved photocatalytic activity with respect to its homogenous counterpart [Co(dmgH)₂(Im)Cl] as well as a previous cobaloxime-PMO system with pyridine axial ligation to the cobaloxime complex. Full article

Extensive decarbonisation efforts result in major changes in energy demand for the extractive industry. In 2021, the extraction and primary processing of metals and minerals accounted for 4.5 Gt of CO₂ eq. per year. The aluminium industry was responsible for 1.1 Gt CO₂ eq. direct and indirect emissions. To reach the European milestone of zero emissions by 2050, a reduction of 3% annually is essential. To this end, the industry needs to take a turn towards less impactful production practices, coupling secondary production with green energy sources. The present work aims to comprehensively compare the lifecycle energy consumption and environmental performance of a secondary aluminium smelter employing alternative thermal and electricity sources. In this frame, a comparative analysis of the environmental impact of different thermal energy sources, namely natural gas, light fuel oil, liquified petroleum gas, hydrogen and electricity, for a secondary aluminium smelter is presented. The results show that H₂ produced by renewables (green H₂) is the most environmentally beneficial option, accounting for −84.156 kg CO₂ eq. By producing thermal energy as well as electricity on site, H₂ technologies also serve as a decentralized power station for green energy production. These technologies account for a reduction of 118% compared to conventionally used natural gas. The results offer a comprehensive overview to aid decision-makers in comparing environmental impacts caused by different energy sources. Full article

During the oxidation of hydrocarbons using hydrogen peroxide solutions, the evolution of gaseous oxygen is a side and undesirable process, in which the consumption of the oxidizer is not associated with the formation of target products. Therefore, no attention is paid to the systematic study of the chemical composition of the gas and the mechanisms of its formation. Filling this gap, the authors discovered a number of new, previously unidentified, interesting facts concerning both gas evolution and the oxidation of hydrocarbons. In a 33% H₂O₂/Cu₂Cl₄·2DMG/CH₃CN system, where DMG is dimethylglyoxime (Butane-2,3-dione dioxime), and is at 50 °C, evidence of significant evolution of gaseous hydrogen, along with the evolution of gaseous oxygen was found. In the authors’ opinion, which requires additional verification, the ratio of gaseous hydrogen and oxygen in the discussed catalytic system can reach up to 1:1. The conditions in which only gaseous oxygen is formed are selected. Using a number of oxidizable hydrocarbons with the first adiabatic ionization potentials (AIPs) of a wide range of values, it was found that the first stage of such a process of evolving only gaseous oxygen was the single electron transfer from hydrogen peroxide molecules to trinuclear copper clusters with the formation, respectively, of hydrogen peroxide radical cations H₂O₂^•+ and radical anions Cu₃Cl₅^•− (AIP = 5 eV). When the conditions for the implementation of such a single electron transfer mechanism are exhausted, the channel of decomposition of hydrogen peroxide molecules into gaseous hydrogen and oxygen is switched on, which is accompanied by the transition of the system to an oscillatory mode of gas evolution. In some cases, the formation of additional amounts of gaseous products is provided by the catalytically activated decomposition of water molecules into hydrogen and oxygen after the complete consumption of hydrogen peroxide molecules in the reaction of gaseous oxygen evolution. The adiabatic electron affinity of various forms of copper molecules involved in chemical processes is calculated by the density functional theory method. Full article

Hydrogen can drastically degrade the mechanical properties of a variety of metallic materials. The so-called hydrogen environment embrittlement of austenitic CrNi-type steels is usually accompanied by the formation of secondary surface cracks, which can be investigated in order to assess the embrittlement process. The occurrence of hydrogen-induced cracks is often related to element segregation effects that locally impact the austenite stability. Since there is as yet a lack of investigation methods that can visualize both structures three-dimensionally, the present study investigates the imageability of hydrogen-induced cracks and element segregation structures in austenitic CrNi-steel via micro-computed tomography (CT). In order to improve the X-ray visibility of segregation structures, modified versions of the reference steel, X2CrNi18-9, that contain W and Si are designed and investigated. The investigations demonstrated that small differences in the X-ray attenuation, caused by the W or Si modifications, can be detected via CT, although segregation structures could not be imaged due to their small size scale and image noise. Hydrogen-induced cracks were characterized successfully; however, the detection of the smaller cracks is limited by the resolution capability. Full article

