• Bulletin of the Korean Chemical Society
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• v.32 no.12
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• pp.4199-4204
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• 2011

Using models simulating the environment of two distinct adsorption sites of $H_2$ in metal-organic framework-5 (MOF-5), binding energies of $H_2$ to MOF-5 were evaluated at the MP2 and CCSD(T) level. For organic linker section modeled as dilithium 1,4-benzenedicarboxylate ($C_6H_4(COO)_2Li_2$), the MP2 and CCSD(T) basis set limit binding energies are estimated to be 5.1 and 4.4 kJ/mol, respectively. For metal oxide cluster section modeled as $Zn_4O(CO_2H)_6$, while the MP2 basis set limit binding energy estimate amounts to 5.4 kJ/mol, CCSD(T) correction to the MP2 results is shown to be insignificant with basis sets of small size. Substitution of benzene ring with pyrazine ring in the model for the organic linker section in MOF-5 is shown to decrease the $H_2$ binding energy noticeably at both the MP2 and CCSD(T) level, in contrast to the previous study based on DFT calculation results which manifested substantial increase of $H_2$ binding energies upon substitution of benzene ring with pyrazine ring in the similar model.

• Proceeding of EDISON Challenge
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• 2014.03a
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• pp.197-209
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• 2014

환경 오염에 대한 우려의 목소리가 높아지면서 Green chemistry 분야가 각광을 받고 있다. 이 분야에서는 환경에 영향을 적게 미치기 위한 방법의 일환으로 촉매를 연구하며, 그 촉매는 착화합물인 경우가 많다. 그러나 착화합물 내에서 리간드와 금속 이온간의 결합은 예측하기 어렵다. 이는 전형금속보다는 전이금속에서 더욱 심하며, 그 중 한 예로 전이금속에서는 여러 개의 금속 이온이 서로 직접적으로 결합한 채 리간드와 결합하는 착화합물이 발견되기도 한다. 다중 금속 착화합물(Multimetal Complex)로 부르는 이러한 구조는 특유의 복잡함 때문에 잘 알려져 있지 않음에도 불구하고 착화합물의 물리적, 화학적 성질에 직접적으로 영향을 주기에 촉매나 센서, 특히 이를 이용하여 구조체를 만드는 MOF(Metal-Organic Framework) 분야에서는 꼭 알고 있어야 하는 사항이다. 이 연구에서는 GAMESS로 density functional theory (B3LYP functional)를 이용한 양자계산을 수행하여 그 중 가장 간단한 구조인 Dimetal Complex, 그 중에서도 MOF 내에서 많이 발견되는 수차 형태(Paddle wheel) 착화합물에 대해서 다루었다. Cu를 기준으로 그와 비슷한 주기나 족에 있는 Ru, Ag, Zn 등의 금속으로 만든 Paddle wheel 구조의 에너지를 비교하여 Cu가 다른 금속에 비해 이 구조를 안정하게 형성할 수 있는 이유를 알아보았다. 더 나아가 이 구조가 MOF의 형성과 성질에 어떠한 연관성이 있는지 분석함으로써 어떠한 조건이 MOF의 성질을 극대화시킬 수 있는지도 알아보았다.

• Korean Chemical Engineering Research
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• v.61 no.2
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• pp.322-327
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• 2023

A design of experiments was evaluated in optimizing MOF-5 synthesis for acetylene adsorption. At first, mixture design was used to optimize precursor concentration, terephthalic acid, zinc acetate dihydrate and N,N-dimethylformamide. More specifically, 13 conditions with various molar ratios were designed by extreme vertices design method. After preparing the samples, XRD, N₂ physisorption and SEM analysis were performed for their characterization. Moreover, acetylene adsorption experiments were carried out over the samples under identical conditions. The optimal precursor composition for MOF-5 synthesis was predicted on a molar basis as follows: terephthalic acid : acetate dihydrate : dimethylformamide = 0.1 : 0.4 : 0.5. Thereafter, multi-level factorial design was designated to investigate the effect of synthesis reaction conditions such as temperature, time and stirring speed. By the statistical analysis of 18 samples designed, 4 reaction parameters were determined for additional adsorption experiments. Therefore, MOF-5 prepared under the synthesis time and temperature of 100 ℃ and 12 h, respectively, showed the maximum adsorption capacity of 15.1 mmol/g.

• Journal of Sensor Science and Technology
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• v.32 no.3
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• pp.147-153
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• 2023

Metal-organic frameworks (MOFs) of cobalt gallate were synthesized and deposited on gold electrodes using self-assembly monolayers (SAMs) and hydrothermal processing. These MOF films exhibit strong adsorption capabilities for gaseous particulates, and the use of SAMs allows the synthesis and deposition processes to be completed in a single step. When cobalt gallate is mixed with SAMs, a coordination bond is formed between the cobalt ion and the carboxylate or hydroxyl groups of the SAMs, particularly under hydrothermal conditions. Additionally, the quartz crystal microbalance (QCM) gas sensor accurately measures the number of particulates adsorbed on the MOF films in real-time. Thus, the QCM gas sensor is a valuable tool for quantitatively measuring gases, such as SO₂, NO₂, and CO₂. Furthermore, the QCM MOF film gas sensor was more effective for gas adsorption than the MOF particles alone and allowed the accurate modeling of gas adsorption. Moreover, the QCM MOF films accurately detect the adsorption-desorption mechanisms of SO₂ and NO₂, which exist as gaseous particulate matter, at specific gas concentrations.

