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Metal–Organic Frameworks

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https://www.readbyqxmd.com/read/30516956/zig-zag-sp2-carbon-chains-passing-through-sp3-framework-a-driving-force-toward-room-temperature-ferromagnetic-graphene
#1
Jiří Tuček, Katerina Hola, Giorgio Zoppellaro, Piotr Blonski, Rostislav Langer, Miroslav Medved, Toma Susi, Michal Otyepka, Radek Zbořil
Stabilization of ferromagnetic ordering in graphene-based systems up to room temperature remains an important challenge owing to huge scope for applications in electronics, spintronics, biomedicine, and separation technologies. To date, several strategies have been proposed, including edge engineering, introduction of defects and dopants, and covalent functionalization. However, these techniques are usually hampered by limited temperature sustainability of ferromagnetic ordering. Here, we describe a method for the well-controlled sp3 functionalization of graphene to synthesize zig-zag conjugated sp2 carbon chains that can act as communication pathways among radical motifs...
December 5, 2018: ACS Nano
https://www.readbyqxmd.com/read/30516766/post-synthetic-exchange-enables-orthogonal-click-chemistry-in-a-metal-organic-framework
#2
Ulrike Fluch, Brian D McCarthy, Sascha Ott
Biphenyl-4,4'-dicarboxylic acid derivatives containing either azide or acetylene functional groups were inserted into UiO-67 metal organic frameworks (MOFs) via post synthetic linker exchange. Sequential and orthogonal click reactions could be performed on these modified MOFs by incubating the crystals with small molecule substrates bearing azide or acetylene groups in the presence of a copper catalyst. 1H NMR of digested MOF samples showed that up to 50% of the incorporated linkers could be converted to their "clicked" triazole products...
December 5, 2018: Dalton Transactions: An International Journal of Inorganic Chemistry
https://www.readbyqxmd.com/read/30516386/highly-conductive-2d-metal-organic-framework-thin-film-fabricated-by-liquid-liquid-interfacial-reaction-using-one-pot-synthesized-benzenehexathiol
#3
Iu-Fan Chen, Chun-Fu Lu, Wei-Fang Su
Metal-organic frameworks (MOF) are studied extensively in applications like catalysts, gas storage and sensors due to their various functional groups and porous structures. Two-dimensional (2D) MOFs such as triphenylene-based materials show excellent charge transport properties but thin film fabrication and organic ligand synthesis are difficult. In this work, we synthesize thiol-based organic ligand, benzenehexathiol (BHT), by a simple one-pot reaction. This facile method is safer and faster than conventional synthesis procedure that requires using liquid ammonia as solvent...
December 5, 2018: Langmuir: the ACS Journal of Surfaces and Colloids
https://www.readbyqxmd.com/read/30516374/metal-organic-framework-showing-selective-and-sensitive-detection-of-exogenous-and-endogenous-formaldehyde
#4
Soutick Nandi, Ena Sharma, Vishal Trivedi, Shyam Biswas
In this work, we report a new hydrazine-functionalized Al(III)- based metal-organic framework having MIL-53 (MIL = Material of Institute Lavoisier) framework topology for the sensitive and selective detection of formaldehyde (FA). The phase purity of the thermally activated and as-synthesized forms of the material was examined by X-ray powder diffraction experiments, Fourier transform infrared spectroscopy, and thermogravimetric analysis. The desolvated material (1') showed great potential for the selective sensing of FA in the existence of other potentially competitive aldehydes in both aqueous and 10 mM HEPES buffer (pH = 7...
December 5, 2018: Inorganic Chemistry
https://www.readbyqxmd.com/read/30516368/ratiometric-monitoring-of-thorium-contamination-in-natural-water-using-a-dual-emission-luminescent-europium-organic-framework
#5
Wei Liu, Xing Dai, Yanlong Wang, Liping Song, Lin-Juan Zhang, Duo Zhang, Jian Xie, Long Chen, Juan Diwu, Jianqiang Wang, Zhi-Fang Chai, Shuao Wang
Traditional analytical methods of thorium contamination suffer from several disadvantages such as time-consuming procedure and equipment-intensive nature, leading to substantial challenges in rapid and onsite monitoring of thorium concentration in complex natural water systems. We report here the first case of luminescent metal organic framework based probe (ThP-1) for highly sensitive and selective self-calibrated sensing of Th4+ contamination in natural fresh water media with a notably facilitated detection procedure...
