Liquid Organic Hydrogen Carriers Research Articles

Scalable Atomic‐Layer Tailoring of Abundant Oxide Supports Unlocks Superior Interfaces for Low‐Metal‐Loading Dehydrogenation

Liquid organic hydrogen carriers (LOHCs) offer a promising solution for global hydrogen infrastructure, but their practical application faces two key challenges: sluggish dehydrogenation processes and the reliance on catalysts with high noble metal loadings. This study presents a scalable approach to reduce noble metal usage while maintaining high catalytic activity. We synthesized an ultralow Pt content (0.1 wt%) catalyst using γ‐Al2O3‐based pellet support with atomic layer deposition (ALD) of TiO2. Advanced characterization techniques reveal that the thin ALD‐TiO2 shell provides a heterogeneous interface, confining electronically rich Pt‐nanoparticle ensembles. The catalyst outperforms both equivalent Pt‐content catalysts and a commercial 0.5 wt% Pt/γ‐Al2O3 catalyst in homocyclic LOHC dehydrogenation. This study provides insights into the beneficial role of ALD‐engineered interfaces for catalytic supports and offers an efficient approach for scalable production of low‐noble‐metal‐content catalysts, with implications for various catalytic processes.

Scalable Atomic-Layer Tailoring of Abundant Oxide Supports Unlocks Superior Interfaces for Low-Metal-Loading Dehydrogenation.

Liquid organic hydrogen carriers (LOHCs) offer a promising solution for global hydrogen infrastructure, but their practical application faces two key challenges: sluggish dehydrogenation processes and the reliance on catalysts with high noble metal loadings. This study presents a scalable approach to reduce noble metal usage while maintaining high catalytic activity. We synthesized an ultralow Pt content (0.1 wt%) catalyst using γ-Al2O3-based pellet support with atomic layer deposition (ALD) of TiO2. Advanced characterization techniques reveal that the thin ALD-TiO2 shell provides a heterogeneous interface, confining electronically rich Pt-nanoparticle ensembles. The catalyst outperforms both equivalent Pt-content catalysts and a commercial 0.5 wt% Pt/γ-Al2O3 catalyst in homocyclic LOHC dehydrogenation. This study provides insights into the beneficial role of ALD-engineered interfaces for catalytic supports and offers an efficient approach for scalable production of low-noble-metal-content catalysts, with implications for various catalytic processes.

Advances in Catalytic Hydrogenation of Liquid Organic Hydrogen Carriers (LOHCs) Using High‐Purity and Low‐Purity Hydrogen

AbstractLiquid organic hydrogen carriers (LOHCs) are emerging as a promising solution for global hydrogen logistics. The LOHC process involves two primary chemical reactions: hydrogenation for hydrogen storage and dehydrogenation for hydrogen reconversion. In the exothermic hydrogenation reaction, hydrogen‐lean compounds are converted to hydrogen‐rich compounds, storing hydrogen from various sources such as water electrolysis, fossil fuel reforming, biomass processing, and industrial by‐products. Conversely, hydrogen is extracted from hydrogen‐rich compounds through an endothermic dehydrogenation reaction and supplied to several hydrogenation utilization offtakers. This review article discusses the development trends in catalytic hydrogenation processes for various LOHC materials, including benzene, toluene, naphthalene, biphenyl‐diphenylmethane, benzyltoluene, dibenzyltoluene, and N‐ethylcarbazole. It introduces references for catalytic hydrogenation processes utilizing both high‐purity and low‐purity (alternatively, mixed) hydrogen feedstocks, with particular emphasis on low‐purity hydrogen applications. The direct storage of hydrogen with minimal purification, using by‐product hydrogen and mixed hydrogen from hydrocarbon and biomass reforming, is crucial for the economic viability of this hydrogen carrier system.

