Search Results (22)

Under the accelerating global energy restructuring and the deepening carbon neutrality strategy, hydrogen energy has emerged with increasing strategic value as a zero-carbon secondary energy carrier. Water electrolysis technology based on renewable energy is regarded as an ideal pathway for large-scale green hydrogen production. However, polymer electrolyte membrane (PEM) conventional water electrolysis faces dual constraints in economic feasibility and scalability due to its high electrical energy consumption and reliance on noble metal catalysts. The mixed ionic-electronic conducting oxygen transport membrane (MIEC–OTM) reactor technology offers an innovative solution to this energy efficiency-cost paradox due to its thermo-electrochemical synergistic energy conversion mechanism and process integration. This not only overcomes the thermodynamic equilibrium limitations in traditional electrolysis but also reduces electrical energy demand by effectively coupling with medium- to high-temperature heat sources such as industrial waste heat and solar thermal energy. Therefore, this review, grounded in the physicochemical mechanisms of oxygen transport membrane reactors, systematically examines the influence of key factors, including membrane material design, catalytic interface optimization, and parameter synergy, on hydrogen production efficiency. Furthermore, it proposes a roadmap and breakthrough directions for industrial applications, focusing on enhancing intrinsic material stability, designing multi-field coupled reactors, and optimizing system energy efficiency. Full article

Background: 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. Data sources: 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. Eligibility criteria: 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)). Data extraction and analysis: 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. Results: 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. Conclusions: 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. Full article

Hydrogen for building fuel cells is primarily produced by natural-gas steam-reforming reactions. Pipeline-transported natural gas in Europe and North America used to contain about 1% to 5% N₂, which reacts with H₂ in steam-reforming reactions to form NH₃. In the case of Ru, one of the catalysts used in natural-gas steam-reforming reactions, the activity of the NH₃-formation reaction is higher than that of Ni and Rh catalysts. Reforming gas containing NH₃ is known to poison Pt catalysts in Polymer Electrolyte Membrane Fuel Cells (PEMFCs) and also poison catalysts in preferential oxidation (PROX). In this study, Langmuir–Hinshelwood-based models of the NH₃-formation reaction considering H₂ and CO were proposed and compared with a simplified form of the Temkin–Pyzhev model for NH₃-formation rate. The kinetic parameters of each model were optimized by performing multi-objective function optimization on the experimental results using a tube-type reactor and the numerical results of a plug-flow one-dimension simple SR (steam-reforming) reactor. 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

Biomass-derived products, such as lignin, are interesting resources for energetic purposes. Lignin is a natural polymer that, when added to the anode of an alkaline exchange membrane water electrolyser, enhances H₂ production rates and efficiencies due to the substitution of the oxygen evolution reaction. Higher efficiencies are reported when different catalytic materials are employed for constructing the lignin anolyte, demonstrating that lower catalytic loadings for the anode improves the H₂ production when compared to higher loadings. Furthermore, when a potential of −1.8 V is applied, higher gains are obtained than when −2.3 V is applied. An increase of 200% of H₂ flow rates with respect to water electrolysis is reported when commercial lignin is used coupled with Pt-Ru at 0.09 mg cm⁻² and E = −1.8 V is applied at the cathode. This article provides deep information about the oxidation process, as well as an optimisation of the method of the lignin electro-oxidation in a flow-reactor as a pre-step for an industrial implementation. Full article

Pd_xNi_y/TiO₂ bimetallic electrocatalysts were used in fuel cell polymeric electrolyte reactors (PER-FC) to convert methane into methanol through the partial oxidation of methane promoted by the activation of water at room temperature. X-ray diffraction measurements showed the presence of Pd and Ni phases and TiO₂ anatase phase. TEM images revealed mean particle sizes larger than those reported for PdNi materials supported, indicating that TiO₂ promotes particle aggregation on its surface. Information on the surface structure of electrocatalysts obtained by Raman spectra indicated the presence or formation of NiO. The PER-FC tests showed the highest power density for the electrocatalyst with the lowest amount of nickel Pd₈₀Ni₂₀/TiO₂ (0.58 mW cm⁻²). The quantification of methanol through the eluents collected from the reactor showed higher concentrations of methanol produced, revealing that the use of TiO₂ as a support also increased the reaction rate. Full article

The search for alternatives for converting methane into value-added products has been of great interest to scientific, technological, and industrial society. An alternative to this could be the use of copper-doped palladium catalysts with different proportions supported on metal oxides, such as Sb₂O₅.SnO₂ (ATO) catalysts. These combinations were employed to convert the methane-to-methanol in mild condition using a fuel cell polymer electrolyte reactor. The catalysts prepared presents Pd, CuO, and Sb₂O₅.SnO₂ phases with a mean particle size of about 9 nm. In activity experiments, the Pd₈₀Cu₂₀/ATO indicated maximum power density and maximum rate reaction for methanol production when compared to other PdCu/ATO materials. The use of ATO as a support favored the production of methanol from methane, while PdCu with high copper content demonstrated the production of more oxidized compounds, such as carbonate and formate. Full article

