Breakthrough analysis has widely been explored for the dynamic separation of gaseous mixtures in porous materials. In general, breakthrough experiments measure the components of a flowing gas when a gaseous mixture is injected into a column filled with an adsorbent material. In this paper, we report on the design and fabrication of a breakthrough curve measurement device to study the dynamic adsorptive separation of hydrogen isotopologues in porous materials. Using the designed system, an experiment was conducted involving a 1:1 mixture of hydrogen and deuterium passed through a column filled with zeolite 13X (1 g). At room temperature, both hydrogen and deuterium were adsorbed in negligible amounts; however, at a temperature of 77 K, deuterium was preferentially adsorbed over hydrogen. The selectivity was different from that in the existing literature due to the different sample shapes, measurement methods, and column structures, but was at a similar level to that of cryogenic distillation (1.5).

Deuterium is a crucial clean energy source required for nuclear fusion and is a future resource needed in various industries and scientific fields. However, it is not easy to enrich deuterium because the proportion of deuterium in the hydrogen mixture is scarce, at approximately 0.016%. Furthermore, the physical and chemical properties of the hydrogen mixture and deuterium are very similar. Therefore, the efficient separation of deuterium from hydrogen mixtures is often a significant challenge when using modern separation technologies. Recently, to effectively separate deuterium, studies utilizing the ‘Kinetic Quantum Sieving Effect (KQS)’ of porous materials are increasing. Therefore, in this review, two different strategies have been discussed for improving KQS efficiency for hydrogen isotope separation performance using nanoporous materials. One is the gating effect, which precisely controls the aperture locally by adjusting the temperature and pressure. The second is the breathing phenomenon, utilizing the volume change of the structure from closed system to open system. It has been reported that efficient hydrogen isotope separation is possible using these two methods, and each of these effects is described in detail in this review. In addition, a specific-isotope responsive system (e.g., 2nd breathing effect in MIL-53) has recently been discovered and is described here as well.

Hydrogen isotopes (i.e. deuterium and tritium) are supplied to the tokamak in the International Thermonuclear Experimental Reactor (ITER) fuel cycle. One important part of the ITER fuel cycle is the recycling of unused fuel back to the tokamak, as almost 99 % of fuel is unburned during fusion reaction. For this, cryogenic distillation has been used in the isotope separation system (ISS) of ITER, but this technique tends to be energy-intensive and to have low selectivity (typically below 1.5 at 24 K). Recently, efficient isotope separation by porous materials has been reported in the so-called quantum sieving process. Hence, in this study, hydrogen isotope adsorption behavior is studied using chemically stable ZIF-11. At low temperature (40 K ~ 70 K), the adsorption increases and the sorption hysteresis becomes stronger as the temperature increases to 70K. Molar ratio of deuterium to hydrogen based on the isotherms shows the highest (max. 14) ratio at 50 K, confirming the possibility of use as a potential isotope separation material.

The magnetocaloric effect (MCE), which is the reversible temperature change of magnetic materials due to an applied magnetic field, occurs largely in the vicinity of the magnetic phase transition temperature. This phenomenon can be used to induce magnetic refrigeration, a viable, energy-efficient solid-state cooling technology. Recently, Metal-organic frameworks (MOFs), due to their structural diversity of tunable crystalline pore structure and chemical functionality, have been studied as good candidates for magnetic refrigeration materials in the cryogenic region. In cryogenic cooling applications, MCE using MOF can have great potential, and is even considered comparable to conventional lanthanum alloys and magnetic nanoparticles. Owing to the presence of large internal pores, however, MOF also exhibits the drawback of low magnetic density. To overcome this problem, therefore, recent reports in literature that achieve high magnetic entropy change using a dense structure formation and ligand tuning are introduced.

The gas adsorption isotherm requires accurate measurement for the analysis of porous materials and is used as an index of surface area, pore distribution, and adsorption amount of gas. Basically, adsorption isotherms of porous materials are measured conventionally at 77K and 87K using liquid nitrogen and liquid argon. The cold volume calibration in this conventional method is done simply by splitting a sample cell into two zones (cold and warm volumes) by controlling the level sensor in a Dewar filled with liquid nitrogen or argon. As a result, BET measurement for textural properties is mainly limited to liquefied gases (i.e. N2 or Ar) at atmospheric pressure. In order to independently investigate other gases (e.g. hydrogen isotopes) at cryogenic temperature, a novel temperature control system in the sample cell is required, and consequently cold volume calibration at various temperatures becomes more important. In this study, a cryocooler system is installed in a commercially available BET device to control the sample cell temperature, and the automated cold volume calibration method of temperature variation is introduced. This developed calibration method presents a reliable and reproducible method of cryogenic measurement for hydrogen isotope separation in porous materials, and also provides large flexibility for evaluating various other gases at various temperature.