Indene as an alternative hydrogen carrier: Performance of supported noble metal catalysts for indene and indane hydrogenation

We propose in this article the use of indene, obtained from the light fraction of coal tar rectification, as a Liquid Organic Hydrogen Carrier (LOHC), with a thorough study of its hydrogenation. The hydrogenation process, conducted on noble metal catalysts (Pd, Pt, Rh, and Ru) supported by activated carbon or alumina, involves the rapid conversion of indene to indane, followed by the formation of cis- and trans-hydrindane. Carbon-supported catalysts exhibited faster reactions rates, with catalytic activities varying among metal phases, Rh and Ru being the most active. Indene was found to have an inhibitory effect on the hydrogenation reactions. While Ru catalysts enhance cracking, Rh catalysts are the most selective for total hydrogenation. The study highlights that Ru catalysts favour cracking reactions more than Rh. The proposed reaction mechanisms involve successive steps and follow a Langmuir-Hinshelwood type kinetics, confirming the inhibitory effect of indene.

Autothermal hydrogen release from liquid organic hydrogen carrier systems

A typical feature that the LOHC technology shares with other types of chemical hydrogen storage is that the release of hydrogen from the carrier requires an input of heat. In many use cases where waste heat from external sources is not available (e.g. in heavy-duty mobility), this is seen as a major drawback. In this paper, we show that autothermal LOHC dehydrogenation offers a very attractive way to overcome this drawback. In detail, we demonstrate autothermal hydrogen release from dicyclohexylmethane using diphenylmethane oxidation to benzophenone as source of heat. The full storage cycle involves benzophenone hydrodeoxygenation to dicyclohexylmethane, dicyclohexylmethane dehydrogenation to diphenylmethane, and diphenylmethane oxidation to benzophenone. We studied both the individual reaction steps using pure feedstocks and the integral cycle in which the intermediates and by-products of each reaction remain in the system for the subsequent reaction step. Although no efforts have yet been made to develop special catalyst materials for this purpose, the results with the applied commercial hydrodeoxygenation (Pd/C), dehydrogenation (Pt on alumina) and partial oxidation (VOx/TiO2) catalysts are already very promising. The storage cycle can be closed with high selectivity and with only minor total oxidation losses. The proposed concept of autothermal LOHC dehydrogenation offers the potential to increase the amount of useable hydrogen from a given amount of charged hydrogen carrier by up to 30%.

Dynamic stable Pt13 clusters anchored on isolated ZnOx nanorafts for efficient cycloparaffin dehydrogenation

Methylcyclohexane (MCH) has attracted wide attention as liquid organic hydrogen carriers for safe alternative and high gravimetric hydrogen density. Pt13 cluster with its fascinating structure exhibits excellent performance in cycloalkane dehydrogenation reactions accompanied by balanced C-H cleavage capability. However, the controllable synthesis of stable Pt13 clusters under reaction conditions remains challenging. Herein, we successfully synthesized low-coordinated Pt13 clusters anchored by isolated ZnOx nanorafts on silanol-rich self-pillared zeolite nanosheets (SP-S-1). In situ XAFS spectra combined with theoretical calculations revealed that Pt13 clusters exhibited strong interfacial Pt-Zn bonds and reduced d-band center through orbital hybridization (Zn 3d - Pt 5d), facilitating C-H bond cleavage and toluene desorption. The optimized catalyst exhibited superior MCH dehydrogenation activity and durability, achieving a hydrogen production rate of 3457.9 mmolH2 gPt−1 min−1 at 400 ˚C and maintaining stable for over 100 hours. This study precisely synthesizes dynamic stable Pt13 clusters and provides valuable insights into the dehydrogenation mechanism.

Reaction kinetics for catalytic hydrogenation of quinoline to decahydroquinoline as liquid organic hydrogen carrier

The catalytic hydrogenation of quinoline to decahydroquinoline (DHQ) formation is studied for various parameters such as temperature, hydrogen pressure, reaction time, solvents, reactant-to-solvent ratio, and catalyst loading over 5%Pd loaded on alumina (Pd/Al2O3) to obtain optimal reaction conditions. The hydrogen uptake of quinoline in the liquid phase reaction using isopropylalcohol (IPA) is studied in an autoclave reactor. The optimum reaction parameters of 50 bar H2 pressure and 175oC with reactant to solvent ratio of 1:9 for reaction time of 5 h are observed. The effect of IPA solvent showed that hydrogen uptake of 6.91 wt% with complete hydrogenation of quinoline and DHQ yield of more than 99% is observed. The reaction kinetic model is developed for a simplified reaction mechanism and is simulated using the Markov Chain Monte Carlo (MCMC) simulation tool to predict the rate constants and the experimental observations are validated with the model predictions. The activation energy for quinoline hydrogenation to py-THQ formation is estimated to be 136.57 kJ/mol. It is envisaged that quinoline hydrogenation to pz-THQ is the rate-limiting step in the DHQ formation.