• 한국전기화학회:학술대회논문집
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• 2005.07a
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• pp.329-334
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• 2005

In order to find out rational design and synthetic strategies toward efficient hydrogen storage materials, we performed quantum mechanical calculations on a series of the Metal-Organic Frameworks (MOFs) containing functionalized organic linkers. Based on the shape of frontier orbitals and the electrostatic potential map of various MOFs from density functional theory calculations, it was found that the delocalization of electron and asymmetric polarization of the organic linker play an important role in the hydrogen storage capacity of Metal-Organic Frameworks. The prediction of the modeling study could be supported by the hydrogen adsorption experiments using MOF-5 and amine substituted MOF-5, which showed more enhanced hydrogen storage capacity of amine substituted MOF-5 compared with that of MOF-5.

• 한국전기화학회:학술대회논문집
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• 2004.06a
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• pp.287-292
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• 2004

In order to understand the relationship between molecular structure of Metal-Organic Framework(MOF) and capacity of hydrogen absorption, quantum mechanical calculations and grand canonical Monte Carlo simulations have been carried out on a series of MOF-5 having various organic linkers. The calculation results about specific surface area and electron density for various frameworks indicated that the capacity of the hydrogen storage is largely dependent on effective surface area rather than the free volume. Based on the iso-electrostatic potential surface from density functional calculation and the amount of adsorbed hydrogens from grand canonical Monte Carlo calculation, it was also found that the electron localization ground organic linker plays an important role in hydrogen capacity of MOFs.

• Journal of the Korea Institute of Military Science and Technology
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• v.17 no.4
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• pp.510-520
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• 2014

Metal-Organic Frameworks(MOFs) are attracting attentions from various fields including chemistry, materials science, physics and medical science because of its exceptionally large pore volumes and surface areas which far exceed those of zeolites. The possibilities of applications of MOFs for gas separation, catalysts, drug delivery, and high explosives detections have already been verified. In these review the author describes the structures, synthetic methods and applications of MOFs based on the literatures published during last 15 years to give the readers general pictures of MOF itself as well as the global research trends of these materials.

• Prospectives of Industrial Chemistry
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• v.23 no.3
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• pp.1-16
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• 2020

식품 산업에서 제품의 품질을 향상시키기 위해서는 약한 세기의 맛에서도 다양한 종류의 맛을 감지해낼 수 있어야만 한다. 이러한 목적 달성을 위해서 2차원 물질과 금속유기골격체(metal-organic framework, MOF)를 이용한 미각 감지 센서에 대한 연구들이 한창 진행 중이다. 2차원 물질 및 MOF는 고유한 특성으로 인하여 현재 다양한 분야에서 많은 관심을 받아오고 있으며 화학 및 생화학 감지 등 다양한 분야에서도 응용될 수 있다. 본 기고문에서는 미각 감지 응용에서 2차원 물질과 MOF의 최신 연구동향을 다루고자 한다. 본 기고문을 통하여 미각 감지 응용 분야에서 2차원 물질과 MOF의 작용 메커니즘을 이해하고 현재의 연구 현황 및 앞으로의 발전 방향을 알아보고자 한다.

• Journal of Electrochemical Science and Technology
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• v.8 no.1
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• pp.61-68
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• 2017

Electrochemical conversion of $CO_2$ and production of $H_2$ were attempted on a three-dimensionally ordered, porous metal organic framework (MOF-74) in which transition metals (Co, Ni, and Zn) were impregnated. A lab-scale proton exchange membrane-based electrolyzer was fabricated and used for the reduction of $CO_2$. Real-time gas chromatography enabled the instantaneous measurement of the amount of carbon monoxide and hydrogen produced. Comprehensive calculations, based on electrochemical measurements and gaseous product analysis, presented a time-dependent selectivity of the produced gases. M-MOF-74 samples with different central metals were successfully obtained because of the simple synthetic process. It was revealed that Co- and Ni-MOF-74 selectively produce hydrogen gas, while Zn-MOF-74 successfully generates a mixture of carbon monoxide and hydrogen. The results indicated that M-MOF-74 can be used as an electrocatalyst to selectively convert $CO_2$ into useful chemicals.

• Advances in nano research
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• v.14 no.4
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• pp.313-327
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• 2023

Zinc metal organic framework (MOF_Zn)-loaded goad nanoparticles (AuNPs) sol (Au@MOF_Zn), which was characterized by TEM, Mapping, FTIR, XRD, and molecular spectrum, was prepared conveniently by solvothermal method. The results indicated that Au@MOF_Zn had a very strong catalytic effect with the nanoreaction of AuNPs formation between sodium oxalate (SO) and HAuCl4. AuNPs in the new indicator reaction had a strong resonance Rayleigh scattering (RRS) signal at 370 nm. The indicator AuNPs generated by this reaction, which had the most intense surface enhanced Raman scattering (SERS) peak at 1621 cm -1. The new SERS/RRS indicator reaction in combination with specific aptamer (Apt) to fabricate a sensitive and selective Au@MOF_Zn catalytic amplification-aptamer SERS/RRS assay platform for carbendazim (CBZ), with SERS/RRS linear range of 0.025-0.5 ng/mL. The detection limit was 0.02 ng/mL. Similarly, this assay platform has been also utilized to detect oxytetracycline (OTC) and profenofos (PF).