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Sample records for hkust metal organic

  1. Transient Mass and Thermal Transport during Methane Adsorption into the Metal-Organic Framework HKUST-1.

    Babaei, Hasan; McGaughey, Alan J H; Wilmer, Christopher E

    2018-01-24

    Methane adsorption into the metal-organic framework (MOF) HKUST-1 and the resulting heat generation and dissipation are investigated using molecular dynamics simulations. Transient simulations reveal that thermal transport in the MOF occurs two orders of magnitude faster than gas diffusion. A large thermal resistance at the MOF-gas interface (equivalent to 127 nm of bulk HKUST-1), however, prevents fast release of the generated heat. The mass transport resistance at the MOF-gas interface is equivalent to 1 nm of bulk HKUST-1 and does not present a bottleneck in the adsorption process. These results provide important insights into the application of MOFs for gas storage applications.

  2. Chemical principles underpinning the performance of the metal-organic framework HKUST-1.

    Hendon, Christopher H; Walsh, Aron

    2015-07-15

    A common feature of multi-functional metal-organic frameworks is a metal dimer in the form of a paddlewheel, as found in the structure of Cu 3 ( btc ) 2 (HKUST-1). The HKUST-1 framework demonstrates exceptional gas storage, sensing and separation, catalytic activity and, in recent studies, unprecedented ionic and electrical conductivity. These results are a promising step towards the real-world application of metal-organic materials. In this perspective, we discuss progress in the understanding of the electronic, magnetic and physical properties of HKUST-1, representative of the larger family of Cu···Cu containing metal-organic frameworks. We highlight the chemical interactions that give rise to its favourable properties, and which make this material well suited to a range of technological applications. From this analysis, we postulate key design principles for tailoring novel high-performance hybrid frameworks.

  3. Photoswitchable nanoporous films by loading azobenzene in metal-organic frameworks of type HKUST-1.

    Müller, Kai; Wadhwa, Jasmine; Singh Malhi, Jasleen; Schöttner, Ludger; Welle, Alexander; Schwartz, Heidi; Hermann, Daniela; Ruschewitz, Uwe; Heinke, Lars

    2017-07-13

    Photoswitchable metal-organic frameworks (MOFs) enable the dynamic remote control of their key properties. Here, a readily producible approach is presented where photochromic molecules, i.e. azobenzene (AB) and o-tetrafluoroazobenzene (tfAB), are loaded in MOF films of type HKUST-1. These nanoporous films, which can be reversibly switched with UV/visible or only visible light, have remote-controllable guest uptake properties.

  4. Electrodeposition of WO3 nanoparticles into surface mounted metal-organic framework HKUST-1 thin films

    Yoo, Hyeonseok; Welle, Alexander; Guo, Wei; Choi, Jinsub; Redel, Engelbert

    2017-03-01

    We describe a novel procedure to fabricate WO3@surface-mounted metal-organic framework (SURMOF) hybrid materials by electrodeposition of WO3 nanoparticles into HKUST-1, also termed Cu3(BTC)2 SURMOFs. These materials have been characterized using x-ray diffraction, time-of-flight secondary ion mass spectrometry, scanning electron microscopy, x-ray photoelectron spectroscopy as well as linear sweep voltammetry. The WO3 semiconductor/SURMOF heterostructures were further tested as hybrid electrodes in their performance for hydrogen evolution reaction from water.

  5. Prediction of molecular separation of polar-apolar mixtures on heterogeneous metal-organic frameworks: HKUST-1.

    Van Assche, Tom R C; Duerinck, Tim; Van der Perre, Stijn; Baron, Gino V; Denayer, Joeri F M

    2014-07-08

    Due to the combination of metal ions and organic linkers and the presence of different types of cages and channels, metal-organic frameworks often possess a large structural and chemical heterogeneity, complicating their adsorption behavior, especially for polar-apolar adsorbate mixtures. By allocating isotherms to individual subunits in the structure, the ideal adsorbed solution theory (IAST) can be adjusted to cope with this heterogeneity. The binary adsorption of methanol and n-hexane on HKUST-1 is analyzed using this segregated IAST (SIAST) approach and offers a significant improvement over the standard IAST model predictions. It identifies the various HKUST-1 cages to have a pronounced polar or apolar adsorptive behavior.

  6. Surface Termination of the Metal-Organic Framework HKUST-1: A Theoretical Investigation.

    Amirjalayer, Saeed; Tafipolsky, Maxim; Schmid, Rochus

    2014-09-18

    The surface morphology and termination of metal-organic frameworks (MOF) is of critical importance in many applications, but the surface properties of these soft materials are conceptually different from those of other materials like metal or oxide surfaces. Up to now, experimental investigations are scarce and theoretical simulations have focused on the bulk properties. The possible surface structure of the archetypal MOF HKUST-1 is investigated by a first-principles derived force field in combination with DFT calculations of model systems. The computed surface energies correctly predict the [111] surface to be most stable and allow us to obtain an unprecedented atomistic picture of the surface termination. Entropic factors are identified to determine the preferred surface termination and to be the driving force for the MOF growth. On the basis of this, reported strategies like employing "modulators" during the synthesis to tailor the crystal morphology are discussed.

  7. Solvothermal growth of a ruthenium metal-organic framework featuring HKUST-1 structure type as thin films on oxide surfaces.

    Kozachuk, Olesia; Yusenko, Kirill; Noei, Heshmat; Wang, Yuemin; Walleck, Stephan; Glaser, Thorsten; Fischer, Roland A

    2011-08-14

    Phase-pure crystalline thin films of a mixed-valence Ru(2)(II,III) metal-organic framework with 1,3,5-benzenetricarboxylate (btc) as a linker were solvothermally grown on amorphous alumina and silica surfaces. Based on the Rietveld refinement, the structure of Ru-MOF was assigned to be analogous to [Cu(3)(btc)(2)] (HKUST-1). This journal is © The Royal Society of Chemistry 2011

  8. Synthesis and characterization of bimetallic metal-organic framework Cu-Ru-BTC with HKUST-1 structure.

    Gotthardt, Meike A; Schoch, Roland; Wolf, Silke; Bauer, Matthias; Kleist, Wolfgang

    2015-02-07

    The bimetallic metal-organic framework Cu-Ru-BTC with the stoichiometric formula Cu2.75Ru0.25(BTC)2·xH2O, which is isoreticular to HKUST-1, was successfully prepared in a direct synthesis using mild reaction conditions. The partial substitution of Cu(2+) by Ru(3+) centers in the paddlewheel structure and the absence of other Ru-containing phases was proven using X-ray absorption spectroscopy.

  9. Experimental and theoretical investigations of the electronic band structure of metal-organic frameworks of HKUST-1 type

    Gu, Zhi-Gang [Institut für Funktionelle Grenzflächen (IFG), Karlsruher Institut für Technologie (KIT), Hermann-von-Helmholtz-Platz 1, 76344 Eggenstein-Leopoldshafen (Germany); State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, 350002 Fuzhou (China); Heinke, Lars, E-mail: Lars.Heinke@KIT.edu; Wöll, Christof [Institut für Funktionelle Grenzflächen (IFG), Karlsruher Institut für Technologie (KIT), Hermann-von-Helmholtz-Platz 1, 76344 Eggenstein-Leopoldshafen (Germany); Neumann, Tobias; Wenzel, Wolfgang; Li, Qiang; Fink, Karin [Institute of Nanotechnology (INT), Karlsruher Institut für Technologie (KIT), Hermann-von-Helmholtz-Platz 1, 76344 Eggenstein-Leopoldshafen (Germany); Gordan, Ovidiu D.; Zahn, Dietrich R. T. [Semiconductor Physics, Technische Universität Chemnitz, 09107 Chemnitz (Germany)

    2015-11-02

    The electronic properties of metal-organic frameworks (MOFs) are increasingly attracting the attention due to potential applications in sensor techniques and (micro-) electronic engineering, for instance, as low-k-dielectric in semiconductor technology. Here, the band gap and the band structure of MOFs of type HKUST-1 are studied in detail by means of spectroscopic ellipsometry applied to thin surface-mounted MOF films and by means of quantum chemical calculations. The analysis of the density of states, the band structure, and the excitation spectrum reveal the importance of the empty Cu-3d orbitals for the electronic properties of HKUST-1. This study shows that, in contrast to common belief, even in the case of this fairly “simple” MOF, the excitation spectra cannot be explained by a superposition of “intra-unit” excitations within the individual building blocks. Instead, “inter-unit” excitations also have to be considered.

  10. Experimental and theoretical investigations of the electronic band structure of metal-organic frameworks of HKUST-1 type

    Gu, Zhi-Gang; Heinke, Lars; Wöll, Christof; Neumann, Tobias; Wenzel, Wolfgang; Li, Qiang; Fink, Karin; Gordan, Ovidiu D.; Zahn, Dietrich R. T.

    2015-11-01

    The electronic properties of metal-organic frameworks (MOFs) are increasingly attracting the attention due to potential applications in sensor techniques and (micro-) electronic engineering, for instance, as low-k-dielectric in semiconductor technology. Here, the band gap and the band structure of MOFs of type HKUST-1 are studied in detail by means of spectroscopic ellipsometry applied to thin surface-mounted MOF films and by means of quantum chemical calculations. The analysis of the density of states, the band structure, and the excitation spectrum reveal the importance of the empty Cu-3d orbitals for the electronic properties of HKUST-1. This study shows that, in contrast to common belief, even in the case of this fairly "simple" MOF, the excitation spectra cannot be explained by a superposition of "intra-unit" excitations within the individual building blocks. Instead, "inter-unit" excitations also have to be considered.

  11. Experimental and theoretical investigations of the electronic band structure of metal-organic frameworks of HKUST-1 type

    Gu, Zhi-Gang; Heinke, Lars; Wöll, Christof; Neumann, Tobias; Wenzel, Wolfgang; Li, Qiang; Fink, Karin; Gordan, Ovidiu D.; Zahn, Dietrich R. T.

    2015-01-01

    The electronic properties of metal-organic frameworks (MOFs) are increasingly attracting the attention due to potential applications in sensor techniques and (micro-) electronic engineering, for instance, as low-k-dielectric in semiconductor technology. Here, the band gap and the band structure of MOFs of type HKUST-1 are studied in detail by means of spectroscopic ellipsometry applied to thin surface-mounted MOF films and by means of quantum chemical calculations. The analysis of the density of states, the band structure, and the excitation spectrum reveal the importance of the empty Cu-3d orbitals for the electronic properties of HKUST-1. This study shows that, in contrast to common belief, even in the case of this fairly “simple” MOF, the excitation spectra cannot be explained by a superposition of “intra-unit” excitations within the individual building blocks. Instead, “inter-unit” excitations also have to be considered

  12. Incorporation of metal-organic framework HKUST-1 into porous polymer monolithic capillary columns to enhance the chromatographic separation of small molecules.

    Yang, Shengchao; Ye, Fanggui; Lv, Qinghui; Zhang, Cong; Shen, Shufen; Zhao, Shulin

    2014-09-19

    Metal-organic framework (MOF) HKUST-1 nanoparticles have been incorporated into poly(glycidyl methacrylate-co-ethylene dimethacrylate) (HKUST-1-poly(GMA-co-EDMA)) monoliths to afford stationary phases with enhanced chromatographic performance of small molecules in the reversed phase capillary liquid chromatography. The effect of HKUST-1 nanoparticles in the polymerization mixture on the performance of the monolithic column was explored in detail. While the bare poly(GMA-co-EDMA) monolith exhibited poor resolution (RsHKUST-1 nanoparticles to the polymerization mixture provide high increased resolution (Rs≥1.3) and high efficiency ranged from 16,300 to 44,300plates/m. Chromatographic performance of HKUST-1-poly(GMA-co-EDMA) monolith was demonstrated by separation of various analytes including polycyclic aromatic hydrocarbons, ethylbenzene and styrene, phenols and aromatic acids using a binary polar mobile phase (CH3CN/H2O). The HKUST-1-poly(GMA-co-EDMA) monolith displayed enhanced hydrophobic and π-π interaction characteristics in the reversed phase separation of test analytes compared to the bare poly(GMA-co-EDMA) monolith. The experiment results showed that HKUST-1-poly(GMA-co-EDMA) monoliths are an alternative to enhance the chromatographic separation of small molecules. Copyright © 2014 Elsevier B.V. All rights reserved.

  13. Coordination-chemistry control of proton conductivity in the iconic metal-organic framework material HKUST-1.

    Jeong, Nak Cheon; Samanta, Bappaditya; Lee, Chang Yeon; Farha, Omar K; Hupp, Joseph T

    2012-01-11

    HKUST-1, a metal-organic framework (MOF) material containing Cu(II)-paddlewheel-type nodes and 1,3,5-benzenetricarboxylate struts, features accessible Cu(II) sites to which solvent or other desired molecules can be intentionally coordinated. As part of a broader investigation of ionic conductivity in MOFs, we unexpectedly observed substantial proton conductivity with the "as synthesized" version of this material following sorption of methanol. Although HKUST-1 is neutral, coordinated water molecules are rendered sufficiently acidic by Cu(II) to contribute protons to pore-filling methanol molecules and thereby enhance the alternating-current conductivity. At ambient temperature, the chemical identities of the node-coordinated and pore-filling molecules can be independently varied, thus enabling the proton conductivity to be reversibly modulated. The proton conductivity of HKUST-1 was observed to increase by ~75-fold, for example, when node-coordinated acetonitrile molecules were replaced by water molecules. In contrast, the conductivity became almost immeasurably small when methanol was replaced by hexane as the pore-filling solvent. © 2011 American Chemical Society

  14. Growth of metal-organic framework HKUST-1 in capillary using liquid-phase epitaxy for open-tubular capillary electrochromatography and capillary liquid chromatography.

    Bao, Tao; Zhang, Juan; Zhang, Wenpeng; Chen, Zilin

    2015-02-13

    Much attention is being paid to applying metal-organic frameworks (MOFs) as stationary phases in chromatography because of their fascinating properties, such as large surface-to-volume ratios, high levels of porosity, and selective adsorption. HKUST-1 is one of the best-studied face-centered-cubic MOF containing nano-sized channels and side pockets for film growth. However, growth of HKUST-1 framework inside capillary column as stationary phase for capillary electrochromatography is a challenge work. In this work, we carry out the growth of HKUST-1 on the inner wall of capillary by using liquid-phase epitaxy process at room temperature. The fabricated HKUST-1@capillary can be successfully used for the separation of substituted benzene including methylbenzene, ethylbenzene, styrene, chlorobenzene, bromobenzene, o-dichlorobenzene, benzene series, phenolic acids, and benzoic acids derivates. High column efficiency of 1.5×10(5) N/m for methylbenzene was achieved. The formation of HKUST-1 grown in the capillary was confirmed and characterized by scanning electron microscopy images, Fourier transform infrared spectra and X-ray diffraction. The column showed long lifetime and excellent stability. The relative standard deviations for intra-day and inter-day repeatability of the HKUST-1@capillary were lower than 7%. Copyright © 2015 Elsevier B.V. All rights reserved.

  15. Particle size studies to reveal crystallization mechanisms of the metal organic framework HKUST-1 during sonochemical synthesis.

    Armstrong, Mitchell R; Senthilnathan, Sethuraman; Balzer, Christopher J; Shan, Bohan; Chen, Liang; Mu, Bin

    2017-01-01

    Systematic studies of key operating parameters for the sonochemical synthesis of the metal organic framework (MOF) HKUST-1(also called CuBTC) were performed including reaction time, reactor volume, sonication amplitude, sonication tip size, solvent composition, and reactant concentrations analyzed through SEM particle size analysis. Trends in the particle size and size distributions show reproducible control of average particle sizes between 1 and 4μm. These results along with complementary studies in sonofragmentation and temperature control were conducted to compare these results to kinetic crystal growth models found in literature to develop a plausible hypothetical mechanism for ultrasound-assisted growth of metal-organic-frameworks composed of a competitive mechanism including constructive solid-on-solid (SOS) crystal growth and a deconstructive sonofragmentation. Copyright © 2016 Elsevier B.V. All rights reserved.

  16. In Situ Monitoring of the Mechanosynthesis of the Archetypal Metal-Organic Framework HKUST-1: Effect of Liquid Additives on the Milling Reactivity.

    Stolar, Tomislav; Batzdorf, Lisa; Lukin, Stipe; Žilić, Dijana; Motillo, Cristina; Friščić, Tomislav; Emmerling, Franziska; Halasz, Ivan; Užarević, Krunoslav

    2017-06-05

    We have applied in situ monitoring of mechanochemical reactions by high-energy synchrotron powder X-ray diffraction to study the role of liquid additives on the mechanochemical synthesis of the archetypal metal-organic framework (MOF) HKUST-1, which was one of the first and is still among the most widely investigated MOF materials to be synthesized by solvent-free procedures. It is shown here how the kinetics and mechanisms of the mechanochemical synthesis of HKUST-1 can be influenced by milling conditions and additives, yielding on occasion two new and previously undetected intermediate phases containing a mononuclear copper core, and that finally rearrange to form the HKUST-1 architecture. On the basis of in situ data, we were able to tune and direct the milling reactions toward the formation of these intermediates, which were isolated and characterized by spectroscopic and structural means and their magnetic properties compared to those of HKUST-1. The results have shown that despite the relatively large breadth of analysis available for such widely investigated materials as HKUST-1, in situ monitoring of milling reactions can help in the detection and isolation of new materials and to establish efficient reaction conditions for the mechanochemical synthesis of porous MOFs.

  17. Kinetics of degradation of sulfur mustard and sarin simulants on HKUST-1 metal organic framework.

    Roy, Anuradha; Srivastava, Avanish K; Singh, Beer; Shah, Dilip; Mahato, Timir Haran; Srivastava, Anchal

    2012-10-28

    The applicability of HKUST-1 for the degradation of sulfur mustard and sarin simulants was studied with and without coadsorbed water. Degradation was found to be via hydrolysis and dependent on the nucleophilic substitution reaction, vapour pressure and molecular diameter of the toxicants.

  18. Study of HKUST (Copper benzene-1,3,5-tricarboxylate, Cu-BTC MOF)-1 metal organic frameworks for CH4 adsorption: An experimental Investigation with GCMC (grand canonical Monte-carlo) simulation

    Sun, Baichuan; Kayal, Sibnath; Chakraborty, Anutosh

    2014-01-01

    We have measured the methane uptakes on HKUST (Copper benzene-1,3,5-tricarboxylate, Cu-BTC MOF)-1 MOF (metal organic framework) for the temperatures ranging from 120 K to 300 K and pressures up to 10 bar. The experimentally measured HKUST-1 + CH 4 isotherms data are compared with uptakes of various adsorbents and methane systems. We have also simulated the methane uptakes and its density distribution on HKUST-1 employing GCMC (grand canonical Monte-carlo) simulation and compare with experimental data. In this article, we also present an extensive study on characterization and property evaluation of HKUST-1 MOF for CH 4 adsorption characteristics employing XRD (X-ray diffraction), SEM (scanning electron microscope) and TGA (thermo gravimetric analysis). Employing GCMC and the thermodynamic property fields of HKUST-1 + CH 4 system, the isosteric heat of adsorption (Q st ) is calculated and Q st is presented in a T-s (temperature-entropy) diagram. - Highlights: • Characterization of HKUST-1 MOFs by XRD, SEM, N 2 adsorption and TGA. • Measurement of CH 4 uptakes on HKUST-1 by volumetric methods. • GCMC simulation of methane uptakes and its density distribution on HKUST-1. • Isosteric heat of adsorption in a T-s (temperature-entropy) diagram

  19. Fixed distance photoinduced electron transfer between Fe and Zn porphyrins encapsulated within the Zn HKUST-1 metal organic framework.

    Larsen, Randy W; Wojtas, Lukasz

    2015-02-21

    An attractive strategy for the development of photocatalytic metal organic framework (MOF) materials is to co-encapsulate a photoactive electron donor with a catalytic electron acceptor within the MOF. Here we report the co-encapsulation of both Zn(ii) tetrakis(tetra 4-sulphonatophenyl)porphyrin (Zn4SP) and Fe(iii) tetrakis(tetra 4-sulphonatophenyl)porphyrin (Fe4SP) into an HKUST-1 (Zn) MOF and demonstrate photoinduced electron transfer (ET) between the co-encapsulated guest. Photo-excitation of the Zn4SP results in fixed-distance inter-molecular ET between the encapsulated (3)Zn4SP and the Fe(iii)4SP as evident by the reduction in the encapsulated (3)Zn4SP lifetime from 890 μs (kobs = 1.1 × 10(3) s(-1)) to 83 μs (kobs = 1.2 × 10(4) s(-1)) in the presence of Fe4SP giving a kET ∼ 1.1 × 10(4) s(-1). The data are consistent with ET taking place between encapsulated porphyrins that are two cages apart in distance with a reorganizational energy of ∼1.65 eV, β = 1.25 and ΔG° = -0.97 eV (within a semi-classical Marcus theory framework).

  20. CO2/H2O adsorption equilibrium and rates on metal-organic frameworks: HKUST-1 and Ni/DOBDC.

    Liu, Jian; Wang, Yu; Benin, Annabelle I; Jakubczak, Paulina; Willis, Richard R; LeVan, M Douglas

    2010-09-07

    Metal-organic frameworks (MOFs) have recently attracted intense research interest because of their permanent porous structures, huge surface areas, and potential applications as novel adsorbents and catalysts. In order to provide a basis for consideration of MOFs for removal of carbon dioxide from gases containing water vapor, such as flue gas, we have studied adsorption equilibrium of CO(2), H(2)O vapor, and their mixtures and also rates of CO(2) adsorption in two MOFs: HKUST-1 (CuBTC) and Ni/DOBDC (CPO-27-Ni or Ni/MOF-74). The MOFs were synthesized via solvothermal methods, and the as-synthesized products were solvent exchanged and regenerated before experiments. Pure component adsorption equilibria and CO(2)/H(2)O binary adsorption equilibria were studied using a volumetric system. The effects of H(2)O adsorption on CO(2) adsorption for both MOF samples were determined, and the results for 5A and NaX zeolites were included for comparison. The hydrothermal stabilities for the two MOFs over the course of repetitive measurements of H(2)O and CO(2)/H(2)O mixture equilibria were also studied. CO(2) adsorption rates from helium for the MOF samples were investigated by using a unique concentration-swing frequency response (CSFR) system. Mass transfer into the MOFs is rapid with the controlling resistance found to be macropore diffusion, and rate parameters were established for the mechanism.

  1. Electrochemical Selective and Simultaneous Detection of Diclofenac and Ibuprofen in Aqueous Solution Using HKUST-1 Metal-Organic Framework-Carbon Nanofiber Composite Electrode

    Sorina Motoc

    2016-10-01

    Full Text Available In this study, the detection protocols for the individual, selective, and simultaneous determination of ibuprofen (IBP and diclofenac (DCF in aqueous solutions have been developed using HKUST-1 metal-organic framework-carbon nanofiber composite (HKUST-CNF electrode. The morphological and electrical characterization of modified composite electrode prepared by film casting was studied by scanning electronic microscopy and four-point-probe methods. The electrochemical characterization of the electrode by cyclic voltammetry (CV was considered the reference basis for the optimization of the operating conditions for chronoamperometry (CA and multiple-pulsed amperometry (MPA. This electrode exhibited the possibility to selectively detect IBP and DCF by simple switching the detection potential using CA. However, the MPA operated under optimum working conditions of four potential levels selected based on CV shape in relation to the potential value, pulse time, and potential level number, and order allowed the selective/simultaneous detection of IBP and DCF characterized by the enhanced detection performance. For this application, the HKUST-CNF electrode exhibited a good stability and reproducibility of the results was achieved.

  2. Electrochemical Selective and Simultaneous Detection of Diclofenac and Ibuprofen in Aqueous Solution Using HKUST-1 Metal-Organic Framework-Carbon Nanofiber Composite Electrode.

    Motoc, Sorina; Manea, Florica; Iacob, Adriana; Martinez-Joaristi, Alberto; Gascon, Jorge; Pop, Aniela; Schoonman, Joop

    2016-10-17

    In this study, the detection protocols for the individual, selective, and simultaneous determination of ibuprofen (IBP) and diclofenac (DCF) in aqueous solutions have been developed using HKUST-1 metal-organic framework-carbon nanofiber composite (HKUST-CNF) electrode. The morphological and electrical characterization of modified composite electrode prepared by film casting was studied by scanning electronic microscopy and four-point-probe methods. The electrochemical characterization of the electrode by cyclic voltammetry (CV) was considered the reference basis for the optimization of the operating conditions for chronoamperometry (CA) and multiple-pulsed amperometry (MPA). This electrode exhibited the possibility to selectively detect IBP and DCF by simple switching the detection potential using CA. However, the MPA operated under optimum working conditions of four potential levels selected based on CV shape in relation to the potential value, pulse time, and potential level number, and order allowed the selective/simultaneous detection of IBP and DCF characterized by the enhanced detection performance. For this application, the HKUST-CNF electrode exhibited a good stability and reproducibility of the results was achieved.

  3. Adsorption of silver nanoparticles from aqueous solution on copper-based metal organic frameworks (HKUST-1).

    Conde-González, J E; Peña-Méndez, E M; Rybáková, S; Pasán, J; Ruiz-Pérez, C; Havel, J

    2016-05-01

    Silver nanoparticles (AgNP) are emerging pollutants. The use of novel materials such as Cu-(benzene 1,3,5-tricarboxylate, BTC) Metal-Organic Framework (MOFs), for AgNP adsorption and their removal from aqueous solutions has been studied. The effect of different parameters was followed and isotherm model was suggested. MOFs adsorbed fast and efficiently AgNP in the range C0 < 10 mg L(-1), being Freundlich isotherm (R = 0.993) these data fitted to. Among studied parameters a remarkable effect of chloride on sorption was found, thus their possible interactions were considered. The high adsorption efficiency of AgNP was achieved and it was found to be very fast. The feasibility of adsorption on Cu-(BTC) was proved in spiked waters. The results showed the potential interest of new material as adsorbent for removing AgNP from environment. Copyright © 2016 Elsevier Ltd. All rights reserved.

  4. High-resolution inelastic neutron scattering and neutron powder diffraction study of the adsorption of dihydrogen by the Cu(II) metal-organic framework material HKUST-1

    Callear, Samantha K.; Ramirez-Cuesta, Anibal J.; David, William I. F.; Millange, Franck; Walton, Richard I.

    2013-12-01

    We present new high-resolution inelastic neutron scattering (INS) spectra (measured using the TOSCA and MARI instruments at ISIS) and powder neutron diffraction data (measured on the diffractometer WISH at ISIS) from the interaction of the prototypical metal-organic framework HKUST-1 with various dosages of dihydrogen gas. The INS spectra show direct evidence for the sequential occupation of various distinct sites for dihydrogen in the metal-organic framework, whose population is adjusted during increasing loading of the guest. The superior resolution of TOSCA reveals subtle features in the spectra, not previously reported, including evidence for split signals, while complementary spectra recorded on MARI present full information in energy and momentum transfer. The analysis of the powder neutron patterns using the Rietveld method shows a consistent picture, allowing the crystallographic indenisation of binding sites for dihydrogen, thus building a comprehensive picture of the interaction of the guest with the nanoporous host.

  5. A Chemical Route to Activation of Open Metal Sites in the Copper-Based Metal-Organic Framework Materials HKUST-1 and Cu-MOF-2.

    Kim, Hong Ki; Yun, Won Seok; Kim, Min-Bum; Kim, Jeung Yoon; Bae, Youn-Sang; Lee, JaeDong; Jeong, Nak Cheon

    2015-08-12

    Open coordination sites (OCSs) in metal-organic frameworks (MOFs) often function as key factors in the potential applications of MOFs, such as gas separation, gas sorption, and catalysis. For these applications, the activation process to remove the solvent molecules coordinated at the OCSs is an essential step that must be performed prior to use of the MOFs. To date, the thermal method performed by applying heat and vacuum has been the only method for such activation. In this report, we demonstrate that methylene chloride (MC) itself can perform the activation role: this process can serve as an alternative "chemical route" for the activation that does not require applying heat. To the best of our knowledge, no previous study has demonstrated this function of MC, although MC has been popularly used in the pretreatment step prior to the thermal activation process. On the basis of a Raman study, we propose a plausible mechanism for the chemical activation, in which the function of MC is possibly due to its coordination with the Cu(2+) center and subsequent spontaneous decoordination. Using HKUST-1 film, we further demonstrate that this chemical activation route is highly suitable for activating large-area MOF films.

  6. H3PW12O40 Encapsulation by Nanoporous Metal Organic Framework HKUST-1: Synthesis, Characterization, Activity and Stability.

    Rafiee, Ezzat; Nobakht, Narges

    2016-01-01

    Hybrid composite material was obtained through encapsulation of H3PW12O40 (PW) into HKUST-1 (Cu3(BTC)2, BTC = 1,3,5-benzenetricarboxylic acid), in molar composition of 5 Cu(NO3)2 · 3H2O/2.8 BTC/0.3 PW/0.6 CTAB by adding solutions of PW and copper salts to mixture of BTC and surfactant. The catalyst was characterized by various techniques including powder X-ray diffraction (XRD), Fourier transform infrared (FT-IR), scanning electron microscopy (SEM), energy dispersive X-ray (EDX), laser particle size analyzer, Brunauer Emmett-Teller (BET). The acidity of the catalyst was measured by a potentiometric titration with n-butylamine and PW/HKUST-1 presented very strong acidic sites with Ei > 100 mV. This nano catalyst was successfully used for the synthesis of various β-keto enol ethers at 45 °C with 51-98% yield after 5-75 min. The catalyst was easily recycled and reused at least four times without significant loss of its activity (94% yield after forth run). The presence of the PW in PW/HKUST-1 and reused PW/HKUST-1 structure, eliminating any doubt about collapse of the HKUST-1 after catalytic reaction and can be followed by FT-IR, XRD and SEM techniques. Brönsted and Lewis acidity of the PW/HKUST-1 catalyst was distinguished by studying the FT-IR and determined by chemisorption of pyridine. The strength and dispersion of the protons on PW/HKUST-1 was considerably high and active surface protons became more available for reactant.

  7. Chemical principles underpinning the performance of the metal–organic framework HKUST-1

    Hendon, Christopher H.

