Hydrogen

We present the analysis of the stability of the (TiO₂)_n nanoclusters, where n = 2–4, supported on the Fe₃O₃-hematite (100) surface. The analysis is focused on the size and geometry of the nanocluster, which defines the contact with the supporting hematite surface. The aim of the work is to explore the role of the interaction within the nanocluster as well as between the nanocluster and the surface in the structure of the composite system. We have used an in-house developed variant of the solids docking procedure to determine the most stable initial configurations of the nanoclusters with respect to the surface. Subsequently, we have carried out molecular dynamics simulations to enable finding a more stable configurations by the systems. The results show the three possible binding modes for the (TiO₂)₂ systems, but many more such modes for the larger clusters. Additionally, we have found that the partial dissociation of the nanocluster takes place upon the contact with the surface. Full article

Oxygen bubble accumulation on the anodic side of a polymer exchange membrane water electrolyzer (PEMWE) may cause a decrease in performance. To understand the behavior of these bubbles, a deep-learning-based bubble flow recognition tool dedicated to a PEMWE is developed. Combining the transparent side of a single PEMWE cell with a high-resolution high-speed camera allows us to acquire images of the two-phase flow in the channels. From these images, a deep learning vision system using a fine-tuned YOLO V7 model is applied to detect oxygen bubbles. The tool achieved a high mean average precision of 70%, confirmed the main observations in the literature, and provided exciting insights into the characteristics of two-phase flow regimes. In fact, increasing the water flow rate from 0.05 to 0.4 L/min decreases the bubble coverage (by around 32%) and the mean single-bubble area. In addition, increasing the current density from 0.3 to 1.4 A/cm² leads to an increase in bubble coverage (by around 40%) and bubble amount. Full article

A proton exchange membrane (PEM) electrolyzer is fed with water and powered by electric power to electrochemically produce hydrogen at low operating temperatures and emits oxygen as a by-product. Due to the complex nature of the performance of PEM electrolyzers, the application of an artificial neural network (ANN) is capable of predicting its dynamic characteristics. A handful of studies have examined and explored ANN in the prediction of the transient characteristics of PEM electrolyzers. This research explores the estimation of the transient behavior of a PEM electrolyzer stack under various operational conditions. Input variables in this study include stack current, oxygen pressure, hydrogen pressure, and stack temperature. ANN models using three differing learning algorithms and time delay structures estimated the hydrogen mass flow rate, which had transient behavior from 0 to 1 kg/h, and forecasted better with a higher count (>5) of hidden layer neurons. A coefficient of determination of 0.84 and a mean squared error of less than 0.005 were recorded. The best-fitting model to predict the dynamic behavior of the hydrogen mass flow rate was an ANN model using the Levenberg–Marquardt algorithm with 40 neurons that had a coefficient of determination of 0.90 and a mean squared error of 0.00337. In conclusion, optimally fit models of hydrogen flow from PEM electrolyzers utilizing artificial neural networks were developed. Such models are useful in establishing an agile flow control system for the electrolyzer system to help decrease power consumption and increase efficiency in hydrogen generation. Full article

For the few past decades, study of new hydrogen storage materials has been captivating scientists worldwide. Magnesium hydride, MgH₂, is considered one of the most promising materials due to its low cost, high hydrogen capacity, reversibility and the abundance of Mg. However, it requires further research to improve its hydrogen storage performance as it has some drawbacks such as poor dehydrogenation kinetic, high operational temperature, which limit its practical application. In this study, we introduce an overview of recent progress in improving the hydrogen storage performance of MgH₂ by the addition of titanium-based additives, which are one of the important groups of additives. The role of Ti-based additive hydrides, oxides, halides, carbides and carbonitrides are overviewed. In addition, the existing challenges and future perspectives of Mg-based hydrides are also discussed. Full article

