Multi-criteria analysis for screening of reversible metal hydrides in hydrogen gas storage and high pressure delivery applications

Metals and alloys forming reversible hydrides with hydrogen gas are potential building blocks for compact, solid state hydrogen storage systems. Based on the materials’ thermodynamic characteristics, their use as temperature-swing gas compression and delivery systems in the hydrogen economy is also possible. Given the wide variety of materials developed and tested at laboratory and pilot scales, a harmonized method of selecting the feasible material(s) for a particular real-life application is required. This study proposes a system selection framework based on a normalized, multi-criteria metric. Using calculated values of multi-criteria metric, multi-criteria screening and ranking of potential materials has been demonstrated for a particular use case. It is found that the alloy TiMn_1.52 having value of additive metric between 0.25 and 0.35 represents the best material for a single stage system. The alloy pair CaNi₅–Ti_1.5CrMn represents the best alternative for a two-stage system with additive metric values between 0.63 and 0.82. Energy and economic characteristics of the metal hydride gas compression and delivery systems are evaluated and compared with an equivalent mechanical compression system producing the same final effect (i.e., delivery of a given quantity of gas at a defined pressure).     

Optimization of hydrogen enrichment via palladium membrane in vacuum environments using Taguchi method and normalized regression analysis

In this study, the separation of hydrogen from gas mixtures using a palladium membrane coupled with a vacuum environment on the permeate side was studied experimentally. The gas mixtures composed of H₂, N₂, and CO₂ were used as the feed. Hydrogen permeation fluxes were measured with membrane operating temperature in the range of 320–380 °C, pressures on the retentate side in the range of 2–5 atm, and vacuum pressures on the permeate side in the range of 15–51 kPa. The Taguchi method was used to design the operating conditions for the experiments based on an orthogonal array. Using the measured H₂ permeation fluxes from the Taguchi approach, the stepwise regression analysis was also employed for establishing the prediction models of H₂ permeation flux, followed by the analysis of variance (ANOVA) to identify the significance and suitability of operating conditions. Based on both the Taguchi approach and ANOVA, the H₂ permeation flux was mostly affected by the gas mixture composition, followed by the retentate side pressure, the vacuum degree, and the membrane temperature. The predicted optimal operating conditions were the gas mixture with 75% H₂ and 25% N₂, the membrane temperature of 320 °C, the retentate side pressure of 5 atm, and the vacuum degree of 51 kPa. Under these conditions, the H₂ permeation flux was 0.185 mol s^?1 m^?2. A second-order normalized regression model with a relative error of less than 7% was obtained based on the measured H₂ permeation flux.     

Recent progress of electrocatalysts for hydrogen proton exchange membrane fuel cells

Due to stringent environmental regulations and the limited resources of fossil-based fuels, there is an urgent demand for clean and eco-friendly energy conversion devices. These criteria appear to be met by hydrogen proton exchange membrane fuel cells (PEMFCs). PEMFCs have attracted tremendous attention on account of their excellent performance with tunable operability and good portability. Nonetheless, their practical applications are hugely influenced by the scarcity and high cost of platinum (Pt) used as electrocatalysts at both cathode and anode. Pt is also susceptible to easy catalyst poisoning. Herein, this paper reviews the progress of the research regarding the development of electrocatalysts practically used in hydrogen PEMFCs, where the corner-stone reactions are cathodic oxygen reduction reaction (ORR) and anodic hydrogen oxidation reaction (HOR). To reduce the costs of PEMFCs, lessening or eliminating the use of Pt is of prime importance. For current and forthcoming laboratory/large-scale PEMFCs, there is much interest in developing substitute catalysts based on cheaper materials. As such are non-platinum (non-Pt), non-platinum group metals (non-PGMs), metal oxides, and non-metal electrocatalysts. Hence, high-performance, state-of-the-art, and novel structured electrocatalysts as replacements for Pt are needed.     

Analysis of suitability of TPP ash-slag waste as materials for hydrogen fuel storage

The current trends in energy were described, the main of which is the use of alternative energy sources, especially hydrogen. The most common methods of hydrogen accumulation were proposed: accumulation of compressed gaseous hydrogen in high-pressure tanks; accumulation of liquid hydrogen in cryogenic tanks; storing hydrogen in a chemically bound state; accumulation of gaseous hydrogen in carriers with a high specific surface area. Based on the combination of advantages and disadvantages, the most promising methods of accumulation were selected: storage of liquid hydrogen and storage of hydrogen in carriers with a high specific surface area. The main requirement for materials for hydrogen storage by these methods was revealed – a high specific surface area. Prospects for the development of waste-free low-emission technologies due to the recycling of secondary raw materials and the development of low-temperature technologies for the synthesis of functional and structural materials were substantiated. The applicability of large-scale ash and slag waste from coal-fired thermal power plants as a raw material for obtaining materials by low-temperature technologies was shown. The traditional ways of using ash and slag waste as a raw material, active additive and filler in the production of cements were described. Modern technologies for the production of innovative materials with a unique set of properties were presented, namely carbon nanotubes, silica aerogel and geopolymer materials. The prospect of using geopolymer matrices as a precursor for the synthesis of a number of materials was described; the most promising type of materials was selected – geopolymer foams, which are mainly used as sorbents for purifying liquids and gases or accumulating target products, as well as heat-insulating materials. The possibility of obtaining products of any shape and size on the basis of geopolymer matrices without high-temperature processing was shown. The special efficiency of the development of the technology of porous granules and powders obtained from a geopolymer precursor using various methods was substantiated. The obtained granules can be used in the following hydrogen storage technologies: direct accumulation of hydrogen in porous granules; creation of insulating layers for liquid hydrogen storage units.     