Alkyl-cyclohexanes can be considered as suitable model compounds to understand the thermochemistry of aromatic compounds and their hydrogenated counterparts discussed as Liquid Organic Hydrogen Carrier systems. Thermochemical measurements on these hydrogen-rich compounds are thwarted by complications due to the 99.9 % purity limitation and sample size specific to these methods. However, the data on vaporisation and formation enthalpies are necessary to optimize the hydrogenation/dehydrogenation processes. In this work, various empirical and theoretical methods are described to reliably assess the gas phase enthalpies of formation and vaporization enthalpies of alkyl-substituted cyclohexanes. The empirical and quantum-chemical methods have been validated against reliable literature data and provide reasonable estimates with an accuracy comparable to that of the experimental data. The liquid phase enthalpies of formation of differently shaped alkyl-cyclohexanes were derived and used to estimate the energetics of their dehydrogenation reactions. The influence of alkyl substituents on the reaction enthalpy is discussed. The vapour pressures of typical hydrogen-rich compounds at technically relevant temperatures were calculated and compared to vapour pressures of biodiesel fuels measured in this work using the static method. Full article

An original non-invasive methodology of the fuel cell diagnosis is proposed to identify different positions of the faults in Proton Exchange Membrane Fuel Cell (PEMFC) stacks from external magnetic field measurements. The approach is based on computing the external magnetic field difference between normal and faulty PEMFC operating conditions. To evaluate the external magnetic field distribution, in this paper, we propose an improved design of the magnetic field analyzer. This analyzer amplifies the magnetic field around the cell to perform an accurate detection of the fault position. Moreover, the main contribution of this work is represented by conceiving and implementing a 3D multi-physical current distribution emulator of a proton exchange membrane fuel cell. The new concept of a proton exchange membrane fuel cell emulator has been specially designed to emulate the magnetic field of a real fuel cell stack. This emulator concept is also beneficial for a new model of the fuel cell, which implies a multi-physical coupling between electrochemical electric conduction and the generated magnetic field. Finally, finally, the numerical model and the emulator have been involved in the realization of numerical simulations and experimental analysis to prove the ability of the system to detect and localize 3D faults. Full article

Ab initio molecular dynamics combines a classical description of nuclear motion with a density-functional description of the electronic cloud. This approach nicely describes chemical reactions. A possible conclusion is that a quantum mechanical description of nuclear motion is not needed. Using Occam’s razor, this means that, being the simpler approach, classical nuclear motion is preferable. In this paper, it is claimed that nuclear motion is classical, and this hypothesis will be tested in comparison to methods with quantum mechanical nuclear motion. In particular, we apply ab initio molecular dynamics to two photoreactions involving hydrogen. Hydrogen, as the lightest element, is often assumed to show quantum mechanical tunneling. We will see that the classical picture is fully sufficient. The quantum mechanical view leads to phenomena that are difficult to understand, such as the entanglement of nuclear motion. In contrast, it is easy to understand the simple classical picture which assumes that nuclear motion is steady and uniform unless a force is acting. Of course, such a hypothesis must be verified for many systems and phenomena, and this paper is one more step in this direction. Full article

Arc brazing is an alternative joining technology well-suited for processing thermally sensitive materials and to produce mixed material connections. Due to the technological similarities of gas metal arc brazing to gas metal arc welding, it can be assumed that the process-related hydrogen input is of similar magnitude for both joining technologies. Since diffusible hydrogen is known to cause embrittlement in metallic materials, it is necessary to know the amount of diffusible hydrogen introduced by different manufacturing processes. Regarding the qualification of welding procedures, hydrogen ingress is an important factor to evaluate the risk of hydrogen-assisted cold cracking, especially when processing high-strength steels. For arc brazing, there is a lack of knowledge about the process-related hydrogen input. Hence, to study the influence of different brazing filler materials and varying levels of heat input on the diffusible hydrogen concentration in arc braze metal, a methodology to determine hydrogen content in arc weld metal in accordance with international standard ISO 3690 based on carrier gas hot extraction was applied to arc brazed specimens. Very low diffusible hydrogen concentrations of about H_D = 0.1 to 0.3 mL/100 g were found for GMAB without significant influence of arc energy or filler metal used. Full article