The influence of acetone and isopropanol crossover on the direct isopropanol fuel cell

Liquid organic hydrogen carriers (LOHC) offer a promising option to store and release hydrogen on demand within existing infrastructure. The direct isopropanol fuel cell (DIFC) uses the electrochemical acetone/isopropanol LOHC couple and combines the advantages of high fuel energy density at ambient conditions with CO2-free direct electricity production. Like other alcohol fuel cells, the DIFC combines two kinetically slow reactions, the isopropanol oxidation reaction (IOR) and the oxygen reduction reaction (ORR), requiring considerable overpotentials to drive the reactions. Accordingly, deconvoluting kinetic characteristics in the full cell is difficult. Therefore, this work uses the electrolytic electrochemical dehydrogenation unit (EDU), consisting of the IOR and the kinetically fast hydrogen evolution reaction in acidic media. This EDU then serves as an IOR full-cell model to get insights on the DIFC. Correspondingly, the demonstrated work is a comparison study investigating in-house fabricated catalyst-coated membrane electrode assemblies as hydrogen fuel cells, DIFC, and EDU. It investigates characteristic features of the DIFC and demonstrates how the acetone and isopropanol crossover affect the cathode of the DIFC.

Liquid Organic Hydrogen Carrier Concepts and Catalysts for Hydrogenation and Dehydrogenation Reactions.

The issue of renewable energy (RE) source intermittency, such as wind and solar, along with the geographically uneven distribution of the global RE potential, makes it imperative to establish an energy transport medium to balance the energy demand and supply areas. A promising energy vector to address this situation is hydrogen, which is considered a clean energy carrier for various mobile and portable applications. Unfortunately, at standard pressure and temperature, its energy content per volume is very low (0.01 kJ/L). This necessitates alternative storage technologies to achieve reasonable capacities and enable economically viable long-distance transportation. Among the hydrogen storage technologies using chemical methods, liquid organic hydrogen carrier (LOHC) systems are considered a promising solution. They can be easily managed under ambient conditions, the H2 storage/release processes are carbon-free, and the carrier liquid is reusable. However, the evolution of the proposals from the carrier liquid type and catalyst elemental composition point of view is scarcely studied, considering that both are critical in the performance of the system (operational parameters, kinetic of the reactions, gravimetric hydrogen content, and others) and impact in the final cost of the technology deployed. The latter is due to the use of the Pt group elements (PGEs) in the catalyst that, for example, have a high demand in the hydrogen production sector, particularly for polymer electrolyte membrane (PEM) water electrolysis. With that in mind, our objective was to examine the evolution and the focus of the research in recent years related to proposals of LOHCs and catalysts for hydrogenation and dehydrogenation reactions in LOHC systems which can be useful in defining routes/strategies for new participants interested in becoming involved in the development of this technology. For this systematic review, we searched the SCOPUS database and forward and backward citations for studies published in the database between January 2011 and December 2022. The criteria include articles which assessed or studied the effect of the type of catalyst, type of organic liquid, reactor design(s)/configuration(s), and modification of the reactor operational parameters, among others, over the performance of the LOHC system (de/hydrogenation reaction(s)). The relevant data from each reviewed study were collected and organized into a pre-designed table on an Excel spreadsheet, categorized by reference, year, carrier organic liquid, reaction (hydrogenation and/or dehydrogenation), investigated catalyst, and primary catalyst element. For processing the data obtained from the selected scientific publications, the data analysis software Orbit Intellixir was employed. For the study, 233 studies were included. For the liquid carrier side, benzyltoluene and carbazole dominate the research strategies. Meanwhile, platinum (Pt) and palladium (Pd) are the most employed catalysts for dehydrogenation reactions, while ruthenium (Ru) is preferred for hydrogenation reactions. From the investigated liquid carrier, those based on benzyltoluene and carbazole together account for over 50% of the total scientific publications. Proposals based on indole, biphenyl, cyclohexane, and cyclohexyl could be considered to be emerging within the time considered in this review, and, therefore, should be monitored for their evolution. A great activity was detected in the development of catalysts oriented toward the dehydrogenation reaction, because this reaction requires high temperatures and presents slow H2 release kinetics, conditioning the success of the implementation of the technology. Finally, from the perspective of the catalyst composition (monometallic and/or bimetallic), it was identified that, for the dehydrogenation reaction, the most used elements are platinum (Pt) and palladium (Pd), while, for the hydrogenation reaction, ruthenium (Ru) widely leads its use in the different catalyst designs. Therefore, the near-term initiatives driving progress in this field are expected to focus on the development of new or improved catalysts for the dehydrogenation reaction of organic liquids based on benzyltoluene and carbazole.

