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Metal–Organic Frameworks

Kyle C Bentz, Seth Mason Cohen
The fields of coordination polymers (CPs) and supramolecular metallopolymers (SMPs) have been extensively studied for decades. Spectacular recent advances in both fields have created new compounds that lie at the interface between these two classes of organic-inorganic hybrid materials. At this interface, materials based on molecular weaving, supramolecular clusters, and metal-organic framework-polymer hybrids have emerged. This minireview provides a perspective on the intellectual emergence and connection between different supramolecular constructs and the state of the art with respect to this new materials interface...
August 11, 2018: Angewandte Chemie
Martin Schroder, Harry Godfrey, Ivan Da Silva, Lydia Briggs, Joe Carter, Christopher Morris, Mathew Savage, Timothy Easun, Pascal Manuel, Claire Murray, Chiu Tang, Mark Frogley, Gianfelice Cinque, Sihai Yang
MFM-300(Al) shows reversible uptake of NH3 (15.7 mmol g-1 at 273 K and 1.0 bar) over 50 cycles with an exceptional packing density of 0.62 g cm-3 at 293 K. In situ neutron powder diffraction and synchrotron FTIR micro-spectroscopy on ND3@MFM-300(Al) confirms reversible H/D site exchange between the adsorbent and adsorbate, representing a new type of adsorption interaction.
August 11, 2018: Angewandte Chemie
Hoyoung D Park, Mircea Dinca, Yuriy Roman-Leshkov
Industrial synthesis of succinic acid relies on hydrocarbon oxidation or biomass fermentation routes that suffer from energy-costly separation processes. Here we demonstrate an alternate route to succinic anhydrides via β-lactone carbonylation by heterogeneous bimetallic ion-pair catalysis in Co(CO)4 - -incorporated Cr-MIL-101 (Co(CO)4⊂Cr-MIL-101, Cr-MIL-101 = Cr3 O(BDC)3 F, H2 BDC = 1,4-benzenedicarboxylic acid). Postsynthetically introduced Co(CO)4 - facilitates CO insertion to β-lactone substrates activated by the Lewis acidic Cr(III) centers of the metal-organic framework (MOF), leading to catalytic carbonylation with activity and selectivity profiles that compare favorably to those reported for homogeneous ion-pair catalysts...
August 10, 2018: Journal of the American Chemical Society
Guanfeng Ji, Xuechuan Gao, Tianxiang Zheng, Weihua Guan, Houting Liu, Zhiliang Liu
The self-assembly of a zinc salt with the novel ligand 4,4',4″-[(1,3,5-triazine-2,4,6-triyl)tris(sulfanediyl)]tribenzoic acid generated 3D microporous metal-organic frameworks (MOFs), namely, {[Zn4 (L3- )2 (O2- )(H2 O)2 ]·4EtOH} n . The frameworks with multiple Lewis basic sites exhibit easily sensitized properties. After encapsulation of the Tb3+ cation in this Zn-MOF, the as-obtained fluorescent-functionalized Tb@Zn-MOFs not only maintain distinguished chemical stabilities but also exhibit strong characteristic emissions of trivalent terbium ions...
August 10, 2018: Inorganic Chemistry
Shuo Lin, Yufeng Zhao, Yeoung-Sang Yun
Nonsteroidal anti-inflammatory pharmaceuticals are emerging organic micropollutants in surface water, groundwater, and wastewater, whose removal is very important yet challenging. As a new class of porous functional materials, metal-organic frameworks (MOFs) have attracted extensive attention for their adsorption applications. Here, we report that Zr(IV)-based MOFs (defective UiO-66, and MOF-808) have extraordinary adsorption ability to remove nonsteroidal anti-inflammatory pharmaceuticals from water. Excellent adsorption performances are obtained for UiO-66 and MOF-808, particularly for UiO-66, of which the adsorption capacities are the highest in a wide series of adsorptive materials previously reported...