The popularity of using phase change materials (PCMs) for heat storage and recovery of metal hydrides’ reaction has grown tremendously. However, a fundamental study of the coupling of such a system with a low-temperature PEM (polymer electrolyte membrane) fuel cell is still lacking. This work presents a numerical investigation of the dehydrogenation performance of a metal hydride reactor (MHR)-PCM system coupled with a fuel cell. It is shown that to supply the fuel cell with a constant H₂ flow rate, the PCM properties need to be in an optimized range. The effects of some design parameters (PCM freezing point, the initial desorption temperature, the nature and the size of the PCM) on the dehydrogenation performance of MHR-PCM system are discussed in detail. The results showed that the MHR-PCM could supply hydrogen at 12 NL/min only for 20 min maximum due to the significant endothermic effect occurring in the MHR. However, reducing the requested H₂ flowrate to 5.5 NL/min, the hydrogen desorption to a fuel cell is prolonged to 79 min. Moreover, this system can accommodate different PCMs such as paraffin and salt hydrates for comparable performance. This study demonstrates the ability of MHR-PCM systems to be used as range extenders in light-duty fuel cell vehicles. Full article

Ammonia is a hydrogen-rich compound that can play an important role in the storage of green hydrogen and the deployment of fuel cell technologies. Nowadays used as a fertilizer, NH₃ has the right peculiarities to be a successful sustainable fuel for the future of the energy sector. This study presents, for the first time in literature, an integration study of ammonia as a hydrogen carrier and a high temperature polymer electrolyte membrane fuel cell (HT-PEMFC) as an energy conversion device. A system design is presented, that integrates a reactor for the decomposition of ammonia with an HT-PEMFC, where hydrogen produced from NH₃ is electrochemically converted into electricity and heat. The overall system based on the two technologies is designed integrating all balance of plant components. A zero-dimensional model was implemented to evaluate system efficiency and study the effects of parametric variations. Thermal equilibrium of the decomposition reactor was studied, and two different strategies were implemented in the model to guarantee thermal energy balance inside the system. The results show that the designed system can operate with an efficiency of 40.1% based on ammonia lower heating value (LHV) at the fuel cell operating point of 0.35 A/cm² and 0.60 V. Full article

This work describes new methods for the chemical recycling of end-use poly(ethylene terephthalate) (PET) in batch, microwave and electrochemical reactors. The reactions are based on basic hydrolysis of the ester moieties in the polymer framework and occur under mild reaction conditions with low-cost reagents. We report end-use PET depolymerization in refluxing methanol with added NaOH with 75% yield of terephthalic acid in batch after 12 h, while yields up to 65% can be observed after only 40 min under microwave irradiation at 85 °C. Using basic conditions produced in the electrochemical reduction of protic solvents, electrolytic experiments have been shown to produce 17% terephthalic acid after 1 h of electrolysis at −2.2 V vs. Ag/AgCl in 50% water/methanol mixtures with NaCl as a supporting electrolyte. The latter method avoids the use of caustic solutions containing high-concentration NaOH at the outset, thus proving the concept for a novel, environmentally benign method for the electrochemical recycling of end-use PET based on low-cost solvents (water and methanol) and reagents (NaCl and electricity). Full article

Polymer electrolyte membrane fuel cells (PEMFCs) are often used for household applications, utilizing hydrogen produced from natural gas from the gas grid. The hydrogen is thereby produced by steam reforming of natural gas followed by a water gas shift (WGS) unit. The H₂-rich gas contains besides CO₂ small amounts of CO, which deactivates the catalyst used in the PEMFCs. Preferential oxidation has so far been a reliable process to reduce this concentration but valuable H₂ is also partly converted. Selective CO methanation considered as an attractive alternative. However, CO₂ methanation consuming the valuable H₂ has to be minimized. The modelling of selective CO methanation in a household fuel cell system is presented. The simulation was conducted for single and two-stage adiabatic fixed bed reactors (in the latter case with intermediate cooling), and the best operating conditions to achieve the required residual CO content (100 ppm) were calculated. This was done by varying the gas inlet temperature as well as the mass of the catalyst. The feed gas represented a reformate gas downstream of a typical WGS reaction unit (0.5%–1% CO, 10%–25% CO₂, and 5%–20% H₂O (rest H₂)). Full article