Unveiling the Potential of Heterogeneous Systems for Reversible Hydrogen Storage in Liquid Organic Hydrogen Carriers.

Transitioning towards a carbon-free economy is the current global need of the hour. The transportation sector is one of the major contributors of CO2 emissions in the atmosphere disturbing the delicate balance on the Earth, leading to global warming. Hydrogen has emerged as a promising alternative energy carrier capable of replacing fossil fuels, with advancements in systems facilitating its storage and long-distance transport. In this context, the concept of liquid organic hydrogen carriers (LOHCs) is taking the lead, offering a plausible solution because of its compatibility with the existing gasoline infrastructure, while eliminating the challenges associated with conventional hydrogen storage methods. Key LOHC systems, such as methylcyclohexane/toluene and H-18-dibenzyltoluene/dibenzyltoluene (H-18-DBT/DBT), have been extensively researched for large-scale applications. However, challenges persist, particularly concerning the endothermic nature of the reactions involved. In this regard, of particular interest are the multifunctional heterogeneous catalysts supported on a single support, offering cost-effective and energy-efficient solutions to circumvent issues related to the endothermicity of the reactions. In this review, solid heterogeneous catalysts that have been developed and investigated for reversible dehydrogenation and hydrogenation reactions have been presented. These catalysts include monometallic, bimetallic, and pincer complexes supported on materials designed for efficient hydrogen uptake and release.

Thermal and Sono-Aqueous Reforming of Alcohols for Sustainable Hydrogen Production.

Hydrogen is a clean-burning fuel with water as its only by-product, yet its widespread adoption is hampered by logistical challenges. Liquid organic hydrogen carriers, such as alcohols from sustainable sources, can be converted to hydrogen through aqueous-phase reforming (APR), a promising technology that bypasses the energy-intensive vaporization of feedstocks. However, the hydrothermal conditions of APR pose significant challenges to catalyst stability, which is crucial for its industrial deployment. This review focuses on the stability of catalysts in APR, particularly in sustaining hydrogen production over extended durations or multiple reaction cycles. Additionally, we explore the potential of ultrasound-assisted APR, where sonolysis enables hydrogen production without external heating. Although the technological readiness of ultrasound-assisted or -induced APR currently trails behind thermal APR, the development of catalysts optimized for ultrasound use may unlock new possibilities in the efficient hydrogen production from alcohols.

Model catalytic studies on the thermal dehydrogenation of the benzaldehyde/cyclohexylmethanol LOHC system on Pt(111).