    2015-01-01

    A common feature of multi-functional metal–organic frameworks is a metal dimer in the form of a paddlewheel, as found in the structure of Cu3(btc)2 (HKUST-1). The HKUST-1 framework demonstrates exceptional gas storage, sensing and separation, catalytic activity and, in recent studies, unprecedented ionic and electrical conductivity. These results are a promising step towards the real-world application of metal–organic materials. In this perspective, we discuss progress in the understanding of the electronic, magnetic and physical properties of HKUST-1, representative of the larger family of Cu···Cu containing metal–organic frameworks. We highlight the chemical interactions that give rise to its favourable properties, and which make this material well suited to a range of technological applications. From this analysis, we postulate key design principles for tailoring novel high-performance hybrid frameworks. PMID:28706713

  8. A template-free method for stable CuO hollow microspheres fabricated from a metal organic framework (HKUST-1).

    Zhang, Suoying; Liu, Hong; Liu, Pengfei; Yang, Zhuhong; Feng, Xin; Huo, Fengwei; Lu, Xiaohua

    2015-06-07

    Uniform CuO hollow microspheres were successfully achieved from a non-uniform metal organic framework by using a template-free method. The process mechanism has been revealed to be spherical aggregation and Ostwald ripening. When tested in CO oxidation and heat treatment, these assembled microspheres exhibited an excellent catalytic performance and show a much better stability than the inherited hollow structure from MOFs.

  9. Carbon Dioxide Adsorption Behavior of Modified HKUST-1

    Ma, Lan; Tang, Huamin; Zhou, Chaohua; Zhang, Hongpeng; Yan, Chunxiao; Hu, Xiaochun; Yang, Yang; Yang, Weiwei; Li, Yuming; He, Dehua

    2014-12-01

    A kind of typical metal-organic frameworks (MOFs) material, HKUST-1 was prepared by hydrothermal method and characterized by XRD and SEM. The results of characterizations manifested that HKUST-1 showed a regular octahedral crystal structure. The as-prepared HKUST-1 was modified by several kinds of organic base materials and the CO2 adsorption behaviors of modified HKUST-1 materials were evaluated. The CO2 adsorption capacities of different base modified HKUST-1 varied with the base intensity of modified organic base materials.

  10. A magnetic-based dispersive micro-solid-phase extraction method using the metal-organic framework HKUST-1 and ultra-high-performance liquid chromatography with fluorescence detection for determining polycyclic aromatic hydrocarbons in waters and fruit tea infusions.

    Rocío-Bautista, Priscilla; Pino, Verónica; Ayala, Juan H; Pasán, Jorge; Ruiz-Pérez, Catalina; Afonso, Ana M

    2016-03-04

    A hybrid material composed by the metal-organic framework (MOF) HKUST-1 and Fe3O4 magnetic nanoparticles (MNPs) has been synthetized in a quite simple manner, characterized, and used in a magnetic-assisted dispersive micro-solid-phase extraction (M-d-μSPE) method in combination with ultra-high-performance liquid chromatography (UHPLC) and fluorescence detection (FD). The application was devoted to the determination of 8 heavy polycyclic aromatic hydrocarbons (PAHs) in different aqueous samples, specifically tap water, wastewaters, and fruit tea infusion samples. The overall M-d-μSPE-UHPLC-FD method was optimized and validated. The method is characterized by: its simplicity in both the preparation of the hybrid material (simple mixing) and the magnetic-assisted approach (∼10min extraction time), the use of low sorbent amounts (20mg of HKUST-1 and 5mg of Fe3O4 MNPs), and the low organic solvent consumption in the overall M-d-μSPE-UHPLC-FD method (1.5mL of acetonitrile in the M-d-μSPE method and 2.8mL of acetonitrile in the UHPLC-FD run). The resulting method has high sensitivity, with LODs down to 0.8ngL(-1); adequate intermediate precision, with relative standard deviation values (RSD) always lower than 6.3% (being the range 5.9-9.0% in tap water for a spiked level of 45ngL(-1), 6.1-14% in wastewaters for a spiked level of 45ngL(-1), and 7.2-17% in fruit tea infusion samples for a spiked level of 45ngL(-1)); and adequate relative recoveries, with average values of 82% in tap water, and 94% and 75% in wastewater and fruit tea infusion samples, respectively, if using the proper matrix-matched calibration. Copyright © 2016 Elsevier B.V. All rights reserved.

  11. The metal-organic framework HKUST-1 as efficient sorbent in a vortex-assisted dispersive micro solid-phase extraction of parabens from environmental waters, cosmetic creams, and human urine.

    Rocío-Bautista, Priscilla; Martínez-Benito, Carla; Pino, Verónica; Pasán, Jorge; Ayala, Juan H; Ruiz-Pérez, Catalina; Afonso, Ana M

    2015-07-01

    Three metal-organic frameworks (MOFs), specifically HKUST-1, MOF-5, and MIL-53(Al), have been synthetized, characterized, studied and compared in a vortex-assisted dispersive micro-solid-phase extraction (VA-D-µ-SPE) procedure in combination with high-performance liquid chromatography (HPLC) with diode-array detection (DAD) for determining seven parabens in environmental waters (tap water, swimming pool water, and water coming from a spa pool), human urine (from two volunteers), and cosmetic creams (two commercial brands). Experimental parameters, such as nature and amount of MOF, sample volume, nature of elution solvent and its amount, vortex and centrifugation time, among others, were properly optimized. HKUST-1 was the most adequate MOF to work with. Detection limits for the overall method down to 0.1 μgL(-1) for butylparaben (BPB) and benzylparaben (BzPB) were obtained, with determination coefficients (R(2)) higher than 0.9966 for a range of 0.5-147 μgL(-1) (depending on the paraben), average relative recoveries (RR, in %) of 80.3% at the low spiked level (7 μgL(-1)), and relative standard deviation (RSD) values below 10% also at the low spiked level. The strength of the affinity between HKUST-1 and parabens was evaluated, and it ranged from 33.5% for isopropylparaben (iPPB) to 77.0% for isobutylparaben (iBPB). When analyzing complex environmental waters, RR values of 78%, inter-day precision values (as RSD) lower than 15%, and intra-day precision values lower than 7.8% were obtained, despite the observed matrix effect. When analyzing cosmetic creams, parabens were detected, with contents ranging from 0.14 ± 0.01 μgg(-1) for EPB in the healing cream analyzed to 1.12 ± 0.07 mgg(-1) for MPB in the mask cream analyzed, with precision values (RSD) lower than 12% and RR values from 63.7% for propylparaben (PPB) to 121% for iPPB. When analyzing human urine, no parabens were detected but the method could be performed with RSD values lower than 19%. These

  12. Tailoring the Adsorption and Reaction Chemistry of the Metal-Organic Frameworks UiO-66, UiO-66-NH2, and HKUST-1 via the Incorporation of Molecular Guests.

    Ploskonka, Ann M; DeCoste, Jared B

    2017-06-28

    Metal-organic frameworks (MOFs) are versatile materials highly regarded for their porous nature. Depending on the synthetic method, various guest molecules may remain in the pores or can be systematically loaded for various reasons. Herein, we present a study that explores the effect of guest molecules on the adsorption and reactivity of the MOF in both the gas phase and solution. The differences between guest molecule interactions and the subsequent effects on their activity are described for each system. Interestingly, different effects are observed and described in detail for each class of guest molecules studied. We determine that there is a strong effect of alcohols with the secondary building unit of UiO MOFs, while Lewis bases have an effect on the reactivity of the -NH 2 group in UiO-66-NH 2 and adsorption by the coordinatively unsaturated copper sites in HKUST-1. These effects must be considered when determining synthesis and activation methods of MOFs toward various applications.

  13. Microwave-assisted synthesis of HKUST-1 and functionalized HKUST-1-@H3PW12O40: selective adsorption of heavy metal ions in water analyzed with synchrotron radiation.

    Zou, Fang; Yu, Runhan; Li, Rongguan; Li, Wei

    2013-08-26

    A simple, rapid and efficient synthesis of the metal-organic framework (MOF) HKUST-1 [Cu3(1,3,5-benzene-tri-carboxilic-acid)2] by microwave irradiation is described, which afforded a homogeneous and highly selective material. The unusually short time to complete the synthesis by microwave irradiation is mainly attributable to rapid nucleation rather than to crystal growth rate. Using this method, HKUST-1-MW (MW=microwave) could be prepared within 20 min, whereas by hydrothermal synthesis, involving conventional heating, the preparation time is 8 h. Work efficiency was improved by the good performance of the obtained HKUST-1-MW which exhibited good selective adsorption of heavy metal ions, as well as a remarkably high adsorption affinity and adsorption capacity, but no adsorption of Hg(2+) under the same experimental conditions. Of particular importance is the preservation of the structure after metal-ion adsorption, which remained virtually intact, with only a few changes in X-ray diffraction intensity and a moderate decline in surface area. Synthesis of the polyoxometalate-containing HKUST-1-MW@H3PW12O40 afforded a MOF with enhanced stability in water, due to the introduced Keggin-type phosphotungstate, which systematically occluded in the cavities constituting the walls between the mesopores. Different Cu/W ratios were investigated according to the extrusion rate of cooper ions concentration, without significant structural changes after adsorption. The MOFs obtained feature particle sizes between 10-20 μm and their structures were determined using synchrotron-based X-ray diffraction. The results of this study can be considered important for potentially wider future applications of MOFs, especially to attend environmental issues. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. Post-synthetic transformation of a Zn(ii) polyhedral coordination network into a new supramolecular isomer of HKUST-1.

    Chen, Yao; Wojtas, Lukasz; Ma, Shengqian; Zaworotko, Michael J; Zhang, Zhenjie

    2017-08-03

    A Zn-based porphyrin containing metal-organic material (porphMOM-1) was transformed into a novel Cu-based porphyrin-encapsulating metal-organic material (porph@HKUST-1-β) via a one-pot post-synthetic modification (PSM) process involving both metal ion exchange and linker installation of trimesic acid. HKUST-1-β is the first example of yao topology and is to our knowledge the first supramolecular isomer of the archetypal coordination network HKUST-1.

  15. Synthesis of novel cellulose- based antibacterial composites of Ag nanoparticles@ metal-organic frameworks@ carboxymethylated fibers.

    Duan, Chao; Meng, Jingru; Wang, Xinqi; Meng, Xin; Sun, Xiaole; Xu, Yongjian; Zhao, Wei; Ni, Yonghao

    2018-08-01

    A novel cellulose-based antibacterial material, namely silver nanoparticles@ metal-organic frameworks@ carboxymethylated fibers composites (Ag NPs@ HKUST-1@ CFs), was synthesized. The results showed that the metal-organic frameworks (HKUST-1) were uniformly anchored on the fiber's surfaces by virtue of complexation between copper ions in HKUST-1 and carboxyl groups on the carboxymethylated fibers (CFs). The silver nanoparticles (Ag NPs) were immobilized and well-dispersed into the pores and/or onto the surfaces of HKUST-1 via in situ microwave reduction, resulting in the formation of novel Ag NPs@ HKUST-1@ CFs composites. The antibacterial assays showed that the as-prepared composites exhibited a much higher antibacterial activity than Ag NPs@ CFs or HKUST-1@ CFs samples. Copyright © 2018 Elsevier Ltd. All rights reserved.

  16. Ultrasonically assisted hydrothermal synthesis of activated carbon-HKUST-1-MOF hybrid for efficient simultaneous ultrasound-assisted removal of ternary organic dyes and antibacterial investigation: Taguchi optimization.

    Azad, F Nasiri; Ghaedi, M; Dashtian, K; Hajati, S; Pezeshkpour, V

    2016-07-01

    Activated carbon (AC) composite with HKUST-1 metal organic framework (AC-HKUST-1 MOF) was prepared by ultrasonically assisted hydrothermal method and characterized by FTIR, SEM and XRD analysis and laterally was applied for the simultaneous ultrasound-assisted removal of crystal violet (CV), disulfine blue (DSB) and quinoline yellow (QY) dyes in their ternary solution. In addition, this material, was screened in vitro for their antibacterial actively against Methicillin-resistant Staphylococcus aureus (MRSA) and Pseudomonas aeruginosa (PAO1) bacteria. In dyes removal process, the effects of important variables such as initial concentration of dyes, adsorbent mass, pH and sonication time on adsorption process optimized by Taguchi approach. Optimum values of 4, 0.02 g, 4 min, 10 mg L(-1) were obtained for pH, AC-HKUST-1 MOF mass, sonication time and the concentration of each dye, respectively. At the optimized condition, the removal percentages of CV, DSB and QY were found to be 99.76%, 91.10%, and 90.75%, respectively, with desirability of 0.989. Kinetics of adsorption processes follow pseudo-second-order model. The Langmuir model as best method with high applicability for representation of experimental data, while maximum mono layer adsorption capacity for CV, DSB and QY on AC-HKUST-1 estimated to be 133.33, 129.87 and 65.37 mg g(-1) which significantly were higher than HKUST-1 as sole material with Qm to equate 59.45, 57.14 and 38.80 mg g(-1), respectively. Copyright © 2016 Elsevier B.V. All rights reserved.

  17. Cu2O-directed in situ growth of Au nanoparticles inside HKUST-1 nanocages.

    Liu, Yongxin; Liu, Ting; Tian, Long; Zhang, Linlin; Yao, Lili; Tan, Taixing; Xu, Jin; Han, Xiaohui; Liu, Dan; Wang, Cheng

    2016-12-07

    Controllable integration of metal nanoparticles (MNPs) and metal-organic frameworks (MOFs) is attracting considerable attention as the obtained composite materials always show synergistic effects in applications of catalysis, delivery, as well as sensing. Herein, a Cu 2 O-directed in situ growth strategy was developed to integrate Au nanoparticles and HKUST-1. In this strategy, Cu 2 O@HKUST-1 core-shell heterostructures, HKUST-1 nanocages, Cu 2 O@Au@HKUST-1 sandwich core-shell heterostructures and Au@HKUST-1 balls-in-cage heterostructures were successfully synthesized. Cu 2 O@HKUST-1 core-shell heterostructures were synthesized by soaking Cu 2 O nanocrystals in benzene-1,3,5-tricarboxylic acid solution. The well-defined Cu 2 O@HKUST-1 core-shell heterostructures were demonstrated to be dominated by the ratio of Cu 2+ cations to btc 3- ligands in solution during the period of HKUST-1 formation. Cu 2 O@Au@HKUST-1 sandwich core-shell or Au@HKUST-1 balls-in-cage heterostructures were obtained by impregnating HAuCl 4 into Cu 2 O@HKUST-1 core-shell heterostructures. Due to the porosity of HKUST-1 and reducibility of Cu 2 O, HAuCl 4 could pass through the HKUST-1 shell and be reduced by the Cu 2 O core in situ forming Au nanoparticles. Finally, CO oxidation reaction at high temperatures was carried out to assess the catalytic functionality of the obtained composite heterostructures. This strategy can circumvent some drawbacks of the existing approaches for integrating MNPs and MOFs, such as nonselective deposition of MNPs at the outer surface of the MOF matrices, extreme treatment conditions and additional surface modifications.

  18. Graphene inclusion controlling conductivity and gas sorption of metal-organic framework

    Lamagni, Paolo; Pedersen, Birgitte Lodberg; Godiksen, Anita; Mossin, Susanne; Hu, Xin Ming; Pedersen, Steen Uttrup; Daasbjerg, Kim; Lock, Nina

    2018-01-01

    A general approach to prepare composite films of metal-organic frameworks and graphene has been developed. Films of copper(ii)-based HKUST-1 and HKUST-1/graphene composites were grown solvothermally on glassy carbon electrodes. The films were chemically tethered to the substrate by diazonium electrografting resulting in a large electrode coverage and good stability in solution for electrochemical studies. HKUST-1 has poor electrical conductivity, but we demonstrate that the addition of graphe...

  19. Oxygen plasma treatment of HKUST-1 for porosity retention upon exposure to moisture.

    Bae, Jaeyeon; Jung, Jin-Woo; Park, Hyo Yul; Cho, Chang-Hee; Park, Jinhee

    2017-11-07

    Despite their remarkable properties, metal-organic frameworks (MOFs) present vulnerable structures that are sensitive to moisture; therefore, their application to real field situations is challenging. Herein, an O 2 plasma technique was introduced as a new method for the activation and protection of porosity in HKUST-1. In an unprecedented manner, O 2 plasma-treated HKUST-1 retains its porosity after a long exposure to moisture as compared to pristine HKUST-1. Porosity retention was examined by N 2 adsorption/desorption measurements of non-activated HKUST-1 after exposure to moisture.

  20. Thermochemistry of paddle wheel MOFs: Cu-HKUST-1 and Zn-HKUST-1.

    Bhunia, Manas K; Hughes, James T; Fettinger, James C; Navrotsky, Alexandra

    2013-06-25

    Metal-organic framework (MOF) porosity relies upon robust metal-organic bonds to retain structural rigidity upon solvent removal. Both the as-synthesized and activated Cu and Zn polymorphs of HKUST-1 were studied by room temperature acid solution calorimetry. Their enthalpies of formation from dense assemblages (metal oxide (ZnO or CuO), trimesic acid (TMA), and N,N-dimethylformamide (DMF)) were calculated from the calorimetric data. The enthalpy of formation (ΔHf) of the as-synthesized Cu-HKUST-H2O ([Cu3TMA2·3H2O]·5DMF) is -52.70 ± 0.34 kJ per mole of Cu. The ΔHf for Zn-HKUST-DMF ([Zn3TMA2·3DMF]·2DMF) is -54.22 ± 0.57 kJ per mole of Zn. The desolvated Cu-HKUST-dg [Cu3TMA2] has a ΔHf of 16.66 ± 0.51 kJ/mol per mole Cu. The ΔHf for Zn-HKUST-amorph [Zn3TMA2·2DMF] is -3.57 ± 0.21 kJ per mole of Zn. Solvent stabilizes the Cu-HKUST-H2O by -69.4 kJ per mole of Cu and Zn-HKUST-DMF by at least -50.7 kJ per mole of Zn. Such strong chemisorption of solvent is similar in magnitude to the strongly exothermic binding at low coverage for chemisorbed H2O on transition metal oxide nanoparticle surfaces. The strongly exothermic solvent-framework interaction suggests that solvent can play a critical role in obtaining a specific secondary building unit (SBU) topology.

  1. Graphene inclusion controlling conductivity and gas sorption of metal-organic framework

    Lamagni, Paolo; Pedersen, Birgitte Lodberg; Godiksen, Anita

    2018-01-01

    A general approach to prepare composite films of metal-organic frameworks and graphene has been developed. Films of copper(ii)-based HKUST-1 and HKUST-1/graphene composites were grown solvothermally on glassy carbon electrodes. The films were chemically tethered to the substrate by diazonium...... electrografting resulting in a large electrode coverage and good stability in solution for electrochemical studies. HKUST-1 has poor electrical conductivity, but we demonstrate that the addition of graphene to HKUST-1 partially restores the electrochemical activity of the electrodes. The enhanced activity......, however, does not result in copper(ii) to copper(i) reduction in HKUST-1 at negative potentials. The materials were characterised in-depth: microscopy and grazing incidence X-ray diffraction demonstrate uniform films of crystalline HKUST-1, and Raman spectroscopy reveals that graphene is homogeneously...

  2. Preparation of Cu@Cu2O Nanocatalysts by Reduction of HKUST-1 for Oxidation Reaction of Catechol

    Seongwan Jang

    2016-11-01

    Full Text Available HKUST-1, a copper-based metal organic framework (MOF, has been investigated as a catalyst in various reactions. However, the HKUST-1 shows low catalytic activity in the oxidation of catechol. Therefore, we synthesized Fe3O4@HKUST-1 by layer-by layer assembly strategy and Cu@Cu2O by reduction of HKUST-1 for enhancement of catalytic activity. Cu@Cu2O nanoparticles exhibited highly effective catalytic activity in oxidation of 3,5-di-tert-butylcatechol. Through this method, MOF can maintain the original core-shell structure and be used in various other reactions with enhanced catalytic activity.

  3. Preparation of Cu@Cu₂O Nanocatalysts by Reduction of HKUST-1 for Oxidation Reaction of Catechol.

    Jang, Seongwan; Yoon, Chohye; Lee, Jae Myung; Park, Sungkyun; Park, Kang Hyun

    2016-11-02

    HKUST-1, a copper-based metal organic framework (MOF), has been investigated as a catalyst in various reactions. However, the HKUST-1 shows low catalytic activity in the oxidation of catechol. Therefore, we synthesized Fe₃O₄@HKUST-1 by layer-by layer assembly strategy and Cu@Cu₂O by reduction of HKUST-1 for enhancement of catalytic activity. Cu@Cu₂O nanoparticles exhibited highly effective catalytic activity in oxidation of 3,5-di- tert -butylcatechol. Through this method, MOF can maintain the original core-shell structure and be used in various other reactions with enhanced catalytic activity.

  4. Preparation of Cu@Cu2O Nanocatalysts by Reduction of HKUST-1 for Oxidation Reaction of Catechol

    Seongwan Jang; Chohye Yoon; Jae Myung Lee; Sungkyun Park; Kang Hyun Park

    2016-01-01

    HKUST-1, a copper-based metal organic framework (MOF), has been investigated as a catalyst in various reactions. However, the HKUST-1 shows low catalytic activity in the oxidation of catechol. Therefore, we synthesized Fe3O4@HKUST-1 by layer-by layer assembly strategy and Cu@Cu2O by reduction of HKUST-1 for enhancement of catalytic activity. Cu@Cu2O nanoparticles exhibited highly effective catalytic activity in oxidation of 3,5-di-tert-butylcatechol. Through this method, MOF can maintain the ...

  5. Copper Metal-Organic Framework Nanoparticles Stabilized with Folic Acid Improve Wound Healing in Diabetes.

    Xiao, Jisheng; Zhu, Yunxiao; Huddleston, Samantha; Li, Peng; Xiao, Baixue; Farha, Omar K; Ameer, Guillermo A

    2018-02-27

    The successful treatment of chronic nonhealing wounds requires strategies that promote angiogenesis, collagen deposition, and re-epithelialization of the wound. Copper ions have been reported to stimulate angiogenesis; however, several applications of copper salts or oxides to the wound bed are required, leading to variable outcomes and raising toxicity concerns. We hypothesized that copper-based metal-organic framework nanoparticles (Cu-MOF NPs), referred to as HKUST-1, which are rapidly degraded in protein solutions, can be modified to slowly release Cu 2+ , resulting in reduced toxicity and improved wound healing rates. Folic acid was added during HKUST-1 synthesis to generate folic-acid-modified HKUST-1 (F-HKUST-1). The effect of folic acid incorporation on NP stability, size, hydrophobicity, surface area, and copper ion release profile was measured. In addition, cytotoxicity and in vitro cell migration processes due to F-HKUST-1 and HKUST-1 were evaluated. Wound closure rates were assessed using the splinted excisional dermal wound model in diabetic mice. The incorporation of folic acid into HKUST-1 enabled the slow release of copper ions, which reduced cytotoxicity and enhanced cell migration in vitro. In vivo, F-HKUST-1 induced angiogenesis, promoted collagen deposition and re-epithelialization, and increased wound closure rates. These results demonstrate that folic acid incorporation into HKUST-1 NPs is a simple, safe, and promising approach to control Cu 2+ release, thus enabling the direct application of Cu-MOF NPs to wounds.

  6. A metal-organic framework nanocomposite made from functionalized magnetite nanoparticles and HKUST-1 (MOF-199) for preconcentration of Cd(II), Pb(II), and Ni(II)

    Ghorbani-Kalhor, Ebrahim

    2016-01-01

    The author describes the preparation of a magnetic metal organic framework of type MOF-199 containing magnetite (Fe 3 O 4 ) nanoparticles carrying covalently immobilized 4-(thiazolylazo) resorcinol (Fe 3 O 4 -TAR). This material is shown to represent a viable sorbent for separation and preconcentration of Cd(II), Pb(II), and Ni(II) ions. Box-Behnken design was applied to optimize the parameters affecting preconcentration. Following elution with 0.6 mol L −1 EDTA, the ions were quantified by FAAS. The capacity of the sorbent ranged between 185 and 210 mg g −1 . The limits of detection are 0.15, 0.40, and 0.8 ng mL −1 for Cd(II), Ni(II), and Pb(II) ions, respectively. The relative standard deviations are <8.5 %. The method was successfully applied to the rapid extraction of trace amounts of these ions from sea food and agri food. (author)

  7. In situ preparation of multilayer coated capillary column with HKUST-1 for separation of neutral small organic molecules by open tubular capillary electrochromatography.

    Xu, Yin-Yin; Lv, Wen-Juan; Ren, Cui-Ling; Niu, Xiao-Ying; Chen, Hong-Li; Chen, Xing-Guo

    2018-01-12

    The popularity of novel nanoparticles coated capillary column has aroused widespread attention of researchers. Metal organic frameworks (MOFs) with special structure and chemical properties have received great interest in separation sciences. This work presents the investigation of HKUST-1 (Hong Kong University of Science and Technology-1, called Cu 3 (BTC) 2 or MOF-199) nanoparticles as a new type of coating material for capillary electrochromatography. For the first time, three layers coating (3-LC), five layers coating (5-LC), ten layers coating (10-LC), fifteen layers coating (15-LC), twenty layers coating(20-LC) and twenty-five layers coating (25-LC) capillary columns coated with HKUST-1 nanoparticles were synthesized by covalent bond with in situ, layer-by-layer self-assembly approach. The results of scanning electron microscopy (SEM), X-ray diffraction (XRD) and plasma atomic emission spectrometry (ICP-AES) indicated that HKUST-1 was successfully grafted on the inner wall of the capillary. The separating performances of 3-LC, 5-LC, 10-LC, 15-LC, 20-LC and 25-LC open tubular (OT) capillary columns were studied with some neutral small organic molecules. The results indicated that the neutral small organic molecules were separated successfully with 10-LC, 15-LC and 20-LC OT capillary columns because of the size selectivity of lattice aperture and hydrophobicity of organic ligands. In addition, 10-LC and 15-LC OT capillary columns showed better performance for the separation of certain phenolic compounds. Furthermore, 10-LC, 15-LC and 20-LC OT capillary columns exhibited good intra-day repeatability with the relative standard deviations (RSDs; %) of migration time and peak areas lying in the range of 0.3-1.2% and 0.5-4.2%, respectively. For inter-day reproducibility, the RSDs of the three OT capillary columns were found to be lying in the range of 0.3-5.5% and 0.3-4.5% for migration time and peak area, respectively. The RSDs of retention times for column

  8. Computational modeling of Metal-Organic Frameworks

    Sung, Jeffrey Chuen-Fai

    In this work, the metal-organic frameworks MIL-53(Cr), DMOF-2,3-NH 2Cl, DMOF-2,5-NH2Cl, and HKUST-1 were modeled using molecular mechanics and electronic structure. The effect of electronic polarization on the adsorption of water in MIL-53(Cr) was studied using molecular dynamics simulations of water-loaded MIL-53 systems with both polarizable and non-polarizable force fields. Molecular dynamics simulations of the full systems and DFT calculations on representative framework clusters were utilized to study the difference in nitrogen adsorption between DMOF-2,3-NH2Cl and DMOF-2,5-NH 2Cl. Finally, the control of proton conduction in HKUST-1 by complexation of molecules to the Cu open metal site was investigated using the MS-EVB methodology.

  9. Synthesis of Nickel (Ni) Doped HKUST-1 Using Solvotermal Method with Addition of Acetic Acid as Modulator

    Safii, Farhan Fikri; Ediati, Ratna

    2015-01-01

    Hong Kong University of Science and Technology-1 (HKUST-1) is metal organic framework (MOF) that composed from ligand BTC (1,3,5-benzene tricarboxylic) and copper ions. The method used in this study is solvotermal with variations nickel ion doping and additions acetic acid as modulator. The purpose of this study is to increase the hydrogen storage capacity. The results obtained were characterized by XRD showed that the HKUST-1 and Ni-HKUST-1 has formed, showed by peaks at 2 theta = 6.7, 9.5, ...

  10. Structure stability of HKUST-1 towards water and ethanol and their effect on its CO2 capture properties.

    Álvarez, J Raziel; Sánchez-González, Elí; Pérez, Eric; Schneider-Revueltas, Emilia; Martínez, Ana; Tejeda-Cruz, Adriana; Islas-Jácome, Alejandro; González-Zamora, Eduardo; Ibarra, Ilich A

    2017-07-18

    Water and ethanol stabilities of the crystal structure of the Cu-based metal-organic framework (MOF) HKUST-1 have been investigated. Vapour (water and ethanol) sorption isotherms and cyclability were measured by a dynamic strategy. The ethanol sorption capacity of HKUST-1 at 303 K remained unchanged contrasting water sorption (which decreased along with the sorption experiment time). Considering the binding energy of each sorbate with the open Cu(ii) sites, obtained by the use of diffusion coefficients, we showed the superior crystal stability of the HKUST-1 framework towards ethanol. Finally, a small quantity of ethanol (pre-adsorbed) slightly enhanced CO 2 capture without crystal structure degradation.

  11. Humidity Detection Using Metal Organic Framework Coated on QCM

    Kosuru, Lakshmoji

    2016-06-28

    Quartz crystal microbalance (QCM) coated with poly-4-vinylpyridine (PVP) and metal organic framework HKUST-1 are investigated and compared for humidity sensing. Drop casting method is employed to coat the PVP and HKUST-1 solutions onto the surface of a quartz crystal microbalance. The resonance frequencies of these sensors with varying relative humidity (RH) from 22% RH to 69% RH are measured using impedance analysis method. The sensitivity, humidity hysteresis, response, and recovery times of these sensors are studied. The sensitivities of uncoated, PVP, and HKUST-1 coated QCM sensors are 7 Hz, 48 Hz, and 720 Hz, respectively, in the range of 22% RH–69% RH. The extraction of desorption rate and adsorption energy associated with the adsorption and desorption of water molecules on these surfaces reveals that HKUST-1 has better sensing properties than PVP and uncoated QCM sensors. In this work, the HKUST-1 coated QCM is shown to be a promising material for moisture detection.

  12. Humidity Detection Using Metal Organic Framework Coated on QCM

    Lakshmoji Kosuru

    2016-01-01

    Full Text Available Quartz crystal microbalance (QCM coated with poly-4-vinylpyridine (PVP and metal organic framework HKUST-1 are investigated and compared for humidity sensing. Drop casting method is employed to coat the PVP and HKUST-1 solutions onto the surface of a quartz crystal microbalance. The resonance frequencies of these sensors with varying relative humidity (RH from 22% RH to 69% RH are measured using impedance analysis method. The sensitivity, humidity hysteresis, response, and recovery times of these sensors are studied. The sensitivities of uncoated, PVP, and HKUST-1 coated QCM sensors are 7 Hz, 48 Hz, and 720 Hz, respectively, in the range of 22% RH–69% RH. The extraction of desorption rate and adsorption energy associated with the adsorption and desorption of water molecules on these surfaces reveals that HKUST-1 has better sensing properties than PVP and uncoated QCM sensors. In this work, the HKUST-1 coated QCM is shown to be a promising material for moisture detection.

