Radiation from spent nuclear fuel (SNF) is one of key factors affecting the dissolution process of SNF and the source term from repository. The dissolution rate of uranium dioxide (UO2) matrix of SNF is expected to control the release of radionuclides from SNF in contact with water under geological disposal conditions. Based on the oxidative dissolution mechanism, the solubility of UO2 can increase significantly if the reducing environment near the fuel surface is altered by water radiolysis caused by radiation from SNF. Therefore, the analysis of water radiolysis products such as radicals (·OH, ·OH2, eaq, ·H) and molecules (H3O+, H2, H2O2) is perquisite for studies on the rate of such dissolution process to determine oxidation/dissolution mechanism and related rate constants. In this study we examined the two-known spectroscopic methods developed for H2O2 determination; one is the luminol-based chemiluminescence (luminol-CL) method and the other is the spectrophotometry using ferrous oxidation-xylenol orange complexation (FOX). Their applicability for quantitative analysis of H2O2 in potential aqueous samples from SNF dissolution studies was evaluated in terms of the analytical dynamic range (ADR), the limit of detection (LOD) and the interfering effects of various metal ions possibly present in real samples. The luminol-CL method exploits the chemiluminescence reaction caused by luminol; when in the presence of a metallic catalyst (e.g., Cu2+, Co2+), luminol emits a blue light (425 nm) at pH 10- 11 in response to oxidizing agents such as hydrogen peroxide. Although a flow-through reaction system is routinely employed to enhance the analytical sensitivity we achieved the ADR up to ~200 μM and LOD < 1 μM by a batch-wise CL detection using conventional cuvette cells and an intensified charge-coupled device (ICCD). Interestingly, it turned out that the interfering effects of other metal ions (e.g., UO2 2+, U4+, Fe2+ and Fe3+) is minimal, which should be advantageous for the luminol-CL method to be employed for samples potentially containing other metal ions. On the other hand, the FOX method spectrophotometrically analyzes H2O2 based on the difference in color (or absorption spectra) of Fe-xylenol orange (XO) complexes. Initially, the Fe2+-XO complex was provided in working solutions at pH 3, which was subsequently mixed with samples having H2O2 and allowed for quantitative oxidation of Fe2+ to Fe3+. Typically, by monitoring the absorbance of Fe3+-XO complex at 560-580 nm (λmax) the ADR up to ~100 μM and LOD ~1.6 μM were achieved. However, it is found that interfering effects from M3+ and M4+ ions are significant; these interfering metal ions can form XO complexes so as to directly contribute the measured absorbance. In contrast, the influence from M2+ ions was found to be negligible. To summarize we conclude that both methods can be applied for H2O2 determination for aqueous samples taken from SNF dissolution tests. However, prior to applying the FOX method the metal ion composition in those samples should be thoroughly identified not to overestimate the H2O2 concentration of samples. More details of underlying chemical reactions in both methods will be discussed in the presentation.

The physicochemical similarities of hydrogen isotopes have made their separation a challenging task. Conventional methods such as cryogenic distillation, Girdler sulfide process, chromatography, and thermal cycling absorption have low separation factors and are energy-intensive. To overcome these limitations, research has focused on kinetic quantum sieving (KQS) and chemical affinity quantum sieving (CAQS) effects for selective separation of hydrogen isotopes. Porous materials such as metal-organic frameworks (MOF), covalent organic frameworks (COF), zeolites, carbon, and organic cages have been studied for hydrogen separation. In this study, we focus the enhancement for CAQS to provide the cations due to the chemical affinity between hydrogen isotope and unsaturated sites by cations in zeolite beads. Cation exchanged zeolite beads was synthesized with cobalt, copper, nickel, iron and silver in zeolite 4A beads. Synthesized cation exchanged zeolite was analyzed for the surface area and pore size in N2 and adsorption behaviors of hydrogen isotopes (D2/H2) for various cation exchanged zeolite beads using BET at 77 K. The study predicts the D2/H2 adsorption selectivity based on the results obtained with BET. These hydrogen isotope adsorption results will provide a foundation for future processes for tritium separation.