The geological storage of hydrogen is a seasonal energy storage solution, and the storage capacity of saline aquifers is most appropriately defined by quantifying the amount of hydrogen that can be injected and reproduced over a relevant time period. Cushion gas, stored in the reservoir to support the production of the working gas, is a CAPEX, which should be reduced to decrease implementation cost for gas storage. The cushion gas to working gas ratio provides a sufficiently accurate reflection of the storage efficiency, with higher ratios equating to larger initial investments. This paper investigates how technical measures, such as well configurations and adjustments to the operational size and schedule, can reduce this ratio, and the outcomes can inform optimisation strategies for hydrogen storage operations. Using a simplified open saline aquifer reservoir model, hydrogen storage is simulated with a single injection and production well. The results show that the injection process is more sensitive to technical measures than the production process; a shorter perforation and a smaller well diameter increases the required cushion gas for the injection process but has little impact on the production. If the storage operation capacity is expanded, and the working gas volume increased, the required cushion gas to working gas ratio increases for injection, reducing the efficiency of the injection process. When the reservoir pressure has more time to equilibrate, less cushion gas is required. It is shown that cushion gas plays an important role in storage operations and that the tested optimisation strategies impart only minor effects on the production process, however, there is significant need for careful optimisation of the injection process. It is suggested that the recoverable part of the cushion gas could be seen as a strategic gas reserve, which can be produced during an energy crisis. In this scenario, the recoverable cushion gas could be owned by the state, and the upfront costs for gas storage to the operator would be reduced, making the implementation of more gas storage and the onset of hydrogen storage more attractive to investors. Full article

In this review, we compare hydrogen production from waste by pyrolysis and bioprocesses. In contrast, the pyrolysis feed was limited to plastic and tire waste unlikely to be utilized by biological decomposition methods. Recent risks of pyrolysis, such as pollutant emissions during the heat decomposition of polymers, and high energy demands were described and compared to thresholds of bioprocesses such as dark fermentation. Many pyrolysis reactors have been adapted for plastic pyrolysis after successful investigation experiences involving waste tires. Pyrolysis can transform these wastes into other petroleum products for reuse or for energy carriers, such as hydrogen. Plastic and tire pyrolysis is part of an alternative synthesis method for smart polymers, including semi-conductive polymers. Pyrolysis is less expensive than gasification and requires a lower energy demand, with lower emissions of hazardous pollutants. Short-time utilization of these wastes, without the emission of metals into the environment, can be solved using pyrolysis. Plastic wastes after pyrolysis produce up to 20 times more hydrogen than dark fermentation from 1 kg of waste. The research summarizes recent achievements in plastic and tire waste pyrolysis development. Full article

This study presents a methodology of a quantitative risk assessment for the scenario of an onboard hydrogen storage tank rupture and tunnel fire incident. The application of the methodology is demonstrated on a road tunnel. The consequence analysis is carried out for the rupture of a 70 MPa, 62.4-litre hydrogen storage tank in a fire, that has a thermally activated pressure relief device (TPRD) failed or blocked during an incident. Scenarios with two states of charge (SoC) of the tank, i.e., SoC = 99% and SoC = 59%, are investigated. The risks in terms of fatalities per vehicle per year and the cost per incident are assessed. It is found that for the reduction in the risk with the hydrogen-powered vehicle in a road tunnel fire incident to the acceptable level of 10⁻⁵ fatality/vehicle/year, the fire-resistance rating (FRR) of the hydrogen storage tank should exceed 84 min. The FRR increase to this level reduces the societal risk to an acceptable level. The increase in the FRR to 91 min reduces the risk in terms of the cost of the incident to GBP 300, following the threshold cost of minor injury published by the UK Health and Safety Executive. The Frequency–Number (F–N) of the fatalities curve is developed to demonstrate the effect of mitigation measures on the risk reduction to socially acceptable levels. The performed sensitivity study confirms that with the broad range of input parameters, including the fire brigade response time, the risk of rupture of standard hydrogen tank-TPRD systems inside the road tunnel is unacceptable. One of the solutions enabling an inherently safer use of hydrogen-powered vehicles in tunnels is the implementation of breakthrough safety technology—the explosion free in a fire self-venting (TPRD-less) tanks. Full article