  13. Metal-organic framework thin films on a surface of optical fibre long period grating for chemical sensing

    Hromadka, J.; Tokay, B.; James, S.; Korposh, S.

    2017-04-01

    An optical fibre long period grating (LPG) modified with a thin film of HKUST-1, a material from metal organic framework (MOF) family, was employed for the detection of carbon dioxide. The sensing mechanism is based on the measurement of the change of the refractive index (RI) of the coating that is induced by the penetration of CO2 molecules into the HKUST-1 pores. The responses of the resonance bands in the transmission spectrum of an LPG modified with 40 layers of HKUST-1 upon exposure to carbon dioxide in mixture with nitrogen were investigated.

  14. Mg2+ Doped into Electro-synthesized HKUST-1 and Their Initial Hydrogen Sorption Properties

    Lestari, W. W.; Ni'maturrohmah, D.; Arrozi, U. S. F.; Suwarno, H.

    2018-01-01

    The hydrogen storage materials are essentially play important roles in supporting the utilization of hydrogen as a promising alternative energy. Several innovative materials have been proposed and intensively investigated in this regard, including Metal-Organic Framework (MOFs). MOFs type HKUST-1 [Cu3(BTC)2] (BTC = benzene-tri-carboxylate) is the most explored materials in hydrogen storage. In this research, HKUST-1 was electro-synthesized under 15 volt for 1.5 h. This material was ex-situ modified with magnesium(II) ion with variation: 3, 5 and 10 wt% to add attractive sites for hydrogen to form Mg2+@HKUST-1. The final materials were characterized by XRD, FTIR, SEM-EDX, and SAA. Hydrogen sorption measurement was conducted using Sievert system at 30 and 80 °C with pressure from 0.2 to 1.5 bar in 10 minutes for each condition. According to XRD analysis, the basic structure of Mg2+@HKUST-1 was remaining stable. In contrary, SEM analysis showed that HKUST-1 morphology was changed after modification with Mg2+. In addition, the surface area of materials significantly increased from 372.112 to 757.617m2/g, based on SAA analysis. The presence of Mg2+ in the HKUST-1 increased the hydrogen sorption capacity up to 0.475 wt% at 1.4 bar at 30 °C and 0.256 wt% at 80 °C (1.4 bar).

  15. Fe3O4@HKUST-1 and Pd/Fe3O4@ HKUST-1 as magnetically recyclable catalysts prepared via conversion from a Cu-based ceramic

    Toyao, Takashi; Styles, Mark J.; Yago, Tokuichiro; Sadiq, Muhammad M.; Ricco, Raffaele; Suzuki, Kiyonori; Horiuchi, Yu; Takahashi, Masahide; Matsuoka, Masaya; Falcaro, Paolo

    2017-01-01

    Nanocomposites obtained by integrating iron oxide magnetic nanoparticles (Fe3O4) into a metal-organic framework (HKUST-1 or Cu-3(BTC)(2), BTC = 1,3,5-benzenetricarboxylate) are synthesized through conversion from a composite of a Cu-based ceramic material and Fe3O4. In situ small-angle X-ray scattering (SAXS) and wide-angle X-ray scattering (WAXS) measurements reveal that the presence of Fe3O4 leads to the fast conversion and synthesis of HKUST-1 with small particle sizes. The prepared MOF co...

  16. A Cooperative Copper Metal-Organic Framework-Hydrogel System Improves Wound Healing in Diabetes.

    Xiao, Jisheng; Chen, Siyu; Yi, Ji; Zhang, Hao; Ameer, Guillermo A

    2017-01-05

    Chronic non-healing wounds remain a major clinical challenge that would benefit from the development of advanced, regenerative dressings that promote wound closure within a clinically relevant time frame. The use of copper ions has shown promise in wound healing applications possibly by promoting angiogenesis. However, reported treatments that use copper ions require multiple applications of copper salts or oxides to the wound bed, exposing the patient to potentially toxic levels of copper ions and resulting in variable outcomes. Herein we set out to assess whether copper metal organic framework nanoparticles (HKUST-1 NPs) embedded within an antioxidant thermoresponsive citrate-based hydrogel would decrease copper ion toxicity and accelerate wound healing in diabetic mice. HKUST-1 and poly-(polyethyleneglycol citrate-co- N -isopropylacrylamide) (PPCN) were synthesized and characterized. HKUST-1 NP stability in a protein solution with and without embedding them in PPCN hydrogel was determined. Copper ion release, cytotoxicity, apoptosis, and in vitro migration processes were measured. Wound closure rates and wound blood perfusion were assessed in vivo using the splinted excisional dermal wound diabetic mouse model. HKUST-1 NP disintegrated in protein solution while HKUST-1 NPs embedded in PPCN (H-HKUST-1) were protected from degradation and copper ions were slowly released. Cytotoxicity and apoptosis due to copper ion release were significantly reduced while dermal cell migration in vitro and wound closure rates in vivo were significantly enhanced. In vivo , H-HKUST-1 induced angiogenesis, collagen deposition, and re-epithelialization during wound healing in diabetic mice. These results suggest that a cooperatively stabilized, copper ion-releasing H-HKUST-1 hydrogel is a promising innovative dressing for the treatment of chronic wounds.

  17. MoS2 @HKUST-1 Flower-Like Nanohybrids for Efficient Hydrogen Evolution Reactions.

    Wang, Chengli; Su, Yingchun; Zhao, Xiaole; Tong, Shanshan; Han, Xiaojun

    2018-01-24

    A novel MoS 2 -based flower-like nanohybrid for hydrogen evolution was fabricated through coating the Cu-containing metal-organic framework (HKUST-1) onto MoS 2 nanosheets. It is the first time that MoS 2 @HKUST-1 nanohybrids have been reported for the enhanced electrochemical performance of HER. The morphologies and components of the MoS 2 @HKUST-1 flower-like nanohybrids were characterized by scanning electron microscopy, X-ray diffraction analysis and Fourier transform infrared spectroscopy. Compared with pure MoS 2 , the MoS 2 @HKUST-1 hybrids exhibit enhanced performance on hydrogen evolution reaction with an onset potential of -99 mV, a smaller Tafel slope of 69 mV dec -1 , and a Faradaic efficiency of nearly 100 %. The MoS 2 @HKUST-1 flower-like nanohybrids exhibit excellent stability in acidic media. This design opens new possibilities to effectively synthesize non-noble metal catalysts with high performance for the hydrogen evolution reaction (HER). © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. Physikochemische Untersuchung der Analyt – HKUST-1 Wechselwirkung unter Verwendung der inversen Gaschromatographie

    Münch, Alexander

    2013-01-01

    Die vorliegende Arbeit hat neben der Untersuchung der Synthese über den Controlled SBU-Approach von HKUST-1, ein poröses Kupfertrimesat, die Abscheidung dieses Metal-Organic Frameworks in dünnen Quarzglaskapillaren mit einer Länge von 10 bis 30 m und Innendurchmessern zwischen 0,53 und 0,25 mm zum Thema. Diese Säulen werden zur gaschromatographischen Trennung wie auch zur Bestimmung physikochemischer Kenngrößen, die den Adsorptionsvorgang verschiedener Analyten auf der HKUST-1 Oberfläche besc...

  19. Enhanced aging properties of HKUST-1 in hydrophobic mixed-matrix membranes for ammonia adsorption.

    DeCoste, Jared B; Denny, Michael S; Peterson, Gregory W; Mahle, John J; Cohen, Seth M

    2016-04-21

    Metal-organic frameworks (MOFs) in their free powder form have exhibited superior capacities for many gases when compared to other materials, due to their tailorable functionality and high surface areas. Specifically, the MOF HKUST-1 binds small Lewis bases, such as ammonia, with its coordinatively unsaturated copper sites. We describe here the use of HKUST-1 in mixed-matrix membranes (MMMs) prepared from polyvinylidene difluoride (PVDF) for the removal of ammonia gas. These MMMs exhibit ammonia capacities similar to their hypothetical capacities based on the weight percent of HKUST-1 in each MMM. HKUST-1 in its powder form is unstable toward humid conditions; however, upon exposure to humid environments for prolonged periods of time, the HKUST-1 MMMs exhibit outstanding structural stability, and maintain their ammonia capacity. Overall, this study has achieved all of the critical and combined elements for real-world applications of MOFs: high MOF loadings, fully accessible MOF surfaces, enhanced MOF stabilization, recyclability, mechanical stability, and processability. This study is a critical step in advancing MOFs to a stable, usable, and enabling technology.

  20. Enhanced Hydrothermal Stability and Catalytic Performance of HKUST-1 by Incorporating Carboxyl-Functionalized Attapulgite.

    Yuan, Bo; Yin, Xiao-Qian; Liu, Xiao-Qin; Li, Xing-Yang; Sun, Lin-Bing

    2016-06-29

    Much attention has been paid to metal-organic frameworks (MOFs) due to their large surface areas, tunable functionality, and diverse structure. Nevertheless, most reported MOFs show poor hydrothermal stability, which seriously hinders their applications. Here a strategy is adopted to tailor the properties of MOFs by means of incorporating carboxyl-functionalized natural clay attapulgite (ATP) into HKUST-1, a well-known MOF. A new type of hybrid material was thus fabricated from the hybridization of HKUST-1 and ATP. Our results indicated that the hydrothermal stability of the MOFs as well as the catalytic performance was apparently improved. The frameworks of HKUST-1 were severely destroyed after hydrothermal treatment (hot water vapor, 60 °C), while that of the hybrid materials was maintained. For the hybrid materials containing 8.4 wt % of ATP, the surface area reached 1302 m(2)·g(-1) and was even higher than that of pristine HKUST-1 (1245 m(2)·g(-1)). In the ring-opening of styrene oxide, the conversion reached 98.9% at only 20 min under catalysis from the hybrid material, which was obviously higher than that over pristine HKUST-1 (80.9%). Moreover, the hybrid materials showed excellent reusability and the catalytic activity was recoverable without loss after six cycles. Our materials provide promising candidates for heterogeneous catalysis owing to the good catalytic activity and reusability.

  1. Strategy for chemotherapeutic delivery using a nanosized porous metal-organic framework with a central composite design.

    Li, Yingpeng; Li, Xiuyan; Guan, Qingxia; Zhang, Chunjing; Xu, Ting; Dong, Yujing; Bai, Xinyu; Zhang, Weiping

    2017-01-01

    Enhancing drug delivery is an ongoing endeavor in pharmaceutics, especially when the efficacy of chemotherapy for cancer is concerned. In this study, we prepared and evaluated nanosized HKUST-1 (nanoHKUST-1), nanosized metal-organic drug delivery framework, loaded with 5-fluorouracil (5-FU) for potential use in cancer treatment. NanoHKUST-1 was prepared by reacting copper (II) acetate [Cu(OAc) 2 ] and benzene-1,3,5-tricarboxylic acid (H 3 BTC) with benzoic acid (C 6 H 5 COOH) at room temperature (23.7°C±2.4°C). A central composite design was used to optimize 5-FU-loaded nanoHKUST-1. Contact time, ethanol concentration, and 5-FU:material ratios were the independent variables, and the entrapment efficiency of 5-FU was the response parameter measured. Powder X-ray diffraction, scanning electron microscopy (SEM), transmission electron microscopy (TEM), and nitrogen adsorption were used to determine the morphology of nanoHKUST-1. In addition, 5-FU release studies were conducted, and the in vitro cytotoxicity was evaluated. Entrapment efficiency and drug loading were 9.96% and 40.22%, respectively, while the small-angle X-ray diffraction patterns confirmed a regular porous structure. The SEM and TEM images of the nanoHKUST-1 confirmed the presence of round particles (diameter: approximately 100 nm) and regular polygon arrays of mesoporous channels of approximately 2-5 nm. The half-maximal lethal concentration (LC 50 ) of the 5-FU-loaded nanoHKUST-1 was approximately 10 µg/mL. The results indicated that nanoHKUST-1 is a potential vector worth developing as a cancer chemotherapeutic drug delivery system.

  2. Direct in Situ Conversion of Metals into Metal-Organic Frameworks: A Strategy for the Rapid Growth of MOF Films on Metal Substrates.

    Ji, Hoon; Hwang, Sunhyun; Kim, Keonmok; Kim, CheolGi; Jeong, Nak Cheon

    2016-11-30

    The fabrication of metal-organic framework (MOF) films on conducting substrates has demonstrated great potential in applications such as electronic conduction and sensing. For these applications, direct contact of the film to the conducting substrate without a self-assembled monolayer (SAM) is a desired step that must be achieved prior to the use of MOF films. In this report, we propose an in situ strategy for the rapid one-step conversion of Cu metal into HKUST-1 films on conducting Cu substrates. The Cu substrate acts both as a conducting substrate and a source of Cu 2+ ions during the synthesis of HKUST-1. This synthesis is possible because of the simultaneous reaction of an oxidizing agent and a deprotonating agent, in which the former agent dissolves the metal substrate to form Cu 2+ ions while the latter agent deprotonates the ligand. Using this strategy, the HKUST-1 film could not only be rapidly synthesized within 5 min but also be directly attached to the Cu substrate. Based on microscopic studies, we propose a plausible mechanism for the growth reaction. Furthermore, we show the versatility of this in situ conversion methodology, applying it to ZIF-8, which comprises Zn 2+ ions and imidazole-based ligands. Using an I 2 -filled HKUST-1 film, we further demonstrate that the direct contact of the MOF film to the conducting substrate makes the material more suitable for use as a sensor or electronic conductor.

  3. Tuning of Nafion® by HKUST-1 as coordination network to enhance proton conductivity for fuel cell applications

    Kim, Hee Jin; Talukdar, Krishan; Choi, Sang-June

    2016-01-01

    Metal-organic frameworks can be intentionally coordinated to achieve improved proton conductivity because they have highly ordered structures and modular nature that serve as a scaffold to anchor acidic groups and develop efficient proton transfer pathways for fuel cell application. Using the concept of a coordination network, the conductivity of Nafion ® was tuned by the incorporation of HKUST-1. It has Cu II –paddle wheel type nodes and 1,3,5-benzenetricarboxylate struts, feature accessible sites that provides an improved protonic channel depending on the water content. In spite of the fact that HKUST-1 is neutral, coordinated water molecules are contributed adequately acidic by Cu II to supply protons to enhance proton conductivity. Water molecules play a vital part in transfer of proton as conducting media and serve as triggers to change proton conductivity through reforming hydrogen bonding networks by water adsorption/desorption process. Increased ion exchange capacity and proton conductivity with lower water uptake of the H 3 PO 4 -doped material, and improved thermal stability (as confirmed by thermogravimetric analysis) were achieved. The structure of HKUST-1 was confirmed via field emission scanning electron microscopy and X-ray diffraction, while the porosity and adsorption desorption capacity were characterized by porosity analysis. Graphical abstract: The H 3 PO 4 -doped HKUST-1/Nafion® composite membrane is demonstrated to be a promising material based on its proton conductivity. HKUST-1 has an average particle diameter of around 15–20 µm. The proton conductivity, IEC values, and the thermal stability of the 2.5 wt% HKUST-1/Nafion® composite membrane suggest that HKUST-1 may be a promising candidate as a proton-conductive material in the polymer electrolyte fuel cell membrane due to its reasonable proton passageway, favorable surface area, lower water uptake with the higher IEC, and proton conductivity of the H 3 PO 4 -doped material and

  4. Metallated metal-organic frameworks

    Bury, Wojciech; Farha, Omar K.; Hupp, Joseph T.; Mondloch, Joseph E.

    2017-08-22

    Porous metal-organic frameworks (MOFs) and metallated porous MOFs are provided. Also provided are methods of metallating porous MOFs using atomic layer deposition and methods of using the metallated MOFs as catalysts and in remediation applications.

  5. Pressure-assisted synthesis of HKUST-1 thin film on polymer hollow fiber at room temperature toward gas separation.

    Mao, Yiyin; Li, Junwei; Cao, Wei; Ying, Yulong; Sun, Luwei; Peng, Xinsheng

    2014-03-26

    The scalable fabrication of continuous and defect-free metal-organic framework (MOF) films on the surface of polymeric hollow fibers, departing from ceramic supported or dense composite membranes, is a huge challenge. The critical way is to reduce the growth temperature of MOFs in aqueous or ethanol solvents. In the present work, a pressure-assisted room temperature growth strategy was carried out to fabricate continuous and well-intergrown HKUST-1 films on a polymer hollow fiber by using solid copper hydroxide nanostrands as the copper source within 40 min. These HKUST-1 films/polyvinylidenefluoride (PVDF) hollow fiber composite membranes exhibit good separation performance for binary gases with selectivity 116% higher than Knudsen values via both inside-out and outside-in modes. This provides a new way to enable for scale-up preparation of HKUST-1/polymer hollow fiber membranes, due to its superior economic and ecological advantages.

  6. Bi2O3 nanoparticles encapsulated in surface mounted metal-organic framework thin films

    Guo, Wei; Chen, Zhi; Yang, Chengwu; Neumann, Tobias; Kübel, Christian; Wenzel, Wolfgang; Welle, Alexander; Pfleging, Wilhelm; Shekhah, Osama; Wöll, Christof; Redel, Engelbert

    2016-03-01

    We describe a novel procedure to fabricate a recyclable hybrid-photocatalyst based on Bi2O3@HKUST-1 MOF porous thin films. Bi2O3 nanoparticles (NPs) were synthesized within HKUST-1 (or Cu3(BTC)2) surface-mounted metal-organic frame-works (SURMOFs) and characterized using X-ray diffraction (XRD), a quartz crystal microbalance (QCM) and transmission electron microscopy (TEM). The Bi2O3 semiconductor NPs (diameter 1-3 nm)/SURMOF heterostructures exhibit superior photo-efficiencies compared to NPs synthesized using conventional routes, as demonstrated via the photodegradation of the nuclear fast red (NFR) dye.We describe a novel procedure to fabricate a recyclable hybrid-photocatalyst based on Bi2O3@HKUST-1 MOF porous thin films. Bi2O3 nanoparticles (NPs) were synthesized within HKUST-1 (or Cu3(BTC)2) surface-mounted metal-organic frame-works (SURMOFs) and characterized using X-ray diffraction (XRD), a quartz crystal microbalance (QCM) and transmission electron microscopy (TEM). The Bi2O3 semiconductor NPs (diameter 1-3 nm)/SURMOF heterostructures exhibit superior photo-efficiencies compared to NPs synthesized using conventional routes, as demonstrated via the photodegradation of the nuclear fast red (NFR) dye. Electronic supplementary information (ESI) available. See DOI: 10.1039/c6nr00532b

  7. Metal-Organic Frameworks for Resonant-Gravimetric Detection of Trace-Level Xylene Molecules.

    Xu, Tao; Xu, Pengcheng; Zheng, Dan; Yu, Haitao; Li, Xinxin

    2016-12-20

    As one of typical VOCs, xylene is seriously harmful to human health. Nowadays, however, there is really lack of portable sensing method to directly detect environmental xylene that has chemical inertness. Especially when the concentration of xylene is lower than the human olfactory threshold of 470 ppb, people are indeed hard to be aware of and avoid this harmful vapor. Herein the metal-organic framework (MOF) of HKUST-1 is first explored for sensing to the nonpolar molecule of p-xylene. And the sensing mechanism is identified that is via host-guest interaction of MOF with xylene molecule. By loading MOFs on mass-gravimetric resonant-cantilevers, sensing experiments for four MOFs of MOF-5, HKUST-1, ZIF-8, and MOF-177 approve that HKUST-1 has the highest sensitivity to p-xylene. The resonant-gravimetric sensing experiments with our HKUST-1 based sensors have demonstrated that trace-level p-xylene of 400 ppb can be detected that is lower than the human olfactory threshold of 470 ppb. We analyze that the specificity of HKUST-1 to xylene comes from Cu 2+ -induced moderate Lewis acidity and the "like dissolves like" interaction of the benzene ring. In situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) is used to elucidate the adsorbing/sensing mechanism of HKUST-1 to p-xylene, where p-xylene adsorbing induced blue-shift phenomenon is observed that confirms the sensing mechanism. Our study also indicates that the sensor shows good selectivity to various kinds of common interfering gases. And the long-term repeatability and stability of the sensing material are also approved for the usage/storage period of two months. This research approves that the MOF materials exhibit potential usages for high performance chemical sensors applications.

  8. Investigation by raman spectroscopy of the decomposition process of HKUST-1 upon exposure to air

    Todaro, M.; Alessi, A.; Sciortino, L.; Agnello, S.; Cannas, M.; Gelardi, F.; Buscarino, G.

    2016-01-01

    We report an experimental investigation by Raman spectroscopy of the decomposition process of Metal-Organic Framework (MOF) HKUST-1 upon exposure to air moisture (T=300 K, 70% relative humidity). The data collected here are compared with the indications obtained from a model of the process of decomposition of this material proposed in literature. In agreement with that model, the reported Raman measurements indicate that for exposure times longer than 20 days relevant irreversible processes t...

  9. Specific oriented metal-organic framework membranes and their facet-tuned separation performance.

    Mao, Yiyin; Su, Binbin; Cao, Wei; Li, Junwei; Ying, Yulong; Ying, Wen; Hou, Yajun; Sun, Luwei; Peng, Xinsheng

    2014-09-24

    Modulating the crystal morphology, or the exposed crystal facets, of metal-organic frameworks (MOFs) expands their potential applications in catalysis, adsorption, and separation. In this article, by immobilizing the citrate modulators on Au nanoparticles and subsequently being fixed on solid copper hydroxide nanostrands, a well-intergrown and oriented HKUST-1 cube crystal membrane was formed at room temperature. In contrast, in the absence of Au nanoparticles, well-intergrown and oriented cuboctahedron and octahedron membranes were formed in water/ethanol and ethanol, respectively. The gas separation performances of these HKUST-1 membranes were tuned via their exposed facets with defined pore sizes. The HKUST-1 cube membrane with exposed {001} facets demonstrated the highest permeance but lowest gas binary separation factors, while the octahedron membrane with exposed {111} facets presented the highest separation factors but lowest permeance, since the window size of {111} facets is 0.46 nm which is smaller than 0.9 nm of {001} facets. Separation of 0.38 nm CO2 from 0.55 nm SF6 was realized by the HKUST-1 octahedron membrane. As a proof of concept, this will open a new way to design MOF-related separation membranes by facet controlling.

  10. Insights into chromatographic separation using core-shell metal-organic frameworks: Size exclusion and polarity effects.

    Qin, Weiwei; Silvestre, Martin E; Kirschhöfer, Frank; Brenner-Weiss, Gerald; Franzreb, Matthias

    2015-09-11

    Porous metal-organic frameworks (MOFs) [Cu3(BTC)2(H2O)3]n (also known as HKUST-1; BTC, benzene-1,3,5-tricarboxylic acid) were synthesized as homogeneous shell onto carboxyl functionalized magnetic microparticles through a liquid phase epitaxy (LPE) process. The as-synthesized core-shell HKUST-1 magnetic microparticles composites were characterized by XRD and SEM, and used as stationary phase in high performance liquid chromatography (HPLC). The effects of the unique properties of MOFs onto the chromatographic performance are demonstrated by the experiments. First, remarkable separation of pyridine and bipyridine is achieved, although both molecules show a strong interaction between the Cu-ions in HKUST-1 and the nitrogen atoms in their heterocyles. The difference can be explained due to size exclusion of bipyridine from the well defined pore structure of crystalline HKUST-1. Second, the enormous variety of possible interactions of sample molecules with the metal ions and linkers within MOFs allows for specifically tailored solid phases for challenging separation tasks. For example, baseline separation of three chloroaniline (CLA) isomers tested can be achieved without the need for gradient elution modes. Along with the experimental HPLC runs, in-depth modelling with a recently developed chromatography modelling software (ChromX) was applied and proofs the software to be a powerful tool for exploring the separation potential of thin MOF films. The pore diffusivity of pyridine and CLA isomers within HKUST-1 are found to be around 2.3×10(-15)m(2)s(-1). While the affinity of HKUST-1 to the tested molecules strongly differs, the maximum capacities are in the same range, with 0.37molL(-1) for pyridine and 0.23molL(-1) for CLA isomers, corresponding to 4.0 and 2.5 molecules per MOF unit cell, respectively. Copyright © 2015 Elsevier B.V. All rights reserved.

  11. Enhanced Hydrogen Storage Capacity over Electro-synthesized HKUST-1

    Witri Wahyu Lestari

    2017-12-01

    Full Text Available HKUST-1 [Cu3(1,3,5-BTC2] (BTC = benzene-tri-carboxylate was synthesized using an electrochemical method and tested for hydrogen storage. The obtained material showed a remarkably higher hydrogen uptake over reported HKUST-1 and reached until 4.75 wt% at room temperature and low pressure up to 1.2 bar. This yield was compared to HKUST-1 obtained from the solvothermal method, which showed a hydrogen uptake of only 1.19 wt%. Enhancement of hydrogen sorption of the electro-synthesized product was due to the more appropriate surface area and pore size, effected by the preferable physical interaction between the hydrogen gasses and the copper ions as unsaturated metal centers in the frameworks of HKUST-1.

  12. Dubinin-Astakhov model for acetylene adsorption on metal-organic frameworks

    Cheng, Peifu; Hu, Yun Hang

    2016-01-01

    Graphical abstract: It was demonstrated that Dubinin-Astakhov equation can be exploited as a general isotherm model for C2H2 adsorption on metal-organic frameworks (MOFs), including MOF-5, ZIF-8, HKUST-1, and MIL-53. - Highlights: • Dubinin-Astakhov equation is demonstrated to be a general model for C_2H_2 adsorption on metal-organic frameworks (MOFs). • Surface areas obtained with Dubinin-Astakhov equation from C_2H_2 adsorption on MOFs are consistent with BET surface areas from N_2 adsorption. • C_2H_2 on MOF-5, ZIF-8, and MIL-53 is a physical adsorption, whereas its adsorption on HKUST-1 is due to a chemical bonding. - Abstract: Acetylene (C_2H_2) is explosive at a pressure above 29 psi, causing a safety issue for its storage and applications. C_2H_2 adsorption on metal-organic frameworks (MOFs) has been explored to solve the issue. However, a suitable isotherm equation for C_2H_2 adsorption on various MOFs has not been found. In this paper, it was demonstrated that Dubinin-Astakhov equation can be exploited as a general isotherm model to depict C_2H_2 adsorption on MOF-5, ZIF-8, HKUST-1, and MIL-53. In contrast, commonly used Langmuir and BET models exhibited their inapplicability for C_2H_2 adsorption on those MOFs.

  13. Deposition of metal-organic frameworks by liquid-phase epitaxy: The influence of substrate functional group density on film orientation

    Liu, J.

    2012-09-05

    The liquid phase epitaxy (LPE) of the metal-organic framework (MOF) HKUST-1 has been studied for three different COOH-terminated templating organic surfaces prepared by the adsorption of self-assembled monolayers (SAMs) on gold substrates. Three different SAMs were used, mercaptohexadecanoic acid (MHDA), 4\\'-carboxyterphenyl-4-methanethiol (TPMTA) and 9-carboxy-10-(mercaptomethyl)triptycene (CMMT). The XRD data demonstrate that highly oriented HKUST-1 SURMOFs with an orientation along the (100) direction was obtained on MHDA-SAMs. In the case of the TPMTA-SAM, the quality of the deposited SURMOF films was found to be substantially inferior. Surprisingly, for the CMMT-SAMs, a different growth direction was obtained; XRD data reveal the deposition of highly oriented HKUST-1 SURMOFs grown along the (111) direction.

  14. Deposition of metal-organic frameworks by liquid-phase epitaxy: The influence of substrate functional group density on film orientation

    Liu, J.; Shekhah, O.; Stammer, X.; Arslan, H.K.; Liu, B.; Schupbach, B.; Terfort, A.; Woll, C.

    2012-01-01

    The liquid phase epitaxy (LPE) of the metal-organic framework (MOF) HKUST-1 has been studied for three different COOH-terminated templating organic surfaces prepared by the adsorption of self-assembled monolayers (SAMs) on gold substrates. Three different SAMs were used, mercaptohexadecanoic acid (MHDA), 4'-carboxyterphenyl-4-methanethiol (TPMTA) and 9-carboxy-10-(mercaptomethyl)triptycene (CMMT). The XRD data demonstrate that highly oriented HKUST-1 SURMOFs with an orientation along the (100) direction was obtained on MHDA-SAMs. In the case of the TPMTA-SAM, the quality of the deposited SURMOF films was found to be substantially inferior. Surprisingly, for the CMMT-SAMs, a different growth direction was obtained; XRD data reveal the deposition of highly oriented HKUST-1 SURMOFs grown along the (111) direction.

  15. Deposition of Metal-Organic Frameworks by Liquid-Phase Epitaxy: The Influence of Substrate Functional Group Density on Film Orientation

    Liu, Jinxuan; Shekhah, Osama; Stammer, Xia; Arslan, Hasan K.; Liu, Bo; Schüpbach, Björn; Terfort, Andreas; Wöll, Christof

    2012-01-01

    The liquid phase epitaxy (LPE) of the metal-organic framework (MOF) HKUST-1 has been studied for three different COOH-terminated templating organic surfaces prepared by the adsorption of self-assembled monolayers (SAMs) on gold substrates. Three different SAMs were used, mercaptohexadecanoic acid (MHDA), 4’-carboxyterphenyl-4-methanethiol (TPMTA) and 9-carboxy-10-(mercaptomethyl)triptycene (CMMT). The XRD data demonstrate that highly oriented HKUST-1 SURMOFs with an orientation along the (100) direction was obtained on MHDA-SAMs. In the case of the TPMTA-SAM, the quality of the deposited SURMOF films was found to be substantially inferior. Surprisingly, for the CMMT-SAMs, a different growth direction was obtained; XRD data reveal the deposition of highly oriented HKUST-1 SURMOFs grown along the (111) direction.