Ceria-based nanostructures, employed as catalytic supports for noble and non-noble metals, are well-known for their remarkable activity in steam-reforming reactions, exceptional resistance to degradation, and thermal stability. However, the catalytic activity and selectivity of such systems are strongly dependent on the size and shape of ceria, making it possible to tune the oxide properties, affecting catalyst design and performance. The rational manipulation of ceria nanostructures offers various features that directly impact steam-reforming transformations, including the possibility of tuning oxygen vacancies, redox properties, and oxygen storage capacity. Thus, the importance of shape control in ceria nanomaterials is highlighted herein, emphasizing how the surface atomic configurations (exposure of different facets) significantly impact their efficiency. Although the main focus of this review is to discuss how the catalyst design may affect the performance of hydrogen production, some other elemental studies are shown, when necessary, to exemplify the level of deepness (or not) that literature has reached. Thus, an overview of ceria properties and how the physicochemical control of nanostructures contributes to their tuning will be presented, as well as a discussion regarding elemental materials design and the most prominent synthetic procedures; then, we select some metals (Ni, Co, and Pt) to discuss the understanding of such aspects for the field. Finally, challenges and perspectives for nanoengineering catalysts based on shape-controlled ceria nanostructures will be described to possibly improve the performance of designed catalysts for steam-reforming reactions. Although there are other literature reviews on ceria-based catalysts for these reactions, they do not specifically focus on the influence of the size and shape of the oxide. Full article

Working towards a more sustainable future with zero emissions, the International Future Laboratory for Hydrogen Economy at the Technical University of Munich (TUM) exhibits concerted efforts across various hydrogen technologies. The current research focuses on pre-reforming processes for high-quality reversible solid oxide cell feedstock preparation. An AI-based machine learning model has been developed, trained, and deployed to predict and optimise the controlled utilisation of methane gas. Using a blend of design of experiments and a validated 3D computational fluid dynamics model, pre-reforming process data have been generated for various syngas mixtures. The results of this study indicate that it is possible to achieve a targeted methane utilisation rate of 20% while decreasing the amount of catalyst material by 11%. Furthermore, it was found that precise process parameters could be determined efficiently and with minimal resource consumption in order to achieve higher methane fuel utilisation rates of 25% and 30%. The machine learning model has been effectively employed to analyse and optimise the fuel outlet conditions of the pre-reforming process, contributing to a better understanding of high-quality syngas preparation and furthering sustainable research efforts for a safe reversible solid oxide cell (r-SOC) process. Full article

Determining how to apply hydrogen as a therapeutic/preventive antioxidant for oxidative-stress-related diseases practically in daily life has not been studied. The effects of bathtubs and buckets filled with hydrogen water (41 °C, >10 min bathing) were investigated on six subjects, without a medical prescription, suffering from skin roughness on the foot, hand, finger, or elbow. They were also treated with an electrolyzer composed of a lattice-shaped, microscopically flat, platinum-plated three-layer electrode, except for one subject who was treated with a micro-porous emittance terminal hydrogen-jetting apparatus, resulting in improvements in both cases. For another subject with similar skin roughness on both hands, immersing the right hand in an electrolytically generated hydrogen water bucket showed more marked improvement than immersing the left hand in a bucket with normal water. The nano-bubbles (average, mode, and median sizes of 157 nm, 136 nm, and 94 nm, respectively) increased 3.79 fold to 2.20 × 10⁸/mL after 30 min electrolysis with 2 L of tap water and were boiling (98 °C, 2 min)-resistant, with heat stability in nano-bubbles as small as 69–101 nm, as evaluated by laser-beam-based Brownian movement trailing Nano-Sight analysis. The marked increase in nano-bubbles caused by electrolysis correlated with an increase in dissolved hydrogen (<15 μg/L to 527 μg/L) but not a decrease in dissolved oxygen (9.45 mg/L to 6.94 mg/L). Thus, the present study proposed the novelty of hydrogen regarding its contribution to health from the perspective that hydrogen-nano-bubble-rich water in a foot bucket, which was additively used together with a conventional bathtub and can be frequently used in daily life, improved diverse types of skin roughness. Full article