We investigated the dehydrogenation reaction and the thermal robustness of the liquid organic hydrogen carrier (LOHC) couple benzaldehyde/cyclohexylmethanol on a Pt(111) model catalyst in situ in synchrotron radiation photoelectron spectroscopy- and complementary temperature-programmed desorption experiments. The system stores hydrogen in a cyclohexyl group and a primary alcohol functionality and achieves an attractive hydrogen storage capacity of 7.0 mass%. We observed a stepwise dehydrogenation mechanism, characterized by a low temperature dehydrogenation of the alcohol group at 235 K. However, stability limitations challenge the system's applicability as reversible hydrogen storage solution, as the resultant aldehyde was found to decompose during the dehydrogenation of its cyclohexyl group (between 250 and 350 K). A comparison of cyclohexylmethanol with the structurally related secondary alcohol (1-cyclo-hexylethanol; 6.3 mass% hydrogen) revealed a parallel stepwise dehydrogenation pattern for both compounds, but a technically relevant superior thermal robustness of the latter. This demonstrates the influence of the alcohol group's substitution degree on the dehydrogenation characteristics of alcohol-functionalized LOHC compounds. Density functional theory calculations are in good agreement with the experimentally observed stability trend.

Catalysts for Liquid Organic Hydrogen Carriers (LOHCs): Efficient Storage and Transport for Renewable Energy.

Restructuring the current energy industry towards sustainability requires transitioning from carbon based to renewable energy sources, reducing CO2 emissions. Hydrogen, is considered a significant clean energy carrier. However, it faces challenges in transportation and storage due to its high reactivity, flammability, and low density under ambient conditions. Liquid organic hydrogen carriers offer a solution for storing hydrogen because they allow for the economical and practical storage of organic compounds in regular vessels through hydrogenation and dehydrogenation. This review evaluates several hydrogen technologies aimed at addressing the challenges associated with hydrogen transportation and its economic viablity. The discussion delves into exploring the catalysts and their activity in the context of catalysts' development. This review highlights the pivotal role of various catalyst materials in enhancing the hydrogenation and dehydrogenation activities of multiple LOHC systems, including benzene/cyclohexane, toluene/methylcyclohexane (MCH), N-ethylcarbazole (NEC)/dodecahydro-N-ethylcarbazole (H12-NEC), and dibenzyltoluene (DBT)/perhydrodibenzyltoluene (H18-DBT). By exploring the catalytic properties of noble metals, transition metals, and multimetallic catalysts, the review provides valuable insights into their design and optimization. Also, the discussion revolved around the implementation of a hydrogen economy on a global scale, with a particular focus on the plans pertaining to Saudi Arabia and the GCC (Gulf Cooperation Council) countries. The review lays out the challenges this technology will face, including the need to increase its H2 capacity, reduce energy consumption by providing solutions, and guarantee the thermal stability of the materials.

Effect of Oxidized Tin Interfacial Atoms on Methylcyclohexane Dehydrogenation Catalyzed by γ‐Alumina Supported Platinum Clusters

AbstractTin (Sn) doped platinum (Pt) nanoparticles supported on γ‐alumina are important materials catalyzing various reactions, such as the dehydrogenation of methylcyclohexane (MCH) into toluene, involved in liquid organic hydrogen carriers process, and naphtha catalytic reforming. The role of oxidized forms of Sn, remains misunderstood. Relying on catalysts' models made of a Pt13cluster on the (100) surface of γ‐alumina, the location and effects of Sn4+and Sn2+ interfacial atoms are investigated by density functional theory (DFT) calculations. A simulated annealing approach based on ab initio molecular dynamics enables to explore the configurations of the catalytic systems. The Pt clusters' stabilities and that of the adsorbed molecular intermediates are linked to the electronic properties of the cluster and to its ductility modulated by the adsorbed species, the alumina support and the Sn atoms. The Gibbs free energy profiles related to the reaction mechanism of the MCH dehydrogenation into toluene are quantified on the basis of transition state search. The energy span concept reveals that the dual (either detrimental or beneficial) impact of Sn oxidized forms on the intrinsic reactivity of the Pt13 cluster depends on temperature. Based on this DFT analysis, we attempt to clarify the debated role of Sn oxidized species.