Tritium is radioactive isotope, emitting beta ray, released as tritiated water from nuclear power plants. Due to the danger of radioactive isotope, the appropriate separation of tritium is essentially carried out for environment and safety. Further, it is also promising material for energy production and research. The tritiated water can be treated by diverse techniques such as water distillation, cryogenic distillation, Girdler-sulfide process, and catalytic exchange. After treatment, it is more desirable to convert as gas phase for storage, comparing to liquid phase. However, achieving complete separation of hydrogen gases with very similar physical and chemical properties is significantly challenging. Thus, it is necessary to develop materials with effective separation properties in gas separation. In this presentation, we present hydrogen isotope separation in the gas phase using modified mesoporous silica. Mesoporous silica is a form of silica that is characterized by its mesoporous structure possessing pores that range from 2 to 50 nm in diameter. This material can be functionalized to selectively capture and separate molecules having specific size and affinity. Here, the silver and copper incorporated mesoporous silica was synthesized to tailor a chemical affinity quantum sieving effect, thereby providing separation efficiency in D2/H2. The adsorption quantities of H2 and D2 were determined by sorption study, and the textural properties of each mesoporous silica were analyzed using N2 physisorption. The selectivity (D2/H2) in diverse feed composition (1:1, 1:9, and 1:99 of D2/H2) was estimated by applying ideal adsorbed solution theory to predict the loading of the gas mixture on bare, Ag- and Cu-mesoporous silica based on their sorption study. Further, the performance of each mesoporous silica was evaluated in the breakthrough adsorption under 1:1 mixture of D2 and H2 at 77 K.

Pt/C catalysts were prepared using black carbon (CB), and evaluated for their potential application as a catalyst of liquid-phase catalystic exchange for tritium treatment. CB was treated with 10% H2O2 solution for 0 and 2 hours at 105°C, Ethylene glycol and 40wt% Pt were added to the dried treated sample to prepare a Pt/C catalyst. The physical and chemical properties of the prepared catalysts were evaluated by BET, XRD, elemental analysis (EA), and TEM analyses. As a result of BET analysis, the surface area of CB without 10% H2O2 was 237.2 m2·g-1, and after treatment with 10% H2O2, it decreased to 181.2 m2·g-1 for 2 hours. However, the internal surface area increased, indicating the possibility that more Pt could be distributed inside the CB treated with 10% H2O2. In the XRD analysis results, the presence of Pt was confirmed by observing the Pt peak in the prepared Pt/C catalyst, and it was also observed through TEM analysis that Pt was evenly distributed within the CB. The elemental analysis (EA) results showed that the ratio of S and N decreased and the ratio of O increased with increasing 10% H2O2 treatment time. The H2O2 treated carbon supported Pt catalysts and polytetrafluoroethylene were then loaded together on a foamed nickel carrier to obtain hydrophobic catalysts. Our hydrophobic Pt catalyst using H2O2 treated black carbon are expected to be usefully used in the tritium treatment system.

Hydrogen isotope separation involves the separation of hydrogen, deuterium, tritium, and their isotopologues. It is an essential technology for removing radioactive tritium contamination and for obtaining valuable hydrogen isotope resources. Among various hydrogen isotope separation technologies, water electrolysis technology exhibits a high separation factor. Consequently, the electrolysis of tritiated water is of paramount importance as a tritium enrichment method for treating tritium-contaminated water and for analyzing tritium in environmental samples. More recently, hydroelectrolysis technology, which utilizes proton exchange membranes (PEM) to reduce water inventory, has gained favor over traditional alkaline hydroelectrolysis. Nevertheless, it is crucial to decrease the hydrogen permeability of the PEM in order to mitigate the explosion risk associated with tritium hydrogen electrolysis devices. Additionally, efforts are needed to enhance the hydrogen isotope selectivity of the PEM and optimize the manufacturing process of the membrane-electrode assembly (MEA), thereby improving both hydrogen isotope separation performance and water electrolysis efficiency. In this presentation, we will delve into two key aspects. Firstly, we’ll explore the reduction of hydrogen permeability and the enhancement of the hydrogen isotope separation factor in PEM through the incorporation of 2D nanomaterial additives. Secondly, we’ll examine the influence of various MEAs preparation methods on electrolysis and isotope separation performances. Lastly, we will discuss the effectiveness of the developed system in separating deuterium and tritium.