Hydrogen (H₂) is regarded as a promising and renewable energy carrier to achieve a sustainable future. Among the various H₂ production routes, photocatalytic water splitting has received particular interest; it strongly relies on the optical and structural properties of photocatalysts such as their sunlight absorption capabilities, carrier transport properties, and amount of oxygen vacancy. Perovskite oxides have been widely investigated as photocatalysts for photocatalytic water splitting to produce H₂ because of their distinct optical properties, tunable band gaps and excellent compositional/structural flexibility. Herein, an aluminum cation (Al³⁺) doping strategy is developed to enhance the photocatalytic performance of Ruddlesden-Popper (RP) Sr₂TiO₄ perovskite oxides for photocatalytic H₂ production. After optimizing the Al³⁺ substitution concentration, Sr₂Ti_0.9Al_0.1O₄ exhibits a superior H₂ evolution rate of 331 μmol h⁻¹ g⁻¹, which is ~3 times better than that of Sr₂TiO₄ under full-range light illumination, due to its enhanced light harvesting capabilities, facilitated charge transfer, and tailored band structure. This work presents a simple and useful Al³⁺ cation doping strategy to boost the photocatalytic performance of RP-phase perovskites for solar water splitting. Full article

The computer-aided engineering approach has made it possible to achieve virtual prototypes and to describe expected performances of new apparatuses. In this study, a direct production of syngas with biogas using the configuration of the cascade conversion cell in the supply feed direction of the system was exhibited. Momentum, heat, mass and charge balances were solved using COMSOL Multiphysics^® commercial software. These simulations allowed calculation of distributions of partial pressures for all gas species within the anode (CH₄, H₂, CO, CO₂, H₂O, N₂), as well as velocity field and temperature. The conversion process included methane reforming (steam and dry) associated with the water–gas shift reaction. The computing results showed that the configuration of three porous oxide solid cells based on a solid oxide fuel cell (SOFC) system conferred a larger active surface area and limited thermal stress in oxide materials. In addition, depending on the production process of the biogas, feeding composition strongly influences the conversion rate of CO₂ and CH₄. We observed that production of syngas was optimal for a CO₂/CH₄ ratio = 1. Full article

Hydrogen embrittlement of a Ni-based superalloy, IN740H, was evaluated after gas-phase hydrogen pre-charging. Specimens with different grain sizes were prepared to induce different precipitation behavior under annealing treatment; the formation of needle-like MC carbide was found only in a specimen with a larger grain size and incoherent twin boundaries after annealing treatment at 1173 K. While other parameters including the grain size and annealing treatment turned out not to undermine the resistance to hydrogen embrittlement, the needle-like MC carbide was found to induce premature failure after hydrogen absorption. Full article

An oxygen pump sensor was constructed using yttria-stabilized zirconia, which is an oxide ion conductor, and oxygen was discharged from steam to generate hydrogen. The oxygen pump sensor consisted of a pump that discharges oxygen and a sensor that controls the oxygen partial pressure by having electrodes in two places. Oxygen was discharged by applying a current to the pump by controlling the potential of the sensor. Hydrogen was then generated from water vapor. Furthermore, an oxygen pump sensor was installed in the second stage, oxygen was supplied by the pump, and the amount of generated hydrogen was measured in situ. This measurement showed that the oxygen partial pressure of the atmosphere decreased as hydrogen was generated. Specifically, the partial pressure of the water vapor generated more hydrogen at 30.8 vol.% than at 12.2 vol.%. Moreover, the amounts of oxygen discharged and hydrogen generated inversely correlated with the potential. Full article

Among all hydrocarbons, the methane molecule contains the highest amount of hydrogen with respect to carbon. Therefore, the catalytic decomposition of methane is considered as an efficient approach to produce hydrogen along with nanostructured carbon product. On the other hand, the presence of hydrogen in the composition of the initial gas mixture is required for the stable operation of the catalyst. In present work, the experiments on the catalytic decomposition of methane–hydrogen mixture were performed in a flow-through quartz reactor equipped with McBain balances under atmospheric pressure. The catalyst NiO-CuO/Al₂O₃ was prepared by the mechanochemical activation technique. The maximum carbon yield of 34.9 g/g_cat was obtained after 2 h of experiment at 610 °C. An excess of hydrogen in the reaction mixture provided the long-term activity of the nickel–copper catalyst. The durability tests ongoing for 6 h within a temperature range of 525–600 °C showed no noticeable deactivation of the catalyst. Two kinetic models, D1a and M1a, were proposed for the studied decomposition of the methane–hydrogen mixture over the nickel–copper catalyst. The kinetic constants for these models were determined by means of mathematical modelling. Full article