Hydrogen represents a promising renewable fuel, and its broad application can lead to drastic reductions in greenhouse gas emissions. Keeping hydrogen in liquid form helps achieve high energy density, but also requires cryogenic conditions for storage as hydrogen evaporates at temperatures of about 20 K, which can lead to a large pressure build-up in the tank. This paper addresses the unsteady thermal modeling of cryogenic tanks with liquid hydrogen. Considering the liquid and vapor phases in the tank as two nodes with averaged properties, a lumped-element method of low computational cost is developed and used for simulating two regimes: self-pressurization (also known as autogenous pressurization, or pressure build-up in the closed tank due to external heat leaks) and constant-pressure venting (when some hydrogen is let out of the tank to maintain pressure at a fixed level). The model compares favorably (within several percent for pressure) to experimental observations for autogenous pressurization in a NASA liquid hydrogen tank. The two processes of interest in this study are numerically investigated in tanks of similar shapes but different sizes ranging from about 2 to 1200 m³. Pressure and temperature growth rates are characterized in closed tanks, where the interfacial mass transfer manifests initial condensation followed by more pronounced evaporation. In tanks where pressure is kept fixed by venting some hydrogen from the vapor domain of the tank, the initial venting rate significantly exceeds evaporation rate, but after a settling period, magnitudes of both rates approach each other and continue evolving at a slower pace. The largest tank demonstrates a six-times-lower pressure rise than the smallest tank over a 100 h period. The relative boil-off losses in continuously vented tanks are found to be approximately proportional to the inverse of the tank diameter, thus generally following simple Galilean scaling with a few percent deviation due to scale effects. The model developed in this work is flexible for analyzing a variety of processes in liquid hydrogen storage systems, raising efficiencies, which is critically important for a future economy based on renewable energy. Full article

In this work, the production of hydrogen from the sodium borohydride (NaBH₄) reaction was studied using an experimental bench test in a passive device operating with or without minimal external energy input. The system consists of a reactor in which a mixture based on sodium borohydride powders and an organic acid is confined. A flow of water feeds the area in which the solid mixture is confined, which undergoes a hydrolysis reaction and this generates gaseous hydrogen. The hydrogen thus produced, already saturated with water vapor, is particularly suitable for feeding polymer electrolyte fuel cells for the production of electricity because it does not require further humidification. The borohydride–organic acid coupling studied for this device, and its chemical process, provides high reaction and conversion kinetics, presenting remarkable chemical stability over time. Full article

The realization of a carbon-neutral civilization, which has been set as a goal for the coming decades, goes directly hand-in-hand with the need for an energy system based on renewable energies (REs). Due to the strong weather-related, daily, and seasonal fluctuations in supply of REs, suitable energy storage devices must be included for such energy systems. For this purpose, an energy system model featuring hybrid energy storage consisting of a hydrogen unit (for long-term storage) and a lithium-ion storage device (for short-term storage) was developed. With a proper design, such a system can ensure a year-round energy supply by using electricity generated by photovoltaics (PVs). In the energy system that was investigated, hydrogen (${\mathrm{H}}_2$) was produced by using an electrolyser (ELY) with a PV surplus during the summer months and then stored in an ${\mathrm{H}}_2$ tank. During the winter, due to the lack of PV power, the ${\mathrm{H}}_2$ is converted back into electricity and heat by a fuel cell (FC). While the components of such a system are expensive, a resource- and cost-efficient layout is important. For this purpose, a Matlab/Simulink model that enabled an energy balance analysis and a component lifetime forecast was developed. With this model, the results of extensive parameter studies allowed an optimized system layout to be created for specific applications. The parameter studies covered different focal points. Several ELY and FC layouts, different load characteristics, different system scales, different weather conditions, and different load levels—especially in winter with variations in heating demand—were investigated. Full article

The influence of the lanthanum and barium addition on the physicochemical properties and catalytic behavior of the Ru/C catalyst for CO methanation was investigated. The catalyst was doped with La or with La plus Ba. It was found out that there are various ways the additives were applied in the study, thus changing the catalytic performance of the basic material and influencing the susceptibility of the carbon support in relation to undesired methanation. The highest catalytic activity, 23.46 (mmol CO/g_C+Ru × h), was achieved for the LaRu/C system, with methane selectivity exceeding 80% over the whole temperature range. Ba addition caused a significant decrease in activity. TG-MS studies revealed that both La and Ba improved the resistance of the carbon support to undesired methanation. Detailed characterization methods, employing XRPD, Raman spectroscopy, CO chemisorption, and SEM-EDX, showed that the catalytic behavior of the studied catalysts was attributed to lanthanum distribution over the Ru/C materials surface and structural changes in the carbon support affecting electron supply to the metallic active phase. Full article