December 5, 2018: Environmental Science & Technology
https://www.readbyqxmd.com/read/30516206/novel-bimetallic-mof-phosphors-with-an-imidazolium-cation-structure-phonons-high-pressure-phase-transitions-and-optical-response
#6
Maciej Ptak, Bartosz Zarychta, Dagmara Stefańska, Aneta Ciupa, Waldeci Paraguassu
We report the synthesis, crystal structure, phonons and luminescence properties of three novel heterometallic metal organic frameworks (MOFs) with perovskite-like topology of the following formulas: [C3H5N2]Na0.5Cr0.5(HCOO)3 (ImNaCr), [C3H5N2]Na0.5Al0.5(HCOO)3 (ImNaAl) and [C3H5N2]Na0.5Al0.475Cr0.025(HCOO)3 (ImNaAlCr with 5 mol% of Cr3+). ImNaCr crystallizes in a monoclinic system (P2/n space group) with one imidazolium cation (Im+) in an asymmetric unit forming six N-HO and four C-HO hydrogen bonds. In contrast to other known heterometallic MOFs, the complete substitution of Cr3+ ions with smaller Al3+ ions leads to a change of the crystal symmetry...
December 5, 2018: Dalton Transactions: An International Journal of Inorganic Chemistry
https://www.readbyqxmd.com/read/30516198/a-heterometallic-metal-organic-framework-based-on-multi-nuclear-clusters-exhibiting-high-stability-and-selective-gas-adsorption
#7
Dongmei Wang, Zihua Liu, Lili Xu, Chunxia Li, Dian Zhao, Genwu Ge, Zhenling Wang, Jun Lin
The design and synthesis of porous heterometallic metal-organic frameworks (MOFs) with high thermal and chemical stability is a challenging task at present. In this work, by the heterometallic cooperative crystallization (HCC) approach, an original heterometallic MOF based on a tetra-carboxylic ligand has been solvothermally synthesized [In6O3Tb3O(CBDA)3]·18DMF·3H2O (In/Tb-CBDA) [CBDA = 5,5'-(carbonylbis(azanediyl))-diisophthalic acid, DMF = N,N-dimethylformamide]. The framework of In/Tb-CBDA is cooperatively assembled from the rarely reported tetra-nuclear In4O2(COO)4 and tri-nuclear Tb3O(COO)6 clusters, and an organic ligand...
December 5, 2018: Dalton Transactions: An International Journal of Inorganic Chemistry
https://www.readbyqxmd.com/read/30516197/tetranuclear-cobalt-ii-isonicotinic-acid-frameworks-selective-co-2-capture-magnetic-properties-and-derived-co-3-o-4-exhibiting-high-performance-in-lithium-ion-batteries
#8
Lei Zhou, Honghong Fan, Baolei Zhou, Zheng Cui, Bowen Qin, Xiaoying Zhang, Wenliang Li, Jingping Zhang
Two new 3D cobalt metal-organic frameworks (MOFs), [Co4(CH3COO)(in)5(μ3-OH)2]·2H2O (1) and [Co4(SO4)2(in)4(DMF)2]·3DMF (2) (Hin = isonicotinic acid), have been prepared through the anion template method. Compound 1 consists of rare odd-number connected (9-connected) cubane-like SBUs, while compound 2 consists of 8-connected high-symmetry square-planar clusters. Magnetic studies indicate that compound 1 exhibits spin-canting antiferromagnetic ordering, while compound 2 shows antiferromagnetic behavior. At 273 K and 1 bar, compound 1 exhibits a high CO2 selectivity over CH4 and a significant CO2 uptake of 13...