Nitrogen is a serious contaminant in natural gas because it decreases the energy density. The natural gas specification in South Korea requires a N2 content of less than 1 mol%. Thus, cost-effective N2 removal technology from natural gas is necessary, but until now the only option has been energy-intensive processes, e.g., cryogenic distillation. Using porous materials for the removal process would be beneficial for an efficient separation of CH4/N2 mixtures, but this still remains one of the challenges in modern separation technology due to the very similar size of the components. Among various porous materials, metal-organic frameworks (MOFs) present a promising candidate for the potential CH4/N2 separation material due to their unique structural flexibility. A MIL-53(Al), the most well-known flexible metal-organic framework, creates dynamic changes with closed pore (cp) transitions to open pores (ops), also called the ‘breathing’ phenomenon. We demonstrate the separation performance of CH4/N2 mixtures of MIL-53(Al) and its derivative MIL-53-NH2. The CH4/N2 selectivity of MIL- 53-NH2 is higher than pristine MIL-53(Al), suggesting a stronger CH4 interaction with NH2.

The stereotype of flexible MOFs(Amino-MIL-53) and carbonized porous carbon prepared from renewable resources is successfully synthesized for CO2 reduction application. The textural properties of these microporous materials are investigated, and their CO2 storage capacity and separation performance are evaluated. Owing to the combined effects of CO2-Amino interaction and its flexibility, a CO2 uptake of 2.5 mmol g−1 is observed in Amino-MIL-53 at 20 bar 298 K. In contrast, CH4 uptake in Amino-MIL-53 is very low up to 20 bar, implying potential sorbent for CO2/CH4 separation. Carbonized samples contain a small quantity of metal residues(K, Ca, Mg, S), resulting in naturally doped porous carbon. Due to the trace metal, even higher CO2 uptake of 4.7 mmol g−1 is also observed at 20 bar 298 K. Furthermore, the CH4 storage capacity is 2.9 mmol g−1 at 298 K and 20 bar. To evaluate the CO2 separation performance, the selectivity based on ideal adsorption solution theory for CO2/CH4 binary mixtures on the presented porous materials is investigated.

이산화탄소(CO2)는 천연 가스, 바이오 가스, 매립 가스의 성분으로 존재할 뿐만 아니라 화석연료의 주요 연소 생성물로써 온실 가스의 주범이다. 특히 내연기관의 연료 고효율을 얻고, 가스 수송시스템의 부식을 방지하며, 기후변화에 선제적으로 대응하기 위해서는 이산화탄소(CO2)의 저감 또는 제거 기술이 필수적이다. 지난 수십 년간, 멤브레인 기반 기술의 구성 및 설계 단순성에 의하여 관련 연구가 많이 이루어져 왔으며 많은 발전을 이루었다. 최근 들어, 기존 멤브레인 기반 분리 뿐만 아니라, 새로운 흡착제 기반 분리 기술 등에 대한 관심도 높아지고 있다. 특히, 최근 각광받고 있는 유기-금속 골격체 (Metal Organic Frameworks, MOFs)의 경우, 일반 다공질 흡착제와는 다른 독특한 성질(Flexibility, Gating effect 또는 Open Metal Sites 등)로 인하여, 이를 활용한 다양한 기체 분리 연구가 늘어나고 있는 추세이다. 따라서 본 연구에서는 대표적 플렉 서블한 물질인 MIL-53(Al)과 강한 결합에너지 site를 다수 보유한 대표적 MOF 물질인 MOF-74(Ni)를 활용하여 온도 및 압력에 따른 이산화탄소 메탄 분리 성능 비교 분석하였으며, 각 물질의 특성별 압력 및 온도에 따라 변화하는 적정 분리 구간을 제시하였다.

With the matters of climate change, energy security and resource depletion, a growing pressure exists to search for replacements for fossil fuels. Among various sustainable energy sources, hydrogen is thought of as a clean energy, and thus efficient hydrogen storage is a major issue. In order to realize efficient and safe hydrogen storage, various porous materials are being explored as solid-states materials for hydrogen storage. For those purposes, it is a prerequisite to characterize a material’s textural properties to evaluate its hydrogen storage performance. In general, the textural properties of porous materials are analyzed by the Brunauer-Emmett-Teller (BET) measurement using nitrogen gas as a probe molecule. However, nitrogen BET analysis is sometimes not suitable for materials possessing small pores and surfaces with high curvatures like MOFs because the nitrogen molecule may sometimes be too large to reach the entire porous framework, resulting in an erroneous value. Hence, a smaller probe molecule for BET measurements (such as hydrogen) may be required. In this study, we describe a cost-effective novel cryostat for BET measurement that can reach temperatures below the liquefaction of hydrogen gas. Temperature and cold volume of the cryostat are corrected, and all measurements are validated using a commercial device. In this way, direct observation of the hydrogen adsorption properties is possible, which can translate directly into the determination of textural properties.

Isosteric heat of hydrogen adsorption is one of the most important parameters required to describe solid-state hydrogen storage systems. Typically, it is calculated from adsorption isotherms measured at 77K (liquid N2) and 87K (liquid Ar). This simple calculation, however, results in a high degree of uncertainty due to the small temperature range. Therefore, the original Sievert type setup is upgraded using a heating and cooling device to regulate the wide sample temperature. This upgraded setup allows a wide temperature range for isotherms (77K ~ 117K) providing a minimized uncertainty (error) of measurement for adsorption enthalpy calculation and yielding reliable results. To this end, we measure the isosteric heats of hydrogen adsorption of two prototypical samples: activated carbon and metal-organic frameworks (e.g. MIL-53), and compared the small temperature range (77~87K) to the wide one (77K ~ 117K).