• Bulletin of the Korean Chemical Society
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• v.32 no.8
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• pp.2705-2710
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• 2011

Four MOFs functionalized with 1-Me, 1-Pr, 1-Ph, and 1-$PhCF_3$ were prepared through post-synthetic modifications of a metal-organic framework (MOF), UMCM-1-$NH_2$ (1) with acetic, butyric, benzoic, and 4-(trifluoromethyl)benzoic anhydrides, respectively. Methane adsorption measurements between 253 and 298 K at pressures up to 1 bar indicated that both 1-Ph and 1-$PhCF_3$ adsorbed more $CH_4$ than the parent MOF, 1. All the functionalized MOFs adsorbed more $CO_2$ than 1 under conditions similar to the $CH_4$ test. The introduction of functional groups promoted adsorption of both $CH_4$ and $CO_2$ despite significantly reducing Brunauer-Emmet-Teller (BET) surface area: 4170 (1), 3550 (1-Me), 2900 (1-Pr), 3680 (1-Ph), and 3520 $m^2/g$ (1-$PhCF_3$). Electron-withdrawing aromatic groups (1-Ph, 1-$PhCF_3$) more effectively enhanced $CO_2$ adsorption than electron-donating alkyl groups (1-Me, 1-Pr). In particular, 1-Ph adsorbed 23% more $CO_2$ at 298 K and 50% more at 253 K than 1.

• Applied Chemistry for Engineering
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• v.33 no.3
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• pp.296-301
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• 2022

Due to the fact that zirconium based metal-organic frameworks (Zr-MOFs), such as UiO-66, have a large specific surface area and excellent selective adsorption capacity, Zr-MOFs are gaining attention as materials that can provide protection from the attack of chemical warfare agents in battleground. However, most of the metal-organic frameworks have an issue of selective adsorption capacity degraded by water molecules when exposed to the atmosphere, because of the weak metal-organic ligand bonds and the presence of voids. Therefore, polydimethylsiloxane (PDMS), a representative hydrophobic polymer material, was coated on the surface of UiO-66 to enhance the sustainability of the diisopropyl methylphosphonate (DIMP) sorption capacity in the battleground condition. Through the analysis of surface structure and organic functional group distribution of PDMS coated UiO-66, silicon was confirmed to be evenly coated. The contact angle increased by over 30° for the PDMS coated UiO-66, indicating that the hydrophobicity was improved. In addition, both the UiO-66 and PDMS coated UiO-66 were used as adsorbents for DIMP, a similar chemical warfare agent, to investigate the durability of adsorption capacity in a high humidity environment. The PDMS coated UiO-66 showed higher durability of adsorption capacity for 20 days than that of pristine UiO-66.

• 한국신재생에너지학회:학술대회논문집
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• 2005.11a
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• pp.84-91
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• 2005

수소저장기술은 수소경제를 달성하기 위해 개발해야할 핵실요소기술이다. 이 논문에서는 고체수소저장기술의 최신 개발 동향을 고찰하였다. 나노구조 탄소계 물질(nanostructured carbon materials), 유기금속구조물(metal organic framework, MOFs), 금속수소화물(metal hydrides), 클래스레이트수화물(clathrate hydrates), 금속착수소화물(complex chemical hydrides)과 같은 고체수소저장매체를 중점적으로 고찰하였다. 그 결과 지금까지 개발된 고체수소저장재료의 수소저장용량은 고체의 표면적에 비례하여 증가함을 알 수 있었다. 탄소나노튜브의 수소저장 메커니즘을 연구하여 탄소나노튜브의 표면적이 수소저장량을 증가시키는데 중요한 인자로 작용함을 알 수 있었다.

• Korean Chemical Engineering Research
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• v.43 no.4
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• pp.439-451
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• 2005

This article provides a panoramic overview of the state-of-the-art technologies in the field of solid-state hydrogen storage methods. The emerging solid-state hydrogen storage techniques, such as nanostructured carbon materials, metal organic framework (MOFs), metal and inter-metal hydrides, clathrate hydrates, complex chemical hydride are discussed. The hydrogen storage capacity of the solid-sate hydrogen storage materials increases in proportion to the surface area of the solid materials. Also, it is believed that new functional nanostructured materials will offer far-reaching solutions to the development of on-board hydrogen storage system for the application of the transportation vehicles.

• Journal of the Korean Ceramic Society
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• v.53 no.2
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• pp.200-205
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• 2016

With high specific surface area and pore structural diversity, MOFs show important applications in gas storage, catalysis, sensing, separation, and biomedicine. However, the stability of the structure of MOFs has restricted their application and development. In this study, zirconium metal organic frameworks with 9,10-dicarboxylic acid anthracene as ligand, named UIO-66 ($H_2DCA$), were synthesized and their properties and structures were characterized by XRD, SEM, and $N_2$ adsorption. We focus on the stability of the structure of UIO-66 ($H_2DCA$) under different conditions (acid, alkali, and water). The structural changes or ruins of UIO-66 ($H_2DCA$) were traced by means of XRD, TG, and FT-IR under different conditions. The results show that the UIO-66 ($H_2DCA$) materials are stable at 583 K, and that this structural stability is greatly influenced by different types of acid and alkali compounds. Importantly, we found that the structures maintain their stability in environments of nitric acid, triethylamine, and boiling water.

• Korean Journal of Materials Research
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• v.27 no.9
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• pp.466-470
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• 2017

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.

