Hydrogen Isotope Separation Research Articles

Optimization of Liquid Phase Catalytic Exchange Process for Hydrogen Isotope Separation Using Orthogonal Experiment Design

Optimization of Liquid Phase Catalytic Exchange Process for Hydrogen Isotope Separation Using Orthogonal Experiment Design

Proton permeation and selective separation of hydrogen isotopes through fullerene nanocages (X12Y12): A DFT insights

To resolve the problem of mobile electrolytes for the permeation of hydrogen isotopes in fuel cells, we have studied herein heteronuclear fullerene nanocages (Al12N12, Al12P12, B12N12, and B12P12) for the separation and permeation of hydrogen isotopes. The separation and permeation of fullerene nanocages for hydrogen isotopes are studied at ωB97XD functional of DFT along with 6–31g (d,p) pople basis set. Zero-point energy (ZPE) is calculated for Protium (H+) and its heavier isotopes including deuterium (D+) and tritium (T+). The Arrhenius equation is employed to calculate the selectivity of protium to deuterium (H+/D+) and deuterium to tritium (H+/T+) isotopes. The selectivity is calculated by using the zero-point energy difference (ZPE) of protium (H+) to its heavier isotopes. The proposed fullerene nanocages estimated better selectivity for proton isotopes. The phosphide-based nanocages (Al12P12, B12P12) provide superior selectivity values of H+/D+ and H+/T+ compared to nitrogen-based nanocages (Al12N12, B12N12). This study provides insights into separation pathways for proton isotopes through nanocages for many industrial applications in the energy sector.

Metal-doped amorphous microporous carbon for isotope separation: Pore size modulation and selective deuterium adsorption

Efficient hydrogen isotope separation is crucial for applications in energy production and advanced scientific research, but separation of these poses significant challenges. In this study, we developed amorphous microporous carbon (AMC) derived from a zeolite template and explored hydrogen isotope separation using quantum sieving. Thermal desorption spectroscopy (TDS) technique was used to evaluate the selectivity of hydrogen (H2) and deuterium (D2) isotope separation. The doping of metal ions, such as Ca2⁺, Mg2⁺, Ni2⁺, and Cu2⁺, in the porous carbon modulates the physicochemical properties of the pores. The metal-doped carbon samples demonstrated D2vs H2 selectivity (SD2/H2) of over 10, compared to the pristine carbon's SD2/H2 of less than 8. Density functional theory (DFT) calculation infers that pore modulation through metal doping enhanced the binding affinity of materials towards D2 resulting in increased separation selectivity compared to pristine carbon samples. This approach not only boosts separation efficiency but also provides a scalable and cost-effective solution for industrial applications.

Large-scale floating polyacrylonitrile hybrid micro-/nanofiber membrane achieves efficient H/D isotope separation via photocatalytic proton transport

Advancements in isotope separation are both essential and challenging. The separation of water isotopes is vital in industrial production, biopharmaceuticals, and healthcare applications. This process is energy-intensive and complex due to the similarity of the isotopes. Pure polyacrylonitrile (PAN) is resistant to proton permeability, but neutral hydrogen radicals are capable of penetration. In this study, we report a novel approach using PAN macroscopic hybrid micro-/nanofibers in combination with a photocatalyst to separate hydrogen ion isotopes. Application of photocatalytic water splitting to generate protons results in significantly slower deuteron permeation in these fibers relative to protons, resulting in a separation factor of approximately 15 at room temperature. The composite PAN fibers exhibit a conductivity of 17.5 mS cm−1 at 25 °C and 95 % relative humidity. Our approach not only converts sunlight directly into storable hydrogen, but also enriches heavy water from H₂O/D₂O by H/D isotope separation. This study provides new insights into proton transport mechanisms in acidic media and demonstrates the significant potential of high molecular weight polymers for hydrogen isotope separation.

The effect of irradiation for Nafion membrane electrode rapid separation of hydrogen-methane by electrochemical hydrogen pumps

Designing an efficient and reliable tritium plant has become a major challenge to developing nuclear fusion, which focuses on efficient and safe hydrogen isotope separation and purification. The electrochemical hydrogen pump (EHP) developed in recent years can be used to separate and compress hydrogen. Herein, we used the commercial Nafion membrane electrode in the EHP, which has excellent H2/CH4 separation performance. When the cell voltage is at 0.8 V, the current density is 2.04 A/cm2, the hydrogen separation rate can reach 14.2 mL/ (min ·cm2), and the hydrogen purity is more than 99.99 %. The damage mechanism of electron beam irradiation on the membrane electrode was revealed. It was found that irradiation caused Nafion’s main chain and branch chain to break, producing hydroxyl and carboxyl functional groups. The degree of chain fracture increased with the radiation dose, perforation and cracks occurred in the proton exchange membrane (PEM). Under the electron beam irradiation dose of 10 kGy, the membrane electrode can still maintain excellent H2/CH4 separation performance, and the hydrogen permeability caused by cracks and perforations is at a very low level. This study reveals the change of macroscopic performance caused by the microscopic mechanism of membrane electrode irradiation damage, provides a promising way to separate hydrogen isotope gases and is expected to promote the development of tritium plants in fusion engineering.