December 5, 2018: Dalton Transactions: An International Journal of Inorganic Chemistry
https://www.readbyqxmd.com/read/30516140/synthesis-structure-and-photoluminescence-properties-of-a-three-dimensional-cadmium-ii-4-5-connected-coordination-network
#9
Ni Ya Li, Dong Liu
The assembly of coordination polymers from metal ions and organic moieties is currently attracting considerable attention in crystal engineering due to their intriguing architectures and potential applications as functional materials. A new coordination polymer, namely poly[[μ2 -trans-1,2-bis(pyridin-3-yl)ethylene-κ2 N:N']bis(μ4 -4,4'-oxydibenzoato-κ6 O:O,O':O'':O'',O''')dicadmium(II)], [Cd2 (C14 H8 O5 )2 (C12 H10 N2 )]n or [Cd2 (4,4'-OBB)2 (3,3'-BPE)]n , has been synthesized by the the self-assembly of Cd(NO3 )2 ·4H2 O, 4,4'-oxydibenzoic acid (4,4'-H2 OBB) and trans-1,2-bis(pyridin-3-yl)ethene (3,3'-BPE) under hydrothermal conditions...
December 1, 2018: Acta Crystallographica. Section C, Structural Chemistry
https://www.readbyqxmd.com/read/30513468/tailored-n-doped-porous-carbon-nanocomposites-through-mof-self-assembling-for-li-na-ion-batteries
#10
Cheng Chen, Mengqiang Wu, Ziqiang Xu, Tingting Feng, Jian Yang, Zhi Chen, Sizhe Wang, Yuesheng Wang
Presently, carbon-based anodes for energy storage, such as graphite for lithium-ion batteries (LlBs) and hard carbon for sodium-ion batteries (SlBs), have low capacity and poor rate properties. However, the capacity and rate capability of these anodes can be improved via morphological control, doping and using nanostructures. In this report, a series of self-assembled N-doped porous carbon nanocomposites (NPCNs) were prepared via pyrolysis of metal-organic frameworks (MOFs)-ZIF-8/carbon nanocomposites grown on various carbon frameworks (1D CNT and/or 2D rGO)...
November 27, 2018: Journal of Colloid and Interface Science
https://www.readbyqxmd.com/read/30513441/adsorption-desorption-kinetics-and-breakthrough-of-gaseous-toluene-for-modified-microporous-mesoporous-uio-66-metal-organic-framework
#11
Xiaodong Zhang, Yang Yang, Xutian Lv, Yuxin Wang, Ning Liu, Dan Chen, Lifeng Cui
In this work, micro-mesoporous UiO-66 was successfully prepared with P123 (EO20 PO70 EO20 ) as structure-directing agent by a simple solvothermal method. Adsorption/desorption kinetics of gaseous toluene over pristine UiO-66 and micro-mesoporous UiO-66 were investigated by breakthrough experiments, toluene vapor adsorption isotherm measurements and temperature programmed desorption (TPD) experiments. The interactions between toluene and UiO-66 samples were assessed through the Henry's law constant (KH ) and the isosteric adsorption heat (ΔHads )...
November 26, 2018: Journal of Hazardous Materials
https://www.readbyqxmd.com/read/30512953/co-guest-interactions-in-sdb-based-metal-organic-frameworks-a-solid-state-nuclear-magnetic-resonance-investigation
#12
Ying-Tung Angel Wong, Troy K Babcock, Shoushun Chen, Bryan E G Lucier, Yining Huang
Metal-organic frameworks (MOFs) are promising materials for greener carbon monoxide (CO) capture and separation processes. SDB-based (SDB = 4,4'-sulfonyldibenzoate) MOFs are particularly attractive due to their remarkable gas adsorption capacity under humid conditions. However, to the best of our knowledge, their CO adsorption abilities have yet to be investigated. In this report, CO-loaded PbSDB and CdSDB were characterized using variable temperature (VT) 13C solid-state nuclear magnetic resonance (SSNMR) spectroscopy...
