MOF-on-MOF Architectures: Applications in Separation, Catalysis, and Sensing

Hong Doo Hwan,Shim Hui Su,하준수,Moon Hoi Ri 대한화학회 2021 Bulletin of the Korean Chemical Society Vol.42 No.7

Metal–organic frameworks (MOFs) are porous crystalline materials with a high tunability. To improve the functionality of the original frameworks, several strategies, such as the use of different metal cations and organic ligands and post-synthetic modification, have been developed, enabling the use of MOFs in numerous practical applications in various fields. Recently, another approach, i.e., MOF-on-MOF architecturing, has been actively studied by combining two or more MOFs into a composite. MOF-on- MOF materials not only possess the intrinsic properties of each MOF but also exhibit unprecedented synergism within a single system, resulting in a considerable potential for various applications. This review summarizes the interesting areas of application of MOF-on-MOF architectures into three categories: separation, catalysis, and sensing. In particular, the synergism occurring within such MOF-on-MOF architectures is discussed.

Microporous metal–organic frameworks: Synthesis and applications

Mahnaz Ahmadi,Maryam Ebrahimnia,Mohammad-Ali Shahbazi,Rüstem Keçili,Fatemeh Ghorbani-Bidkorbeh 한국공업화학회 2022 Journal of Industrial and Engineering Chemistry Vol.115 No.-

Metal-organic frameworks (MOFs) have emerged as porous hybrid materials composed of metal ions andorganic ligands. MOFs have attracted the attention of many researchers due to their promising characteristics,including high porosity, surface area, and drug loading capacity, tunable pore size and structure,good biodegradability and biocompatibility, and ease of functionalization. MOFs are categorized intothree groups based on their pore widths, including microporous, mesoporous, and macroporous MOFs. MOFs with micropores have shown special features. The internal pore widths of microporous MOFsare less than 2 nm, which leads to their high porosity and surface area. Microporous MOFs could be synthesizedthrough different strategies, including modulator-induced defect-formation, structure-directingagents, pillared-layer assembly, bridging helical chain secondary building units, coordination capabilitiesof P@O moieties in the structure of a ligand, and using octahedral cage-like building units. Because oftheir unique properties, microporous MOFs have shown great potential for many applications such asseparation, storage, catalysis, and sensing. A description of synthesis approaches and applications ofmicroporous MOFs in recent years is provided in this review.

총설 : 금속유기구조체를 이용한 이산화탄소 흡착 연구

안화승 ( Wha Seung Ahn ),김준 ( Jun Kim ),김희영 ( Hee Young Kim ) 한국화학공학회 2013 Korean Chemical Engineering Research(HWAHAK KONGHA Vol.51 No.2

금속유기구조체(metal-organic frameworks, MOF)는 넓은 비표면적, 규칙적인 구조 및 높게 분산된 금속 성분 등 뛰 어난 물리화학적 특성으로 인해 활발한 연구가 이뤄지고 있는 다공성 물질이며, 특히 가스의 흡착, 분리 매체로서 뛰 어난 성능이 보고되고 있다. MOF를 이용한 온실가스 이산화탄소의 흡착 연구는 상온 고압 영역에서 이산화탄소 저장 공정과 상온 저압 영역에서 이산화탄소 흡착 공정의 두 범주로 나눌 수 있으며, MOF의 넓은 비표면적 외에도 (1) MOF 의 빈 배위결합 자리, (2) MOF의 기능화, (3) MOF의 상호 침투 효과, 및 (4) 이온 교환 효과를 이용한 연구 결과가 보고되고 있다. MOF 물질들은 비교적 낮은 수분 및 열에 대한 안정성이 문제로 제기되고 있으며, 제올라이트 유사 구 조체(zeolitic imidazolate frameworks, ZIF) 또는 유기 골격 구조체(covalent organic frameworks, COF) 물질의 이산화 탄소 흡착 특성이 거론되고 있다. 본 소고에서는 MOF를 이용한 이산화탄소 흡착에 대한 최근의 연구 결과를 본 연구 실의 실험 결과를 중심으로 간략히 소개하고자 한다. Metal organic frameworks (MOFs) are a class of crystalline organic-inorganic hybrid compounds formed by coordination of metal clusters or ions with organic linkers. MOFs have recently attracted intense research interest due to their permanent porous structures, large surface areas and pore volume, high-dispersed metal species, and potential applications in gas adsorption, separation, and catalysis. CO2 adsorption in MOFs has been investigated in two areas of CO2 storage at high pressures and CO2 adsorption at atmospheric pressure conditions. In this short review, CO2 adsorption/ separation results using MOFs conducted in our laboratory was explained in terms of four contributing effects; (1) coordinatively unsaturated open metal sites, (2) functionalization, (3) interpenetration/catenation, and (4) ion-exchange. Zeolitic imidazolate frameworks (ZIFs) and covalent organic frameworks (COFs) were also considered as a candidate material.