Combined water electrolysis and 2D hydron separator for enhanced hydrogen isotope separation

This research presents the fabrication and analysis of a graphene/Nafion composite membrane designed to enhance the hydrogen separation performance of a water electrolyzer by leveraging the isotope effect in hydron transport through monolayer graphene, serving as a 2D hydron separator. The composite membrane exhibits lower proton conductivity than a Nafion membrane, leading to a 12 % decrease in water electrolysis cell efficiency at 75 °C. However, the incorporation of monolayer graphene substantially enhances the hardness of the membrane by a factor of 1.38, as measured by nanoindentation. The addition of monolayer graphene also increases the activation energy required for through-plane conduction of H+ and D+, with the graphene itself showing a twofold higher conductivity for H+ over D+. In electrolysis cells containing the composite membrane, the H/D and H/T separation factors improved by approximately 1.4 and 2 times, respectively, compared with those of a Nafion membrane, with a maximum H/T separation factor of ∼ 15 at 15 °C. Although increases in temperature reduce the separation factor, the operation time and the concentration of heavier isotopes in the feed water were found to minimally affect the separation efficiency.

Stepwise tuning carbon slits at sub-angstrom scale for dynamical separation of hydrogen isotope

Heavier hydrogen isotope is indispensable for many applications such as isotope tracing and labeling, neutron scattering, and nuclear fusion reaction. Thus it calls for efficient hydrogen isotope separation. Cryogenic adsorptive separation is an energy-efficient way for deuterium/protium (D2/H2) separation, requiring nanopores with precisely tuned pore size and suitable geometry to induce the quantum sieving effect. Herein, we report on the stepwise tuned slit-shaped ultramicropores at sub-angstrom (Å) scale for highly efficient D2/H2 separation. The opening width of carbon nanoslits was precisely tuned by the devised thermal-induced molecularly imprinting method. The adsorbent with 4.0 Å centered nanoslits showed an excellent D2/H2 uptake ratio of 1.9 with a high D2 uptake of 10.1mmol/g at 40 K and 100 kPa. Column breakthrough experiments revealed a high D2/H2 selectivity of 10.1 at 40 K. It evidenced that the 4.0 Å centered slits enable an optimal balance between the barrier induced by zero-point energy and the adsorption potential at 40 K, thereby reaching a selectively quantized configurational diffusion of D2/H2. Programmed thermal desorption experiments indicated that a 0.1 Å alteration of the slit size enhanced the quantum sieving effect of D2/H2 by 180 %. These results would benefit the understanding of D2/H2 separation behavior, and the design principle may inspire other isotope separations.

Performance of Structured Packing for the Deuterated Water Distillation Process at Above Atmospheric Pressure

The National Research and Development Institute for Cryogenics and Isotopic Technologies (ICSI) was established in 1970 for research focused the industrial pilot plant. ICSI was created with the purpose of developing the heavy water production technology needed mainly for the operation of the CANDU reactors that equip the Cernavoda Nuclear Power Plant in Romania. This technology has been demonstrated and has been successfully transferred to the heavy water production plant. The accumulated experience in the field of isotopic separation allowed for the development of a second pilot plant, also for the purpose of heavy water, but this time for the purpose of separating deuterium and tritium for the recovery of tritium, mainly from the tritiated heavy water of the CANDU reactors. This experimental pilot is based on a technology that combines two hydrogen isotope separation processes: liquid-phase water-hydrogen catalytic isotopic exchange and hydrogen isotope cryogenic distillation. The success of the separation process consists of the technical solution given to the exchange area, its geometry (distillation-isotopic exchange), and last but not least, the performance of the hydrophilic packing, respectively, of the catalyst. Thus, an extensive research program was initiated and carried out over many years for the development of mixed catalytic packages consisting of a hydrophobic Pt/carbon catalyst (with different concentrations of platinum up to 2%) and hydrophilic packing (stainless steel or phosphorous bronze) manufactured within ICSI and made in different configurations (successive layers, random or structured). This program for the improvement of catalytic packages continues by implementing new solutions regarding the improvement of materials that ensure a large contact surface between the liquid and vapors, respectively, vapor and gas, thus increasing the isotopic separation performance. This paper presents an experimental analysis of two types of hydrophilic stainless steel packings developed for the purpose of separating hydrogen isotopes by water distillation to be used in the manufacture of mixed catalytic packages for the catalytic isotopic exchange process. This paper refers to the experiments performed with deuterated water on the hydrophilic packing in conditions of total reflux. The experiments were performed on a column equipped with two types of hydrophilic packing.