December 4, 2018: Langmuir: the ACS Journal of Surfaces and Colloids
https://www.readbyqxmd.com/read/30511777/outer-surface-hydrophobic-shielding-strategy-to-enhance-the-chemical-stability-of-metal-organic-polyhedra
#13
Samraj Mollick, Soumya Mukherjee, Dongwook Kim, Qiao Zhiwei, Aamod V Desai, Rajat Saha, Yogeshwar D More, Jianwen Jiang, Myoung Soo Lah, Sujit K Ghosh
Metal-organic polyhedra (MOPs) are a promising class of crystalline porous materials with multifarious potential applications. Although MOPs and Metal-organic frameworks (MOFs) have similar potentials in terms of their intrinsic porosity and physicochemical properties, the exploitation of carboxylate MOPs is still rudimentary due to lack of systematic development addressing their chemical stability. Here we describe the fabrication of chemically robust carboxylate MOPs via outer surface functionalization as an a priori methodology which could be applied to stabilize of those MOPs system also where metal-ligand bond is not so strong...
December 4, 2018: Angewandte Chemie
https://www.readbyqxmd.com/read/30511412/nylon-mof-composites-via-postsynthetic-polymerization
#14
Mark Kalaj, Michael Denny, Kyle Bentz, Joseph Palomba, Seth Mason Cohen
Hybridization of metal-organic frameworks (MOFs) and polymers into composites yields materials that display the exceptional properties of MOFs with the robustness of polymers. However, realization of MOF-polymer composites requires efficient dispersion and interactions of MOF particles with polymer matrices, which remains a significant challenge. Herein, we report a simple, scalable, bench-top approach to covalently tethered nylon-MOF polymer composite materials by an interfacial polymerization technique. The copolymerization of a modified UiO-66-NH2 MOF with a growing polyamide fiber (PA-66) during an interfacial polymerization gave hybrid materials with up to ~29 weight percent MOF...
December 3, 2018: Angewandte Chemie
https://www.readbyqxmd.com/read/30510262/cooperative-adsorption-of-carbon-disulfide-in-diamine-appended-metal-organic-frameworks
#15
C Michael McGuirk, Rebecca L Siegelman, Walter S Drisdell, Tomče Runčevski, Phillip J Milner, Julia Oktawiec, Liwen F Wan, Gregory M Su, Henry Z H Jiang, Douglas A Reed, Miguel I Gonzalez, David Prendergast, Jeffrey R Long
Over one million tons of CS2 are produced annually, and emissions of this volatile and toxic liquid, known to generate acid rain, remain poorly controlled. As such, materials capable of reversibly capturing this commodity chemical in an energy-efficient manner are of interest. Recently, we detailed diamine-appended metal-organic frameworks capable of selectively capturing CO2 through a cooperative insertion mechanism that promotes efficient adsorption-desorption cycling. We therefore sought to explore the ability of these materials to capture CS2 through a similar mechanism...
December 3, 2018: Nature Communications
https://www.readbyqxmd.com/read/30510207/insights-into-functionalization-of-metal-organic-frameworks-using-in-situ-nmr-spectroscopy
#16
Ning Yuan, Tamara L Church, Erik G Brandt, Niklas Hedin, Xiaodong Zou, Diana Bernin
Postsynthetic reactions of metal-organic frameworks (MOFs) are versatile tools for producing functional materials, but the methods of evaluating these reactions are cumbersome and destructive. Here we demonstrate and validate the use of in situ NMR spectroscopy of species in the liquid state to examine solvent-assisted ligand exchange (SALE) and postsynthetic modification (PSM) reactions of metal-organic frameworks. This technique allows functionalization to be monitored over time without decomposing the product for analysis, which simplifies reaction screening...