  16. Deposition of Metal-Organic Frameworks by Liquid-Phase Epitaxy: The Influence of Substrate Functional Group Density on Film Orientation

    Christof Wöll

    2012-09-01

    Full Text Available The liquid phase epitaxy (LPE of the metal-organic framework (MOF HKUST-1 has been studied for three different COOH-terminated templating organic surfaces prepared by the adsorption of self-assembled monolayers (SAMs on gold substrates. Three different SAMs were used, mercaptohexadecanoic acid (MHDA, 4’-carboxyterphenyl-4-methanethiol (TPMTA and 9-carboxy-10-(mercaptomethyltriptycene (CMMT. The XRD data demonstrate that highly oriented HKUST-1 SURMOFs with an orientation along the (100 direction was obtained on MHDA-SAMs. In the case of the TPMTA-SAM, the quality of the deposited SURMOF films was found to be substantially inferior. Surprisingly, for the CMMT-SAMs, a different growth direction was obtained; XRD data reveal the deposition of highly oriented HKUST-1 SURMOFs grown along the (111 direction.

  17. Post-synthetic transformation of a Zn( ii ) polyhedral coordination network into a new supramolecular isomer of HKUST-1

    Chen, Yao [State Key Laboratory of Medicinal Chemical Biology; Nankai University; Tianjin 300071; P. R. China; College of Pharmacy; Wojtas, Lukasz [Department of Chemistry; University of South Florida; 4202 East Fowler Avenue; Tampa; USA; Ma, Shengqian [Department of Chemistry; University of South Florida; 4202 East Fowler Avenue; Tampa; USA; Zaworotko, Michael J. [Department of Chemistry & Environmental Sciences, Bernal Institute, University of Limerick; Limerick; Republic of Ireland; Zhang, Zhenjie [College of Chemistry, Nankai University; Tianjin; P. R. China; State Key Laboratory of Medicinal Chemical Biology; Nankai University

    2017-01-01

    A Zn-based porphyrin containing metal–organic material (porphMOM-1) was post-synthetically transformed into a Cu-based porphyrin-encapsulating metal–organic material (porph@HKUST-1-β).HKUST-1-βis a new supramolecular isomer ofHKUST-1.

  18. Magnetic copper-based metal organic framework as an effective and recyclable adsorbent for removal of two fluoroquinolone antibiotics from aqueous solutions.

    Wu, Gege; Ma, Jiping; Li, Shuang; Guan, Jing; Jiang, Bo; Wang, Liyan; Li, Jinhua; Wang, Xiaoyan; Chen, Lingxin

    2018-05-30

    Fe 3 O 4 /HKUST-1 magnetic copper based metal-organic frameworks (MOF) were synthesized by a simple and facile method and applied as an effective and recyclable adsorbent for the adsorptive removal of two widely used ciprofloxacin (CIP) and norfloxacin (NOR) fluoroquinolone antibiotics (FQAs) from aqueous solutions. Fe 3 O 4 /HKUST-1 was thoroughly characterized, and the major influence factors including solution pH, adsorbent amount and salt concentration were investigated. Compared to the reported adsorbents, Fe 3 O 4 /HKUST-1 has a very high adsorption rate, and it is found that CIP and NOR could be removed within 30 min. Moreover, the maximum adsorption capacities of the magnetic composites toward CIP and NOR reached as high as 538 mg g -1 and 513 mg g -1 , respectively, much higher than those of most of the reported adsorbents for these two FQAs. The saturation magnetization value of Fe 3 O 4 /HKUST-1 was 44 emu g -1 , which was sufficient for the separation of the Fe 3 O 4 /HKUST-1adsorbent from the aqueous solution by the application of an external magnetic field. Additionally, this magnetic material showed a good reusability with the adsorption capability decreasing only slightly after reuse for ten cycles. These results indicated that the magnetic composites Fe 3 O 4 /HKUST-1 may be a promising adsorbent in the decontamination of FQAs from wastewater due to its high adsorption capability, fast kinetics, easy separation from water, and excellent recyclability. The adsorption mechanism was proposed based on the effects of pH on adsorption and on the zeta potential of the adsorbent. For the adsorption of CIP and NOR by Fe 3 O 4 /HKUST-1, both electrostatic and π-π interactions may be important. Copyright © 2018 Elsevier Inc. All rights reserved.

  19. Time-Resolved In Situ Liquid-Phase Atomic Force Microscopy and Infrared Nanospectroscopy during the Formation of Metal-Organic Framework Thin Films.

    Mandemaker, Laurens D B; Filez, Matthias; Delen, Guusje; Tan, Huanshu; Zhang, Xuehua; Lohse, Detlef; Weckhuysen, Bert M

    2018-04-19

    Metal-organic framework (MOF) thin films show unmatched promise as smart membranes and photocatalytic coatings. However, their nucleation and growth resulting from intricate molecular assembly processes are not well understood yet are crucial to control the thin film properties. Here, we directly observe the nucleation and growth behavior of HKUST-1 thin films by real-time in situ AFM at different temperatures in a Cu-BTC solution. In combination with ex situ infrared (nano)spectroscopy, synthesis at 25 °C reveals initial nucleation of rapidly growing HKUST-1 islands surrounded by a continuously nucleating but slowly growing HKUST-1 carpet. Monitoring at 13 and 50 °C shows the strong impact of temperature on thin film formation, resulting in (partial) nucleation and growth inhibition. The nucleation and growth mechanisms as well as their kinetics provide insights to aid in future rational design of MOF thin films.

  20. Strategy for chemotherapeutic delivery using a nanosized porous metal-organic framework with a central composite design

    Li YP

    2017-02-01

    Full Text Available Yingpeng Li,1 Xiuyan Li,2 Qingxia Guan,2 Chunjing Zhang,2 Ting Xu,2 Yujing Dong,2 Xinyu Bai,2 Weiping Zhang3 1College of Pharmacy, Tianjin University of Traditional Chinese Medicine, Tianjin, 2College of Pharmacy, Heilongjiang University of Traditional Chinese Medicine, Harbin, People’s Republic of China; 3Pope John XXIII High School, Everett, MA, USA Background: Enhancing drug delivery is an ongoing endeavor in pharmaceutics, especially when the efficacy of chemotherapy for cancer is concerned. In this study, we prepared and evaluated nanosized HKUST-1 (nanoHKUST-1, nanosized metal-organic drug delivery framework, loaded with 5-fluorouracil (5-FU for potential use in cancer treatment.Materials and methods: NanoHKUST-1 was prepared by reacting copper (II acetate [Cu(OAc2] and benzene-1,3,5-tricarboxylic acid (H3BTC with benzoic acid (C6H5COOH at room temperature (23.7°C±2.4°C. A central composite design was used to optimize 5-FU-loaded nanoHKUST-1. Contact time, ethanol concentration, and 5-FU:material ratios were the independent variables, and the entrapment efficiency of 5-FU was the response parameter measured. Powder X-ray diffraction, scanning electron microscopy (SEM, transmission electron microscopy (TEM, and nitrogen adsorption were used to determine the morphology of nanoHKUST-1. In addition, 5-FU release studies were conducted, and the in vitro cytotoxicity was evaluated.Results: Entrapment efficiency and drug loading were 9.96% and 40.22%, respectively, while the small-angle X-ray diffraction patterns confirmed a regular porous structure. The SEM and TEM images of the nanoHKUST-1 confirmed the presence of round particles (diameter: approximately 100 nm and regular polygon arrays of mesoporous channels of approximately 2–5 nm. The half-maximal lethal concentration (LC50 of the 5-FU-loaded nanoHKUST-1 was approximately 10 µg/mL.Conclusion: The results indicated that nanoHKUST-1 is a potential vector worth developing as a

  1. High-resolution inelastic neutron scattering and neutron powder diffraction study of the adsorption of dihydrogen by the Cu(II) metal–organic framework material HKUST-1

    Callear, Samantha K.; Ramirez-Cuesta, Anibal J.; David, William I.F. [ISIS Facility, Rutherford Appleton Laboratory, Harwell Science and Innovation Campus, Didcot, OX11 0QX (United Kingdom); Millange, Franck [Institut Lavoisier Versailles (CNRS UMR 8180), Université de Versailles, 78035 Versailles (France); Walton, Richard I., E-mail: r.i.walton@warwick.ac.uk [Department of Chemistry, University of Warwick, CV4 7AL, Coventry (United Kingdom)

    2013-12-12

    Highlights: • Binding sites for dihydrogen in a metal–organic framework have been identified. • The combination of diffraction and spectroscopy shows competitive filling of various adsorption sites. • Inelastic neutron scattering over wide-momentum transfer reveals new models for hydrogen-framework interactions. - Abstract: We present new high-resolution inelastic neutron scattering (INS) spectra (measured using the TOSCA and MARI instruments at ISIS) and powder neutron diffraction data (measured on the diffractometer WISH at ISIS) from the interaction of the prototypical metal–organic framework HKUST-1 with various dosages of dihydrogen gas. The INS spectra show direct evidence for the sequential occupation of various distinct sites for dihydrogen in the metal–organic framework, whose population is adjusted during increasing loading of the guest. The superior resolution of TOSCA reveals subtle features in the spectra, not previously reported, including evidence for split signals, while complementary spectra recorded on MARI present full information in energy and momentum transfer. The analysis of the powder neutron patterns using the Rietveld method shows a consistent picture, allowing the crystallographic indenisation of binding sites for dihydrogen, thus building a comprehensive picture of the interaction of the guest with the nanoporous host.

  2. High-resolution inelastic neutron scattering and neutron powder diffraction study of the adsorption of dihydrogen by the Cu(II) metal–organic framework material HKUST-1

    Callear, Samantha K.; Ramirez-Cuesta, Anibal J.; David, William I.F.; Millange, Franck; Walton, Richard I.

    2013-01-01

    Highlights: • Binding sites for dihydrogen in a metal–organic framework have been identified. • The combination of diffraction and spectroscopy shows competitive filling of various adsorption sites. • Inelastic neutron scattering over wide-momentum transfer reveals new models for hydrogen-framework interactions. - Abstract: We present new high-resolution inelastic neutron scattering (INS) spectra (measured using the TOSCA and MARI instruments at ISIS) and powder neutron diffraction data (measured on the diffractometer WISH at ISIS) from the interaction of the prototypical metal–organic framework HKUST-1 with various dosages of dihydrogen gas. The INS spectra show direct evidence for the sequential occupation of various distinct sites for dihydrogen in the metal–organic framework, whose population is adjusted during increasing loading of the guest. The superior resolution of TOSCA reveals subtle features in the spectra, not previously reported, including evidence for split signals, while complementary spectra recorded on MARI present full information in energy and momentum transfer. The analysis of the powder neutron patterns using the Rietveld method shows a consistent picture, allowing the crystallographic indenisation of binding sites for dihydrogen, thus building a comprehensive picture of the interaction of the guest with the nanoporous host

  3. Mimicking heme enzymes in the solid state: metal-organic materials with selectively encapsulated heme.

    Larsen, Randy W; Wojtas, Lukasz; Perman, Jason; Musselman, Ronald L; Zaworotko, Michael J; Vetromile, Carissa M

    2011-07-13

    To carry out essential life processes, nature has had to evolve heme enzymes capable of synthesizing and manipulating complex molecules. These proteins perform a plethora of chemical reactions utilizing a single iron porphyrin active site embedded within an evolutionarily designed protein pocket. We herein report the first class of metal-organic materials (MOMs) that mimic heme enzymes in terms of both structure and reactivity. The MOMzyme-1 class is based upon a prototypal MOM, HKUST-1, into which catalytically active metalloporphyrins are selectively encapsulated in a "ship-in-a-bottle" fashion within one of the three nanoscale cages that exist in HKUST-1. MOMs offer unparalleled levels of permanent porosity and their modular nature affords enormous diversity of structures and properties. The MOMzyme-1 class could therefore represent a new paradigm for heme biomimetic catalysis since it combines the activity of a homogeneous catalyst with the stability and recyclability of heterogeneous catalytic systems within a single material.

  4. Metal-Organic Framework Thin Films as Stationary Phases in Microfabricated Gas-Chromatography Columns.

    Read, Douglas [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States); Sillerud, Colin Halliday [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)

    2016-01-01

    The overarching goal of this project is to integrate Sandia's microfabricated gas-chromatography ( GC) columns with a stationary phase material that is capable of retaining high-volatility chemicals and permanent gases. The successful integration of such a material with GCs would dramatically expand the repertoire of detectable compounds for Sandia's various microanalysis systems. One such promising class of candidate materials is metal-organic frameworks (MOFs). In this report we detail our methods for controlled deposition of HKUST-1 MOF stationary phases within GC columns. We demonstrate: the chromatographic separation of natural gas; a method for determining MOF film thickness from chromatography alone; and the first-reported GC x GC separation of natural gas -- in general -- let alone for two disparate MOF stationary phases. In addition we determine the fundamental thermodynamic constant for mass sorption, the partition coefficient, for HKUST-1 and several light hydrocarbons and select toxic industrial chemicals.

  5. Metal Nanoparticles Covered with a Metal-Organic Framework: From One-Pot Synthetic Methods to Synergistic Energy Storage and Conversion Functions.

    Kobayashi, Hirokazu; Mitsuka, Yuko; Kitagawa, Hiroshi

    2016-08-01

    Hybrid materials composed of metal nanoparticles and metal-organic frameworks (MOFs) have attracted much attention in many applications, such as enhanced gas storage and catalytic, magnetic, and optical properties, because of the synergetic effects between the metal nanoparticles and MOFs. In this Forum Article, we describe our recent progress on novel synthetic methods to produce metal nanoparticles covered with a MOF (metal@MOF). We first present Pd@copper(II) 1,3,5-benzenetricarboxylate (HKUST-1) as a novel hydrogen-storage material. The HKUST-1 coating on Pd nanocrystals results in a remarkably enhanced hydrogen-storage capacity and speed in the Pd nanocrystals, originating from charge transfer from Pd nanocrystals to HKUST-1. Another material, Pd-Au@Zn(MeIM)2 (ZIF-8, where HMeIM = 2-methylimidazole), exhibits much different catalytic activity for alcohol oxidation compared with Pd-Au nanoparticles, indicating a design guideline for the development of composite catalysts with high selectivity. A composite material composed of Cu nanoparticles and Cr3F(H2O)2O{C6H3(CO2)3}2 (MIL-100-Cr) demonstrates higher catalytic activity for CO2 reduction into methanol than Cu/γ-Al2O3. We also present novel one-pot synthetic methods to produce composite materials including Pd/ZIF-8 and Ni@Ni2(dhtp) (MOF-74, where H4dhtp = 2,5-dihydroxyterephthalic acid).

  6. Metal-organic framework templated electrodeposition of functional gold nanostructures

    Worrall, Stephen D.; Bissett, Mark A.; Hill, Patrick I.; Rooney, Aidan P.; Haigh, Sarah J.; Attfield, Martin P.; Dryfe, Robert A.W.

    2016-01-01

    Highlights: • Electrodeposition of anisotropic Au nanostructures templated by HKUST-1. • Au nanostructures replicate ∼1.4 nm pore spaces of HKUST-1. • Encapsulated Au nanostructures active as SERS substrate for 4-fluorothiophenol. - Abstract: Utilizing a pair of quick, scalable electrochemical processes, the permanently porous MOF HKUST-1 was electrochemically grown on a copper electrode and this HKUST-1-coated electrode was used to template electrodeposition of a gold nanostructure within the pore network of the MOF. Transmission electron microscopy demonstrates that a proportion of the gold nanostructures exhibit structural features replicating the pore space of this ∼1.4 nm maximum pore diameter MOF, as well as regions that are larger in size. Scanning electron microscopy shows that the electrodeposited gold nanostructure, produced under certain conditions of synthesis and template removal, is sufficiently inter-grown and mechanically robust to retain the octahedral morphology of the HKUST-1 template crystals. The functionality of the gold nanostructure within the crystalline HKUST-1 was demonstrated through the surface enhanced Raman spectroscopic (SERS) detection of 4-fluorothiophenol at concentrations as low as 1 μM. The reported process is confirmed as a viable electrodeposition method for obtaining functional, accessible metal nanostructures encapsulated within MOF crystals.

  7. Polystyrene Sulfonate Threaded through a Metal-Organic Framework Membrane for Fast and Selective Lithium-Ion Separation.

    Guo, Yi; Ying, Yulong; Mao, Yiyin; Peng, Xinsheng; Chen, Banglin

    2016-11-21

    Extraction of lithium ions from salt-lake brines is very important to produce lithium compounds. Herein, we report a new approach to construct polystyrene sulfonate (PSS) threaded HKUST-1 metal-organic framework (MOF) membranes through an in situ confinement conversion process. The resulting membrane PSS@HKUST-1-6.7, with unique anchored three-dimensional sulfonate networks, shows a very high Li + conductivity of 5.53×10 -4  S cm -1 at 25 °C, 1.89×10 -3  S cm -1 at 70 °C, and Li + flux of 6.75 mol m -2  h -1 , which are five orders higher than that of the pristine HKUST-1 membrane. Attributed to the different size sieving effects and the affinity differences of the Li + , Na + , K + , and Mg 2+ ions to the sulfonate groups, the PSS@HKUST-1-6.7 membrane exhibits ideal selectivities of 78, 99, and 10296 for Li + /Na + , Li + /K + , Li + /Mg 2+ and real binary ion selectivities of 35, 67, and 1815, respectively, the highest ever reported among ionic conductors and Li + extraction membranes. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. Investigation by Raman Spectroscopy of the Decomposition Process of HKUST-1 upon Exposure to Air

    Michela Todaro

    2016-01-01

    Full Text Available We report an experimental investigation by Raman spectroscopy of the decomposition process of Metal-Organic Framework (MOF HKUST-1 upon exposure to air moisture (T=300 K, 70% relative humidity. The data collected here are compared with the indications obtained from a model of the process of decomposition of this material proposed in literature. In agreement with that model, the reported Raman measurements indicate that for exposure times longer than 20 days relevant irreversible processes take place, which are related to the occurrence of the hydrolysis of Cu-O bonds. These processes induce small but detectable variations of the peak positions and intensities of the main Raman bands of the material, which can be related to Cu-Cu, Cu-O, and O-C-O stretching modes. The critical analyses of these changes have permitted us to obtain a more detailed description of the process of decomposition taking place in HKUST-1 upon interaction with moisture. Furthermore, the reported Raman data give further strong support to the recently proposed model of decomposition of HKUST-1, contributing significantly to the development of a complete picture of the properties of this considerable deleterious effect.

  9. Tuning of Nafion{sup ®} by HKUST-1 as coordination network to enhance proton conductivity for fuel cell applications

    Kim, Hee Jin, E-mail: zammanbo814@knu.ac.kr [Kyungpook National University, Research Institute of Advanced Energy Technology (Korea, Republic of); Talukdar, Krishan, E-mail: krishantu@yahoo.com; Choi, Sang-June, E-mail: sjchoi@knu.ac.kr [Kyungpook National University, Department of Environmental Engineering (Korea, Republic of)

    2016-02-15

    Metal-organic frameworks can be intentionally coordinated to achieve improved proton conductivity because they have highly ordered structures and modular nature that serve as a scaffold to anchor acidic groups and develop efficient proton transfer pathways for fuel cell application. Using the concept of a coordination network, the conductivity of Nafion{sup ®} was tuned by the incorporation of HKUST-1. It has Cu{sup II}–paddle wheel type nodes and 1,3,5-benzenetricarboxylate struts, feature accessible sites that provides an improved protonic channel depending on the water content. In spite of the fact that HKUST-1 is neutral, coordinated water molecules are contributed adequately acidic by Cu{sup II} to supply protons to enhance proton conductivity. Water molecules play a vital part in transfer of proton as conducting media and serve as triggers to change proton conductivity through reforming hydrogen bonding networks by water adsorption/desorption process. Increased ion exchange capacity and proton conductivity with lower water uptake of the H{sub 3}PO{sub 4}-doped material, and improved thermal stability (as confirmed by thermogravimetric analysis) were achieved. The structure of HKUST-1 was confirmed via field emission scanning electron microscopy and X-ray diffraction, while the porosity and adsorption desorption capacity were characterized by porosity analysis. Graphical abstract: The H{sub 3}PO{sub 4}-doped HKUST-1/Nafion® composite membrane is demonstrated to be a promising material based on its proton conductivity. HKUST-1 has an average particle diameter of around 15–20 µm. The proton conductivity, IEC values, and the thermal stability of the 2.5 wt% HKUST-1/Nafion® composite membrane suggest that HKUST-1 may be a promising candidate as a proton-conductive material in the polymer electrolyte fuel cell membrane due to its reasonable proton passageway, favorable surface area, lower water uptake with the higher IEC, and proton conductivity of the H

  10. Step-by-step seeding procedure for preparing HKUST-1 membrane on porous α-alumina support.

    Nan, Jiangpu; Dong, Xueliang; Wang, Wenjin; Jin, Wanqin; Xu, Nanping

    2011-04-19

    Metal-organic framework (MOF) membranes have attracted considerable attention because of their striking advantages in small-molecule separation. The preparation of an integrated MOF membrane is still a major challenge. Depositing a uniform seed layer on a support for secondary growth is a main route to obtaining an integrated MOF membrane. A novel seeding method to prepare HKUST-1 (known as Cu(3)(btc)(2)) membranes on porous α-alumina supports is reported. The in situ production of the seed layer was realized in step-by-step fashion via the coordination of H(3)btc and Cu(2+) on an α-alumina support. The formation process of the seed layer was observed by ultraviolet-visible absorption spectroscopy and atomic force microscopy. An integrated HKUST-1 membrane could be synthesized by the secondary hydrothermal growth on the seeded support. The gas permeation performance of the membrane was evaluated. © 2011 American Chemical Society

  11. Graphene Oxide Directed One-Step Synthesis of Flowerlike Graphene@HKUST-1 for Enzyme-Free Detection of Hydrogen Peroxide in Biological Samples.

    Wang, Qingxiang; Yang, Yizhen; Gao, Feng; Ni, Jiancong; Zhang, Yanhui; Lin, Zhenyu

    2016-11-30

    A novel metal-organic framework (MOF)-based electroactive nanocomposite containing graphene fragments and HKUST-1 was synthesized via a facile one-step solvothermal method using graphene oxide (GO), benzene-1,3,5-tricarboxylic acid (BTC), and copper nitrate (Cu(NO 3 ) 2 ) as the raw materials. The morphology and structure characterization revealed that the GO could induce the transformation of HKUST-1 from octahedral structure to the hierarchical flower shape as an effective structure-directing agent. Also, it is interesting to find out that the GO was torn into small fragments to participate in the formation of HKUST-1 and then transformed into the reduction form during the solvothermal reaction process, which dramatically increased the surface area, electronic conductivity, and redox-activity of the material. Electrochemical assays showed that the synergy of graphene and HKUST-1 in the nanocomposite leaded to high electrocatalysis, fast response, and excellent selectivity toward the reduction of hydrogen peroxide (H 2 O 2 ). Based on these remarkable advantages, satisfactory results were obtained when the nanocomposite was used as a sensing material for electrochemical determination of H 2 O 2 in the complex biological samples such as human serum and living Raw 264.7 cell fluids.

  12. Diffusion Control in the in Situ Synthesis of Iconic Metal-Organic Frameworks within an Ionic Polymer Matrix.

    Lim, Jungho; Lee, Eun Ji; Choi, Jae Sun; Jeong, Nak Cheon

    2018-01-31

    Ionic polymers that possess ion-exchangeable sites have been shown to be a greatly useful platform to fabricate mixed matrices (MMs) where metal-organic frameworks (MOFs) can be in situ synthesized, although the in situ synthesis of MOF has been rarely studied. In this study, alginate (ALG), an anionic green polymer that possesses metal-ion-exchangeable sites, is employed as a platform of MMs for the in situ synthesis of iconic MOFs, HKUST-1, and MOF-74(Zn). We demonstrate for the first time that the sequential order of supplying MOF ingredients (metal ion and deprotonated ligand) into the alginate matrix leads to substantially different results because of a difference in the diffusion of the MOF components. For the examples examined, whereas the infusion of BTC 3- ligand into Cu 2+ -exchanged ALG engendered the eggshell-shaped HKUST-1 layers on the surface of MM spheres, the infusion of Cu 2+ ions into BTC 3- -included alginate engendered the high dispersivity and junction contact of HKUST-1 crystals in the alginate matrix. This fundamental property has been exploited to fabricate a flexible MOF-containing mixed matrix membrane by coincorporating poly(vinyl alcohol). Using two molecular dyes, namely, methylene blue and rhodamine 6G, further, we show that this in situ strategy is suitable for fabricating an MOF-MM that exhibits size-selective molecular uptake.

  13. Copper-Based Metal-Organic Porous Materials for CO2 Electrocatalytic Reduction to Alcohols.

    Albo, Jonathan; Vallejo, Daniel; Beobide, Garikoitz; Castillo, Oscar; Castaño, Pedro; Irabien, Angel

    2017-03-22

    The electrocatalytic reduction of CO 2 has been investigated using four Cu-based metal-organic porous materials supported on gas diffusion electrodes, namely, (1) HKUST-1 metal-organic framework (MOF), [Cu 3 (μ 6 -C 9 H 3 O 6 ) 2 ] n ; (2) CuAdeAce MOF, [Cu 3 (μ 3 -C 5 H 4 N 5 ) 2 ] n ; (3) CuDTA mesoporous metal-organic aerogel (MOA), [Cu(μ-C 2 H 2 N 2 S 2 )] n ; and (4) CuZnDTA MOA, [Cu 0.6 Zn 0.4 (μ-C 2 H 2 N 2 S 2 )] n . The electrodes show relatively high surface areas, accessibilities, and exposure of the Cu catalytic centers as well as favorable electrocatalytic CO 2 reduction performance, that is, they have a high efficiency for the production of methanol and ethanol in the liquid phase. The maximum cumulative Faradaic efficiencies for CO 2 conversion at HKUST-1-, CuAdeAce-, CuDTA-, and CuZnDTA-based electrodes are 15.9, 1.2, 6, and 9.9 %, respectively, at a current density of 10 mA cm -2 , an electrolyte-flow/area ratio of 3 mL min cm -2 , and a gas-flow/area ratio of 20 mL min cm -2 . We can correlate these observations with the structural features of the electrodes. Furthermore, HKUST-1- and CuZnDTA-based electrodes show stable electrocatalytic performance for 17 and 12 h, respectively. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. Dubinin-Astakhov model for acetylene adsorption on metal-organic frameworks

    Cheng, Peifu; Hu, Yun Hang, E-mail: yunhangh@mtu.edu

    2016-07-30

    Graphical abstract: It was demonstrated that Dubinin-Astakhov equation can be exploited as a general isotherm model for C2H2 adsorption on metal-organic frameworks (MOFs), including MOF-5, ZIF-8, HKUST-1, and MIL-53. - Highlights: • Dubinin-Astakhov equation is demonstrated to be a general model for C{sub 2}H{sub 2} adsorption on metal-organic frameworks (MOFs). • Surface areas obtained with Dubinin-Astakhov equation from C{sub 2}H{sub 2} adsorption on MOFs are consistent with BET surface areas from N{sub 2} adsorption. • C{sub 2}H{sub 2} on MOF-5, ZIF-8, and MIL-53 is a physical adsorption, whereas its adsorption on HKUST-1 is due to a chemical bonding. - Abstract: Acetylene (C{sub 2}H{sub 2}) is explosive at a pressure above 29 psi, causing a safety issue for its storage and applications. C{sub 2}H{sub 2} adsorption on metal-organic frameworks (MOFs) has been explored to solve the issue. However, a suitable isotherm equation for C{sub 2}H{sub 2} adsorption on various MOFs has not been found. In this paper, it was demonstrated that Dubinin-Astakhov equation can be exploited as a general isotherm model to depict C{sub 2}H{sub 2} adsorption on MOF-5, ZIF-8, HKUST-1, and MIL-53. In contrast, commonly used Langmuir and BET models exhibited their inapplicability for C{sub 2}H{sub 2} adsorption on those MOFs.

  15. Mechanical properties of metal-organic frameworks: An indentation study on epitaxial thin films

    Bundschuh, S.; Kraft, O.; Arslan, H. K.; Gliemann, H.; Weidler, P. G.; Wöll, C.

    2012-09-01

    We have determined the hardness and Young's modulus of a highly porous metal-organic framework (MOF) using a standard nanoindentation technique. Despite the very low density of these films, 1.22 g cm-3, Young's modulus reaches values of almost 10 GPa for HKUST-1, demonstrating that this porous coordination polymer is substantially stiffer than normal polymers. This progress in characterizing mechanical properties of MOFs has been made possible by the use of high quality, oriented thin films grown using liquid phase epitaxy on modified Au substrates.

  16. Excellent performance of copper based metal organic framework in adsorptive removal of toxic sulfonamide antibiotics from wastewater.

    Azhar, Muhammad Rizwan; Abid, Hussein Rasool; Sun, Hongqi; Periasamy, Vijay; Tadé, Moses O; Wang, Shaobin

    2016-09-15

    The increasing concerns on toxicity of sulfonamide antibiotics in water require a prompt action to establish efficient wastewater treatment processes for their removal. In this study, adsorptive removal of a model sulfonamide antibiotic, sulfachloropyridazine (SCP), from wastewater is presented for the first time using a metal organic framework (MOF). A high surface area and thermally stable MOF, HKUST-1, was synthesized by a facile method. Batch adsorption studies were systematically carried out using HKUST-1. The high surface area and unsaturated metal sites resulted in a significant adsorption capacity with faster kinetics. Most of the SCP was removed in 15min and the kinetic data were best fitted with the pseudo second order model. Moreover, isothermal data were best fitted with the Langmuir model. The thermodynamic results showed that the adsorption is a spontaneous and endothermic process. The adsorption capacity of HKUST-1 is 384mg/g at 298K which is the highest compared to most of the materials for the antibiotics. The high adsorption capacity is attributed mainly to π-π stacking, hydrogen bonding and electrostatic interactions. Copyright © 2016 Elsevier Inc. All rights reserved.

  17. Tuning of Nafion® by HKUST-1 as coordination network to enhance proton conductivity for fuel cell applications

    Kim, Hee Jin; Talukdar, Krishan; Choi, Sang-June

    2016-02-01

    Metal-organic frameworks can be intentionally coordinated to achieve improved proton conductivity because they have highly ordered structures and modular nature that serve as a scaffold to anchor acidic groups and develop efficient proton transfer pathways for fuel cell application. Using the concept of a coordination network, the conductivity of Nafion® was tuned by the incorporation of HKUST-1. It has CuII-paddle wheel type nodes and 1,3,5-benzenetricarboxylate struts, feature accessible sites that provides an improved protonic channel depending on the water content. In spite of the fact that HKUST-1 is neutral, coordinated water molecules are contributed adequately acidic by CuII to supply protons to enhance proton conductivity. Water molecules play a vital part in transfer of proton as conducting media and serve as triggers to change proton conductivity through reforming hydrogen bonding networks by water adsorption/desorption process. Increased ion exchange capacity and proton conductivity with lower water uptake of the H3PO4-doped material, and improved thermal stability (as confirmed by thermogravimetric analysis) were achieved. The structure of HKUST-1 was confirmed via field emission scanning electron microscopy and X-ray diffraction, while the porosity and adsorption desorption capacity were characterized by porosity analysis.