Investigations on Hydrogen Isotope Separation Factor Employing Palladium-Based Solid Metallic Membranes

At present, there are several methods for hydrogen isotope separation (in elemental form), the most important being cryogenic distillation, thermal diffusion, and gas chromatography. However, these methods have a series of drawbacks, namely, high complexity, high energy consumption, and associated costs. Taking into account these disadvantages, a promising separation method is the one based on solid metallic membranes because of its advantages like low energy consumption and reduced complexity. This method uses the difference between some of the isotopes’ properties, namely, solubility; diffusivity; and, implicitly, permeability. This work envisages the integration of an isotopic separation module, based on membrane permeation, on the exhaust gas line from the current experimental rigs employed at ICSI, to recover and store the hydrogen isotopes. We obtained a maximum separation factor of 5.66 for the lowest studied concentration of deuterium in the hydrogen isotopic mixture (0.05 atomic fraction). The results show that hydrogen isotope separation is possible using palladium/silver membranes. Still, the throughput of the permeated gas is very low, and a significant number of stages will be necessary to obtain the desired purity (above 99.5%).

A Mini Review on Liquid Phase Catalytic Exchange for Hydrogen Isotope Separation: Current Status and Future Potential

Liquid phase catalytic exchange (LPCE) appears a highly promising technology for separating hydrogen isotopes due to being less energy-intensive and having a high separation factor. This paper provides an overview of the current development of the hydrophobic catalysts used in the LPCE process, including the LPCE fundamentals, factors influencing its effectiveness, and proposals for future research areas. This paper specifically reviews the active metal catalysts, catalyst supports, operating temperatures, and molar feed ratio(gas-to-liquid,G/L). The addition of a second metal such as Ir, Fe, Ru, Ni, or Cr and modified catalyst supports showed enhancement of LPCE performance. Additionally, the validated optimized temperature of 60–80 °C and G/L of 1.5–2.5 provide an important basis for designing LPCE systems to improve separation efficiency. This paper concludes by highlighting potential research areas and challenges for future advancements in the sustainability of LPCE for hydrogen isotope separation, which include the optimization, scalability, techno-economic analysis, and life-cycle analysis of modified catalyst materials.

NiP2 as an efficient non-noble metal cathode catalyst for enhanced hydrogen isotope separation in proton exchange membrane water electrolysis

Proton exchange membrane (PEM) water electrolysis is crucial for efficient hydrogen isotope separation (HIS) in liquid water. However, current cathode catalysts like platinum (Pt) suffer from scarcity and limited HIS performance. To overcome this challenge, we propose a simple and effective approach involving the synthesis of highly dispersed NiP2 nanoparticles supported on carbon (NiP2/C) through a solid-phase phosphidation reaction, and for the first time report its enhanced HIS performance as the cathode catalyst in PEM electrolyzer. The NiP2/C catalyst demonstrates excellent catalytic properties as a cathode catalyst for hydrogen evolution reaction (HER) in an acidic electrolyte, achieving low overpotential of only 157 mV at 10 mA/cm2 and Tafel slope of 95.6 mV/dec. Meticulous investigations and density functional theory (DFT) calculations reveal the intrinsic factors behind its performance. Furthermore, DFT calculations predict the HIS performance of both NiP2/C and Ni/C catalysts, revealing the advantages of NiP2/C over Ni/C. Experimental results obtained in practical PEM water electrolysis validate these predictions, as NiP2/C exhibits an impressive separation factor α of 6.36, nearly twice that of the Pt/C catalyst. Moreover, NiP2/C demonstrates reliable and consistent HIS performance during a 100-hour PEM electrolysis process. Importantly, our calculation model for deuterium enrichment in liquid water reveals that catalysts with higher separation factors α show faster deuterium enrichment and higher deuterium recovery rates. The utilization of NiP2/C as a non-noble metal cathode catalyst holds great promise for efficient and sustainable hydrogen isotope separation, addressing the limitations of precious metal catalysts and advancing clean energy technologies.