Methanol as a hydrogen carrier can be reformed with steam over Cu/ZnO/Al₂O₃ catalysts. In this paper a comprehensive pseudo-homogenous model of a multi-tubular packed-bed reformer has been developed to investigate the impact of operating conditions and geometric parameters on its performance. A kinetic Langmuir-Hinshelwood model of the methanol steam reforming process was proposed. In addition to the kinetic model, the pressure drop and the mass and heat transfer phenomena along the reactor were taken into account. This model was verified by a dynamic model in the platform of ASPEN. The diffusion effect inside catalyst particles was also estimated and accounted for by the effectiveness factor. The simulation results showed axial temperature profiles in both tube and shell side with different operating conditions. Moreover, the lower flow rate of liquid fuel and higher inlet temperature of thermal air led to a lower concentration of residual methanol, but also a higher concentration of generated CO from the reformer exit. The choices of operating conditions were limited to ensure a tolerable concentration of methanol and CO in H₂-rich gas for feeding into a high temperature polymer electrolyte membrane fuel cell (HT-PEMFC) stack. With fixed catalyst load, the increase of tube number and decrease of tube diameter improved the methanol conversion, but also increased the CO concentration in reformed gas. In addition, increasing the number of baffle plates in the shell side increased the methanol conversion and the CO concentration. Full article

Membrane electrode assemblies (MEA) based on proton-conducting electrolyte membranes offer opportunities for the electrochemical compression of hydrogen. Mechanical hydrogen compression, which is more-mature technology, can suffer from low reliability, noise, and maintenance costs. Proton-conducting electrolyte membranes may be polymers (e.g., Nafion) or protonic-ceramics (e.g., yttrium-doped barium zirconates). Using a thermodynamics-based analysis, the paper explores technology implications for these two membrane types. The operating temperature has a dominant influence on the technology, with polymers needing low-temperature and protonic-ceramics needing elevated temperatures. Polymer membranes usually require pure hydrogen feed streams, but can compress H ${}_2$ efficiently. Reactors based on protonic-ceramics can effectively integrate steam reforming, hydrogen separation, and electrochemical compression. However, because of the high temperature (e.g., 600 $°$ C) needed to enable viable proton conductivity, the efficiency of protonic-ceramic compression is significantly lower than that of polymer-membrane compression. The thermodynamics analysis suggests significant benefits associated with systems that combine protonic-ceramic reactors to reform fuels and deliver lightly compressed H ${}_2$ (e.g., 5 bar) to an electrochemical compressor using a polymer electrolyte to compress to very high pressure. Full article

Carbon dioxide (CO₂) is considered as the prime reason for the global warming effect and one of the useful ways to transform it into an array of valuable products is through electrochemical reduction of CO₂ (ERC). This process requires an efficient electrocatalyst with high faradaic efficiency at low overpotential and enhanced reaction rate. Herein, we report an innovative way of reducing CO₂ using copper-metal supported on titanium oxide nanotubes (TNT) electrocatalysts. The TNT support material was synthesized using alkaline hydrothermal process with Degussa (P-25) as a starting material. Copper nanoparticles were anchored on the TNT by homogeneous deposition-precipitation method (HDP) with urea as precipitating agent. The prepared catalysts were tested in a home-made H-cell with 0.5 M NaHCO₃ aqueous solution in order to examine their activity for ERC and the optimum copper loading. Continuous gas-phase ERC was carried out in a solid polymer electrolyte (SPE) reactor. The 10% Cu/TNT catalysts were employed in the gas diffusion layer (GDL) on the cathode side with Pt-Ru/C on the anode side. Faradaic efficiencies for the three major products namely methanol, methane, and CO were found to be 4%, 3%, and 10%, respectively at −2.5 V with an overall current density of 120 mA/cm². The addition of TNT significantly increased the catalytic activity of electrocatalyst for ERC. It is mainly attributed to their better stability towards oxidation, increased CO₂ adsorption capacity and stabilization of the reaction intermediate, layered titanates, and larger surface area (400 m²/g) as compared with other support materials. Considering the low cost of TNT, it is anticipated that TNT support electrocatalyst for ECR will gain popularity. Full article

Polymer electrolyte membrane fuel cells (PEMFCs) for household applications utilize H₂ produced from natural gas via steam reforming followed by a water gas shift (WGS) unit. The H₂-rich gas contains CO₂ and small amounts of CO, which is a poison for PEMFCs. Today, CO is mostly converted by addition of O₂ and preferential oxidation, but H₂ is then also partly oxidized. An alternative is selective CO methanation, studied in this work. CO₂ methanation is then a highly unwanted reaction, consuming additional H₂. The kinetics of CO methanation in CO₂/H₂ rich gases were studied with a home-made Ru catalyst in a fixed bed reactor at 1 bar and 160–240 °C. Both CO and CO₂ methanation can be well described by a Langmuir Hinshelwood approach. The rate of CO₂ methanation is slow compared to CO. CO₂ is directly converted to methane, i.e., the indirect route via reverse water gas shift (WGS) and subsequent CO methanation could be excluded by the experimental data and in combination with kinetic considerations. Pore diffusion may affect the CO conversion (>200 °C). The kinetic equations were applied to model an adiabatic fixed bed methanation reactor of a fuel cell appliance. Full article