  18. Metal Organic Frameworks (MOFs)

    Home; Journals; Resonance – Journal of Science Education; Volume 12; Issue 11. Molecule Matters - Metal Organic Frameworks (MOFs). R Sarvanakumar S Sankararaman. Feature Article Volume 12 Issue 11 November 2007 pp 77-86. Fulltext. Click here to view fulltext PDF. Permanent link:

  19. Origin of the Strong Interaction between Polar Molecules and Copper(II) Paddle-Wheels in Metal Organic Frameworks.

    Ongari, Daniele; Tiana, Davide; Stoneburner, Samuel J; Gagliardi, Laura; Smit, Berend

    2017-07-20

    The copper paddle-wheel is the building unit of many metal organic frameworks. Because of the ability of the copper cations to attract polar molecules, copper paddle-wheels are promising for carbon dioxide adsorption and separation. They have therefore been studied extensively, both experimentally and computationally. In this work we investigate the copper-CO 2 interaction in HKUST-1 and in two different cluster models of HKUST-1: monocopper Cu(formate) 2 and dicopper Cu 2 (formate) 4 . We show that density functional theory methods severely underestimate the interaction energy between copper paddle-wheels and CO 2 , even including corrections for the dispersion forces. In contrast, a multireference wave function followed by perturbation theory to second order using the CASPT2 method correctly describes this interaction. The restricted open-shell Møller-Plesset 2 method (ROS-MP2, equivalent to (2,2) CASPT2) was also found to be adequate in describing the system and used to develop a novel force field. Our parametrization is able to predict the experimental CO 2 adsorption isotherms in HKUST-1, and it is shown to be transferable to other copper paddle-wheel systems.

  20. Thiol-functionalization of metal-organic framework by a facile coordination-based postsynthetic strategy and enhanced removal of Hg2+ from water.

    Ke, Fei; Qiu, Ling-Guang; Yuan, Yu-Peng; Peng, Fu-Min; Jiang, Xia; Xie, An-Jian; Shen, Yu-Hua; Zhu, Jun-Fa

    2011-11-30

    The presence of coordinatively unsaturated metal centers in metal-organic frameworks (MOFs) provides an accessible way to selectively functionalize MOFs through coordination bonds. In this work, we describe thiol-functionalization of MOFs by choosing a well known three-dimensional (3D) Cu-based MOF, i.e. [Cu(3)(BTC)(2)(H(2)O)(3)](n) (HKUST-1, BTC=benzene-1,3,5-tricarboxylate), by a facile coordination-based postsynthetic strategy, and demonstrate their application for removal of heavy metal ion from water. A series of [Cu(3)(BTC)(2)](n) samples stoichiometrically decorated with thiol groups has been prepared through coordination bonding of coordinatively unsaturated metal centers in HKUST-1 with -SH group in dithioglycol. The obtained thiol-functionalized samples were characterized by powder X-ray diffraction, scanning electron microscope, energy dispersive X-ray spectroscopy, infrared spectroscopy, and N(2) sorption-desorption isothermal. Significantly, the thiol-functionalized [Cu(3)(BTC)(2)](n) exhibited remarkably high adsorption affinity (K(d)=4.73 × 10(5)mL g(-1)) and high adsorption capacity (714.29 mg g(-1)) for Hg(2+) adsorption from water, while the unfunctionalized HKUST-1 showed no adsorption of Hg(2+) under the same condition. Copyright © 2011 Elsevier B.V. All rights reserved.

  1. Block Copolymer-Templated Approach to Nanopatterned Metal-Organic Framework Films.

    Zhou, Meimei; Wu, Yi-Nan; Wu, Baozhen; Yin, Xianpeng; Gao, Ning; Li, Fengting; Li, Guangtao

    2017-08-17

    The fabrication of patterned metal-organic framework (MOF) films with precisely controlled nanoscale resolution has been a fundamental challenge in nanoscience and nanotechnology. In this study, nanopatterned MOF films were fabricated using a layer-by-layer (LBL) growth method on functional templates (such as a bicontinuous nanoporous membrane or a structure with highly long-range-ordered nanoscopic channels parallel to the underlying substrate) generated by the microphase separation of polystyrene-b-poly(2-vinylpyridine) (PS-b-P2VP) block copolymers. HKUST-1 can be directly deposited on the templates without any chemical modification because the pyridine groups in P2VP interact with metal ions via metal-BCP complexes. As a result, nanopatterned HKUST-1 films with feature sizes below 50 nm and controllable thicknesses can be fabricated by controlling the number of LBL growth cycles. The proposed fabrication method further extends the applications of MOFs in various fields. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. Evaluation of the impact of H2O, O2, and SO2 on postcombustion CO2 capture in metal-organic frameworks.

    Yu, Jiamei; Ma, Yuguang; Balbuena, Perla B

    2012-05-29

    Molecular modeling methods are used to estimate the influence of impurity species: water, O(2), and SO(2) in flue gas mixtures present in postcombustion CO(2) capture using a metal organic framework, HKUST-1, as a model sorbent material. Coordinated and uncoordinated water effects on CO(2) capture are analyzed. Increase of CO(2) adsorption is observed for both cases, which can be attributed to the enhanced binding energy between CO(2) and HKUST-1 due to the introduction of a small amount of water. Density functional theory calculations indicate that the binding energy between CO(2) and HKUST-1 with coordinated water is ~1 kcal/mol higher than that without coordinated water. It is found that the improvement of CO(2)/N(2) selectivity induced by coordinated water may mainly be attributed to the increased CO(2) adsorption on the hydrated HKUST-1. On the other hand, the enhanced selectivity induced by uncoordinated water in the flue gas mixture can be explained on the basis of the competition of adsorption sites between water and CO(2) (N(2)). At low pressures, a significant CO(2)/N(2) selectivity increase is due to the increase of CO(2) adsorption and decrease of N(2) adsorption as a consequence of competition of adsorption sites between water and N(2). However, with more water molecules adsorbed at higher pressures, the competition between water and CO(2) leads to the decrease of CO(2) adsorption capacity. Therefore, high pressure operation should be avoided in HKUST-1 sorbents for CO(2) capture. In addition, the effects of O(2) and SO(2) on CO(2) capture in HKUST-1 are investigated: The CO(2)/N(2) selectivity does not change much even with relatively high concentrations of O(2) in the flue gas (up to 8%). A slightly lower CO(2)/N(2) selectivity of a CO(2)/N(2)/H(2)O/SO(2) mixture is observed compared with that in a CO(2)/N(2)/H(2)O mixture, especially at high pressures, due to the strong SO(2) binding with HKUST-1.

  3. Computational evaluation of metal-organic frameworks for carbon dioxide capture

    Yu, Jiamei

    Metal-organic frameworks (MOFs), a new class of porous solids comprised of metal-containing nodes linked by organic ligands, have become promising materials for gas separations. In particular, their flexible chemistry makes them attractive for CO2 capture from flue gas streams in post-combustion plants. Although numerous efforts have been exerted on the investigation of MOFs for CO2 capture, the exploration of the effects from coexisting components present in very dilute proportions in flue gases is limited because of the experimental difficulty to determine the coadsorption of CO2 with trace components. In this regard, molecular simulations show superiority. In this study, molecular simulations are used to estimate the influence of impurities: water, O2, and SO2 on post-combustion CO2 capture in MOFs. Firstly, two MOFs with coordinatively unsaturated metal sites (CUMs), HKUST-1 and Mg-MOF-74 are explored. Increase of CO 2 adsorption is observed for hydrated HKUST-1; on the contrary, the opposite water adsorption behavior is observed in hydrated Mg-MOF-74, leading to decrease of CO2 adsorption. Further, water effects on CO 2 capture in M-HKUST1 (M = Mg, Zn, Co, Ni) are evaluated to test whether comparing the binding energy could be a general method to evaluate water effects in MOFs with CUMs. It is found that the method works well for Zn-, Co-, and Ni-HKUST1 but partially for Mg-HKUST1. In addition, the effects of O2 and SO2 on CO2 capture in MOFs are also investigated for the first time, showing that the effects of O2 may be negligible but SO2 has negative effects in the CO 2 capture process in HKUST-1 systems. Secondly, the influences of water on CO2 capture in three UiO-66 MOFs with functional groups, --NH2, --OH and --Br are explored, respectively. For UiO-66-NH2 and -OH, the presence of water lowers CO2 adsorption significantly; in contrast, water shows much smaller effects in UiO-66-Br. Moreover, the presence of SO 2 decreases water adsorption but enhances CO

  4. Rapid Formation of Metal-Organic Frameworks (MOFs) Based Nanocomposites in Microdroplets and Their Applications for CO2 Photoreduction.

    He, Xiang; Gan, Zhuoran; Fisenko, Sergey; Wang, Dawei; El-Kaderi, Hani M; Wang, Wei-Ning

    2017-03-22

    A copper-based metal-organic framework (MOF), [Cu 3 (TMA) 2 (H 2 O) 3 ] n (also known as HKUST-1, where TMA stands for trimesic acid), and its TiO 2 nanocomposites were directly synthesized in micrometer-sized droplets via a rapid aerosol route for the first time. The effects of synthesis temperature and precursor component ratio on the physicochemical properties of the materials were systematically investigated. Theoretical calculations on the mass and heat transfer within the microdroplets revealed that the fast solvent evaporation and high heat transfer rates are the major driving forces. The fast droplet shrinkage because of evaporation induces the drastic increase in the supersaturation ratio of the precursor, and subsequently promotes the rapid nucleation and crystal growth of the materials. The HKUST-1-based nanomaterials synthesized via the aerosol route demonstrated good crystallinity, large surface area, and great photostability, comparable with those fabricated by wet-chemistry methods. With TiO 2 embedded in the HKUST-1 matrix, the surface area of the composite is largely maintained, which enables significant improvement in the CO 2 photoreduction efficiency, as compared with pristine TiO 2 . In situ diffuse reflectance infrared Fourier transform spectroscopy analysis suggests that the performance enhancement was due to the stable and high-capacity reactant adsorption by HKUST-1. The current work shows great promise in the aerosol route's capability to address the mass and heat transfer issues of MOFs formation at the microscale level, and ability to synthesize a series of MOFs-based nanomaterials in a rapid and scalable manner for energy and environmental applications.

  5. Thermodynamics of Methane Adsorption on Copper HKUST-1 at Low Pressure.

    Wu, Di; Guo, Xiaofeng; Sun, Hui; Navrotsky, Alexandra

    2015-07-02

    Metal-organic frameworks (MOFs) can be engineered as natural gas storage materials by tuning the pore structures and surface properties. Here we report the direct measurement of CH4 adsorption enthalpy on a paddlewheel MOF (Cu HKUST-1) using gas adsorption calorimetry at 25 °C at low pressures (below 1 bar). In this pressure region, the CH4-CH4 intermolecular interactions are minimized and the energetics solely reflects the CH4-MOF interactions. Our results suggest moderately exothermic physisorption with an enthalpy of -21.1 ± 1.1 kJ/mol CH4 independent of coverage. This calorimetric investigation complements previous computational and crystallographic studies by providing zero coverage enthalpies of CH4 adsorption. The analysis of the new and literature data suggests that in initial stages of adsorption the CH4-HKUST-1 interaction tends to be more sensitive to the pore dimension than to the guest polarizability, suggesting a less specific chemical binding role for the open Cu site.

  6. Thermally driven refrigeration by methanol adsorption on coatings of HKUST-1 and MIL-101(Cr)

    Kummer, Harry; Baumgartner, Max; Hügenell, Philipp; Fröhlich, Dominik; Henninger, Stefan K.; Gläser, Roger

    2017-01-01

    Highlights: • A novel approach of shaping MOFs as coatings on Al-substrates used as HX materials. • The efficiency of HKUST-1 and MIL-101(Cr) for refrigeration via Methanol sorption. • The thermal stability of the MOF coatings under application relevant conditions. • Focus on early implementation by use of commercially and pre-industrially MOFs. • Modelling of sorption uptakes under application conditions for apparatus design. - Abstract: A new and versatile binder-based metal organic framework-(MOF-) coating enables efficient use in fast-cycle adsorption chillers for cooling and refrigeration applications. Two different adsorbents were presented, HKUST-1 and Mil-101(Cr), with promising methanol adsorption characteristics and high loading capacities up to 1.22 g g"−"1. Polysiloxane-based coatings containing 65 and 80 wt% of the MOF adsorbents were produced and the adsorption characteristics were studied before and after extensive thermal treatment over 1000 cycles between 20 °C and 130 °C under methanol atmosphere by thermogravimetric analysis and X-ray diffractometry. Using the Dubinin-Astakhov approach, possible methanol loading lifts in a refrigeration process under different application conditions were quantified.

  7. Synthesis of metal-organic framework films by pore diffusion method

    Murayama, Naohiro; Nishimura, Yuki; Kajiro, Hiroshi; Kishida, Satoru; Kinoshita, Kentaro; Tottori Univ Team; Nippon Steel; Sumitomo Metal Co. Collaboration; Tottori Integrated Frontier Resaerch Center (Tifrec) Collaboration; Tottori University Electronic Display Resaerch Center (Tedrec) Collaboration

    Metal-organic frameworks (MOFs) presents high controllability in designing the nano-scale pore, and this enable molecular storages, catalysts, gas sensors, gas separation membranes, and electronic devices for next-generation. Therefore, a simple method for film synthesis of MOFs compared with conventional methods [1] is strongly required. In this paper, we provide pore diffusion method, in which a substrate containing constituent metals of MOF is inserted in solution that includes only linker molecules of MOF. As a result, 2D growth of MOF was effectively enhanced, and the formation of flat and dense MOF films was attained. The growth time, t, dependence of film thickness, d, can be expressed by the relation of d = Aln(t + 1) + B, where A and B are constants. It means that ionized coppers diffuse through the pores of MOFs and the synthesis reaction proceeds at the MOF/solvent interface. We demonstrated the fabrication of a HKUST-1/Cu-TPA hetero structure by synthesizing a Cu-TPA film continuously after the growth of a HKUST-1 film on the CuOx substrate.

  8. Encapsulation of Hemin in Metal-Organic Frameworks for Catalyzing the Chemiluminescence Reaction of the H2O2-Luminol System and Detecting Glucose in the Neutral Condition.

    Luo, Fenqiang; Lin, Yaolin; Zheng, Liyan; Lin, Xiaomei; Chi, Yuwu

    2015-06-03

    Novel metal-organic frameworks (MOFs) based solid catalysts have been synthesized by encapsulating Hemin into the HKUST-1 MOF materials. These have been first applied in the chemiluminescence field with outstanding performance. The functionalized MOFs not only maintain an excellent catalytic activity inheriting from Hemin but also can be cyclically utilized as solid mimic peroxidases in the neutral condition. The synthesized Hemin@HKUST-1 composites have been used to develop practical sensors for H2O2 and glucose with wide response ranges and low detection limits. It was envisioned that catalyst-functionalized MOFs for chemiluminescence sensing would have promising applications in green, selective, and sensitive detection of target analytes in the future.

  9. Lanthanide metal-organic frameworks

    Cheng, Peng

    2015-01-01

    This book contains the following nine chapters: lanthanide metal-organic frameworks: syntheses, properties, and potential applications (Stephen Fordham, Xuan Wang, Mathieu Bosch, Hong-Cai Zhou); 2. chiral lanthanide metal-organic frameworks (Weisheng Liu, Xiaoliang Tang); 3. Porous lanthanide metal-organic frameworks for gas storage and separation (Bin Li, Banglin Chen); 4. Luminescent lanthanide metal-organic frameworks (Xue-Zhi Song, Shu-Yan Song, Hong-Jie Zhang); 5. Metal-organic frameworks based on lanthanide clusters (Lian Chen, Feilong Jiang, Kang Zhou, Mingyan Wu, Maochun Hong); 6. metal-organic frameworks with d-f cyanide bridges: structural diversity, bonding regime, and magnetism (Marilena Ferbinteanu, Fanica Cimpoesu, Stefania Tanase); 7. transition-lanthanide heterometal-organic frameworks: synthesis, structures, and properties (Wei Shi, Ke Liu, Peng Cheng); 8: MOFs of uranium and the actinides (Juan Su, Jiesheng Chen); 9. Nanostructured and/or nanoscale lanthanide metal-organic frameworks (Zhonghao Zhang, Zhiping Zheng).

  10. Lanthanide metal-organic frameworks

    Cheng, Peng (ed.) [Nankai Univ., Tianjin (China). Dept. of Chemistry

    2015-03-01

    This book contains the following nine chapters: lanthanide metal-organic frameworks: syntheses, properties, and potential applications (Stephen Fordham, Xuan Wang, Mathieu Bosch, Hong-Cai Zhou); 2. chiral lanthanide metal-organic frameworks (Weisheng Liu, Xiaoliang Tang); 3. Porous lanthanide metal-organic frameworks for gas storage and separation (Bin Li, Banglin Chen); 4. Luminescent lanthanide metal-organic frameworks (Xue-Zhi Song, Shu-Yan Song, Hong-Jie Zhang); 5. Metal-organic frameworks based on lanthanide clusters (Lian Chen, Feilong Jiang, Kang Zhou, Mingyan Wu, Maochun Hong); 6. metal-organic frameworks with d-f cyanide bridges: structural diversity, bonding regime, and magnetism (Marilena Ferbinteanu, Fanica Cimpoesu, Stefania Tanase); 7. transition-lanthanide heterometal-organic frameworks: synthesis, structures, and properties (Wei Shi, Ke Liu, Peng Cheng); 8: MOFs of uranium and the actinides (Juan Su, Jiesheng Chen); 9. Nanostructured and/or nanoscale lanthanide metal-organic frameworks (Zhonghao Zhang, Zhiping Zheng).

  11. Double-Sided Electrochromic Device Based on Metal-Organic Frameworks.

    Mjejri, Issam; Doherty, Cara M; Rubio-Martinez, Marta; Drisko, Glenna L; Rougier, Aline

    2017-11-22

    Devices displaying controllably tunable optical properties through an applied voltage are attractive for smart glass, mirrors, and displays. Electrochromic material development aims to decrease power consumption while increasing the variety of attainable colors, their brilliance, and their longevity. We report the first electrochromic device constructed from metal organic frameworks (MOFs). Two MOF films, HKUST-1 and ZnMOF-74, are assembled so that the oxidation of one corresponds to the reduction of the other, allowing the two sides of the device to simultaneously change color. These MOF films exhibit cycling stability unrivaled by other MOFs and a significant optical contrast in a lithium-based electrolyte. HKUST-1 reversibly changed from bright blue to light blue and ZnMOF-74 from yellow to brown. The electrochromic device associates the two MOF films via a PMMA-lithium based electrolyte membrane. The color-switching of these MOFs does not arise from an organic-linker redox reaction, signaling unexplored possibilities for electrochromic MOF-based materials.

  12. Chromium metal organic frameworks and synthesis of metal organic frameworks

    Zhou, Hong-Cai; Liu, Tian-Fu; Lian, Xizhen; Zou, Lanfang; Feng, Dawei

    2018-04-24

    The present invention relates to monocrystalline metal organic frameworks comprising chromium ions and carboxylate ligands and the use of the same, for example their use for storing a gas. The invention also relates to methods for preparing metal organic frameworks comprising chromium, titanium or iron ions and carboxylate ligands. The methods of the invention allow such metal organic frameworks to be prepared in monocrystalline or polycrystalline forms.

  13. Rapid ultrasound-assisted magnetic microextraction of gallic acid from urine, plasma and water samples by HKUST-1-MOF-Fe3O4-GA-MIP-NPs: UV-vis detection and optimization study.

    Asfaram, Arash; Ghaedi, Mehrorang; Dashtian, Kheibar

    2017-01-01

    Magnetite (Fe 3 O 4 nanoparticles (NPs)) HKUST-1 metal organic framework (MOF) composite as a support was used for surface imprinting of gallic acid imprinted polymer (HKUST-1-MOF-Fe 3 O 4 -GA-MIP) using vinyltrimethoxysilane (VTMOS) as the cross-linker. Subsequently, HKUST-1-MOF-Fe 3 O 4 -NPs-GA-MIP characterized by FT-IR, XRD and FE-SEM analysis and applied for fast and selective and sensitive ultrasound assisted dispersive magnetic solid phase microextraction of gallic acid (GA) by UV-Vis (UA-DMSPME-UV-Vis) detection method. Plackett-Burman design (PBD) and central composite design (CCD) according to desirability function (DF) indicate the significant variables among the extraction factors vortex (mixing) time (min), sonication time (min), temperature (°C), eluent volume (L), pH and HKUST-1-MOF-Fe 3 O 4 -NPs-GA-MIP mass (mg) and their contribution on the response. Optimum conditions and values correspond to pH, HKUST-1-MOF-Fe 3 O 4 -NPs-GA-MIP mass, sonication time and the eluent volume were set as follow 3.0, 1.6mg, 4.0min and 180μL, respectively. The average recovery (ER%) of GA was 98.13% with desirability of 0.997, while the present method has best operational performance like wide linear range 8-6000ngmL -1 with a Limit of detection (LOD) of 1.377ngmL -1 , limit of quantification (LOQ) 4.591ngmL -1 and precision (<3.50% RSD). The recovery of GA in urine, human plasma and water samples within the range of 92.3-100.6% that strongly support high applicability of present method for real samples analysis, which candidate this method as promise for further application. Copyright © 2016. Published by Elsevier B.V.

  14. Processing and Performance of MOF (Metal Organic Framework)-Loaded PAN Nanofibrous Membrane for CO2 Adsorption

    Wahiduzzaman; Khan, Mujibur R.; Harp, Spencer; Neumann, Jeffrey; Sultana, Quazi Nahida

    2016-04-01

    The objective of this experimental study is to produce a nanofibrous membrane functionalized with adsorbent particles called metal organic framework (MOF) in order to adsorb CO2 from a gas source. Therefore, Polyacrylonitrile (PAN) was chosen as the precursor for nanofibers and HKUST-1, a Cu-based MOF, was chosen as adsorbent. The experimental process consists of electrospinning PAN solution blended with HKUST-1 to produce a nanofibrous mat as working substrates. The fibers were collected in a cylindrical canister model. SEM image of this mat showed nanofibers with the presence of small adsorbent particles, impregnated into the as-spun fibers discretely. To increase the amount of MOF particles for effectual gas adsorption, a secondary solvothermal process of producing MOF particles on the fibers was required. This process consists of multiple growth cycles of HKUST-1 particles by using a sol-gel precursor. SEM images showed uniform distribution of porous MOF particles of 2-4 µm in size on the fiber surface. Energy dispersive spectroscopy report of the fiber confirmed the presence of MOF particles through the identification of characteristic Copper elemental peaks of HKUST-1. To determine the thermal stability of the fibrous membrane, Thermogravimetric analysis of HKUST-1 consisting of PAN fiber was performed where a total weight loss of 40% between 210 and 360 °C was observed, hence proving the high-temperature durability of the synthesized membrane. BET surface area of the fiber membrane was measured as 540.73 m2/g. The fiber membrane was then placed into an experimental test bench containing a mixed gas inflow of CO2 and N2. Using non-dispersive infrared CO2 sensors connected to the inlet and outlet port of the bench, significant reduction of CO2 in concentration was measured. Comparative IR spectroscopic analysis between the gas-treated and gas untreated fiber samples showed the presence of characteristic peak in the vicinity of 2300 and 2400 cm-1 which

  15. Hydrogen storage in Pd nanocrystals covered with a metal-organic framework

    Li, Guangqin; Kobayashi, Hirokazu; Taylor, Jared M.; Ikeda, Ryuichi; Kubota, Yoshiki; Kato, Kenichi; Takata, Masaki; Yamamoto, Tomokazu; Toh, Shoichi; Matsumura, Syo; Kitagawa, Hiroshi

    2014-08-01

    Hydrogen is an essential component in many industrial processes. As a result of the recent increase in the development of shale gas, steam reforming of shale gas has received considerable attention as a major source of H2, and the more efficient use of hydrogen is strongly demanded. Palladium is well known as a hydrogen-storage metal and an effective catalyst for reactions related to hydrogen in a variety of industrial processes. Here, we present remarkably enhanced capacity and speed of hydrogen storage in Pd nanocrystals covered with the metal-organic framework (MOF) HKUST-1 (copper(II) 1,3,5-benzenetricarboxylate). The Pd nanocrystals covered with the MOF have twice the storage capacity of the bare Pd nanocrystals. The significantly enhanced hydrogen storage capacity was confirmed by hydrogen pressure-composition isotherms and solid-state deuterium nuclear magnetic resonance measurements. The speed of hydrogen absorption in the Pd nanocrystals is also enhanced by the MOF coating.

  16. Nanomechanical investigation of thin-film electroceramic/metal-organic framework multilayers

    Best, James P.; Michler, Johann; Liu, Jianxi; Wang, Zhengbang; Tsotsalas, Manuel; Maeder, Xavier; Röse, Silvana; Oberst, Vanessa; Liu, Jinxuan; Walheim, Stefan; Gliemann, Hartmut; Weidler, Peter G.; Redel, Engelbert; Wöll, Christof

    2015-09-01

    Thin-film multilayer stacks of mechanically hard magnetron sputtered indium tin oxide (ITO) and mechanically soft highly porous surface anchored metal-organic framework (SURMOF) HKUST-1 were studied using nanoindentation. Crystalline, continuous, and monolithic surface anchored MOF thin films were fabricated using a liquid-phase epitaxial growth method. Control over respective fabrication processes allowed for tuning of the thickness of the thin film systems with a high degree of precision. It was found that the mechanical indentation of such thin films is significantly affected by the substrate properties; however, elastic parameters were able to be decoupled for constituent thin-film materials (EITO ≈ 96.7 GPa, EHKUST-1 ≈ 22.0 GPa). For indentation of multilayer stacks, it was found that as the layer thicknesses were increased, while holding the relative thickness of ITO and HKUST-1 constant, the resistance to deformation was significantly altered. Such an observation is likely due to small, albeit significant, changes in film texture, interfacial roughness, size effects, and controlling deformation mechanism as a result of increasing material deposition during processing. Such effects may have consequences regarding the rational mechanical design and utilization of MOF-based hybrid thin-film devices.

  17. Nanomechanical investigation of thin-film electroceramic/metal-organic framework multilayers

    Best, James P., E-mail: james.best@empa.ch, E-mail: engelbert.redel@kit.edu, E-mail: christof.woell@kit.edu; Michler, Johann; Maeder, Xavier [Empa, Swiss Federal Laboratories for Materials Science and Technology, Laboratory for Mechanics of Materials and Nanostructures, Feuerwerkerstrasse 39, CH-3602 Thun (Switzerland); Liu, Jianxi; Wang, Zhengbang; Tsotsalas, Manuel; Liu, Jinxuan; Gliemann, Hartmut; Weidler, Peter G.; Redel, Engelbert, E-mail: james.best@empa.ch, E-mail: engelbert.redel@kit.edu, E-mail: christof.woell@kit.edu; Wöll, Christof, E-mail: james.best@empa.ch, E-mail: engelbert.redel@kit.edu, E-mail: christof.woell@kit.edu [Institute of Functional Interfaces (IFG), Karlsruhe Institute of Technology (KIT), Hermann-von-Helmholtz-Platz 1, 76344 Eggenstein-Leopoldshafen (Germany); Röse, Silvana [Preparative Macromolecular Chemistry, Institute for Chemical Technology and Polymer Chemistry (ICTP), Karlsruhe Institute of Technology (KIT), Engesserstrasse 18, 76128 Karlsruhe (Germany); Institute for Biological Interfaces (IBG), Karlsruhe Institute of Technology (KIT), Herrmann-von-Helmholtz-Platz 1, 76344 Eggenstein-Leopoldshafen (Germany); Oberst, Vanessa [Institute of Applied Materials (IAM), Karlsruhe Institute of Technology (KIT), Hermann-von-Helmholtz-Platz 1, 76344 Eggenstein-Leopoldshafen (Germany); Walheim, Stefan [Institute of Nanotechnology (INT), Karlsruhe Institute of Technology (KIT), Hermann-von-Helmholtz-Platz 1, 76344 Eggenstein-Leopoldshafen (Germany)

    2015-09-07

    Thin-film multilayer stacks of mechanically hard magnetron sputtered indium tin oxide (ITO) and mechanically soft highly porous surface anchored metal-organic framework (SURMOF) HKUST-1 were studied using nanoindentation. Crystalline, continuous, and monolithic surface anchored MOF thin films were fabricated using a liquid-phase epitaxial growth method. Control over respective fabrication processes allowed for tuning of the thickness of the thin film systems with a high degree of precision. It was found that the mechanical indentation of such thin films is significantly affected by the substrate properties; however, elastic parameters were able to be decoupled for constituent thin-film materials (E{sub ITO} ≈ 96.7 GPa, E{sub HKUST−1} ≈ 22.0 GPa). For indentation of multilayer stacks, it was found that as the layer thicknesses were increased, while holding the relative thickness of ITO and HKUST-1 constant, the resistance to deformation was significantly altered. Such an observation is likely due to small, albeit significant, changes in film texture, interfacial roughness, size effects, and controlling deformation mechanism as a result of increasing material deposition during processing. Such effects may have consequences regarding the rational mechanical design and utilization of MOF-based hybrid thin-film devices.