Hydrogen isotope effect on thermodynamic and kinetic properties of Pd based ternary alloys: Pd–Ag-M (M = Au, Zr)

Owing to the importance of hydrogen and its isotopes in energy sector, the present study investigates thermodynamic and kinetic hydrogen isotope effects on desorption reaction of newly synthesized Pd-based ternary alloy-hydrides/deuterides viz., Pd0.89Ag0.05M0.06 (M = Au, Zr)–H/D. Alloys were prepared by arc melting method followed by characterization using PXRD, SEM, TXRF and EDX techniques. The effect of hydrogen isotopes on thermodynamics of H2/D2 desorption reaction was investigated by generating pressure-temperature isotherms (PCIs) at various temperatures using a Sieverts' type volumetric apparatus. The PCT diagram of alloys depicts a single plateau which confirms desorption to be a one-step process. Both alloy systems display a normal isotope effect as indicated by higher plateau pressure for deuterides as compared to hydrides. The enthalpy and entropy changes for the desorption reactions were calculated using Van't Hoff equation. The separation factor derived from PCT data indicates that Pd0.89Ag0.05Au0.06 alloy has a significantly high separation factor as compared to other Pd based alloys reported in the literature. To get more insight into this behavior, non-isothermal kinetic analysis of H2/D2 desorption based on Differential Scanning Calorimeter (DSC) data acquired at four different heating rates was conducted and activation energies of desorption were calculated by invoking Kissinger's equation. The activation energies of alloys were found to be lower than that of palladium which explains the high separation factor of alloys as compared to Pd. The desired combination of higher separation factor and lower activation energy makes Pd0.89Ag0.05Au0.06 alloy a promising material for practical application in the separation of hydrogen isotopes via self-displacement gas chromatography (SDGC).

Enhanced Solar-to-Hydrogen Conversion and Hydrogen Isotope Separation through Interfacial Hydrogen-Bond Engineering and Homolytic O–H Cleavage on Multianionic Sulfides in Large-Scale Floating Nanocomposites

Enhanced Solar-to-Hydrogen Conversion and Hydrogen Isotope Separation through Interfacial Hydrogen-Bond Engineering and Homolytic O–H Cleavage on Multianionic Sulfides in Large-Scale Floating Nanocomposites

A Brief Review on Membrane-Based Hydrogen Isotope Separation

A Brief Review on Membrane-Based Hydrogen Isotope Separation

Applicability of self-consistent reaction field (SCRF) method to DFT estimation of hydrogen isotope separation factors in reversible processes

ABSTRACT In earlier quantum chemical calculations of isotope effects, chemical species in the liquid phase were generally treated as existing in the gas phase. In recent years, however, advances in computational programs have made it easier for the self-consistent reaction field (SCRF) method to handle chemical species in the liquid phase, and as a result, it has become easier to apply the SCRF method to isotope effect calculations. This paper concerns the scope of application of the DFT-SCRF method to reversible processes for hydrogen isotope enrichment. It is found that the applicability of the method depends on the type of the intermolecular interaction in the liquid phase and the degree of hydrogen isotope effect (separation factor) on which the process is based. When the magnitude of the isotope effect of the separation system is greater than 10–1, the simple SCRF method is fully applicable; when the magnitude is around 10–2, SCRF with a dimer model, in which the monomer is replaced by a dimer, is applicable for the analysis of the liquid phase with relatively strong intermolecular interactions. Anharmonic correction to the separation factor calculated based on harmonic frequencies may be effective to systems with the liquid phase with weak intermolecular interactions.

Atomic hydrogen production in a cold plasma for application in a metal foil pump

Any good design of fuel cycles for thermonuclear fusion reactors, which operate on deuterium-tritium fusion, comes with minimized tritium inventory. The direct internal recycling concept can significantly reduce the tritium inventory of a fusion power plant by introducing a bypass for most of the unburned fuel from the torus exhaust. It requires a technology that can sharply separate hydrogen isotopes from other gases in the given environment in the reactor's pump duct. The prime candidate for this task is a metal foil pump (MFP) using plasma-driven permeation. A workflow toward a performance predicting modeling tool of a MFP is introduced. It is based on the characterization of the employed cold plasma by using a plasma simulation, which is experimentally validated using optical emission spectroscopy and the actinometry method. The used approach accounts for the radial inhomogeneity of the linearly extended plasma. We determine the atomic hydrogen content down to pressures of 1 Pa and condense the complex processes that contribute to the hydrogen atom production into a single excitation probability. This value can be used in Monte Carlo based modeling approaches to determine the particle exhaust performance of the vacuum pump.