Korea Atomic Energy Research Institute (KAERI) has been operating the Post Irradiation Examination Facility (PIEF). The facility has many PIE equipment and one of them is a hydrogen analyzer for measuring hydrogen contents in Zr cladding of spent fuel. The cladding tube of fuel is oxidized in the core environment of high temperature and pressure and absorbs some of the hydrogen generated during the oxidation. The hydrogen content increases with the increase of burn-up, and causes hydriding of the material, which degrades the mechanical properties. Therefore, hydrogen content analysis of the cladding tube is required for the performance and integrity evaluation of spent fuel. In PIEF, the hydrogen analyzer extracts hydrogen gas from Zr cladding by the hot extraction method. The hydrogen gas flows with inert gas and oxidizes to H2O through a CuO reagent. Finally, an IR detector measures the hydrogen amount from the absorbed IR intensity at a specific wavelength. Because the equipment is in the glove box and has some consumable parts, the maintenance work was performed as a radiation work.

Zircaloy-4 is utillzed in nuclear fuel rod cladding due to its strength and corrosion resistance. However, it can undergo deformation over time, known as creep, which poses a safety risk in reactors. Furthermore, hydrogen absorption during reactor operation can alter its properties and affect creep rates. Previous research suggests a trend in which hydrogen concentration corelates unidirectionally with creep rates, either increasing or decreasing as the concentration rises. This trend can also be observed in EPRI’s creep model, EDF-CEA Model-3. However, recent literature has suggested that creep behavior may vary depending on the state of hydrogen presence. Therefore, it has become evident that creep behavior can be influenced not only by hydrogen concentration but also by the state of hydrogen presence, whether it is in a solid solution state or precipitated as hydrides. Our study aimed to compare creep behavior in specimens with hydrogen concentrations below and above solubility limits. We fabricated Zircaloy-4 plate specimens with varying hydrogen concentrations and conducted creep tests. The results revealed that specimens below the solubility limit exhibited decreasing creep rates as hydrogen concentration increased, while those above the limit displayed increasing creep rates. This investigation confirms that the state of hydrogen presence significantly impacts creep behavior within Zircaloy-4 cladding. As part of our additional research plans, we intend to conduct creep tests on the material based on its orientation, whether it is in the rolling direction (RD) or the transverse direction (TD). We also plan to perform creep tests on ring specimens. Additionally, for the ring specimens, we aim to evaluate how creep behavior differs between the cold-worked stress-relieved (CWSR) condition and the recrystallized annealed (RXA) condition achieved through high-temperature heat treatment.

The thermocatalytic decomposition of methane is a promising method for hydrogen production. To determine the cause of carbonaceous catalyst deactivation and to produce high-value carbon, methane decomposition behavior and deactivated catalysts were analyzed. The surface properties and crystallinity of a commercial activated carbon material, MSP20, used as a methane decomposition catalyst, varied with the reaction time at a reaction temperature of 900 °C. During the initial reaction, MSP20 provided a methane conversion of ≥ 50%; however, the catalyst exhibited rapid deactivation as crystalline carbon grew at surface defects; after 15 min of reaction, approximately 33% methane conversion was maintained. With increasing reaction time, the specific surface area of the catalyst decreased, whereas crystallinity increased. The R-square value of the conversion–crystallinity relationship was significantly higher than that of the conversion–specific surface area relationship; however, neither profile was linear. The activity of the activated carbon catalyst for methane decomposition is mainly determined by the complex actions of the specific surface area and defect sites. The activity was maintained after an initial sharp decline caused by the continuous growth of crystalline carbon product. This study presents the application of carbonaceous catalysts for the decomposition reaction of methane to form COx- free hydrogen, while simultaneously yielding porous carbon materials with an improved electrical conductivity.