  18. Nanomechanical investigation of thin-film electroceramic/metal-organic framework multilayers

    Best, James P.; Michler, Johann; Maeder, Xavier; Liu, Jianxi; Wang, Zhengbang; Tsotsalas, Manuel; Liu, Jinxuan; Gliemann, Hartmut; Weidler, Peter G.; Redel, Engelbert; Wöll, Christof; Röse, Silvana; Oberst, Vanessa; Walheim, Stefan

    2015-01-01

    Thin-film multilayer stacks of mechanically hard magnetron sputtered indium tin oxide (ITO) and mechanically soft highly porous surface anchored metal-organic framework (SURMOF) HKUST-1 were studied using nanoindentation. Crystalline, continuous, and monolithic surface anchored MOF thin films were fabricated using a liquid-phase epitaxial growth method. Control over respective fabrication processes allowed for tuning of the thickness of the thin film systems with a high degree of precision. It was found that the mechanical indentation of such thin films is significantly affected by the substrate properties; however, elastic parameters were able to be decoupled for constituent thin-film materials (E ITO  ≈ 96.7 GPa, E HKUST−1  ≈ 22.0 GPa). For indentation of multilayer stacks, it was found that as the layer thicknesses were increased, while holding the relative thickness of ITO and HKUST-1 constant, the resistance to deformation was significantly altered. Such an observation is likely due to small, albeit significant, changes in film texture, interfacial roughness, size effects, and controlling deformation mechanism as a result of increasing material deposition during processing. Such effects may have consequences regarding the rational mechanical design and utilization of MOF-based hybrid thin-film devices

  19. Functionalization of silicon nanowire surfaces with metal-organic frameworks

    Liu, Nian

    2011-12-28

    Metal-organic frameworks (MOFs) and silicon nanowires (SiNWs) have been extensively studied due to their unique properties; MOFs have high porosity and specific surface area with well-defined nanoporous structure, while SiNWs have valuable one-dimensional electronic properties. Integration of the two materials into one composite could synergistically combine the advantages of both materials and lead to new applications. We report the first example of a MOF synthesized on surface-modified SiNWs. The synthesis of polycrystalline MOF-199 (also known as HKUST-1) on SiNWs was performed at room temperature using a step-by-step (SBS) approach, and X-ray photoelectron spectroscopy, X-ray diffraction, scanning electron microscopy, transmission electron microscopy, and energy dispersive spectroscopy elemental mapping were used to characterize the material. Matching of the SiNW surface functional groups with the MOF organic linker coordinating groups was found to be critical for the growth. Additionally, the MOF morphology can by tuned by changing the soaking time, synthesis temperature and precursor solution concentration. This SiNW/MOF hybrid structure opens new avenues for rational design of materials with novel functionalities. © 2011 Tsinghua University Press and Springer-Verlag Berlin Heidelberg.

  20. Synthesis of Hierarchically Structured Hybrid Materials by Controlled Self-Assembly of Metal-Organic Framework with Mesoporous Silica for CO2 Adsorption.

    Chen, Chong; Li, Bingxue; Zhou, Lijin; Xia, Zefeng; Feng, Nengjie; Ding, Jing; Wang, Lei; Wan, Hui; Guan, Guofeng

    2017-07-12

    The HKUST-1@SBA-15 composites with hierarchical pore structure were constructed by in situ self-assembly of metal-organic framework (MOF) with mesoporous silica. The structure directing role of SBA-15 had an obvious impact on the growth of MOF crystals, which in turn affected the morphologies and structural properties of the composites. The pristine HKUST-1 and the composites with different content of SBA-15 were characterized by XRD, N 2 adsorption-desorption, SEM, TEM, FT-IR, TG, XPS, and CO 2 -TPD techniques. It was found that the composites were assembled by oriented growth of MOF nanocrystals on the surfaces of SBA-15 matrix. The interactions between surface silanol groups and metal centers induced structural changes and resulted in the increases in surface areas as well as micropore volumes of hybrid materials. Besides, the additional constraints from SBA-15 also restrained the expansion of HKUST-1, contributing to their smaller crystal sizes in the composites. The adsorption isotherms of CO 2 on the materials were measured and applied to calculate the isosteric heats of adsorption. The HS-1 composite exhibited an increase of 15.9% in CO 2 uptake capacity compared with that of HKUST-1. Moreover, its higher isosteric heats of CO 2 adsorption indicated the stronger interactions between the surfaces and CO 2 molecules. The adsorption rate of the composite was also improved due to the introduction of mesopores. Ten cycles of CO 2 adsorption-desorption experiments implied that the HS-1 had excellent reversibility of CO 2 adsorption. This study was intended to provide the possibility of assembling new composites with tailored properties based on MOF and mesoporous silica to satisfy the requirements of various applications.

  1. Selective removal of U(VI) from low concentration wastewater by functionalized HKUST-1@H3PW12O40

    Hui Zhang; Jinhua Xue; Nan Hu; Jing Sun; Dexin Ding; Yongdong Wang; Le Li

    2016-01-01

    The adsorption of U(VI) from low concentration solution by HKUST-1@H 3 PW 12 O 40 was studied as a function of various experimental parameters including pH, interfering ions, contact time, initial uranium concentration and temperature by batch experiments. Equilibrium data were found to fit with Langmuir isotherm model better than Freundlich isotherm model. The kinetic adsorption was fitted by the pseudo-second-order model well. Thermodynamic data from the adsorption experiments indicate that adsorption process is spontaneous and endothermic. HKUST-1@H 3 PW 12 O 40 can selectively adsorb U(VI) from multi-metal ion solutions and the adsorption capacity of HKUST-1@H 3 PW 12 O 40 don't decrease significantly after three cycles of desorption-reuse. The results show that HKUST-1@H 3 PW 12 O 40 is suitable for removal of U(VI) from low concentration solutions. (author)

  2. Photothermal Activation of Metal-Organic Frameworks Using a UV-Vis Light Source.

    Espín, Jordi; Garzón-Tovar, Luis; Carné-Sánchez, Arnau; Imaz, Inhar; Maspoch, Daniel

    2018-03-21

    Metal-organic frameworks (MOFs) usually require meticulous removal of the solvent molecules to unlock their potential porosity. Herein, we report a novel one-step method for activating MOFs based on the photothermal effect induced by directly irradiating them with a UV-vis lamp. The localized light-to-heat conversion produced in the MOF crystals upon irradiation enables a very fast solvent removal, thereby significantly reducing the activation time to as low as 30 min and suppressing the need for time-consuming solvent-exchange procedures and vacuum conditions. This approach is successful for a broad range of MOFs, including HKUST-1, UiO-66-NH 2 , ZIF-67, CPO-27-M (M = Zn, Ni, and Mg), Fe-MIL-101-NH 2 , and IRMOF-3, all of which exhibit absorption bands in the light emission range. In addition, we anticipate that this photothermal activation can also be used to activate covalent organic frameworks (COFs).

  3. Hydrogen adsorption in HKUST-1: a combined inelastic neutron scattering and first-principles study

    Brown, Craig M; Liu Yun; Yildirim, Taner; Peterson, Vanessa K; Kepert, Cameron J

    2009-01-01

    Hydrogen adsorption in high surface area nanoporous coordination polymers has attracted a great deal of interest in recent years due to the potential applications in energy storage. Here we present combined inelastic neutron scattering measurements and detailed first-principles calculations aimed at unraveling the nature of hydrogen adsorption in HKUST-1 (Cu 3 (1,3,5-benzenetricarboxylate) 2 ), a metal-organic framework (MOF) with unsaturated metal centers. We reveal that, in this system, the major contribution to the overall binding comes from the classical Coulomb interaction which is not screened due to the open metal site; this explains the relatively high binding energies and short H 2 -metal distances observed in MOFs with exposed metal sites as compared to traditional ones. Despite the short distances, there is no indication of an elongation of the H-H bond for the bound H 2 molecule at the metal site. We find that both the phonon and rotational energy levels of the hydrogen molecule are closely similar, making the interpretation of the inelastic neutron scattering data difficult. Finally, we show that the orientation of H 2 has a surprisingly large effect on the binding potential, reducing the classical binding energy by almost 30%. The implication of these results for the development of MOF materials for better hydrogen storage is discussed.

  4. Hydrogen adsorption in HKUST-1: a combined inelastic neutron scattering and first-principles study

    Brown, Craig M; Liu Yun; Yildirim, Taner [National Institute of Standards and Technology Center for Neutron Research, 100 Bureau Drive, MS 6102 (United States); Peterson, Vanessa K [Bragg Institute, Australian Nuclear Science and Technology Organisation, Menai, NSW 2234 (Australia); Kepert, Cameron J [School of Chemistry, The University of Sydney, NSW 2006 (Australia)], E-mail: craig.brown@nist.gov

    2009-05-20

    Hydrogen adsorption in high surface area nanoporous coordination polymers has attracted a great deal of interest in recent years due to the potential applications in energy storage. Here we present combined inelastic neutron scattering measurements and detailed first-principles calculations aimed at unraveling the nature of hydrogen adsorption in HKUST-1 (Cu{sub 3}(1,3,5-benzenetricarboxylate){sub 2}), a metal-organic framework (MOF) with unsaturated metal centers. We reveal that, in this system, the major contribution to the overall binding comes from the classical Coulomb interaction which is not screened due to the open metal site; this explains the relatively high binding energies and short H{sub 2}-metal distances observed in MOFs with exposed metal sites as compared to traditional ones. Despite the short distances, there is no indication of an elongation of the H-H bond for the bound H{sub 2} molecule at the metal site. We find that both the phonon and rotational energy levels of the hydrogen molecule are closely similar, making the interpretation of the inelastic neutron scattering data difficult. Finally, we show that the orientation of H{sub 2} has a surprisingly large effect on the binding potential, reducing the classical binding energy by almost 30%. The implication of these results for the development of MOF materials for better hydrogen storage is discussed.

  5. Hydrogen adsorption in HKUST-1: a combined inelastic neutron scattering and first-principles study

    Brown, Craig M.; Liu, Yun; Yildirim, Taner; Peterson, Vanessa K.; Kepert, Cameron J.

    2009-05-01

    Hydrogen adsorption in high surface area nanoporous coordination polymers has attracted a great deal of interest in recent years due to the potential applications in energy storage. Here we present combined inelastic neutron scattering measurements and detailed first-principles calculations aimed at unraveling the nature of hydrogen adsorption in HKUST-1 (Cu3(1,3,5-benzenetricarboxylate)2), a metal-organic framework (MOF) with unsaturated metal centers. We reveal that, in this system, the major contribution to the overall binding comes from the classical Coulomb interaction which is not screened due to the open metal site; this explains the relatively high binding energies and short H2-metal distances observed in MOFs with exposed metal sites as compared to traditional ones. Despite the short distances, there is no indication of an elongation of the H-H bond for the bound H2 molecule at the metal site. We find that both the phonon and rotational energy levels of the hydrogen molecule are closely similar, making the interpretation of the inelastic neutron scattering data difficult. Finally, we show that the orientation of H2 has a surprisingly large effect on the binding potential, reducing the classical binding energy by almost 30%. The implication of these results for the development of MOF materials for better hydrogen storage is discussed.

  6. Nucleation and Early Stages of Layer-by-Layer Growth of Metal Organic Frameworks on Surfaces

    2015-01-01

    High resolution atomic force microscopy (AFM) is used to resolve the evolution of crystallites of a metal organic framework (HKUST-1) grown on Au(111) using a liquid-phase layer-by-layer methodology. The nucleation and faceting of individual crystallites is followed by repeatedly imaging the same submicron region after each cycle of growth and we find that the growing surface is terminated by {111} facets leading to the formation of pyramidal nanostructures for [100] oriented crystallites, and triangular [111] islands with typical lateral dimensions of tens of nanometres. AFM images reveal that crystallites can grow by 5–10 layers in each cycle. The growth rate depends on crystallographic orientation and the morphology of the gold substrate, and we demonstrate that under these conditions the growth is nanocrystalline with a morphology determined by the minimum energy surface. PMID:26709359

  7. Dubinin-Astakhov model for acetylene adsorption on metal-organic frameworks

    Cheng, Peifu; Hu, Yun Hang

    2016-07-01

    Acetylene (C2H2) is explosive at a pressure above 29 psi, causing a safety issue for its storage and applications. C2H2 adsorption on metal-organic frameworks (MOFs) has been explored to solve the issue. However, a suitable isotherm equation for C2H2 adsorption on various MOFs has not been found. In this paper, it was demonstrated that Dubinin-Astakhov equation can be exploited as a general isotherm model to depict C2H2 adsorption on MOF-5, ZIF-8, HKUST-1, and MIL-53. In contrast, commonly used Langmuir and BET models exhibited their inapplicability for C2H2 adsorption on those MOFs.

  8. High-pressure, ambient temperature hydrogen storage in metal-organic frameworks and porous carbon

    Beckner, Matthew; Dailly, Anne

    2014-03-01

    We investigated hydrogen storage in micro-porous adsorbents at ambient temperature and pressures up to 320 bar. We measured three benchmark adsorbents: two metal-organic frameworks, Cu3(1,3,5-benzenetricarboxylate)2 [Cu3(btc)2; HKUST-1] and Zn4O(1,3,5-benzenetribenzoate)2 [Zn4O(btb)2; MOF-177], and the activated carbon MSC-30. In this talk, we focus on adsorption enthalpy calculations using a single adsorption isotherm. We use the differential form of the Claussius-Clapeyron equation applied to the Dubinin-Astakhov adsorption model to calculate adsorption enthalpies. Calculation of the adsorption enthalpy in this way gives a temperature independent enthalpy of 5-7 kJ/mol at the lowest coverage for the three materials investigated. Additionally, we discuss the assumptions and corrections that must be made when calculating adsorption isotherms at high-pressure and adsorption enthalpies.

  9. Liquid- and Gas-Phase Diffusion of Ferrocene in Thin Films of Metal-Organic Frameworks

    Wencai Zhou

    2015-06-01

    Full Text Available The mass transfer of the guest molecules in nanoporous host materials, in particular in metal-organic frameworks (MOFs, is among the crucial features of their applications. By using thin surface-mounted MOF films in combination with a quartz crystal microbalance (QCM, the diffusion of ferrocene vapor and of ethanolic and hexanic ferrocene solution in HKUST-1 was investigated. For the first time, liquid- and gas-phase diffusion in MOFs was compared directly in the identical sample. The diffusion coefficients are in the same order of magnitude (~10−16 m2·s−1, whereas the diffusion coefficient of ferrocene in the empty framework is roughly 3-times smaller than in the MOF which is filled with ethanol or n-hexane.

  10. Liquid- and Gas-Phase Diffusion of Ferrocene in Thin Films of Metal-Organic Frameworks

    Zhou, Wencai; Wöll, Christof; Heinke, Lars

    2015-01-01

    The mass transfer of the guest molecules in nanoporous host materials, in particular in metal-organic frameworks (MOFs), is among the crucial features of their applications. By using thin surface-mounted MOF films in combination with a quartz crystal microbalance (QCM), the diffusion of ferrocene vapor and of ethanolic and hexanic ferrocene solution in HKUST-1 was investigated. For the first time, liquid- and gas-phase diffusion in MOFs was compared directly in the identical sample. The diffusion coefficients are in the same order of magnitude (~10−16 m2·s−1), whereas the diffusion coefficient of ferrocene in the empty framework is roughly 3-times smaller than in the MOF which is filled with ethanol or n-hexane.

  11. Reticular synthesis of HKUST-like tbo MOFs with enhanced CH4 storage

    Spanopoulos, Ioannis

    2015-12-22

    Successful implementation of reticular chemistry using a judiciously designed rigid octatopic carboxylate organic linker allowed the construction of expanded HKUST-1-like tbo-MOF series with intrinsic strong CH4 adsorption sites. The Cu-analogue displayed a concomitant enhancement of the gravimetric and volumetric surface area with the highest reported CH4 uptake among the tbo family, comparable to the best performing MOFs for CH4 storage. The corresponding gravimetric (BET) and volumetric surface area of 3971 m2 g-1 and 2363 m2 cm-3 represent an increase of respectively 115 % and 47 % in comparison to the corresponding values for the prototypical HKUST-1 (tbo-MOF-1), and 42 % and 20 % higher than tbo-MOF-2. High pressure methane adsorption isotherms revealed a high total gravimetric and volumetric CH4 uptakes, reaching 372 cm3 (STP) g-1 and 221 cm3 (STP) cm-3 respectively at 85 bar and 298 K. The corresponding working capacities between 5-80 bar were found to be 294 cm3 (STP) g-1 and 175 cm3 (STP) cm-3 and are placed among the best performing MOFs for CH4 storage particularly at relatively low temperature (e.g. 326 cm3 (STP) g-1 and 194 cm3 (STP) cm-3 at 258 K). To better understand the structure-property relationship and gain insight on the mechanism accounting for the resultant enhanced CH4 storage capacity, molecular simulation study was performed and revealed the presence of very strong CH4 adsorption sites at the vicinity of the organic linker with similar adsorption energetics as the open metal sites. The present findings supports the potential of tbo-MOFs based on the supermolecular building layer (SBL) approach as an ideal platform to further enhance the CH4 storage capacity via expansion and functionalization of the quadrangular pillars.

  12. Reticular synthesis of HKUST-like tbo MOFs with enhanced CH4 storage

    Spanopoulos, Ioannis; Tsangarakis, Constantinos; Klontzas, Emmanuel; Tylianakis, Emmanuel; Froudakis, George; Adil, Karim; Belmabkhout, Youssef; Eddaoudi, Mohamed; Trikalitis, Pantelis N.

    2015-01-01

    Successful implementation of reticular chemistry using a judiciously designed rigid octatopic carboxylate organic linker allowed the construction of expanded HKUST-1-like tbo-MOF series with intrinsic strong CH4 adsorption sites. The Cu-analogue displayed a concomitant enhancement of the gravimetric and volumetric surface area with the highest reported CH4 uptake among the tbo family, comparable to the best performing MOFs for CH4 storage. The corresponding gravimetric (BET) and volumetric surface area of 3971 m2 g-1 and 2363 m2 cm-3 represent an increase of respectively 115 % and 47 % in comparison to the corresponding values for the prototypical HKUST-1 (tbo-MOF-1), and 42 % and 20 % higher than tbo-MOF-2. High pressure methane adsorption isotherms revealed a high total gravimetric and volumetric CH4 uptakes, reaching 372 cm3 (STP) g-1 and 221 cm3 (STP) cm-3 respectively at 85 bar and 298 K. The corresponding working capacities between 5-80 bar were found to be 294 cm3 (STP) g-1 and 175 cm3 (STP) cm-3 and are placed among the best performing MOFs for CH4 storage particularly at relatively low temperature (e.g. 326 cm3 (STP) g-1 and 194 cm3 (STP) cm-3 at 258 K). To better understand the structure-property relationship and gain insight on the mechanism accounting for the resultant enhanced CH4 storage capacity, molecular simulation study was performed and revealed the presence of very strong CH4 adsorption sites at the vicinity of the organic linker with similar adsorption energetics as the open metal sites. The present findings supports the potential of tbo-MOFs based on the supermolecular building layer (SBL) approach as an ideal platform to further enhance the CH4 storage capacity via expansion and functionalization of the quadrangular pillars.

  13. Thiol-functionalization of metal-organic framework by a facile coordination-based postsynthetic strategy and enhanced removal of Hg2+ from water

    Ke, Fei; Qiu, Ling-Guang; Yuan, Yu-Peng; Peng, Fu-Min; Jiang, Xia; Xie, An-Jian; Shen, Yu-Hua; Zhu, Jun-Fa

    2011-01-01

    Highlights: ► A novel type of functionalized MOF for heavy metal removal. ► Functionalization of MOF by a facile coordination-based postsynthetic strategy. ► Thiol-functionalization of MOF has been realized for the first time. ► Enhanced removal of Hg 2+ by thiol-functionalized MOFs. - Abstract: The presence of coordinatively unsaturated metal centers in metal-organic frameworks (MOFs) provides an accessible way to selectively functionalize MOFs through coordination bonds. In this work, we describe thiol-functionalization of MOFs by choosing a well known three-dimensional (3D) Cu-based MOF, i.e. [Cu 3 (BTC) 2 (H 2 O) 3 ] n (HKUST-1, BTC = benzene-1,3,5-tricarboxylate), by a facile coordination-based postsynthetic strategy, and demonstrate their application for removal of heavy metal ion from water. A series of [Cu 3 (BTC) 2 ] n samples stoichiometrically decorated with thiol groups has been prepared through coordination bonding of coordinatively unsaturated metal centers in HKUST-1 with –SH group in dithioglycol. The obtained thiol-functionalized samples were characterized by powder X-ray diffraction, scanning electron microscope, energy dispersive X-ray spectroscopy, infrared spectroscopy, and N 2 sorption–desorption isothermal. Significantly, the thiol-functionalized [Cu 3 (BTC) 2 ] n exhibited remarkably high adsorption affinity (K d = 4.73 × 10 5 mL g −1 ) and high adsorption capacity (714.29 mg g −1 ) for Hg 2+ adsorption from water, while the unfunctionalized HKUST-1 showed no adsorption of Hg 2+ under the same condition.

  14. Thiol-functionalization of metal-organic framework by a facile coordination-based postsynthetic strategy and enhanced removal of Hg{sup 2+} from water

    Ke, Fei [Laboratory of Advanced Porous Materials, School of Chemistry and Chemical Engineering, Anhui University, Hefei 230039 (China); Qiu, Ling-Guang, E-mail: lgqiu@ahu.edu.cn [Laboratory of Advanced Porous Materials, School of Chemistry and Chemical Engineering, Anhui University, Hefei 230039 (China); Yuan, Yu-Peng; Peng, Fu-Min; Jiang, Xia; Xie, An-Jian; Shen, Yu-Hua [Laboratory of Advanced Porous Materials, School of Chemistry and Chemical Engineering, Anhui University, Hefei 230039 (China); Zhu, Jun-Fa [National Synchrotron Radiation Laboratory, University of Science and Technology of China, Hefei 230029 (China)

    2011-11-30

    Highlights: Black-Right-Pointing-Pointer A novel type of functionalized MOF for heavy metal removal. Black-Right-Pointing-Pointer Functionalization of MOF by a facile coordination-based postsynthetic strategy. Black-Right-Pointing-Pointer Thiol-functionalization of MOF has been realized for the first time. Black-Right-Pointing-Pointer Enhanced removal of Hg{sup 2+} by thiol-functionalized MOFs. - Abstract: The presence of coordinatively unsaturated metal centers in metal-organic frameworks (MOFs) provides an accessible way to selectively functionalize MOFs through coordination bonds. In this work, we describe thiol-functionalization of MOFs by choosing a well known three-dimensional (3D) Cu-based MOF, i.e. [Cu{sub 3}(BTC){sub 2}(H{sub 2}O){sub 3}]{sub n} (HKUST-1, BTC = benzene-1,3,5-tricarboxylate), by a facile coordination-based postsynthetic strategy, and demonstrate their application for removal of heavy metal ion from water. A series of [Cu{sub 3}(BTC){sub 2}]{sub n} samples stoichiometrically decorated with thiol groups has been prepared through coordination bonding of coordinatively unsaturated metal centers in HKUST-1 with -SH group in dithioglycol. The obtained thiol-functionalized samples were characterized by powder X-ray diffraction, scanning electron microscope, energy dispersive X-ray spectroscopy, infrared spectroscopy, and N{sub 2} sorption-desorption isothermal. Significantly, the thiol-functionalized [Cu{sub 3}(BTC){sub 2}]{sub n} exhibited remarkably high adsorption affinity (K{sub d} = 4.73 Multiplication-Sign 10{sup 5} mL g{sup -1}) and high adsorption capacity (714.29 mg g{sup -1}) for Hg{sup 2+} adsorption from water, while the unfunctionalized HKUST-1 showed no adsorption of Hg{sup 2+} under the same condition.

  15. Optimization on electrochemical synthesis of HKUST-1 as candidate catalytic material for Green diesel production

    Lestari, W. W.; Nugraha, R. E.; Winarni, I. D.; Adreane, M.; Rahmawati, F.

    2016-04-01

    In the effort to support the discovery of new renewable energy sources in Indonesia, biofuel is one of promising options. The conversion of vegetable oil into ready-biofuel, especially green diesel, needs several steps, one of which is a hydrogenation or hydro-deoxygenation reaction. In this case, the catalyst plays a very important role regarding to its activity and selectivity, and Metal-Organic Frameworks (MOFs) becoming a new generation of heterogeneous catalyst in this area. In this research, a preliminary study to optimize electrochemical synthesis of the catalytic material based on MOFs, namely HKUST-1 [Cu3(BTC)2], has been conducted. Some electrochemical reaction parameters were tested, for example by modifying the electrochemical synthetic conditions, i.e. by performing variation of voltages (12, 13, 14, and 15 Volt), temperatures (RT, 40, 60, and 80 °C) and solvents (ethanol, water, methanol and dimethyl-formamide (DMF)). Material characterization was carried out by XRD, SEM, FTIR, DTA/TG and SAA. The results showed that the optimum synthetic conditions of HKUST-1 are performed at room temperature in a solvent combination of water: ethanol (1: 1) and a voltage of 15 Volt for 2 hours. The XRD-analysis revealed that the resulted peaks are identical to the simulated powder pattern generated from single crystal data and comparable to the peaks of solvothermal method. However, the porosity of the resulting material through electrochemical method is still in the range of micro-pore according to IUPAC and 50% smaller than the porosity resulted from solvothermal synthesis. The corresponding compounds are thermally stable until 300 °C according to TG/DTA.

  16. Cu(1+) in HKUST-1: selective gas adsorption in the presence of water.

    Nijem, Nour; Bluhm, Hendrik; Ng, May L; Kunz, Martin; Leone, Stephen R; Gilles, Mary K

    2014-09-11

    Spectroscopic evidence for an enhanced binding of Nitric Oxide (NO) to metal centers with lower oxidation states (open Cu(1+) sites) in Cu3(btc)2 (HKUST-1) is presented. The Cu(1+) sites created by thermal treatment or X-ray exposure exhibit a preferential adsorption of NO compared to H2O. This phenomenon demonstrates the potential use of MOFs with lower oxidation state metal centers for selective gas separation.

  17. Analysis of organic sulfur compounds in atmospheric aerosols at the HKUST supersite in Hong Kong using HR-ToF-AMS.

    Huang, Dan Dan; Li, Yong Jie; Lee, Berto P; Chan, Chak K

    2015-03-17

    Organic sulfur compounds have been identified in ambient secondary organic aerosols, but their contribution to organic mass is not well quantified. In this study, using a high-resolution time-of-flight aerosol mass spectrometer (AMS), concentrations of organic sulfur compounds were estimated based on the high-resolution fragmentation patterns of methanesulfonic acid (MSA), and organosulfates (OS), including alkyl, phenyl, and cycloalkyl sulfates, obtained in laboratory experiments. Mass concentrations of MSA and minimum mass concentrations of OS were determined in a field campaign conducted at a coastal site of Hong Kong in September 2011. MSA and OS together accounted for at least 5% of AMS detected organics. MSA is of marine origin with its formation dominated by local photochemical activities and enhanced by aqueous phase processing. OS concentrations are better correlated with particle liquid water content (LWC) than with particle acidity. High-molecular-weight OS were detected in the continental influenced period probably because they had grown into larger molecules during long-range transport or they were formed from large anthropogenic precursors. This study highlights the importance of both aqueous-phase processing and regional influence, i.e., different air mass origins, on organic sulfur compound formation in coastal cities like Hong Kong.

  18. Metal-Organic Framework Modified Glass Substrate for Analysis of Highly Volatile Chemical Warfare Agents by Paper Spray Mass Spectrometry.

    Dhummakupt, Elizabeth S; Carmany, Daniel O; Mach, Phillip M; Tovar, Trenton M; Ploskonka, Ann M; Demond, Paul S; DeCoste, Jared B; Glaros, Trevor

    2018-03-07

    Paper spray mass spectrometry has been shown to successfully analyze chemical warfare agent (CWA) simulants. However, due to the volatility differences between the simulants and real G-series (i.e., sarin, soman) CWAs, analysis from an untreated paper substrate proved difficult. To extend the analytical lifetime of these G-agents, metal-organic frameworks (MOFs) were successfully integrated onto the paper spray substrates to increase adsorption and desorption. In this study, several MOFs and nanoparticles were tested to extend the analytical lifetimes of sarin, soman, and cyclosarin on paper spray substrates. It was found that the addition of either UiO-66 or HKUST-1 to the paper substrate increased the analytical lifetime of the G-agents from less than 5 min detectability to at least 50 min.

  19. Time-resolved terahertz spectroscopy of electrically conductive metal-organic frameworks doped with redox active species

    Alberding, Brian G.; Heilweil, Edwin J.

    2015-09-01

    Metal-Organic Frameworks (MOFs) are three-dimensional coordination polymers that are well known for large pore surface area and their ability to adsorb molecules from both the gaseous and solution phases. In general, MOFs are electrically insulating, but promising opportunities for tuning the electronic structure exist because MOFs possess synthetic versatility; the metal and organic ligand subunits can be exchanged or dopant molecules can be introduced into the pore space. Two such MOFs with demonstrated electrical conductivity are Cu3(1,3,5-benzenetricarboxylate)2, a.k.a HKUST-1, and Cu[Ni(pyrazine-2,3-dithiolate)2]. Herein, these two MOFs have been infiltrated with the redox active species 7,7,8,8-tetracyanoquinodimethane (TCNQ) and iodine under solution phase conditions and shown to produce redox products within the MOF pore space. Vibrational bands assignable to TCNQ anion and triiodide anion have been observed in the Mid-IR and Terahertz ranges using FTIR Spectroscopy. The MOF samples have been further investigated by Time-Resolved Terehertz Spectroscopy (TRTS). Using this technique, the charge mobility, separation, and recombination dynamics have been followed on the picosecond time scale following photoexcitation with visible radiation. The preliminary results show that the MOF samples have small inherent photoconductivity with charge separation lifetimes on the order of a few picoseconds. In the case of HKUST-1, the MOF can also be supported by a TiO2 film and initial results show that charge injection into the TiO2 layer occurs with a comparable efficiency to the dye sensitizer N3, [cis-Bis(isothiocyanato)-bis(2,2'-bipyridyl-4,4'-dicarboxylato ruthenium(II)], and therefore this MOF has potential as a new light absorbing and charge conducting material in photovoltaic devices.

  20. Thin films of metal-organic compounds and metal nanoparticle

    Thin films of metal-organic compounds and metal nanoparticle-embedded polymers for nonlinear optical applications. S Philip Anthony Shatabdi Porel D ... Thin films based on two very different metal-organic systems are developed and some nonlinear optical applications are explored. A family of zinc complexes which ...