Study of Metal-Organic Frameworks(MOFs) Based Drug Delivery System

임현주,윤수경,임은경,최민서,고문규 한국공업화학회 2020 한국공업화학회 연구논문 초록집 Vol.2020 No.-

Metal-Organic Frameworks(MOFs) are porous hybrid materials constructed by metal nodes and bridging organic linkers. MOFs with their exceptionally high surface area are potential candidates in various fields of application such as drug delivery system, catalysis, gas storage, sensing. Three types of water-stable, biocompatible MOFs(MIL- 100(Fe), UiO-66(Zr) and MOF-5) were selected as drug delivery carrier of ibuprofen(isobutylpropanoic acid) which is a hydrophobic(logP=3.97) and commonly used nonsteroidal anti-inflammatory drug. Delivery of ibuprofen experiment was perfomed with different pH conditions at 36.5°C, under continuous bidimensional stirring. Synthesized MOFs were characterized by BET, XRD, EDX, FT-IR and UV-vis.

Effect of Cu-MOFs incorporation on gas separation of Pebax thin film nanocomposite (TFN) membrane

Mahdi Fakoori,Amin Azdarpour,Reza Abedini,Bizhan Honarvar 한국화학공학회 2021 Korean Journal of Chemical Engineering Vol.38 No.1

MOF-based membranes, which have appropriate MOF dispersion and suitable interaction, have shown high CO2 permeability and significant CO2/CH4 and CO2/N2 selectivity. In this study, a layer of Pebax was coated on polysulfone (PSF), which this layer incorporated by various content of Cu-MOFs to improve the performance (permeability and CO2/CH4 and CO2/N2 selectivity) of all membranes. Characterization techniques such as SEM, TGA, BET, and gas adsorption verified that Cu-BTC was successfully dispersed into the Pebax matrix. Pure CO2 and CH4 gases permeation experiments were performed to investigate the impact of Cu-MOFs on the gas permeability of prepared MOF-based membranes. The “Pebax” embedded by 15 wt% CuBTC and 15 wt% of NH2-CuBTC over PSF support exhibited higher gas separation performance compared to the pristine one. They demonstrated a CO2 permeability of 228.6 and 258.3 Barrer, respectively, while the blank membrane had a CO2 permeability of 110.6 Barrer. Embedding the NH2-Cu-BTC intensified the interaction between incorporated MOF particles and the polymer phase that led to increase the CO2/CH4 and CO2/N2 selectivity. In addition, the performance of prepared membranes was evaluated at various feed pressures with the range of 2-10 bar. The CO2/CH4 and CO2/N2 separation was enhanced as the feed pressure surged.

Modern progress in metal-organic frameworks and their composites for diverse applications

Kumar, P.,Vellingiri, K.,Kim, K.H.,Brown, R.J.C.,Manos, M.J. Elsevier 2017 Microporous and mesoporous materials Vol.253 No.-

Over the last decade, metal-organic frameworks (MOFs) have received a great deal of interest in materials science due to their excellent material properties such as high surface area, porosity, high chemical and thermal stability, luminescence, high sorptive capacity, and potential use in a wide range of applications. However, several shortcomings, including laborious synthesis and analysis processes, low aqueous solubility, and poor electrical properties, are currently limiting factors for their practical application. As a means to overcome such limitations, enormous effort has been put into the development and use of MOFs composite materials (e.g., MOF-nanomaterials, MOF-carbon materials, and MOFs-polymers) in a range of applications including the energy, environmental, biomedical, and sensing areas. In this review, we present the current state-of-the-art in MOF composite materials and their diverse applications. In addition, we also discuss the advantageous features of MOF composites as a promising avenue for future development.

Porphyrinic zirconium metal-organic frameworks: Synthesis and applications for adsorption/catalysis

유광선,원동일,이완인,안화승 한국화학공학회 2021 Korean Journal of Chemical Engineering Vol.38 No.4

Zr-based porphyrinic MOFs, which have isolated porphyrin units imbedded in MOFs' rigid structure, exhibit excellent textural properties and high stability. Among the porphyrin ligands, tetrakis(4-carboxyphenyl)-porphyrin (TCPP) is broadly employed, and so far, seven Zr-based porphyrinic MOFs of MOF-525, MOF-545 (also named PCN-222), PCN-221, PCN-223, PCN-224, PCN-225, and NU-902 have been synthesized using TCCP. The built-in TCPP ligand with various functionality and coordinatively unsaturated Zr clusters can be subjected to diverse pre- and post-synthesis functionalization or guest encapsulation. Aided by the excellent hydrothermal/chemical stability and high porosity, these Zr-based porphyrinic MOFs are gaining attention for applications in adsorption, sensors, heterogeneous catalysis for chemical conversions, photocatalysis, electrocatalysis, and others. This paper reviews the current status of research and development on the synthesis, characterization, functionalization, and adsorption/catalysis applications of Zr-based porphyrinic MOFs.