December 3, 2018: Scientific Reports
https://www.readbyqxmd.com/read/30508484/rational-construction-of-ti3c2tx-co-mof-derived-laminated-co-tio2-c-hybrids-for-enhanced-electromagnetic-wave-absorption
#17
Qiang Liao, Man He, Yuming Zhou, Shuangxi Nie, Yongjuan Wang, Beibei Wang, Xiaoming Yang, Xiaohai Bu, Ruili Wang
The lightweight and compatible metal-organic framework (MOF)-derived carbon-based composites are widely used in electromagnetic (EM) absorption field. Their combination with laminated TiO2-C (derived from Ti3C2Tx) is expected to further strengthen the EM attenuation ability. Herein, novel laminated Co/TiO2-C hybrids were derived from Ti3C2Tx/Co-MOF using heat treatment. Compared with pristine MOF-derived carbon-based composites, the EM absorption ability of Co/TiO2-C was improved by multiple reflections between multilayered microstructures and the improved polarization loss (due to the heterogeneous interfaces, residual defects and dipole polarization) and the strengthened conductivity loss caused by the carbon layers...
December 3, 2018: Langmuir: the ACS Journal of Surfaces and Colloids
https://www.readbyqxmd.com/read/30508373/controlled-synthesis-of-porous-hierarchical-znfe-2-o-4-micro-nanostructures-with-multifunctional-photocatalytic-performance
#18
Shumin Wu, Yan Xu, Xianliang Li, Ruifei Tong, Lu Chen, Yide Han, Junbiao Wu, Xia Zhang
Engineering semiconductors with porous hierarchical micro-/nanostructures is a feasible strategy to obtain high solar-light utilization efficiency and strong photocatalytic performance. In this work, an integrated strategy of solvent evaporation and morphology-inherited annealing for the Fe-based metal-organic framework was developed to prepare the hierarchical spinel zinc ferrite (ZnFe2 O4 ) micro-/nanostructure. The morphology and porosity of the hierarchical ZnFe2 O4 structures can be adjusted by optimizing the annealing temperatures...
December 3, 2018: Inorganic Chemistry
https://www.readbyqxmd.com/read/30502036/metal-azolate-framework-66-coated-fiber-for-headspace-solid-phase-microextraction-of-polycyclic-aromatic-hydrocarbons
#19
Manman Liu, Jinfei Liu, Chao Guo, Yan Li
Metal azolate frameworks (MAFs) as a subfamily of metal-organic frameworks (MOFs) have received much attention in analyzing organic volatiles owing to their remarkable structures. In this work, the headspace solid-phase microextraction (SPME) fiber based on MAF-66 has been fabricated by a layer-by-layer deposition method. To evaluate the performance of the MAF-66-coated fibers, polycyclic aromatic hydrocarbons (PAHs) were tested as analytes with gas chromatography (GC). Relevant experimental parameters were optimized including extraction temperature, extraction time, desorption temperature, desorption time, the stirring rate and salt concentration...
November 22, 2018: Journal of Chromatography. A
https://www.readbyqxmd.com/read/30501180/elucidating-co2-chemisorption-in-diamine-appended-metal-organic-frameworks
#20
Alexander C Forse, Phillip J Milner, Jung-Hoon Lee, Halle N Redfearn, Julia Oktawiec, Rebecca L Siegelman, Jeffrey D Martell, Bhavish Dinakar, Leo B Porter-Zasada, Miguel I Gonzalez, Jeffrey B Neaton, Jeffrey R Long, Jeffrey A Reimer
The widespread deployment of carbon capture and sequestration as a climate change mitigation strategy could be facilitated by the development of more energy-efficient adsorbents. Diamine-appended metal-organic frameworks of the type diamine-M2 (dobpdc) (M = Mg, Mn, Fe, Co, Ni, Zn; dobpdc4- = 4,4'-dioxidobiphenyl-3,3'-dicarboxylate) have shown promise for carbon capture applications, although questions remain regarding the molecular mechanisms of CO2 uptake in these materials. Here, we leverage the crystallinity and tunability of this class of frameworks to perform a comprehensive study of CO2 chemisorption...
December 2, 2018: Journal of the American Chemical Society
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