The decreasing effect of ammonia enrichment on the combustion emission of hydrogen,methane, and propane fuels

In the present study, non-premixed combustion and NOx emission of H₂, NH₃, C₃H₈, and CH₄ fuels have been studied in a combustion test unit under lean mixture conditions (λ = 4) at 8.6 kW thermal capacity. Furthermore, the combustion and NOx emission of the H₂, C₃H₈, and CH₄ fuels have been investigated for various NH₃ enrichment ratios (5, 10, 20, and 50%) and excess air coefficients (λ = 1.1, 2, 3, and 4) at the same thermal capacity. The obtained results have been compared for each fuel. Numerical simulation results show that H₂ emits intense energy through the reaction zone despite the lowest fuel consumption in mass, among others, due to its high calorific value. Therefore, it has a higher flame temperature than others. At the same time, C₃H₈ has the lowest flame temperature. Besides, NH₃ has the shortest flame length among others, while C₃H₈ has the most extended flame form. The highest level of NOx is released from the NH₃ flame in the combustion chamber, while the lowest NOx is released from the CH₄. However, the lowest NOx emission at the combustion chamber exit is obtained in NH₃ combustion, while the highest NOx emission is obtained with H₂ combustion. It results from the shortest flame length of NH₃, short residence time, and backward NOx reduction to N₂ for NH₃. As for H₂, high flame temperature and relatively long flame, and high residence time of the products trigger NOx formation and keep the NOx level high. On the other hand, excess air coefficient from 1.1 to 2 increases NOx for H₂, CH₄, and NH₃ due to their large flame diameters, unlike propane. Then, NOx emission levels decrease sharply as the excess air coefficient increases to 4 for each fuel. NH₃ fuel also emits minimum NOx in other excess air coefficients at the exit, while H₂ emits too much emission. With NH₃ enrichment, the NOx emissions of H₂, CH₄, and C₃H₈ fuels at the combustion chamber exit decrease gradually almost every excess air coefficient apart from λ = 1.1. As a general conclusion, like renewable fuels, H₂ appears to be a source of pollution in terms of NOx emissions in combustion applications. In contrast, NH₃ appears to be a relatively modest fuel with a low NOx level. In addition, the high amount of NOx emission released from H₂ and other fuels during the combustion can be remarkably reduced by NH₃ enrichment with an excess air combustion.     

Techno-economic feasibility assessment of sorption enhanced gasification of municipal solid waste for hydrogen production

Waste-to-fuel coupled with carbon capture and storage is forecasted to be an effective way to mitigate the greenhouse gas emissions, reduce the waste sent to landfill and, simultaneously, reduce the dependence of fossil fuels. This study evaluated the techno-economic feasibility of sorption enhanced gasification, which involves in-situ CO₂ capture, and benchmarked it with the conventional steam gasification of municipal solid waste for H₂ production. The impact of a gate fee and tax levied on the fossil CO₂ emissions in economic feasibility was assessed. The results showed that the hydrogen production was enhanced in sorption enhanced gasification, that achieved an optimum H₂ production efficiency of 48.7% (T = 650 °C and SBR = 1.8). This was 1.0% points higher than that of the conventional steam gasification (T = 900 °C and SBR = 1.2). However, the total efficiency, which accounts for H₂ production and net power output, for sorption enhanced gasification was estimated to be 49.3% (T = 650 °C and SBR = 1.8). This was 4.4% points lower than the figure estimated for the conventional gasification (T = 900 °C and SBR = 1.2). The economic performance assessment showed that the sorption enhanced gasification will result in a significantly higher levelised cost of hydrogen (5.0 €/kg) compared to that estimated for conventional steam gasification (2.7 €/kg). The levelised cost of hydrogen can be reduced to 4.5 €/kg on an introduction of the gate fee of 40.0 €/t_MSW. The cost of CO₂ avoided was estimated to be 114.9 €/tCO₂ (no gate fee and tax levied). However, this value can be reduced to 90.1 €/tCO₂ with the introduction of an emission allowance price of 39.6 €/tCO₂. Despite better environmental performance, the capital cost of sorption enhanced gasification needs to be reduced for this technology to become competitive with mature gasification technologies.     