Water adsorption/desorption over metal-organic frameworks with ammonium group for possible application in adsorption heat transformation

An, Hyung Jun,Sarker, Mithun,Yoo, Dong Kyu,Jhung, Sung Hwa Elsevier 2019 CHEMICAL ENGINEERING JOURNAL -LAUSANNE- Vol.373 No.-

<P><B>Abstract</B></P> <P>Typical metal-organic frameworks (MOFs) such as UiO-66 and MIL-125 were modified to introduce –NH<SUB>2</SUB> and –NH<SUB>3</SUB> <SUP>+</SUP>Cl<SUP>−</SUP> groups in order to improve their performances for water adsorption and for possible applications in adsorption heat transformation (AHT). Not only adsorption isotherms but also dynamic water adsorption/desorption (in 10 cycles) results showed that the functionalization, especially loading of the –NH<SUB>3</SUB> <SUP>+</SUP>Cl<SUP>−</SUP> group, was very effective for such purposes. Both the adsorption capacity (especially, at low vapor pressure) and dynamic water uptake (via cyclic adsorption/desorption of water) increased notably with the modification of the MOFs. The positive effect could be explained by hydrogen bonding and electrostatic interactions, which are not possible with the pristine MOFs. Therefore, it could be suggested that loading moieties with charge and ample hydrogen (such as ammonium group) is a very effective means of modifying MOFs for water adsorption or for application in AHT.</P> <P><B>Highlight</B></P> <P> <UL> <LI> Metal-organic frameworks were modified to load amino and ammonium groups. </LI> <LI> The modified MOFs showed highly enhanced performances for water adsorption. </LI> <LI> Adsorption capacity and dynamic water uptake increased much with the modification. </LI> <LI> The favorable effect could be explained with H-bonding and electrostatic interaction. </LI> <LI> The modified MOFs were very stable in dynamic adsorption/desorption for 10 cycles. </LI> </UL> </P> <P><B>Graphical abstract</B></P> <P>[DISPLAY OMISSION]</P>

Glutamic Acid-Grafted Metal-Organic Framework: Preparation, Characterization, and Heavy Metal Ion Removal Studies

( Phani Brahma Somayajulu Rallapalli ),( Jeong Hyub Ha ) 한국공업화학회 2023 공업화학 Vol.34 No.5

Fast industrial and agricultural expansion result in the production of heavy metal ions (HMIs). These are exceedingly hazardous to both humans and the environment, and the necessity to eliminate them from aqueous systems prompts the development of novel materials. In the present study, a UIO-66 (COOH)₂ metal-organic framework (MOF) containing free carboxylic acid groups was post-synthetically modified with L-glutamic acid via the solid-solid reaction route. Pristine and glutamic acid-treated MOF materials were characterized in detail using several physicochemical techniques. Single-ion batch adsorption studies of Pb(II) and Hg(II) ions were carried out using pristine as well as amino acid-modified MOFs. We further examined parameters that influence removal efficiency, such as the initial concentration and contact time. The bare MOF had a higher ion adsorption capacity for Pb(II) (261.87 mg/g) than for Hg(II) ions (10.54 mg/g) at an initial concentration of 150 ppm. In contrast, an increased Hg(II) ion adsorption capacity was observed for the glutamic acid-modified MOF (80.6 mg/g) as compared to the bare MOF. The Hg(II) ion adsorption capacity increased by almost 87% after modification with glutamic acid. Fitting results of isotherm and kinetic data models indicated that the adsorption of Pb(II) on both pristine and glutamic acid-modified MOFs was due to surface complexation of Pb(II) ions with available -COOH groups (pyromellitic acid). Adsorption of Hg(II) on the glutamic acid-modified MOF was attributed to chelation, in which glutamic acid grafted onto the surface of the MOF formed chelates with Hg(II) ions.

Revolutionizing Energy Storage: Exploring Processing Approaches and Electrochemical Performance of Metal-Organic Frameworks (MOFs) and Their Hybrids

Wajahat Khalid,Muhammad Ramzan Abdul Karim,Mohsin Ali Marwat The Korean Electrochemical Society 2024 Journal of electrochemical science and technology Vol.15 No.1

The text highlights the growing need for eco-friendly energy storage and the potential of metal-organic frameworks (MOFs) to address this demand. Despite their promise, challenges in MOF-based energy storage include stability, reproducible synthesis, cost-effectiveness, and scalability. Recent progress in supercapacitor materials, particularly over the last decade, has aimed to overcome these challenges. The review focuses on the morphological characteristics and synthesis methods of MOFs used in supercapacitors to achieve improved electrochemical performance. Various types of MOFs, including monometallic, binary, and tri-metallic compositions, as well as derivatives like hybrid nanostructures, sulfides, phosphides, and carbon composites, are explored for their energy storage potential. The review emphasizes the quest for superior electrochemical performance and stability with MOF-based materials. By analyzing recent research, the review underscores the potential of MOF-based supercapacitors to meet the increasing demands for high power and energy density solutions in the field of energy storage.