  1. Structural properties of metal-organic frameworks within the density-functional based tight-binding method

    Lukose, Binit; Supronowicz, Barbara; Kuc, Agnieszka B.; Heine, Thomas [School of Engineering and Science, Jacobs University Bremen (Germany); Petkov, Petko S.; Vayssilov, Georgi N. [Faculty of Chemistry, University of Sofia (Bulgaria); Frenzel, Johannes [Lehrstuhl fuer Theoretische Chemie, Ruhr-Universitaet Bochum (Germany); Seifert, Gotthard [Physikalische Chemie, Technische Universitaet Dresden (Germany)

    2012-02-15

    Density-functional based tight-binding (DFTB) is a powerful method to describe large molecules and materials. Metal-organic frameworks (MOFs), materials with interesting catalytic properties and with very large surface areas, have been developed and have become commercially available. Unit cells of MOFs typically include hundreds of atoms, which make the application of standard density-functional methods computationally very expensive, sometimes even unfeasible. The aim of this paper is to prepare and to validate the self-consistent charge-DFTB (SCC-DFTB) method for MOFs containing Cu, Zn, and Al metal centers. The method has been validated against full hybrid density-functional calculations for model clusters, against gradient corrected density-functional calculations for supercells, and against experiment. Moreover, the modular concept of MOF chemistry has been discussed on the basis of their electronic properties. We concentrate on MOFs comprising three common connector units: copper paddlewheels (HKUST-1), zinc oxide Zn{sub 4}O tetrahedron (MOF-5, MOF-177, DUT-6 (MOF-205)), and aluminum oxide AlO{sub 4}(OH){sub 2} octahedron (MIL-53). We show that SCC-DFTB predicts structural parameters with a very good accuracy (with less than 5% deviation, even for adsorbed CO and H{sub 2}O on HKUST-1), while adsorption energies differ by 12 kJ mol{sup -1} or less for CO and water compared to DFT benchmark calculations. (Copyright copyright 2012 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  2. Solvothermal and electrochemical synthetic method of HKUST-1 and its methane storage capacity

    Wahyu Lestari, Witri; Adreane, Marisa; Purnawan, Candra; Fansuri, Hamzah; Widiastuti, Nurul; Budi Rahardjo, Sentot

    2016-02-01

    A comparison synthetic strategy of Metal-Organic Frameworks, namely, Hongkong University of Techhnology-1 {HKUST-1[Cu3(BTC)]2} (BTC = 1,3,5-benzene-tri-carboxylate) through solvothermal and electrochemical method in ethanol:water (1:1) has been conducted. The obtained material was analyzed using powder X-ray diffraction, Scanning Electron Microscopy (SEM), Fourier Transform Infrared Spectroscopy (FTIR), Thermo-Gravimetric Analysis (TGA) and Surface Area Analysis (SAA). While the voltage in the electrochemical method are varied, ranging from 12 to 15 Volt. The results show that at 15 V the texture of the material has the best degree of crystallinity and comparable with solvothermal product. This indicated from XRD data and supported by the SEM image to view the morphology. The thermal stability of the synthesized compounds is up to 320 °C. The shape of the nitrogen sorption isotherm of the compound corresponds to type I of the IUPAC adsorption isotherm classification for microporous materials with BET surface area of 629.2 and 324.3 m2/g (for solvothermal and electrochemical product respectively) and promising for gas storage application. Herein, the methane storage capacities of these compounds are also tested.

  3. Hydrogen storage in metal-organic frameworks: An investigation of structure-property relationships

    Rowsell, Jesse

    Metal-organic frameworks (MOFs) have been identified as candidate hydrogen storage materials due to their ability to physisorb large quantities of small molecules. Thirteen compounds (IRMOF-1, -2, -3, -6, -8, -9, -11, -13, -18, -20, MOF-74, MOF-177 and HKUST-1) have been prepared and fully characterized for the evaluation of their dihydrogen (H2) adsorption properties. All compounds display approximately type I isotherms with no hysteresis at 77 K up to 1 atm. The amount adsorbed ranges from 0.89 to 2.54 wt%; however, saturation is not achieved under these conditions. The influences of link functionalization, catenation and topology are examined for the eleven MOFs composed of Zn4O(O2C-)6 clusters. Enhanced H2 uptake by catenated compounds is rationalized by increased overlap of the surface potentials within their narrower pores. This is corroborated by the larger isosteric heat of adsorption of IRMOF-11 compared to IRMOF-1. Inelastic neutron scattering spectroscopic analysis of four Zn4O-based materials (IRMOF-1, -8, -11, and MOF-74) under a range of H2 loading suggests the presence of multiple localized adsorption sites on both the inorganic and organic moieties. To determine the structural details of the adsorption sites, variable temperature single crystal X-ray diffraction was used to analyze adsorbed argon and dinitrogen molecules in IRMOF-1. The principle binding site was found to be the same for both adsorbates and is located on faces of the octahedral Zn4O(O2C-)6 clusters with close contacts to three carboxylate groups. A total of eight symmetry-independent adsorption sites were identified for argon at 30 K. Similar sites were observed for dinitrogen, suggesting that they are good model adsorbates for the behaviour of dihydrogen. Two additional materials composed of inorganic clusters with coordinatively unsaturated metal sites (MOF-74, HKUST-1) were examined and their increased capacities and isosteric heats of adsorption provide further evidence that the

  4. Gas adsorption on metal-organic frameworks

    Willis, Richard R [Cary, IL; Low, John J. , Faheem, Syed A.; Benin, Annabelle I [Oak Forest, IL; Snurr, Randall Q [Evanston, IL; Yazaydin, Ahmet Ozgur [Evanston, IL

    2012-07-24

    The present invention involves the use of certain metal organic frameworks that have been treated with water or another metal titrant in the storage of carbon dioxide. The capacity of these frameworks is significantly increased through this treatment.

  5. Site-selective growth of surface-anchored metal-organic frameworks on self-assembled monolayer patterns prepared by AFM nanografting

    Tatjana Ladnorg

    2013-10-01

    Full Text Available Surface anchored metal-organic frameworks, SURMOFs, are highly porous materials, which can be grown on modified substrates as highly oriented, crystalline coatings by a quasi-epitaxial layer-by-layer method (liquid-phase epitaxy, or LPE. The chemical termination of the supporting substrate is crucial, because the most convenient method for substrate modification is the formation of a suitable self-assembled monolayer. The choice of a particular SAM also allows for control over the orientation of the SURMOF. Here, we demonstrate for the first time the site-selective growth of the SURMOF HKUST-1 on thiol-based self-assembled monolayers patterned by the nanografting technique, with an atomic force microscope as a structuring tool. Two different approaches were applied: The first one is based on 3-mercaptopropionic acid molecules which are grafted in a 1-decanethiolate SAM, which serves as a matrix for this nanolithography. The second approach uses 16-mercaptohexadecanoic acid, which is grafted in a matrix of an 1-octadecanethiolate SAM. In both cases a site-selective growth of the SURMOF is observed. In the latter case the roughness of the HKUST-1 is found to be significantly higher than for the 1-mercaptopropionic acid. The successful grafting process was verified by time-of-flight secondary ion mass spectrometry and atomic force microscopy. The SURMOF structures grown via LPE were investigated and characterized by atomic force microscopy and Fourier-transform infrared microscopy.

  6. Site-selective growth of surface-anchored metal-organic frameworks on self-assembled monolayer patterns prepared by AFM nanografting

    Ladnorg, Tatjana; Welle, Alexander; Heißler, Stefan; Wöll, Christof

    2013-01-01

    Summary Surface anchored metal-organic frameworks, SURMOFs, are highly porous materials, which can be grown on modified substrates as highly oriented, crystalline coatings by a quasi-epitaxial layer-by-layer method (liquid-phase epitaxy, or LPE). The chemical termination of the supporting substrate is crucial, because the most convenient method for substrate modification is the formation of a suitable self-assembled monolayer. The choice of a particular SAM also allows for control over the orientation of the SURMOF. Here, we demonstrate for the first time the site-selective growth of the SURMOF HKUST-1 on thiol-based self-assembled monolayers patterned by the nanografting technique, with an atomic force microscope as a structuring tool. Two different approaches were applied: The first one is based on 3-mercaptopropionic acid molecules which are grafted in a 1-decanethiolate SAM, which serves as a matrix for this nanolithography. The second approach uses 16-mercaptohexadecanoic acid, which is grafted in a matrix of an 1-octadecanethiolate SAM. In both cases a site-selective growth of the SURMOF is observed. In the latter case the roughness of the HKUST-1 is found to be significantly higher than for the 1-mercaptopropionic acid. The successful grafting process was verified by time-of-flight secondary ion mass spectrometry and atomic force microscopy. The SURMOF structures grown via LPE were investigated and characterized by atomic force microscopy and Fourier-transform infrared microscopy. PMID:24205458

  7. Superconductivity in Layered Organic Metals

    Jochen Wosnitza

    2012-04-01

    Full Text Available In this short review, I will give an overview on the current understanding of the superconductivity in quasi-two-dimensional organic metals. Thereby, I will focus on charge-transfer salts based on bis(ethylenedithiotetrathiafulvalene (BEDT-TTF or ET for short. In these materials, strong electronic correlations are clearly evident, resulting in unique phase diagrams. The layered crystallographic structure leads to highly anisotropic electronic as well as superconducting properties. The corresponding very high orbital critical field for in-plane magnetic-field alignment allows for the occurrence of the Fulde–Ferrell– Larkin–Ovchinnikov state as evidenced by thermodynamic measurements. The experimental picture on the nature of the superconducting state is still controversial with evidence both for unconventional as well as for BCS-like superconductivity.

  8. Liquid metal-organic frameworks

    Gaillac, Romain; Pullumbi, Pluton; Beyer, Kevin A.; Chapman, Karena W.; Keen, David A.; Bennett, Thomas D.; Coudert, François-Xavier

    2017-11-01

    Metal-organic frameworks (MOFs) are a family of chemically diverse materials, with applications in a wide range of fields, covering engineering, physics, chemistry, biology and medicine. Until recently, research has focused almost entirely on crystalline structures, yet now a clear trend is emerging, shifting the emphasis onto disordered states, including `defective by design’ crystals, as well as amorphous phases such as glasses and gels. Here we introduce a strongly associated MOF liquid, obtained by melting a zeolitic imidazolate framework. We combine in situ variable temperature X-ray, ex situ neutron pair distribution function experiments, and first-principles molecular dynamics simulations to study the melting phenomenon and the nature of the liquid obtained. We demonstrate from structural, dynamical, and thermodynamical information that the chemical configuration, coordinative bonding, and porosity of the parent crystalline framework survive upon formation of the MOF liquid.

  9. Stress-induced chemical detection using flexible metal-organic frameworks.

    Allendorf, Mark D; Houk, Ronald J T; Andruszkiewicz, Leanne; Talin, A Alec; Pikarsky, Joel; Choudhury, Arnab; Gall, Kenneth A; Hesketh, Peter J

    2008-11-05

    In this work we demonstrate the concept of stress-induced chemical detection using metal-organic frameworks (MOFs) by integrating a thin film of the MOF HKUST-1 with a microcantilever surface. The results show that the energy of molecular adsorption, which causes slight distortions in the MOF crystal structure, can be converted to mechanical energy to create a highly responsive, reversible, and selective sensor. This sensor responds to water, methanol, and ethanol vapors, but yields no response to either N2 or O2. The magnitude of the signal, which is measured by a built-in piezoresistor, is correlated with the concentration and can be fitted to a Langmuir isotherm. Furthermore, we show that the hydration state of the MOF layer can be used to impart selectivity to CO2. Finally, we report the first use of surface-enhanced Raman spectroscopy to characterize the structure of a MOF film. We conclude that the synthetic versatility of these nanoporous materials holds great promise for creating recognition chemistries to enable selective detection of a wide range of analytes.

  10. Minerals with metal-organic framework structures.

    Huskić, Igor; Pekov, Igor V; Krivovichev, Sergey V; Friščić, Tomislav

    2016-08-01

    Metal-organic frameworks (MOFs) are an increasingly important family of advanced materials based on open, nanometer-scale metal-organic architectures, whose design and synthesis are based on the directed assembly of carefully designed subunits. We now demonstrate an unexpected link between mineralogy and MOF chemistry by discovering that the rare organic minerals stepanovite and zhemchuzhnikovite exhibit structures found in well-established magnetic and proton-conducting metal oxalate MOFs. Structures of stepanovite and zhemchuzhnikovite, exhibiting almost nanometer-wide and guest-filled apertures and channels, respectively, change the perspective of MOFs as exclusively artificial materials and represent, so far, unique examples of open framework architectures in organic minerals.

  11. Screening metal-organic frameworks for selective noble gas adsorption in air: effect of pore size and framework topology.

    Parkes, Marie V; Staiger, Chad L; Perry, John J; Allendorf, Mark D; Greathouse, Jeffery A

    2013-06-21

    The adsorption of noble gases and nitrogen by sixteen metal-organic frameworks (MOFs) was investigated using grand canonical Monte Carlo simulation. The MOFs were chosen to represent a variety of net topologies, pore dimensions, and metal centers. Three commercially available MOFs (HKUST-1, AlMIL-53, and ZIF-8) and PCN-14 were also included for comparison. Experimental adsorption isotherms, obtained from volumetric and gravimetric methods, were used to compare krypton, argon, and nitrogen uptake with the simulation results. Simulated trends in gas adsorption and predicted selectivities among the commercially available MOFs are in good agreement with experiment. In the low pressure regime, the expected trend of increasing adsorption with increasing noble gas polarizabilty is seen. For each noble gas, low pressure adsorption correlates with several MOF properties, including free volume, topology, and metal center. Additionally, a strong correlation exists between the Henry's constant and the isosteric heat of adsorption for all gases and MOFs considered. Finally, we note that the simulated and experimental gas selectivities demonstrated by this small set of MOFs show improved performance compared to similar values reported for zeolites.

  12. A novel mechanochemical method for reconstructing the moisture-degraded HKUST-1.

    Sun, Xuejiao; Li, Hao; Li, Yujie; Xu, Feng; Xiao, Jing; Xia, Qibin; Li, Yingwei; Li, Zhong

    2015-07-11

    A novel mechanochemical method was proposed to reconstruct quickly moisture-degraded HKUST-1. The degraded HKUST-1 can be restored within minutes. The reconstructed samples were characterized, and confirmed to have 95% surface area and 92% benzene capacity of the fresh HKUST-1. It is a simple and effective strategy for degraded MOF reconstruction.

  13. Self-organization in metal complexes

    Radecka-Paryzek, W.

    1999-01-01

    Inorganic self-organization involves the spontaneous generation of well-defined supramolecular architectures from metal ions and organic ligands. The basic concept of supramolecular chemistry is a molecular recognition. When the substrate are metal ions, recognition is expressed in the stability and selectivity of metal ion complexation by organic ligands and depends on the geometry of the ligand and on their binding sites that it contains. The combination of the geometric features of the ligand units and the coordination geometries of the metal ions provides very efficient tool for the synthesis of novel, intriguing and highly sophisticated species such as catenanes, box structures, double and triple helicates with a variety of interesting properties. The article will focus on the examples of inorganic self-organization involving the templating as a first step for the assembly of supramolecular structures of high complexity. (author)

  14. Metal organic frameworks for gas storage

    Alezi, Dalal

    2016-06-09

    Embodiments provide a method of storing a compound using a metal organic framework (MOF). The method includes contacting one or more MOFs with a fluid and sorbing one or more compounds, such as O2 and CH4. O2 and CH4 can be sorbed simultaneously or in series. The metal organic framework can be an M-soc-MOF, wherein M can include aluminum, iron, gallium, indium, vanadium, chromium, titanium, or scandium.

  15. Tailoring the nanoscale morphology of HKUST-1 thin films via codeposition and seeded growth.

    Brower, Landon J; Gentry, Lauren K; Napier, Amanda L; Anderson, Mary E

    2017-01-01

    Integration of surface-anchored metal-organic frameworks (surMOFs) within hierarchical architectures is necessary for potential sensing, electronic, optical, or separation applications. It is important to understand the fundamentals of film formation for these surMOFs in order to develop strategies for their incorporation with nanoscale control over lateral and vertical dimensions. This research identified processing parameters to control the film morphology for surMOFs of HKUST-1 fabricated by codeposition and seeded deposition. Time and temperature were investigated to observe film formation, to control film thickness, and to tune morphology. Film thickness was investigated by ellipsometry, while film structure and film roughness were characterized by atomic force microscopy. Films formed via codeposition resulted in nanocrystallites anchored to the gold substrate. A dynamic process at the interface was observed with a low density of large particulates (above 100 nm) initially forming on the substrate; and over time these particulates were slowly replaced by the prevalence of smaller crystallites (ca. 10 nm) covering the substrate at a high density. Elevated temperature was found to expedite the growth process to obtain the full range of surface morphologies with reasonable processing times. Seed crystals formed by the codeposition method were stable and nucleated growth throughout a subsequent layer-by-layer deposition process. These seed crystals templated the final film structure and tailor the features in lateral and vertical directions. Using codeposition and seeded growth, different surface morphologies with controllable nanoscale dimensions can be designed and fabricated for integration of MOF systems directly into device architectures and sensor platforms.

  16. Tailoring the nanoscale morphology of HKUST-1 thin films via codeposition and seeded growth

    Landon J. Brower

    2017-11-01

    Full Text Available Integration of surface-anchored metal-organic frameworks (surMOFs within hierarchical architectures is necessary for potential sensing, electronic, optical, or separation applications. It is important to understand the fundamentals of film formation for these surMOFs in order to develop strategies for their incorporation with nanoscale control over lateral and vertical dimensions. This research identified processing parameters to control the film morphology for surMOFs of HKUST-1 fabricated by codeposition and seeded deposition. Time and temperature were investigated to observe film formation, to control film thickness, and to tune morphology. Film thickness was investigated by ellipsometry, while film structure and film roughness were characterized by atomic force microscopy. Films formed via codeposition resulted in nanocrystallites anchored to the gold substrate. A dynamic process at the interface was observed with a low density of large particulates (above 100 nm initially forming on the substrate; and over time these particulates were slowly replaced by the prevalence of smaller crystallites (ca. 10 nm covering the substrate at a high density. Elevated temperature was found to expedite the growth process to obtain the full range of surface morphologies with reasonable processing times. Seed crystals formed by the codeposition method were stable and nucleated growth throughout a subsequent layer-by-layer deposition process. These seed crystals templated the final film structure and tailor the features in lateral and vertical directions. Using codeposition and seeded growth, different surface morphologies with controllable nanoscale dimensions can be designed and fabricated for integration of MOF systems directly into device architectures and sensor platforms.

  17. Stress-induced chemical detection using flexible metal-organic frameworks.

    Allendorf, Mark D.; Hesketh, Peter J. (Georgia Institute of Technology, Atlanta, GA); Gall, Kenneth A. (Georgia Institute of Technology, Atlanta, GA); Choudhury, A. (Georgia Institute of Technology, Atlanta, GA); Pikarsky, J. (Georgia Institute of Technology, Atlanta, GA); Andruszkiewicz, Leanne (Georgia Institute of Technology, Atlanta, GA); Houk, Ronald J. T.; Talin, Albert Alec (National Institute of Standards & Technology, Gaithersburg, MD)

    2009-09-01

    In this work we demonstrate the concept of stress-induced chemical detection using metal-organic frameworks (MOFs) by integrating a thin film of the MOF HKUST-1 with a microcantilever surface. The results show that the energy of molecular adsorption, which causes slight distortions in the MOF crystal structure, can be efficiently converted to mechanical energy to create a highly responsive, reversible, and selective sensor. This sensor responds to water, methanol, and ethanol vapors, but yields no response to either N{sub 2} or O{sub 2}. The magnitude of the signal, which is measured by a built-in piezoresistor, is correlated with the concentration and can be fitted to a Langmuir isotherm. Furthermore, we show that the hydration state of the MOF layer can be used to impart selectivity to CO{sub 2}. We also report the first use of surface-enhanced Raman spectroscopy to characterize the structure of a MOF film. We conclude that the synthetic versatility of these nanoporous materials holds great promise for creating recognition chemistries to enable selective detection of a wide range of analytes. A force field model is described that successfully predicts changes in MOF properties and the uptake of gases. This model is used to predict adsorption isotherms for a number of representative compounds, including explosives, nerve agents, volatile organic compounds, and polyaromatic hydrocarbons. The results show that, as a result of relatively large heats of adsorption (> 20 kcal mol{sup -1}) in most cases, we expect an onset of adsorption by MOF as low as 10{sup -6} kPa, suggesting the potential to detect compounds such as RDX at levels as low as 10 ppb at atmospheric pressure.

  18. Methane storage in metal-organic frameworks.

    He, Yabing; Zhou, Wei; Qian, Guodong; Chen, Banglin

    2014-08-21

    Natural gas (NG), whose main component is methane, is an attractive fuel for vehicular applications. Realization of safe, cheap and convenient means and materials for high-capacity methane storage can significantly facilitate the implementation of natural gas fuelled vehicles. The physisorption based process involving porous materials offers an efficient storage methodology and the emerging porous metal-organic frameworks have been explored as potential candidates because of their extraordinarily high porosities, tunable pore/cage sizes and easily immobilized functional sites. In this view, we provide an overview of the current status of metal-organic frameworks for methane storage.

  19. Impacts of metal and metal oxide nanoparticles on marine organisms

    Baker, Tony J.; Tyler, Charles R.; Galloway, Tamara S.

    2014-01-01

    Increasing use of metal and metal oxide nanoparticles [Me(O)NPs] in products means many will inevitably find their way into marine systems. Their likely fate here is sedimentation following hetero-aggregation with natural organic matter and/or free anions, putting benthic, sediment-dwelling and filter feeding organisms most at risk. In marine systems, Me(O)NPs can absorb to micro-organisms with potential for trophic transfer following consumption. Filter feeders, especially bivalves, accumulate Me(O)NPs through trapping them in mucus prior to ingestion. Benthic in-fauna may directly ingest sedimented Me(O)NPs. In fish, uptake is principally via the gut following drinking, whilst Me(O)NPs caught in gill mucus may affect respiratory processes and ion transport. Currently, environmentally-realistic Me(O)NP concentrations are unlikely to cause significant adverse acute health problems, however sub-lethal effects e.g. oxidative stresses have been noted in many organisms, often deriving from dissolution of Ag, Cu or Zn ions, and this could result in chronic health impacts. -- Highlights: • Nanoparticle (NP) use increasing, and NPs ultimately discharged to marine systems. • Metal ion dissolution from NPs causes oxidative stress at relevant concentrations. • Bioaccumulation and trophic transfer of NPs likely at all levels of marine food webs. • Biofilms and filter feeders are major NP accumulators, but many Classes lack study. • Current release levels unlikely to cause chronic damage, but may be a future issue. -- Exposure to metal (oxide) nanoparticles causes sub-lethal effects in marine organisms, the extent of which is related principally to the organisms' feeding regime, habitat and lifestyle

  20. Disorder and conductivity of organic metal

    Bouffard, Serge

    1982-02-01

    At high temperature, quasi-one-dimensional organic conductors are metallic; at low temperature, the electron gas instabilities drive either a metal to insulator transition or a metal to superconductor transition. Precursors of these 3-D ordering could be appear at higher temperature. A study of the effects of irradiation induced defects on a few organic complexes has shown that defects are produced by radiolitic process. Their concentration can be easily deduced from resistivity measurement at room temperature. In the metallic state, the defects act as strong potentials which break the conducting chains and force the electron to jump to the neighbourg stack. The defects produce a mixing between longitudinal and transverse conductivities. While, it is the 3-D effect of the defects which pins the charge density waves and thus the 3-D ordering can not be acheived: the metal to insulator transition is destroyed, the metallic state is stabilized. In the same time, the fluctuative conductivity is suppress. The superconducting regime has been found to be extremely sensitive to irradiation induced defects. Thus we can demonstrate that the 1-D superconducting fluctuations contribute to the conductivity and that the transition temperature is correlated to the 3-D superconducting fluctuations. [fr

  1. Manipulating Light with Transition Metal Clusters, Organic Dyes, and Metal Organic Frameworks

    Ogut, Serdar [Univ. of Illinois, Chicago, IL (United States)

    2017-09-11

    The primary goals of our research program is to develop and apply state-of-the-art first-principles methods to predict electronic and optical properties of three systems of significant scientific and technological interest: transition metal clusters, organic dyes, and metal-organic frameworks. These systems offer great opportunities to manipulate light for a wide ranging list of energy-related scientific problems and applications. During this grant period, we focused our investigations on the development, implementation, and benchmarking of many-body Green’s function methods (GW approximation and the Bethe-Salpeter equation) to examine excited-state properties of transition metal/transition-metal-oxide clusters and organic molecules that comprise the building blocks of dyes and metal-organic frameworks.

  2. Supercapacitors of nanocrystalline metal-organic frameworks.

    Choi, Kyung Min; Jeong, Hyung Mo; Park, Jung Hyo; Zhang, Yue-Biao; Kang, Jeung Ku; Yaghi, Omar M

    2014-07-22

    The high porosity of metal-organic frameworks (MOFs) has been used to achieve exceptional gas adsorptive properties but as yet remains largely unexplored for electrochemical energy storage devices. This study shows that MOFs made as nanocrystals (nMOFs) can be doped with graphene and successfully incorporated into devices to function as supercapacitors. A series of 23 different nMOFs with multiple organic functionalities and metal ions, differing pore sizes and shapes, discrete and infinite metal oxide backbones, large and small nanocrystals, and a variety of structure types have been prepared and examined. Several members of this series give high capacitance; in particular, a zirconium MOF exhibits exceptionally high capacitance. It has the stack and areal capacitance of 0.64 and 5.09 mF cm(-2), about 6 times that of the supercapacitors made from the benchmark commercial activated carbon materials and a performance that is preserved over at least 10000 charge/discharge cycles.

  3. Metal organic frameworks for gas storage

    Alezi, Dalal; Belmabkhout, Youssef; Eddaoudi, Mohamed

    2016-01-01

    Embodiments provide a method of storing a compound using a metal organic framework (MOF). The method includes contacting one or more MOFs with a fluid and sorbing one or more compounds, such as O2 and CH4. O2 and CH4 can be sorbed simultaneously

  4. The relevance of metal organic frameworks (MOFs)

    The metal organic frameworks (MOFs) have evolved to be an important family and a corner stone for research in the area of inorganic chemistry. The progress made since 2000 has attracted researchers from other disciplines to actively engage themselves in this area. This cooperative synergy of different scientific believes ...

  5. Magnetic behaviour in metal-organic frameworks

    The article describes the synthesis, structure and magnetic investigations of a series of metal-organic framework compounds formed with Mn+2 and Ni+2 ions. The structures, determined using the single crystal X-ray diffraction, indicated that the structures possess two- and three-dimensional structures with magnetically ...

  6. Preparation of Hydrophobic Metal-Organic Frameworks via Plasma Enhanced Chemical Vapor Deposition of Perfluoroalkanes for the Removal of Ammonia

    DeCoste, Jared B.; Peterson, Gregory W.

    2013-01-01

    Plasma enhanced chemical vapor deposition (PECVD) of perfluoroalkanes has long been studied for tuning the wetting properties of surfaces. For high surface area microporous materials, such as metal-organic frameworks (MOFs), unique challenges present themselves for PECVD treatments. Herein the protocol for development of a MOF that was previously unstable to humid conditions is presented. The protocol describes the synthesis of Cu-BTC (also known as HKUST-1), the treatment of Cu-BTC with PECVD of perfluoroalkanes, the aging of materials under humid conditions, and the subsequent ammonia microbreakthrough experiments on milligram quantities of microporous materials. Cu-BTC has an extremely high surface area (~1,800 m2/g) when compared to most materials or surfaces that have been previously treated by PECVD methods. Parameters such as chamber pressure and treatment time are extremely important to ensure the perfluoroalkane plasma penetrates to and reacts with the inner MOF surfaces. Furthermore, the protocol for ammonia microbreakthrough experiments set forth here can be utilized for a variety of test gases and microporous materials. PMID:24145623

  7. Chemical Property Change in a Metal-Organic Framework by Fluoro Functionality

    Ko, Nakeun; Hong, Jisu; You, Laekyeong; Park, Hye Jeong; Yang, Jin Kuk; Kim, Jaheon

    2015-01-01

    A fluorine-functionalized HKUST-1 (HKUST-1-F) has been synthesized by a solvo thermal reaction between copper nitrate and a potassium salt of 2-fluoro-1,3,5-benzenetricarboxylic acid (K[H 2 BTC-F]). HKUST-1-F shows nearly the same crystal structure as that of UHM-31, a known fluorinated HKUST-1. Because of its reduced surface area, HKUST-1-F takes up smaller amounts of gases (N 2 , H 2 , CO 2 ) than UHM-31 at 1 bar. After a water vapor adsorption measurement at 298 K, HKUST-1-F turned into an unknown structure, based on powder X-ray diffraction analyses. HKUST-1-F could be further functionalized with benzylamine in a post synthetic modification; the nucleophilic replacement of the F atom in BTC-F with benzylamine in methylene chloride at room temperature took place in a conversion yield of -38% based on 1H NMR analyses

  8. Preparation and Drug-Delivery Properties of HKUST-1/GO Hybrid.

    Sun, Ke Ke; Li, Ling; He, Yu Qi; Fan, Lu; Wu, Ya Qi; Liu, Li

    2016-01-01

    A hybrid HKUST-1/GO composite was synthesized and its drug loading and drug release abilities were investigated. The adsorption of IBU (ibuprofen) onto the surface of HKUST-1/GO and HKUST-1 composites was compared, and it was found that the addition of GO enhanced both IBU loading and stability. The addition of GO also enhanced the specific surface area. Drug release experiments on IBU loaded HKUST-1 and HKUST-1/GO were conducted, and it was found that drug release of HKUST-1/GO was slower, which can be explained by the hydrogen bonding between GO and IBU. It can be concluded that the addition of GO not only enhances drug loading, but can also achieve a more desirable slow-release of the drug.

  9. Current at Metal-Organic Interfaces

    Kern, Klaus

    2012-02-01

    Charge transport through atomic and molecular constrictions greatly affects the operation and performance of organic electronic devices. Much of our understanding of the charge injection and extraction processes in these systems relays on our knowledge of the electronic structure at the metal-organic interface. Despite significant experimental and theoretical advances in studying charge transport in nanoscale junctions, a microscopic understanding at the single atom/molecule level is missing. In the present talk I will present our recent results to probe directly the nanocontact between single molecules and a metal electrode using scanning probe microscopy and spectroscopy. The experiments provide unprecedented microscopic details of single molecule and atom junctions and open new avenues to study quantum critical and many body phenomena at the atomic scale. Implications for energy conversion devices and carbon based nanoelectronics will also be discussed.