• Bulletin of the Korean Chemical Society
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• v.33 no.11
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• pp.3777-3787
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• 2012

Three kinds of 3D isomorphous and isostructural coordination polymers, namely, $\{[Ln_2(PDA)_3(H_2O)_3]{\cdot}0.25H_2O\}_{\infty}$ (Ln = La(1), Sm(2), and Gd(3)) ($PDA^{2-}$ = pyridine-2,6-dicarboxylate anion) have been synthesized under hydrothermal conditions and characterized by elemental analyses, IR spectroscopy, thermal analyses and single crystal X-ray diffraction. In these MOFs, Ln(III) centers adopt eight-coordinated and nine-coordinated with the $N_1O_7$ and $N_2O_7$ donor sets to construct distorted trianglar dodecahedron geometry and tricapped trigonal prism configurations, respectively. Based on the building block of tetranuclear homometallic $Ln_4C_4O_8$ unit (16-membered ring), 1-3 are connected into highly ordered 2D sheets via O-C-O linkers and further constructed into 3D architectures through hydrogen bonds. Crystallographic parameters suggest that the lanthanide contraction effect exist in these coordination polymers. Luminescent properties of the lanthanide-based MOFs (metal-organic frameworks) have been measured at room temperature, which reveal that they presenting ionselective characters toward certain metals, such as $Mg^{2+}$, $Cd^{2+}$ and $Pb^{2+}$ ions.

• Journal of Environmental Science International
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• v.30 no.1
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• pp.97-108
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• 2021

In the current study, MIL-101(Cr)-SO3H[HCl] as metal-organic frameworks (MOFs) was fabricated via a hydrothermal method. The physicochemical properties of the synthesized material were characterized using XRD, FT-IR, FE-SEM, TEM, and BET surface area analysis. The XRD diffraction pattern of the prepared MIL-101(Cr)-SO3H[HCl] was similar to previously reported patterns of MIL-101(Cr) type materials, indicating successful synthesis of MIL-101(Cr)-SO3H[HCl]. The FT-IR spectrum revealed the molecular structure and functional groups of the synthesized MIL-101(Cr)-SO3H[HCl]. FE-SEM and TEM images indicated the formation of rectangular parallelopiped structures in the prepared MIL-101(Cr)-SO3H[HCl]. Furthermore, the EDS spectrum showed that the synthesized material consisted of the elements of Cr, O, S, and C. The fabricated MIL-101(Cr)-SO3H[HCl] was then employed as an adsorbent for the removal of Sr2+ and Cs+ from aqueous solutions. The adsorption kinetics and adsorption isotherm models were studied in detail. The maximum adsorption capacities of MIL-101(Cr)-SO3H[HCl] for Sr2+ and Cs+ according to pH (3, 5.3~5.8, 10) were 35.05, 43.35, and 79.72 mg/g and 78.58, 74.58, and 169.74 mg/g, respectively. These results demonstrate the potential of the synthesized MOFs, which can be effectively applied as an adsorbent for the removal of Sr2+ and Cs+ ions from aqueous solutions and other diverse applications.

• Journal of Sensor Science and Technology
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• v.30 no.6
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• pp.369-375
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• 2021

In this study, heterogeneous ZnO/CNTF composites were developed to improve the NO₂-sensing response, facilitated by the self-heating property. Highly conductive and mechanically stable CNTFs were prepared by a wet-spinning process assisted by the liquid crystal (LC) behavior of CNTs. Metal-organic frameworks (MOFs) of ZIF-8 were precipitated on the surface of the CNTF (ZIF-8/CNTF) via one-pot synthesis in solution. The subsequent calcination process resulted in the formation of the ZnO/CNTF composites. The calcination temperatures were controlled at 400, 500, and 600 ℃ in an N₂ atmosphere to confirm the evolution of the microstructures and NO₂-sensing properties. Gas sensor characterization was performed at 100 ℃ by applying a DC voltage to induce Joule heating through the CNTF. The results revealed that the ZnO/CNTF composite after calcination at 500 ℃ (ZnO/CNTF-500) exhibited an improved response (R_air/R_gas = 1.086) toward 20 ppm NO₂ as compared to the pristine CNTF (R_air/R_gas = 1.063). Selective NO₂-sensing properties were demonstrated with negligible responses toward interfering gas species such as H₂S, NH₃, CO, and toluene. Our approach for the synthesis of MOF-driven ZnO/CNTF composites can provide a new strategy for the fabrication of wearable gas sensors integrated with textile materials.

• Korean Chemical Engineering Research
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• v.61 no.1
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• pp.1-7
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• 2023

Gas separation technology becomes more useful because key gases such as H₂ and CO₂ regarding renewable energy resources and environmental pollutant can be effectively extracted in mixed gases. For reducing energy consumption on gas separation, membrane and adsorption processes are widely used. In both processes, porous materials are needed as membrane and adsorbent. In particular, metal-organic frameworks (MOFs), one class of the porous materials, have been developed for the purpose of gas adsorption and separation. While the number of the MOF structures is increasing due to chemical and structural tunability, good MOF membranes and adsorbents have been rarely reported by trial-and-error experiments. To accelerate the discovery of high-performing porous materials that can separate H₂ and CO₂, a high-throughput computational screening technique was used as efficient skill. This review introduces crucial studies of porous materials and the high-throughput computational screening works focusing on gas separation of H₂ and CO₂.