August 10, 2018: ACS Applied Materials & Interfaces
Hui-Yan Liu, Jie Liu, Gui-Mei Gao, Hai-Ying Wang
Solvothermal reaction of 3,5-di(pyridin-4-yl) benzoic acid (HDPB) with Co(II) leads to a novel metal-organic framework, [Co2 O(DPB)2 (DMF)2 ]· xS (1), which represents a rare reo-type net with trigonal prismatic cobalt dimer, [Co2 O(CO2 )2 N4 ], as building blocks to construct a 3D framework containing three different types of nanoscale M12 L12 and M24 L12 polyhedron cages. More interestingly, under the same condition, the assembly of 4-methyl-3,5-di(pyridin-4-yl) benzoic acid (HMDPB) with Co(II) facilitates the formation of a cationic framework, [Co2 (MDPB)3 (DMF)](NO3 )· xS (2), with cobalt dimer, [Co2 (CO2 )3 N4 ], as building blocks...
August 10, 2018: Inorganic Chemistry
Yuyin Wang, Mingming Zhao, Qunxing Zhao, Qing Li, Huan Pang
The development of inexpensive, highly active, bifunctional electrocatalysts for oxygen evolution reaction (OER) and oxygen reduction reaction (ORR) is required for many energy conversion systems, including water splitting, fuel cells, and metal-air batteries. This study reports silver nanowires-zeolitic imidazolate framework (Ag NWs-ZIF67) composites as bifunctional electrocatalysts for OER and ORR. The synergistic effects of Co2+, organic ligands, and Ag NWs enhance the bifunctional electrocatalytic properties...
August 10, 2018: Nanoscale
Hilal Daglar, Seda Keskin
It has become a significant challenge to select the best metal-organic frameworks (MOFs) for membrane-based gas separations because the number of synthesized MOFs is growing exceptionally fast. In this work, we used high-throughput computational screening to identify the top MOF membranes for flue gas separation. Grand canonical Monte Carlo and molecular dynamics simulations were performed to assess adsorption and diffusion properties of CO2 and N2 in 3806 different MOFs. Using these data, selectivities and permeabilities of MOF membranes were predicted and compared with those of conventional membranes, polymers, and zeolites...
August 2, 2018: Journal of Physical Chemistry. C, Nanomaterials and Interfaces
Dengke Shen, Gang Wang, Zhichang Liu, Peng Li, Kang Cai, Chuyang Cheng, Yi Shi, Ji-Min Han, Chung-Wei Kung, Xirui Gong, Qinghui Guo, Hongliang Chen, Andrew Chi-Hau Sue, Youssry Y Botros, Antonio Facchetti, Omar K Farha, Tobin J Marks, J Fraser Stoddart
A class of metal-organic frameworks (MOFs)-namely CD-MOFs-obtained from natural products has been grown in an epitaxial fashion as films on the surfaces of glass substrates, which are modified with self-assembled monolayers (SAMs) of γ-cyclodextrin (γ-CD) molecules. The SAMs are created by host-guest complexation of γ-CD molecules with surface-functionalized pyrene units. The CD-MOF film has a continuous polycrystalline morphology with a structurally out-of-plane (c-axial) orientation, covering an area of several square mm with a thickness of ~2 µm...
August 9, 2018: Journal of the American Chemical Society
Mostakim Sk, Soutick Nandi, Rakesh Kumar Singh, Vishal Trivedi, Shyam Biswas
The first boronic acid functionalized Hf-based UiO-66 (UiO = University of Oslo) metal-organic framework (MOF) having the ability to detect both extracellular and intracellular peroxynitrite is presented. The Hf-UiO-66-B(OH)2 material (1) was synthesized under solvothermal conditions from a mixture of HfCl4 and 2-borono-1,4-benzenedicarboxylic acid [H2 BDC-B(OH)2 ] ligand in DMF in the presence of formic acid (modulator) at 130 °C for 48 h. The desolvated material (1') was utilized as a fluorescent turn-on probe for the rapid sensing of extracellular peroxynitrite (ONOO- ) under conditions mimicking those of biological medium (10 mM HEPES buffer, pH 7...