A new analysis of two phase flow on hydrogen production from water electrolysis

It is clear that the entire world have to research, develop, demonstrate and plan for alternative energy systems for shorter term and also longer term. As a clean energy carrier, hydrogen has become increasingly important. It owes its prestige to the increase within the energy costs as a result of the equivocalness in the future availability. Two phase flow and hydrogen gas flow dynamics effect on performance of water electrolysis. Hydrogen bubbles are recognized to influence energy and mass transfer in gas-evolving electrodes. The movement of hydrogen bubbles on the electrodes in alkaline electrolysis is known to affect the reaction efficiency. Within the scope of this research, a physical modeling for the alkaline electrolysis is determined and the studies about the two-phase flow model are carried out for this model. Internal and external forces acting on the resulting bubbles are also determined. In this research, the analytical solution of two-phase flow analysis of hydrogen in the electrolysis is analyzed.     

Amorphous-crystalline cobalt-molybdenum bimetallic phosphide heterostructured nanosheets as Janus electrocatalyst for efficient water splitting

Efficient and sustainable Janus catalysts toward hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) are highly desirable for future hydrogen production via water electrolysis. Herein we report an active Janus electrocatalyst of amorphous-crystalline cobalt-molybdenum bimetallic phosphide heterostructured nanosheets on nickel foam (CoMoP/CoP/NF) for efficient electrolysis of alkaline water. As-reported CoMoP/CoP/NF consists of amorphous bimetal phosphide nanosheets doped with crystalline CoMoP/CoP heterostructured nanoparticles on NF. It can efficiently catalyze both HER (η = 127 mV@100 mA cm^?2) and OER (η = 308 mV@100 mA cm^?2) in alkaline electrolyte with long-term durability. Serving as anode and cathode of water electrolyzer, CoMoP/CoP/NF generates electrolytic current of 10, 50 and 100 mA cm^?2 at low voltage of 1.50, 1.59, and 1.67 V, respectively.     

Lanthanide-organic-frameworks modified ZnIn2S4 for boosting hydrogen generation under UV–Vis and visible light

Novel Ln-MOF with microrods shape were successfully combined with ZnIn₂S₄ (ZIS) microsphere and used for photocatalytic hydrogen generation under UV–Vis and visible light. The Ln-MOFs/ZIS system comprises lanthanide-carboxylate coordination networks (Tm and Gd as metal ions, and 1,3,5-benzenetricarboxylic acid (BTC) as the organic linker) deposited on ZnIn₂S₄ microspheres. Effect of the amount of ((Tm,Gd)-BTC) (1, 5, 10 wt%) on the optical properties and photocatalytic hydrogen evolution performance was investigated. ZIS microsphere shows the marigold flower-like morphology and hexagonal polytopic crystal form. Our results proved that the combination of ZIS microsphere, Ln-MOF and Pt nanoparticles (NPs) caused significant enhancement in hydrogen generation. Amount of formed hydrogen was raised from 196.3 to 7782.1 μmol g^?1 for pristine ZIS and ZIS decorated with 1% (Tm, Gd)-BTC/Pt under UV–Vis light, respectively.     

Structure-dependent activity and stability of Al2O3 supported Rh catalysts for the steam reforming of n-dodecane

Steam reforming of liquid hydrocarbon fuels is an appealing way for the production of hydrogen. In this work, the Rh/Al₂O₃ catalysts with nanorod (NR), nanofiber (NF) and sponge-shaped (SP) alumina supports were successfully designed for the steam reforming of n-dodecane as a surrogate compound for diesel/jet fuels. The catalysts before and after reaction were well characterized by using ICP, XRD, N₂ adsorption, TEM, HAADF-STEM, H₂-TPR, CO chemisorption, NH₃-TPD, CO₂-TPD, XPS, Al²⁷ NMR and TG. The results confirmed that the dispersion and surface structure of Rh species is quite dependent on the enclosed various morphologies. Rh/Al₂O₃-NR possesses highly dispersed, uniform and accessible Rh particles with the highest percentage of surface electron deficient Rh⁰ active species, which due to the unique properties of Al₂O₃ nanorod including high crystallinity, relatively large alumina particle size, thermal stability, and large pore volume and size. As a consequent, Rh/Al₂O₃-NR catalyst exhibited superior catalytic activity towards steam reforming reactions and hydrogen production rate over other two catalysts. Especially, Rh/Al₂O₃-NR catalyst showed the highest hydrogen production rate of 87,600 mmol g_fuel^?1 g_Rh^?1min^?1 among any Rh-based catalysts and other noble metal-based catalysts to date. After long-term reaction, a significant deactivation occurred on Rh/Al₂O₃–NF and Rh/Al₂O₃-SP catalysts, due to aggregation and sintering of Rh metal particles, coke deposition and poor hydrothermal stability of nanofibrous structure. In contrast, the Rh/Al₂O₃-NR catalyst shows excellent reforming stability with negligible coke formation. No significantly sintering and aggregation of the Rh particles is observed after long-term reaction. Such great catalyst stability can be explained by the role of hydrothermal stable nanorod alumina support, which not only provides a unique environment for the stabilization of uniform and small-size Rh particles but also affords strong surface basic sites.