Pt supported on modified-coal gasification slag for efficient dehydrogenation of methylcyclohexane in a fixed bed reactor

Coal gasification slag (CGS) was used for modification and loaded platinum (Pt) to liquid organic hydrogen carrier (LOHC) for the first time. The carbon hybrid silica (C/SiO2) was prepared by removing metal oxides and carbon residue of CGS through acid treatment and calcination. The C/SiO2 loaded Pt (Pt-C/SiO2) exhibited only a 1.3% decrease in dehydrogenation conversion rate after 30 h of continuous catalytic dehydrogenation of methylcyclohexane (MCH), and even after 100 h, the decrease was only 4.9%. When Pt was directly loaded on CGS (Pt-CGS), it showed higher catalytic activity (dehydrogenation conversion rate was 20.4%), but lower catalytic stability (dehydrogenation conversion rate decreased by 56% after 7 h). Additionally, commercial Pt-SiO2 catalysts exhibited poor dehydrogenation conversion rate, significantly lower than that of Pt-C/SiO2. Density functional theory calculations confirmed the influence of carbon hybrid SiO2 on the adsorption energy, electron transfer and density of states for the catalytic dehydrogenation of MCH. The highly active and stable Pt-C/SiO2 catalyst can be effectively utilized for LOCH while achieving high-value utilization of CGS solid waste.

Comparative energy, emissions and economic assessment of low-carbon iron and steel making processes using imported liquid organic hydrogen carrier options

Hydrogen (H2)-based steel making is expected to become a major driver of intercontinental low-carbon H2 imports. Eight H2 supply scenarios based on either local H2 production at major steel producing locations (Germany/Japan), or liquid H2 carrier (dibenzyltoluene/perhydrodibenzyltiluene, DBT/PDBT) import from the United Arab Emirates, and their integration with H2 direct reduced iron (H-DRI) and electric arc furnace (EAF) processes, are investigated using process modeling. Solar energy-based PDBT import using surplus heat for dehydrogenation is the most cost-competitive H2 import scenario in Germany's case (levelized steel production cost, ∼685 $/tLS, with carbon emissions, ∼237 kgCO2/tLS). In Japan's case this scenario is the most economically favorable of all scenarios (∼736 $/tLS), with emissions (∼350 kgCO2/tLS) comparable to natural gas-DRI-EAF with 50% carbon capture. Steam methane reforming with carbon capture-based PDBT import is neither environmentally nor economically viable. PDBT-based H-DRI-EAF production cost is sensitive to electricity, H2 production, dehydrogenation energy, and carbon costs.

Fully Exposed Ru Clusters for the Efficient Multi-Step Toluene Hydrogenation Reaction.

Liquid organic hydrogen carriers (LOHCs) are attractive platform molecules that play an important role in hydrogen energy storage and utilization. The multi-step hydrogenation of toluene (TOL) to methylcyclohexane (MCH) has been widely studied in the LOCHs systems, due to their relatively low toxicity and reasonable hydrogen storage capacity. Noble metal catalysts such as Ru has exhibited good performance in multi-step hydrogenation reactions, while the application is still hindered by their high cost and low specific activity. Therefore, the primary challenge lies in the development of noble metal catalysts with both robust activity and efficient atomic utilization. In this study, a series of Ru species ranging from single atoms, fully exposed clusters to nanoparticles were fabricated to investigate their structural evolution in the TOL multi-step hydrogenation reaction. The fully exposed and atomically dispersed Ru clusters, composed of an average of 3 Ru atoms, exhibit superior catalytic performance and recycle ability in TOL multi-step hydrogenation. Moreover, it delivers a high turnover frequency of 9850.3 h-1 under the relatively mild reaction (100 °C, 1.5 MPa), compared with those of single atoms and nanoparticles, and shows a notable advantage over catalysts reported in previous studies. From density functional theory (DFT) calculations, the overall barrier of the TOL multi-step hydrogenation reaction over the fully exposed Ru clusters is significantly lower than that of single atoms and nanoparticles, resulting in its higher activity. The present work provides an efficient strategy to regulate the reaction pathway of multi-step complicated catalytic reactions by designing fully exposed metal cluster catalysts.