August 9, 2018: Inorganic Chemistry
Mónica Giménez-Marqués, Elena Bellido, Thomas Berthelot, Teresa Simón-Yarza, Tania Hidalgo, Rosana Simón-Vázquez, África González-Fernández, José Avila, Maria Carmen Asensio, Ruxandra Gref, Patrick Couvreur, Christian Serre, Patricia Horcajada
Controlling the outer surface of nanometric metal-organic frameworks (nanoMOFs) and further understanding the in vivo effect of the coated material are crucial for the convenient biomedical applications of MOFs. However, in most studies, the surface modification protocol is often associated with significant toxicity and/or lack of selectivity. As an alternative, how the highly selective and general grafting GraftFast method leads, through a green and simple process, to the successful attachment of multifunctional biopolymers (polyethylene glycol (PEG) and hyaluronic acid) on the external surface of nanoMOFs is reported...
August 9, 2018: Small
Qi Zhang, Chen-Feng Wang, Yun-Kai Lv
Metal-organic frameworks (MOFs) as sensing materials have experienced explosive growth in recent years due to their intrinsic merits, such as structural diversity, high porosity, large surface area, extraordinary adsorption affinities, etc. Biomolecules such as DNA, protein, and vitamins play vital roles in metabolism. Moreover, the sensitive detection of biomolecules is of importance in the disease prevention and treatment. This review intends to provide an update on the recent progress in the detection of various biomolecules via MOF-based luminescent sensors...
August 9, 2018: Analyst
M Infas H Mohideen, Youssef Belmabkhout, Prashant M Bhatt, Aleksander Shkurenko, Zhijie Chen, Karim Adil, Mohamed Eddaoudi
Separation of paraffin isomers is of great importance in the refining industry because of their potential applications for energy efficiency, as reflected by their associated Research Octane Number (RON) values. Here, we report the synthesis of the first zeolite-like metal-organic framework (ZMOF) with ana topology that displays helicoidally/cylindrically-shaped channels with a pore-aperture size of ca. 3.8 × 6.2 Å. Markedly, such structural features offer potential for the selective separation of linear, and mono- and dibranched paraffins...
August 9, 2018: Chemical Communications: Chem Comm
Mohammad Wahiduzzaman, Sujing Wang, Benjamin J Sikora, Christian Serre, Guillaume Maurin
A structure prediction tool has been developed to guide the discovery of MOF materials. This computational strategy has been trained over a series of existing MOFs and further successfully applied in tandem with an experimental effort to produce novel Zr MOFs based on naturally occurring carboxylic acids.
August 9, 2018: Chemical Communications: Chem Comm
Shuai Yuan, Peng Zhang, Liangliang Zhang, Angel T Garcia-Esparza, Dimosthenis Sokaras, Junsheng Qin, Liang Feng, Gregory S Day, Wenmiao Chen, Hannah F Drake, Palani Elumalai, Sherzod Madrahimov, Daofeng Sun, Hong-Cai Zhou
Metal-organic frameworks (MOFs) provide highly designable platforms to construct complex coordination architectures for targeted applications. Herein, we demonstrate that trans-coordinated metal centers with exposed equatorial positions can be placed in a MOF matrix. A Zr-based MOF, namely PCN-160, was initially synthesized as a scaffold structure. Postsynthetic linker labilization was subsequently implemented to partially remove the original dicarboxylate linkers and incorporate pyridinecarboxylates. A pair of neighboring pyridyl groups was arranged at proper proximity within the framework to form trans-binding sites that accommodate different metal cations including Mn2+, Fe2+, Co2+, Ni2+, Cu2+, and Pd2+...