Solution plasma is a gas-phase discharge in the vapor bubbles in a solution and has the potential to efficiently produce H₂ by decomposing aqueous alcohols. However, the mechanism of alcohol decomposition in solution plasma remains unclear. In this study, lower monohydric alcohols (methanol and ethanol, as well as 1- and 2-propanol) were treated in solution plasma, and in this paper, the gasification mechanism is discussed. The gases produced from these alcohols were mainly H₂ and CO, with small ratios of C₁–C₃ hydrocarbons. Thus, the O/C ratio in the product gas was close to 1 for all alcohols, and most of the C atoms in the alcohols were bonded to O atoms. This excess of O atoms could have only come from water, suggesting a strong contribution of OH radicals from water for gasification. However, the C₁–C₃ hydrocarbons were produced solely by the decomposition of the alcohol. For both decomposition routes, possible reaction pathways are proposed that are consistent with the experimental facts such as the composition of the product gas and the intermediates detected. Full article

This contribution presents the results of continued investigations on the production of hydrogen by means of pyrolysis in a liquid metal bubble column reactor, as developed at the Karlsruhe Institute of Technology in recent years. Part I of this contribution described the motivation and the methodology of this study, as well as a significant scale-up, and discussed its results for pure methane pyrolysis. Here in part II, two additional experimental campaigns with methane–ethane mixtures (MEMs) and high-calorific natural gas (nGH) will be presented and discussed for the first time, using the up-scaled liquid metal bubble column reactor. It could be proven that an MEM as the feed gas led to an increase in methane conversion at low temperatures, which is consistent with the literature data. The nGH pyrolysis confirms this trend and also results in a significant rise in methane conversion compared to pure methane pyrolysis. Furthermore, the nGH pyrolysis leads to an increased methane conversion even at higher temperatures compared to MEM pyrolysis. Additionally, both MEM and nGH pyrolysis also showed a shift in the formation of by-products toward lower temperatures. Full article

The energy intensity and high emissions of extractive industries bring a major need for decarbonisation actions. In 2021, extraction and primary processing of metals and minerals were responsible for 4.5 Gt of equivalent CO₂. The aluminium industry specifically accounted for total emissions of 1.1 Gt CO₂ eq. per year. Reaching the European milestone of zero emissions by 2050, requires a 3% annual reduction. To achieve this, the industry has searched for innovative solutions, considering the treatment of emitted CO₂ with techniques such as Carbon Capture Utilisation and Storage (CCUS), or the prevention of CO₂ formation on the first place by utilising alternative fuels such as hydrogen (H₂). This study aims to comprehensively compare the overall environmental performance of different strategies for addressing not only greenhouse gas (GHG) emission reduction potential, but also emissions to air in general, as well as freshwater and terrestrial ecotoxicity, which are commonly overlooked. Specifically, a Life Cycle Assessment (LCA) is conducted, analysing four scenarios for primary Al production, utilising (1) a combination of fossil fuels, specifically Natural Gas (NG), Light Fuel Oil (LFO) and Heavy Fuel Oil (HFO) (conventional approach); (2) carbon capture and geological storage; (3) Carbon Capture and Utilisation (CCU) for methanol (MeOH) production and (4) green H₂, replacing NG. The results show that green H₂ replacing NG is the most environmentally beneficial option, accounting for a 10.76% reduction in Global Warming Potential (GWP) and 1.26% in Photochemical Ozone Formation (POF), while all other impact categories were lower compared to CCUS. The results offer a comprehensive overview to support decision-makers in comparing the overall environmental impact and the emission reduction potential of the different solutions. Full article