Sustainable Liquid‐Organic‐Hydrogen‐Carrier‐Based Hydrogen‐Storage Technology Using Crude or Waste Feedstock/Hydrogen

For liquid organic hydrogen carrier (LOHC) technology to be competitive with other H2‐storage methods, it is crucial to reduce the cost of LOHC materials occupying the high proportion of the embodied energy required for system implementation. Promising approaches are to convert crude or waste feedstock into LOHC materials and to utilize crude hydrogen sources obtained from various routes. Thus, in this review, the state‐of‐the‐art advances in sustainable LOHC‐based hydrogen storage using crude or waste feedstock, associated with their conversion into LOHC materials, and coupling crude hydrogen with LOHC system to obtain high‐purity H2 without separation and purification are highlighted. Petroleum sources like light cycle oil and pyrolysis fuel oil are used after liquid–liquid extraction, combined distillation/hydroprocessing, and one‐pot hydrotreating–hydrocracking. In case of converting renewable resources (e.g., biomass and plastic waste), depolymerization followed by hydrodeoxygenation is an effective approach. To utilize crude hydrogen sources for hydrogen storage, catalysts should be designed and synthesized toward activating LOHC hydrogenation reaction at lower temperatures, along with high CO resistance. Consequently, this context provides guidance for the development of LOHC technology to accelerate its commercialization.

Feasibility Study on Production of Slush Hydrogen Based on Liquid and Solid Phase for Long Term Storage

To achieve net-zero objectives, the expansion of renewable energy sources is anticipated to be accompanied by an increased use of carbon-free fuels, such as hydrogen. Internationally, there are proposals for transporting hydrogen by synthesizing it into carriers like ammonia or Liquid Organic Hydrogen Carriers (LOHCs). However, considering the energy consumption required for hydrogenation and dehydrogenation processes and the need for high-purity hydrogen production, the development of liquid hydrogen transportation technologies is becoming increasingly important. Liquid hydrogen, with a density approximately one-sixth that of liquid natural gas and a boiling point roughly 90 K lower, poses significant challenges in suppressing and managing boil-off gas during transportation. Slush hydrogen, a mixture of liquid and solid phases, offers potential benefits. with an approximate 15% increase in density and an 18% increase in thermal capacity compared to liquid hydrogen. The latent heat of fusion of solid hydrogen effectively suppresses boil-off gas (BOG), and the increased density can reduce transportation costs. This study experimentally validated the long-duration storage and transportation concept of slush hydrogen by adapting NASA’s (National Aeronautics and Space Administration) proposed IRAS (Integrated Refrigeration and Storage) technology for compact and mobile tanks. Slush hydrogen was successfully produced by reaching the triple point of hydrogen, resulting in a composition of 47% solid and 53% liquid, with a density of approximately 80.9 kg/m3. Most importantly, methodologies were presented to observe and measure whether the hydrogen was indeed in the slush state and to determine its density. Additionally, CFD (Computational Fluid Dynamics) analysis was performed using solid hydrogen properties, and the results were compared with experimental values. Notably, this analytical technique can be utilized in designing large-capacity tanks for storing slush hydrogen.

Anchored Ru nanoclusters strategy enhances hydrogen spillover effect for high-efficiency hydrogen storage

Enhancing the hydrogen spillover effect of catalysts is an effective method for optimizing hydrogen storage reactions. In this study, we report a catalyst consisting of Ru nanoclusters (1.2–2.7 nm) anchored on nitrogen-doped carbon (NC) that are highly dispersed on an Al2O3 substrate. Both experimental and density functional theory-based calculations indicate that these constrained, highly dispersed ultrafine nanoclusters significantly improve the intrinsic catalytic activity of Ru and reduce the reaction barriers. Moreover, the electron transfer between NC and Ru clusters increases the adsorption inertness of Ru with hydrogen, enhances hydrogen desorption, and promotes hydrogen spillover, synergistically improving the activity of catalytic hydrogen storage. Notably, the aromatic compounds in the ethylene tar narrow fraction were effectively converted at a low temperature of 80 °C, and the total cycloalkanes yield reached 99.04 %. The hydrogen storage capacity can be about 5.70 wt%. Liquid Organic Hydrogen Carriers model compounds were fully hydrogenated at temperatures no higher than 70 °C with low Ru loading (2 wt%). This work provides a potential utilization strategy of ethylene tar narrow fraction as hydrogen carriers based on its hydrogenation over the highly active and stable Ru nanocluster catalysts.