August 8, 2018: Journal of the American Chemical Society
José Manuel Vicent-Luna, Juan-Jose Gutiérrez-Sevillano, Said Hamad, Juan Antonio Anta, Sofía Calero
We study the adsorption performance of metal-organic frameworks (MOFs) impregnated of ionic liquids (ILs). To this aim we calculated adsorption and diffusion of light gases (CO2, CH4, N2) and their mixtures in hybrid composites using molecular simulations. The hybrid composites consist of 1-ethyl-3-methylimidazolium thiocyanate impregnated in IRMOF-1, HMOF-1, MIL-47, and MOF-1. We found that the increase of the amount of IL enhances the adsorption selectivity in favour of carbon dioxide for the mixtures CO2/CH4 and CO2/N2 and in favour of methane in the mixture CH4/N2...
August 8, 2018: ACS Applied Materials & Interfaces
Weiwei Wang, Li Zhang, Guancheng Xu, Huijun Song, Lifan Yang, Chi Zhang, Jinling Xu, Dianzeng Jia
Metal-organic framework-based supercapacitors have been widely recognized as the best energy storage devices for future portable electronic equipment. Herein, CoP- T ( T = 300, 350, and 400 °C) microcubes with a solid and hollow microstructure were successfully synthesized by low-temperature phosphorization of [CH3 NH3 ][Co(HCOO)3 ] precursor at desired temperatures. The morphology, structure, and composition of the prepared CoP-350 °C samples were analyzed by scanning electron microscopy, transmission electron microscopy, and X-ray photoelectron spectroscopy...
August 8, 2018: Inorganic Chemistry
Shu-Yin Zhu, Bing Yan
A zirconium metallic organic framework UiO-66-NH2 has been synthesized and is further modified with imidazole-2-carboxaldehyde by a covalent post synthetic route which is based on a Schiff-base reaction. The as-prepared, functionalized MOF named UiO-66-NH2-IM is fully characterized. It retains its structural integrity during the PSM process and shows excellent luminescence and good fluorescence stability in water. It has also been further utilized as a sensitive fluorescent probe for sensing ions. The results show that UiO-66-NH2-IM can be developed into a highly selective and sensitive sensor for the detection of S2O82- (detection limit, 8...
August 8, 2018: Dalton Transactions: An International Journal of Inorganic Chemistry
Yutaka Inoue, Ayumi Nanri, Isamu Murata, Ikuo Kanamoto
The aim of the current study was to evaluate the physicochemical properties of a solid dispersion of coenzyme Q10 (CoQ10)/cyclodextrin metal organic frameworks-1 (CD-MOF-1). As a result of the powder X-ray diffraction (PXRD), it was confirmed that the CD-MOF-1 was changed from the α form to the β form by evaporation (EVP). A diffraction peak due to melting of CoQ10 disappeared the EVP (CoQ10/CD-MOF-1 = 1/2). The structure of this complex is presumed to be similar to the β form of CD-MOF-1. As a result of the differential scanning calorimetry (DSC), the endothermic peak due to the melting of CoQ10 disappeared the EVP (CoQ10/CD-MOF-1 = 1/2)...
August 7, 2018: AAPS PharmSciTech
Leide P Cavalcanti, Georgios N Kalantzopoulos, Juergen Eckert, Kenneth D Knudsen, Jon Otto Fossum
In order to mitigate climate change driven by the observed high levels of carbon dioxide (CO2 ) in the atmosphere, many micro and nano-porous materials are being investigated for CO2 selectivity, capture and storage (CCS) purposes, including zeolites, metal organic frameworks (MOFs), functionalized polymers, activated carbons and nano-silicate clay minerals. Key properties include availability, non-toxicity, low cost, stability, energy of adsorption/desorption, sorbent regeneration, sorption kinetics and CO2 storage capacity...
August 7, 2018: Scientific Reports
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