In this work, geochemical modelling using PhreeqC was carried out to evaluate the effects of geochemical reactions on the performance of underground hydrogen storage (UHS). Equilibrium, exchange, and mineral reactions were considered in the model. Moreover, reaction kinetics were considered to evaluate the geochemical effect on underground hydrogen storage over an extended period of 30 years. The developed model was first validated against experimental data adopted from the published literature by comparing the modelling and literature values of H₂ and CO₂ solubility in water at varying conditions. Furthermore, the effects of pressure, temperature, salinity, and CO₂% on the H₂ and CO₂ inventory and rock properties in a typical sandstone reservoir were evaluated over 30 years. Results show that H₂ loss over 30 years is negligible (maximum 2%) through the studied range of conditions. The relative loss of CO₂ is much more pronounced compared to H₂ gas, with losses of up to 72%. Therefore, the role of CO₂ as a cushion gas will be affected by the CO₂ gas losses as time passes. Hence, remedial CO₂ gas injections should be considered to maintain the reservoir pressure throughout the injection and withdrawal processes. Moreover, the relative volume of CO₂ increases with the increase in temperature and decrease in pressure. Furthermore, the reservoir rock properties, porosity, and permeability, are affected by the underground hydrogen storage process and, more specifically, by the presence of CO₂ gas. CO₂ dissolves carbonate minerals inside the reservoir rock, causing an increase in the rock’s porosity and permeability. Consequently, the rock’s gas storage capacity and flow properties are enhanced. Full article

Hydrogen barrier coatings are protective layers consisting of materials with a low intrinsic hydrogen diffusivity and solubility, showing the potential to delay, reduce or hinder hydrogen permeation. Hydrogen barrier coatings are expected to enable steels, which are susceptible to hydrogen embrittlement, specifically cost-effective low alloy-steels or light-weight high-strength steels, for applications in a hydrogen economy. Predominantly, ceramic coating materials have been investigated for this purpose, including oxides, nitrides and carbides. In this review, the state of the art with respect to hydrogen permeation is discussed for a variety of coatings. Al₂O₃, TiAlN and TiC appear to be the most promising candidates from a large pool of ceramic materials. Coating methods are compared with respect to their ability to produce layers with suitable quality and their potential for scaling up for industrial use. Different setups for the characterisation of hydrogen permeability are discussed, using both gaseous hydrogen and hydrogen originating from an electrochemical reaction. Finally, possible pathways for improvement and optimisation of hydrogen barrier coatings are outlined. Full article

Hydrogen is not only an important industrial chemical but also an energy carrier with increasing demand. However, the current production techniques are based on technologies that result in massive CO₂ emissions. In contrast, the pyrolysis of alkanes in a liquid metal bubble column reactor does not lead to direct CO₂ emissions. In order to transfer this technology from lab-scale to industrial applications, it has to be scaled up and the influences of the most common constituent of natural gas on the pyrolysis process have to be determined. For this study, the liquid metal bubble column technology developed at the KIT was scaled up by a factor of 3.75, referred to as the reactor volume. In this article, the experimental setup containing the reactor is described in detail. In addition, new methods for the evaluation of experimental data will be presented. The reactor, as well as the experimental results from pure methane pyrolysis (PM), will be compared to the previous generation of reactors in terms of methane conversion. It could be proven that scaling up the reactor volume did not result in a decrease in methane conversion. For part II of this publication, methane-ethane (MEM) gas mixtures and high calorific natural gas (nGH) were pyrolyzed, and the results were discussed on the basis of the present part I. Full article

The concept of classical nuclear motion is extremely successful in describing motion at the atomic scale. In describing chemical reactions, it is even far more convincing than the picture obtained by using the Schrödinger equation for time development. However, this theory must be subject to critical tests. In particular, it must be checked if vibrational and rotational spectra are obtained correctly. Particularly critical are the spectra of small molecules containing the light hydrogen atom, since they have a distinctive rotational structure. The present study presents computations of the spectra of ammonia and hydrogen chloride using ab initio molecular dynamics, that is, by describing nuclear motion classically. Full article

Cottonseed oil (CSO) is well known as one of the commercial cooking oils. However, CSO still needs to compete with other edible oils available in the market due to its small production scale and high processing cost, which makes it a potential candidate as a feedstock for biodiesel production. To date, transesterification is the most widely applied technique in the conversion of vegetable oil to biodiesel, with glycerol produced as a by-product. Large-scale biodiesel production also implies that more glycerol will be produced, which can be further utilized to synthesize hydrogen via the steam reforming route. Therefore here, an integrated biodiesel and hydrogen production from CSO was simulated using Aspen Hysys v11. Simulation results showed that the produced biodiesel has good characteristics compared to standard biodiesel. An optimum steam-to-glycerol ratio for hydrogen production was found to be 4.5, with higher reaction temperatures up to 750 °C resulting in higher hydrogen yield and selectivity. In addition, a simple economic analysis of this study showed that the integrated process is economically viable. Full article