An under-expanded hydrogen jet from high-pressure equipment or storage tank is a potential incident scenario. Experiments demonstrated that the delayed ignition of a highly turbulent under-expanded hydrogen jet generates a blast wave able to harm people and damage property. There is a need for engineering tools to predict the pressure effects during such incidents to define hazard distances. The similitude analysis is applied to build a correlation using available experimental data. The dimensionless blast wave overpressure generated by delayed ignition and the follow-up deflagration or detonation of hydrogen jets at an any location from the jet, $∆P_{exp}/P_0$, is correlated to the original dimensionless parameter composed of the product of the dimensionless ratio of storage pressure to atmospheric pressure, $P_s/P_0$, and the ratio of the jet release nozzle diameter to the distance from the centre of location of the fast-burning near-stoichiometric mixture on the jet axis (30% of hydrogen in the air by volume) to the location of a target (personnel or property), $d/R_w$. The correlation is built using the analysis of 78 experiments regarding this phenomenon in the wide range of hydrogen storage pressure of 0.5–65.0 MPa and release diameter of 0.5–52.5 mm. The correlation is applicable to hydrogen free jets at ambient and cryogenic temperatures. It is found that the generated blast wave decays inversely proportional to the square of the distance from the fast-burning portion of the jet. The correlation is used to calculate the hazard distances by harm thresholds for five typical hydrogen applications. It is observed that in the case of a vehicle with onboard storage tank at pressure 70 MPa, the “no-harm” distance for humans reduces from 10.5 m to 2.6 m when a thermally activated pressure relief device (TPRD) diameter decreases from 2 mm to a diameter of 0.5 mm. Full article

The successful and fast start-up of proton exchange membrane fuel cells (PEMFCs) at subfreezing temperatures (cold start) is very important for the use of PEMFCs as energy sources for automotive applications. The effective thermal management of PEMFCs is of major importance. When hydrogen is stored in hydride-forming intermetallics, significant amounts of heat are released due to the exothermic nature of the reaction. This excess of heat can potentially be used for PEMFC thermal management and to accelerate the cold start. In the current work, this possibility is extensively studied. Three hydride-forming intermetallics are introduced and their hydrogenation behavior is evaluated. In addition, five thermal management scenarios of the metal hydride beds are studied in order to enhance the kinetics of the hydrogenation. The optimum combination of the intermetallic, hydrogenation behavior, weight and complexity of the thermal management system was chosen for the study of thermal coupling with the PEMFCs. A 1D GT-SUITE model was built to stimulate the thermal coupling of a 100 kW fuel cell stack with the metal hydride. The results show that the use of the heat from the metal hydride system was able to reduce the cold start by up to 8.2%. Full article

With increasing shares of variable and uncertain renewable generation in many power systems, there is an associated increase in the importance of energy storage to help balance supply and demand. Gas networks currently store and transport energy, and they have the potential to play a vital role in longer-term renewable energy storage. Gas and electricity networks are becoming more integrated with quick-responding gas-fired power plants, providing a significant backup source for renewable electricity in many systems. This study investigates Ireland’s gas network and operation when a variable green hydrogen input from excess wind power is blended with natural gas. How blended hydrogen impacts a gas network’s operational variables is also assessed by modelling a quasi-transient gas flow. The modelling approach incorporates gas density and a compressibility factor, in addition to the gas network’s main pressure and flow rate characteristics. With an increasing concentration of green hydrogen, up to 20%, in the gas network, the pipeline flow rate must be increased to compensate for reduced energy quality due to the lower energy density of the blended gas. Pressure drops across the gas pipeline have been investigated using different capacities of P2H from 18 MW to 124 MW. The results show significant potential for the gas network to store and transport renewable energy as hydrogen and improve renewable energy utilisation without upgrading the gas network infrastructure. Full article