In this study, numerical analysis was performed for the purpose of analyzing the flow characteristics and performance according to the change in the inflow hydrogen temperature and differential pressure of the receptacle of the hydrogen charging system. The pressure distribution and turbulent kinetic energy in the filter area were analyzed by changing the outlet pressure condition under the inlet hydrogen temperature condition, and the flow velocity change at the outlet was compared and analyzed. As a result of the analysis, as the differential pressure decreased, the flow rate at the outlet of the receptacle decreased by up to about 70% at the 2.86 MPa condition compared to the 1.86 MPa condition, and the mass flow rate decreased by about 56.5% at the maximum. It was found that the standard CV performance was not satisfied when the differential pressure at the inlet and outlet was 1.12 MPa or less under the 363K temperature condition.

The emergence of Mo2C- based catalysts in recent years has been favored as promising contender within diverse class MXenes. In terms of rapid development in the photocatalytic application, these intriguing compounds exhibit excellent photocatalytic performance because of their superior optical properties and peculiar structure characteristics. Unfortunately, a systematic review of Mo2C- based catalysts is lacking. In this review, we abstract the implication of structure—property relationship of emerging Mo2C- based MXenes materials and their applications toward the photocatalytic hydrogen evolution reaction (HER). Furthermore, synthetic pathways to prepare high-quality, low cost Mo2C- based MXenes materials and their outcomes for high HER applications are systematically described. Finally, several insights are provided into the prospects and future challenges for the development of highly reactive Mo2C- based MXenes materials, which present large range opportunities in this promising 2D materials for green and clean energy in environmental fields. This review provides a comprehensive scientific guide to the preparation, modification, and photocatalytic HER of MXenes-based materials.

Amorphous molybdenum sulfide ( MoSx) has been regarded as a promising hydrogen evolution reaction (HER) catalyst due to its mild preparation conditions and low-cost precursor materials. In this work, we report a simple strategy combining the growth of amorphous MoSx on the surface of metal organic frameworks (ZIF-67) and annealing treatment to prepare Co-doped MoSx nanopolyhedrons (denoted as CoMoSx NPs). The CoMoSx NPs exhibit excellent HER activity in acid condition with an overpotential of 188 mV at a current density of 10 mA cm− 2 (η10), and a relatively stable overpotential after 2000 cyclic voltammetry (CV) cycles testing. The excellent HER performance of the CoMoSx NPs can be attributed to the doping of Co element adjust the electronic structure and increase the conductivity of catalyst, and the nanopolyhedrons structure which can expose more active sites for HER electrocatalytic. This study offers a low-cost and simple strategy to prepare high-activity HER catalyst, which holds great promises in developing advanced electrocatalysts for energy storage.

Hydrogen is considered as one of the most promising future energy carriers due to its noteworthy advantages of renewable and high calorific value. The long-term storage of liquid hydrogen with low heat leakage is essential for future deep space exploration. Because of low critical temperature and volatility, liquid hydrogen tank poses severe requirements to multi-layer insulation (MLI). In order to reduce heat leak into tank, vapor cooled shield (VCS) was set up to cool MLI by retrieving the heat of discharged cryogenic gas hydrogen. This paper presents an parametric study on insulation system in liquid hydrogen storage vessel with MLI and VCS. Thermal model was developed, and heat transfer analysis by varying VCS position was conducted. Temperature and heat flux distributions along time passing were derived, and effect of VCS position on insulation performance was investigated.