Enhanced Separation Performance of Graphene Oxide Membrane through Modification with Graphitic Carbon Nitride

The treatment of tritiated nuclear wastewater is facing greater challenges with the continuous expansion of the nuclear industry. The key to solving the issue of detritium in low-abundance tritium water lies in developing highly efficient and cost-effective hydrogen isotope separation technology. Graphene oxide (GO) membrane separation method exhibits greater potential compared to other existing energy-intensive technologies for the challenging task of hydrogen isotope separation in nuclear wastewater. In recent years, researchers have explored few strategies to enhance the performance of graphene oxide (GO) membranes in hydrogen isotope water treatment, recognizing the current limitations in separation efficiency. In this study, the GO/g-C3N4 composite membrane has been successfully employed for the first time in the separation of hydrogen isotopes in water. A series of GO membranes were prepared and their performances were tested by a self-made experimental device. As a result, the separation performance of the GO membrane was enhanced by the modification with graphitic carbon nitride (g-C3N4). The permeation rate of the GO/g-C3N4 membrane was higher than that of the GO membrane, while maintaining a high separation factor. Our study also demonstrated that this phenomenon can be attributed to the changes in membrane structure at the microscopic scale. The H/D separation factor and the permeate flux of the composite membrane containing g-C3N4 of 6.7% by mass were 1.10 and 7.2 × 10−5 g·min−1·cm−2 are both higher than that of the GO membrane under the same experimental conditions, which is promising for the isotope treatment.

Advanced modular system for tritium separation by CECE type process

The main source of tritium is fission reactors PHWR (CANDU) or molten salt (MSR), nuclear fusion reactors (JET, ITER, DEMO) which, in operation, generate significant amounts of tritiated light water or tritiated heavy water, whose efficient processing, through an advanced technology, would contribute to the reduction of stocks and the recovery of tritium and deuterium.The research presented in this work aims to promote a modern management of tritium and its associated materials, by developing a technology for separating hydrogen isotopes through the CECE (Combined Electrolysis and Catalytic Exchange) separation process, for the concentration of tritium in liquid state (HTO, DTO).The conceptual diagram of the Advanced Modular System (AMS), the main component elements, together with the description of 3 modes of experimentation will be presented.The technological process that takes place within AMS is electrolysis of process water and, respectively, isotopic exchange on mixed catalytic packing.

Experimental activities in view of hydrogen- deuterium equilibrium reaction in dielectric barrier discharge reactor: Effects of plasma treatment parameters and reactor design

Cryogenic distillation (CD) is a crucial process for separating and concentrating tritium in the tritium fuel cycle of fusion reactors. The equilibrator plays a vital role in decomposing HD, DT, and HT to improve the separation efficiency of hydrogen isotopes in CD. As the equilibrium reaction temperature decreases, a larger proportion of HD, HT, and DT decomposes into H2, D2, and T2, which enhances the performance of the equilibrator. While Pt/Al2O3 catalyst exhibits high activity at 303 K in the H2-D2 equilibrium reaction, it is almost inactive at 77 K. Non-thermal plasma (NTP) technology offers a promising and attractive alternative to conventional catalytic technology. In this study, H2-D2 equilibrium reaction was carried out without catalysts in a dielectric barrier discharge (DBD) reactor, achieving efficient conversion of HD even at 77 K. In the single-electrode DBD plasma reactor (S-P-Reactor), with an input power of 50 W, the conversion efficiency of HD was found to be 99.5% at 303 K, 99.5% at 273 K, and 99.2% at 77 K. To further optimize the energy efficiency of the S-P-Reactor, the reactor structure was enhanced, leading to the development of a multi-high-voltage DBD reactor (M-P-Reactor). The input power of the M-P-Reactor was reduced by approximately 10 W compared to the S-P-Reactor, while maintaining a conversion efficiency of over 95% for HD. The energy density of the reactor was calculated using the Q-V Lissajous graphic method, demonstrating that the M-P-Reactor exhibited superior energy conversion efficiency compared to the S-P-Reactor. Furthermore, the yield of HD was solely determined by the energy density and temperature. At a specific energy density, the yield of HD remained consistent for the same temperature. However, generating HD at lower temperatures required more energy due to the lower reactant activity. These results illustrate the potential application of NTP technology in improving hydrogen isotope separation performance in the cryogenic distillation process for fusion applications.

Hydrogen Isotope Separation Technique by Quantum Tunneling Effect Used Graphene

Hydrogen Isotope Separation Technique by Quantum Tunneling Effect Used Graphene