  10. Nanomaterials derived from metal-organic frameworks

    Dang, Song; Zhu, Qi-Long; Xu, Qiang

    2018-01-01

    The thermal transformation of metal-organic frameworks (MOFs) generates a variety of nanostructured materials, including carbon-based materials, metal oxides, metal chalcogenides, metal phosphides and metal carbides. These derivatives of MOFs have characteristics such as high surface areas, permanent porosities and controllable functionalities that enable their good performance in sensing, gas storage, catalysis and energy-related applications. Although progress has been made to tune the morphologies of MOF-derived structures at the nanometre scale, it remains crucial to further our knowledge of the relationship between morphology and performance. In this Review, we summarize the synthetic strategies and optimized methods that enable control over the size, morphology, composition and structure of the derived nanomaterials. In addition, we compare the performance of materials prepared by the MOF-templated strategy and other synthetic methods. Our aim is to reveal the relationship between the morphology and the physico-chemical properties of MOF-derived nanostructures to optimize their performance for applications such as sensing, catalysis, and energy storage and conversion.

  11. Enhanced aging properties of HKUST-1 in hydrophobic mixed-matrix membranes for ammonia adsorption† †Electronic supplementary information (ESI) available: Experimental procedures. See DOI: 10.1039/c5sc04368a Click here for additional data file.

    Denny, Jr., Michael S.; Peterson, Gregory W.; Mahle, John J.

    2016-01-01

    Metal–organic frameworks (MOFs) in their free powder form have exhibited superior capacities for many gases when compared to other materials, due to their tailorable functionality and high surface areas. Specifically, the MOF HKUST-1 binds small Lewis bases, such as ammonia, with its coordinatively unsaturated copper sites. We describe here the use of HKUST-1 in mixed-matrix membranes (MMMs) prepared from polyvinylidene difluoride (PVDF) for the removal of ammonia gas. These MMMs exhibit ammonia capacities similar to their hypothetical capacities based on the weight percent of HKUST-1 in each MMM. HKUST-1 in its powder form is unstable toward humid conditions; however, upon exposure to humid environments for prolonged periods of time, the HKUST-1 MMMs exhibit outstanding structural stability, and maintain their ammonia capacity. Overall, this study has achieved all of the critical and combined elements for real-world applications of MOFs: high MOF loadings, fully accessible MOF surfaces, enhanced MOF stabilization, recyclability, mechanical stability, and processability. This study is a critical step in advancing MOFs to a stable, usable, and enabling technology. PMID:28660045

  12. Zeolite-like metal-organic frameworks with ana topology

    Eddaoudi, Mohamed; Mohideen, Mohamed Infas Haja; Adil, Karim; Belmabkhout, Youssef; Bhatt, Prashant M.; Shekhah, Osama; Chernikova, Valeriya

    2017-01-01

    Embodiments of the present disclosure describe a zeolite-like metal-organic framework composition comprising a metal-organic framework composition with ana topology characterized by the formula [MIII(4, 5-imidazole dicarboxylic acid)2X

  13. Microporous Metal Organic Materials for Hydrogen Storage

    S. G. Sankar; Jing Li; Karl Johnson

    2008-11-30

    We have examined a number of Metal Organic Framework Materials for their potential in hydrogen storage applications. Results obtained in this study may, in general, be summarized as follows: (1) We have identified a new family of porous metal organic framework materials with the compositions M (bdc) (ted){sub 0.5}, {l_brace}M = Zn or Co, bdc = biphenyl dicarboxylate and ted = triethylene diamine{r_brace} that adsorb large quantities of hydrogen ({approx}4.6 wt%) at 77 K and a hydrogen pressure of 50 atm. The modeling performed on these materials agree reasonably well with the experimental results. (2) In some instances, such as in Y{sub 2}(sdba){sub 3}, even though the modeling predicted the possibility of hydrogen adsorption (although only small quantities, {approx}1.2 wt%, 77 K, 50 atm. hydrogen), our experiments indicate that the sample does not adsorb any hydrogen. This may be related to the fact that the pores are extremely small or may be attributed to the lack of proper activation process. (3) Some samples such as Zn (tbip) (tbip = 5-tert butyl isophthalate) exhibit hysteresis characteristics in hydrogen sorption between adsorption and desorption runs. Modeling studies on this sample show good agreement with the desorption behavior. It is necessary to conduct additional studies to fully understand this behavior. (4) Molecular simulations have demonstrated the need to enhance the solid-fluid potential of interaction in order to achieve much higher adsorption amounts at room temperature. We speculate that this may be accomplished through incorporation of light transition metals, such as titanium and scandium, into the metal organic framework materials.

  14. H?, D? and HD adsorption upon the metal-organic framework [Cu?Zn?(btc)?]? studied by pulsed ENDOR and HYSCORE spectroscopy

    Jee, Bettina; Hartmann, Martin; Pöppl, Andreas

    2013-10-01

    The adsorption of hydrogen has become interesting in terms of gas separation as well as safe and reversible storage of hydrogen as an energy carrier. In this regard, metal-organic framework compounds are potential candidates. The metal-organic framework [Cu?Zn?(btc)?]? as a partially Zn-substituted analogue of the well known compound HKUST-1 is well suited for studying adsorption geometries at cupric ions by electron paramagnetic resonance (EPR) methods due to the formation of few mixed Cu/Zn paddle wheel units with isolated S = 1/2 electron spins. The adsorption of hydrogen (H2) as well as the deuterium (D2) and HD molecules were investigated by continuous wave EPR and pulsed ENDOR and HYSCORE spectroscopy. The principal values of the proton and deuterium hyperfine coupling tensors ? and ? were determined by spectral simulations as well as of the deuterium nuclear quadrupole tensor ? for adsorbed HD and D2. The results show a side-on coordination of HD and D2 with identical Cu-H and Cu-D distances rCuX = 2.8 Å with the tensors ? and ? aligned parallel to the C4 symmetry axis of the paddle wheel unit. A thermodynamic non-equilibrium state with J = 1, mJ = ±1 is indicated by the experimental data with ? and ? averaged by rotation around C4.

  15. On the dielectric and optical properties of surface-anchored metal-organic frameworks: A study on epitaxially grown thin films

    Redel, Engelbert; Wang, Zhengbang; Walheim, Stefan; Liu, Jinxuan; Gliemann, Hartmut; Wöll, Christof

    2013-08-01

    We determine the optical constants of two highly porous, crystalline metal-organic frameworks (MOFs). Since it is problematic to determine the optical constants for the standard powder modification of these porous solids, we instead use surface-anchored metal-organic frameworks (SURMOFs). These MOF thin films are grown using liquid phase epitaxy (LPE) on modified silicon substrates. The produced SURMOF thin films exhibit good optical properties; these porous coatings are smooth as well as crack-free, they do not scatter visible light, and they have a homogenous interference color over the entire sample. Therefore, spectroscopic ellipsometry (SE) can be used in a straightforward fashion to determine the corresponding SURMOF optical properties. After careful removal of the solvent molecules used in the fabrication process as well as the residual water adsorbed in the voids of this highly porous solid, we determine an optical constant of n = 1.39 at a wavelength of 750 nm for HKUST-1 (stands for Hong Kong University of Science and Technology-1; and was first discovered there) or [Cu3(BTC)2]. After exposing these SURMOF thin films to moisture/EtOH atmosphere, the refractive index (n) increases to n = 1.55-1.6. This dependence of the optical properties on water/EtOH adsorption demonstrates the potential of such SURMOF materials for optical sensing.

  16. Metal-organic frameworks in chromatography.

    Yusuf, Kareem; Aqel, Ahmad; ALOthman, Zeid

    2014-06-27

    Metal-organic frameworks (MOFs) emerged approximately two decades ago and are the youngest class of porous materials. Despite their short existence, MOFs are finding applications in a variety of fields because of their outstanding chemical and physical properties. This review article focuses on the applications of MOFs in chromatography, including high-performance liquid chromatography (HPLC), gas chromatography (GC), and other chromatographic techniques. The use of MOFs in chromatography has already had a significant impact; however, the utilisation of MOFs in chromatography is still less common than other applications, and the number of MOF materials explored in chromatography applications is limited. Copyright © 2014 Elsevier B.V. All rights reserved.

  17. Thin metal electrodes for semitransparent organic photovoltaics

    Lee, Kyusung

    2013-08-01

    We demonstrate semitransparent organic photovoltaics (OPVs) based on thin metal electrodes and polymer photoactive layers consisting of poly(3-hexylthiophene) and [6,6]-phenyl C61 butyric acid methyl ester. The power conversion efficiency of a semitransparent OPV device comprising a 15-nm silver (Ag) rear electrode is 1.98% under AM 1.5-G illumination through the indium-tin-oxide side of the front anode at 100 mW/cm2 with 15.6% average transmittance of the entire cell in the visible wavelength range. As its thickness increases, a thin Ag electrode mainly influences the enhancement of the short circuit current density and fill factor. Its relatively low absorption intensity makes a Ag thin film a viable option for semitransparent electrodes compatible with organic layers. © 2013 ETRI.

  18. Metal-organic frameworks in mixed-matrix membranes for gas separation.

    Tanh Jeazet, Harold B; Staudt, Claudia; Janiak, Christoph

    2012-12-14

    Mixed-matrix membranes (MMMs) with metal-organic frameworks (MOFs) as additives (fillers) exhibit enhanced gas permeabilities and possibly also selectivities when compared to the pure polymer. Polyimides (Matrimid®) and polysulfones are popular polymer matrices for MOF fillers. Presently investigated MOFs for MMMs include [Cu(SiF(6))(4,4'-BIPY)(2)], [Cu(3)(BTC)(2)(H(2)O)(3)] (HKUST-1, Cu-BTC), [Cu(BDC)(DMF)], [Zn(4)O(BDC)(3)] (MOF-5), [Zn(2-methylimidazolate)(2)] (ZIF-8), [Zn(purinate)(2)] (ZIF-20), [Zn(2-carboxyaldehyde imidazolate)(2)] (ZIF-90), Mn(HCOO)(2), [Al(BDC)(μ-OH)] (MIL-53(Al)), [Al(NH(2)-BDC)(μ-OH)] (NH(2)-MIL-53(Al)) and [Cr(3)O(BDC)(3)(F,OH)(H(2)O)(2)] (MIL-101) (4,4'-BIPY = 4,4'-bipyridine, BTC = benzene-1,3,5-tricarboxylate, BDC = benzene-1,4-dicarboxylate, terephthalate). MOF particle adhesion to polyimide and polysulfone organic polymers does not represent a problem. MOF-polymer MMMs are investigated for the permeability of the single gases H(2), N(2), O(2), CH(4), CO(2) and of the gas mixtures O(2)/N(2), H(2)/CH(4), CO(2)/CH(4), H(2)/CO(2), CH(4)/N(2) and CO(2)/N(2) (preferentially permeating gas named first). Permeability increases can be traced to the MOF porosity. Since the porosity of MOFs can be tuned very precisely, which is not possible with polymeric material, MMMs offer the opportunity of significantly increasing the selectivity compared to the pure polymeric matrix. Additionally in most of the cases the permeability is increased for MMM membranes compared to the pure polymer. Addition of MOFs to polymers in MMMs easily yields performances similar to the best polymer membranes and gives higher selectivities than those reported to date for any pure MOF membrane for the same gas separation. MOF-polymer MMMs allow for easier synthesis and handability compared to pure MOF membranes.

  19. Hydrogen Storage in Metal-Organic Frameworks

    Long, Jeffrey R. [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)

    2016-04-28

    The design and characterization of new materials for hydrogen storage is an important area of research, as the ability to store hydrogen at lower pressures and higher temperatures than currently feasible would lower operating costs for small hydrogen fuel cell vehicles. In particular, metal-organic frameworks (MOFs) represent promising materials for use in storing hydrogen in this capacity. MOFs are highly porous, three-dimensional crystalline solids that are formed via linkages between metal ions (e.g., iron, nickel, and zinc) and organic molecules. MOFs can store hydrogen via strong adsorptive interactions between the gas molecules and the pores of the framework, providing a high surface area for gas adsorption and thus the opportunity to store hydrogen at significantly lower pressures than with current technologies. By lowering the energy required for hydrogen storage, these materials hold promise in rendering hydrogen a more viable fuel for motor vehicles, which is a highly desirable outcome given the clean nature of hydrogen fuel cells (water is the only byproduct of combustion) and the current state of global climate change resulting from the combustion of fossil fuels. The work presented in this report is the result of collaborative efforts between researchers at Lawrence Berkeley National Lab (LBNL), the National Institute of Standards and Technology (NIST), and General Motors Corporation (GM) to discover novel MOFs promising for H2 storage and characterize their properties. Described herein are several new framework systems with improved gravimetric and volumetric capacity to strongly bind H2 at temperatures relevant for vehicle storage. These materials were rigorously characterized using neutron diffraction, to determine the precise binding locations of hydrogen within the frameworks, and high-pressure H2 adsorption measurements, to provide a comprehensive picture of H2 adsorption at all relevant pressures. A

  20. Organic modification of metal / semiconductor Schottky contacts

    Mendez Pinzon, H.A.

    2006-07-10

    In the present work a Metal / organic / inorganic semiconductor hybrid heterostructure (Ag / DiMe-PTCDI / GaAs) was built under UHV conditions and characterised in situ. The aim was to investigate the influence of the organic layer in the surface properties of GaAs(100) and in the electrical response of organic-modified Ag / GaAs Schottky diodes. The device was tested by combining surface-sensitive techniques (Photoemission spectroscopy and NEXAFS) with electrical measurements (current-voltage, capacitance-voltage, impedance and charge transient spectroscopies). Core level examination by PES confirms removal of native oxide layers on sulphur passivated (S-GaAs) and hydrogen plasma treated GaAs(100) (H+GaAs) surfaces. Additional deposition of ultrathin layers of DiMe-PTCDI may lead to a reduction of the surface defects density and thereby to an improvement of the electronic properties of GaAs. The energy level alignment through the heterostructure was deduced by combining UPS and I-V measurements. This allows fitting of the I-V characteristics with electron as majority carriers injected over a barrier by thermionic emission as a primary event. For thin organic layers (below 8 nm thickness) several techniques (UPS, I-V, C-V, QTS and AFM) show non homogeneous layer growth, leading to formation of voids. The coverage of the H+GaAs substrate as a function of the nominal thickness of DiMe-PTCDI was assessed via C-V measurements assuming a voltage independent capacitance of the organic layer. The frequency response of the device was evaluated through C-V and impedance measurements in the range 1 kHz-1 MHz. The almost independent behaviour of the capacitance in the measured frequency range confirmed the assumption of a near geometrical capacitor, which was used for modelling the impedance with an equivalent circuit of seven components. From there it was found a predominance of the space charge region impedance, so that A.C. conduction can only takes place through the

  1. Dual Mechanism Nonlinear Response of Selected Metal Organic Chromophores

    Peak, John D

    2007-01-01

    13 The goal for the research described herein is the development of a series of transition metal based metal organic chromophores that display both two-photon and excited state absorption (TPA/ESA) character...

  2. An Electrically Switchable Metal-Organic Framework

    Fernandez, Carlos A.; Martin, Paul C.; Schaef, Todd; Bowden, Mark E.; Thallapally, Praveen K.; Dang, Liem; Xu, Wu; Chen, Xilin; McGrail, B. Peter

    2014-08-01

    Crystalline metal organic framework (MOF) materials containing interconnected porosity can be chemically modified to promote stimulus-driven (light, magnetic or electric fields) structural transformations that can be used in a number of devices. Innovative research strategies are now focused on understanding the role of chemical bond manipulation to reversibly alter the free volume in such structures of critical importance for electro-catalysis, molecular electronics, energy storage technologies, sensor devices and smart membranes. In this letter, we study the mechanism for which an electrically switchable MOF composed of Cu(TCNQ) (TCNQ = 7,7,8,8-tetracyanoquinodimethane) transitions from a high-resistance state to a conducting state in a reversible fashion by an applied potential. The actual mechanism for this reversible electrical switching is still not understood even though a number of reports are available describing the application of electric-field-induced switching of Cu(TCNQ) in device fabrication.

  3. Metal-adeninate vertices for the construction of an exceptionally porous metal-organic framework.

    An, Jihyun; Farha, Omar K; Hupp, Joseph T; Pohl, Ehmke; Yeh, Joanne I; Rosi, Nathaniel L

    2012-01-03

    Metal-organic frameworks comprising metal-carboxylate cluster vertices and long, branched organic linkers are the most porous materials known, and therefore have attracted tremendous attention for many applications, including gas storage, separations, catalysis and drug delivery. To increase metal-organic framework porosity, the size and complexity of linkers has increased. Here we present a promising alternative strategy for constructing mesoporous metal-organic frameworks that addresses the size of the vertex rather than the length of the organic linker. This approach uses large metal-biomolecule clusters, in particular zinc-adeninate building units, as vertices to construct bio-MOF-100, an exclusively mesoporous metal-organic framework. Bio-MOF-100 exhibits a high surface area (4,300 m(2) g(-1)), one of the lowest crystal densities (0.302 g cm(-3)) and the largest metal-organic framework pore volume reported to date (4.3 cm(3) g(-1)).

  4. Hydrogen adsorption in metal-organic frameworks

    Senkovska, Irena; Kaskel, Stefan [Department of Inorganic Chemistry, Technical University, Dresden (Germany)

    2008-07-01

    Metal-Organic Frameworks (MOFs) have recently received considerable attention because of their high specific micropore volume and the ability to store gas molecules exceeding the storage capacity of traditional adsorbents. A variety of differences in the MOFs structures makes it difficult to analyze the influence of different factors on hydrogen uptake capabilities in MOFs. We have investigated the influence of the minor structural changes of the MOFs on their hydrogen storage capacity. The influence of the incorporated metal was shown for following isostructural compounds: Cu{sub 3}(BTC){sub 2} (BTC=1,3,5-benzenetricarboxylate) and Mo{sub 3}(BTC){sub 2}; Zn{sub 2}(BDC){sub 2}DABCO and Co{sub 2}(BDC){sub 2}DABCO (BDC=1,4-benzenedicarboxylate, DABCO=1,4-diazabicyclo[2.2.2]octane). Our research interest is directed also towards the discovery of new MOFs, as well as adjusting the pore dimensions of MOFs, using different building blocks, solvent and solvent mixtures, in order to improve gas uptake and adsorption properties. Magnesium-based MOFs were found with the same network topology, very small pore size and selective adsorption behaviour. They show a guest-induced reversible structure transformation due to the flexibility of the Mg{sub 3}-cluster and the organic linkers. This effect could be used for fitting the pore sizes and for the increase of gas sorption capability in Mg contained MOFs after all. The hydrogen adsorption was also studied in several Al-based IRMOFs.

  5. Zeolite-like metal-organic frameworks with ana topology

    Eddaoudi, Mohamed

    2017-04-20

    Embodiments of the present disclosure describe a zeolite-like metal-organic framework composition comprising a metal-organic framework composition with ana topology characterized by the formula [MIII(4, 5-imidazole dicarboxylic acid)2X(solvent)a]n wherein MIII comprises a trivalent cation of a rare earth element, X comprises an alkali metal element or alkaline earth metal element, and solvent comprises a guest molecule occupying pores. Embodiments of the present disclosure describe a method of separating paraffins comprising contacting a zeolite-like metal-organic framework with ana topology with a flow of paraffins, and separating the paraffins by size.

  6. Inelastic neutron scattering of H2 adsorbed in HKUST-1

    Liu, Y.; Brown, C.M.; Neumann, D.A.; Peterson, V.K.; Kepert, C.J.

    2007-01-01

    A series of inelastic neutron scattering (INS) investigations of hydrogen adsorbed in activated HKUST-1 (Cu 3 (1,3,5-benzenetricarboxylate) 2 ) result in INS spectra with rich features, even at very low loading ( 2 :Cu). The distinct inelastic features in the spectra show that there are three binding sites that are progressively populated when the H 2 loading is less than 2.0 H 2 :Cu, which is consistent with the result obtained from previous neutron powder diffraction experiments. The temperature dependence of the INS spectra reveals the relative binding enthalpies for H 2 at each site

  7. Energy-level alignment at metal-organic and organic-organic interfaces

    Veenstra, Sjoerd; Jonkman, H.T.

    2003-01-01

    This article reports on the electronic structure at interfaces found in organic semiconductor devices. The studied organic materials are C-60 and poly (para-phenylenevinylene) (PPV)-like oligomers, and the metals are polycrystalline Au and Ag. To measure the energy levels at these interfaces,

  8. Elaboration of a Highly Porous RuII,II Analogue of HKUST-1.

    Zhang, Wenhua; Freitag, Kerstin; Wannapaiboon, Suttipong; Schneider, Christian; Epp, Konstantin; Kieslich, Gregor; Fischer, Roland A

    2016-12-19

    When the dinuclear Ru II,II precursor [Ru 2 (OOCCH 3 ) 4 ] is employed under redox-inert conditions, a Ru II,II analogue of HKUST-1 was successfully prepared and characterized as a phase-pure microcrystalline powder. X-ray absorption near-edge spectroscopy confirms the oxidation state of the Ru centers of the paddle-wheel nodes in the framework. The porosity of 1371 m 2 /mmol of Ru II,II -HKUST-1 exceeds that of the parent compound HKUST1 (1049 m 2 / mmol).

  9. Text Mining Metal-Organic Framework Papers.

    Park, Sanghoon; Kim, Baekjun; Choi, Sihoon; Boyd, Peter G; Smit, Berend; Kim, Jihan

    2018-02-26

    We have developed a simple text mining algorithm that allows us to identify surface area and pore volumes of metal-organic frameworks (MOFs) using manuscript html files as inputs. The algorithm searches for common units (e.g., m 2 /g, cm 3 /g) associated with these two quantities to facilitate the search. From the sample set data of over 200 MOFs, the algorithm managed to identify 90% and 88.8% of the correct surface area and pore volume values. Further application to a test set of randomly chosen MOF html files yielded 73.2% and 85.1% accuracies for the two respective quantities. Most of the errors stem from unorthodox sentence structures that made it difficult to identify the correct data as well as bolded notations of MOFs (e.g., 1a) that made it difficult identify its real name. These types of tools will become useful when it comes to discovering structure-property relationships among MOFs as well as collecting a large set of data for references.

  10. Hydrogen storage in metal-organic frameworks: A review

    Langmi, Henrietta W

    2014-05-01

    Full Text Available Metal-organic frameworks (MOFs) for hydrogen storage have continued to receive intense interest over the past decade. MOFs are a class of organic-inorganic hybrid crystalline materials consisting of metallic moieties that are linked by strong...

  11. Ionic Transport Through Metal-Rich Organic Coatings

    2016-08-19

    important for metal substrates, as it is well-known that chloride increases corrosion of metals . 3 For metal -loaded primers, it has been established...volume (MPV) percent, solvent polarity, and resin molecular weight impact corrosion protection of metal -rich organic (MRO) coatings. Following design of...pH and chloride ion concentration levels over time. As the corrosion protection of the coating decreases, chloride ion concentration will increase

  12. Recent Advances as Materials of Functional Metal-Organic Frameworks

    Xiao-Lan Tong

    2013-01-01

    Full Text Available Metal-organic frameworks (MOFs, also known as hybrid inorganic-organic materials, represent an emerging class of materials that have attracted the imagination of solid-state chemists because MOFs combine unprecedented levels of porosity with a range of other functional properties that occur through the metal moiety and/or the organic ligand. The purpose of this critical review is to give a representative and comprehensive overview of the arising developments in the field of functional metal-organic frameworks, including luminescence, magnetism, and porosity through presenting examples. This review will be of interest to researchers and synthetic chemists attempting to design multifunctional MOFs.

  13. HKUST-1 Membranes Anchored on Porous Substrate by Hetero MIL-110 Nanorod Array Seeds.

    Mao, Yiyin; Cao, Wei; Li, Junwei; Sun, Luwei; Peng, Xinsheng

    2013-09-02

    Great anchors and seeds: Hetero-seeding growth processes and anchored nanorod arrays were successfully utilized in the synthesis of HKUST-1 membranes. These arrays were firmly anchored on porous substrates by using a MIL-110 nanorod array as both the anchor and seed. The resulting HKUST-1 membranes demonstrated good separation factors for binary gases exceeding the Knudson selectivity. Copyright © 2013 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. Thin films of metal-organic compounds and metal nanoparticle ...

    Optical limiting capability of the nanoparticle-embedded polymer film is demonstrated. Keywords. Polar crystal; uniaxial orientational order; thin film; second harmonic gen- eration; silver ... able content of metal nanoparticles would be of considerable value from an appli- ... polar chain and perpendicular to it [10].

  15. Au-HKUST-1 Composite Nanocapsules: Synthesis with a Coordination Replication Strategy and Catalysis on CO Oxidation.

    Liu, Yongxin; Zhang, Jiali; Song, Lingxiao; Xu, Wenyuan; Guo, Zanru; Yang, Xiaomin; Wu, Xiaoxin; Chen, Xi

    2016-09-07

    A novel coordination replication of Cu2O redox-template strategy is reported to efficiently fabricate Au-HKUST-1 composite nanocapsule, with a HKUST-1 sandwich shell and an embedded Au nanoparticles layer. The novel synthesis procedure involves forming Au nanoparticles on the surface of Cu2O, transforming partial Cu2O into HKUST-1 shell via coordination replication, and removing the residual Cu2O by acid. The as-prepared Au-HKUST-1 composite nanocapsules displayed high catalytic activity on CO oxidation.

  16. Carbon Dioxide Removal from Flue Gas Using Microporous Metal Organic Frameworks

    Lesch, David A

    2010-06-30

    UOP LLC, a Honeywell Company, in collaboration with Professor Douglas LeVan at Vanderbilt University (VU), Professor Adam Matzger at the University of Michigan (UM), Professor Randall Snurr at Northwestern University (NU), and Professor Stefano Brandani at the University of Edinburgh (UE), supported by Honeywell's Specialty Materials business unit and the Electric Power Research Institute (EPRI), have completed a three-year project to develop novel microporous metal organic frameworks (MOFs) and an associated vacuum-pressure swing adsorption (vPSA) process for the removal of CO{sub 2} from coal-fired power plant flue gas. The project leveraged the team's complementary capabilities: UOP's experience in materials development and manufacturing, adsorption process design and process commercialization; LeVan and Brandani's expertise in high-quality adsorption measurements; Matzger's experience in syntheis of MOFs and the organic components associated with MOFs; Snurr's expertise in molecular and other modeling; Honeywell's expertise in the manufacture of organic chemicals; and, EPRI's knowledge of power-generation technology and markets. The project was successful in that a selective CO{sub 2} adsorbent with good thermal stability and reasonable contaminant tolerance was discovered, and a low cost process for flue gas CO{sub 2} capture process ready to be evaluated further at the pilot scale was proposed. The team made significant progress toward the current DOE post-combustion research targets, as defined in a recent FOA issued by NETL: 90% CO{sub 2} removal with no more than a 35% increase in COE. The team discovered that favorable CO{sub 2} adsorption at more realistic flue gas conditions is dominated by one particular MOF structure type, M/DOBDC, where M designates Zn, Co, Ni, or Mg and DOBDC refers to the form of the organic linker in the resultant MOF structure, dioxybenzenedicarboxylate. The structure of the M/DOBDC MOFs

  17. Chemical Property Change in a Metal-Organic Framework by Fluoro Functionality

    Ko, Nakeun; Hong, Jisu; You, Laekyeong; Park, Hye Jeong; Yang, Jin Kuk; Kim, Jaheon [Soongsil University, Seoul (Korea, Republic of)

    2015-01-15

    A fluorine-functionalized HKUST-1 (HKUST-1-F) has been synthesized by a solvo thermal reaction between copper nitrate and a potassium salt of 2-fluoro-1,3,5-benzenetricarboxylic acid (K[H{sub 2}BTC-F]). HKUST-1-F shows nearly the same crystal structure as that of UHM-31, a known fluorinated HKUST-1. Because of its reduced surface area, HKUST-1-F takes up smaller amounts of gases (N{sub 2}, H{sub 2}, CO{sub 2}) than UHM-31 at 1 bar. After a water vapor adsorption measurement at 298 K, HKUST-1-F turned into an unknown structure, based on powder X-ray diffraction analyses. HKUST-1-F could be further functionalized with benzylamine in a post synthetic modification; the nucleophilic replacement of the F atom in BTC-F with benzylamine in methylene chloride at room temperature took place in a conversion yield of -38% based on 1H NMR analyses.

  18. Bioremediation of Heavy Metals and Organic Toxicants by Composting

    Allen V. Barker

    2002-01-01

    Full Text Available Hazardous organic and metallic residues or by-products can enter into plants, soils, and sediments from processes associated with domestic, municipal, agricultural, industrial, and military activities. Handling, ingestion, application to land or other distributions of the contaminated materials into the environment might render harm to humans, livestock, wildlife, crops, or native plants. Considerable remediation of the hazardous wastes or contaminated plants, soils, and sediments can be accomplished by composting. High microbial diversity and activity during composting, due to the abundance of substrates in feedstocks, promotes degradation of xenobiotic organic compounds, such as pesticides, polycyclic aromatic hydrocarbons (PAHs, and polychlorinated biphenyls (PCBs. For composting of contaminated soils, noncontaminated organic matter should be cocomposted with the soils. Metallic pollutants are not degraded during composting but may be converted into organic combinations that have less bioavailability than mineral combinations of the metals. Degradation of organic contaminants in soils is facilitated by addition of composted or raw organic matter, thereby increasing the substrate levels for cometabolism of the contaminants. Similar to the composting of soils in vessels or piles, the on-site addition of organic matter to soils (sheet composting accelerates degradation of organic pollutants and binds metallic pollutants. Recalcitrant materials, such as organochlorines, may not undergo degradation in composts or in soils, and the effects of forming organic complexes with metallic pollutants may be nonpermanent or short lived. The general conclusion is, however, that composting degrades or binds pollutants to innocuous levels or into innocuous compounds in the finished product.

  19. Neutron powder diffraction of metal-organic frameworks for ...

    We review recent structural studies that we have undertaken aimed at elucidating the fundamental properties of metal-organic framework materials and their interactions with hydrogen. We have shown that exposing coordinatively unsaturated metal centers can greatly enhance the hydrogen binding energy and that they ...

  20. Trace Metals And Organic Matter Diagenesis At The Oman Margin

    Alagarsamy, R.

    Trace Metals (e.g. Mn and Fe) play an important role as secondary oxidants in the degradation of sedimentary OM under sub-oxic conditions. Hence the remineralisation of organic constituents of sediments in the marine environment may significantly...

  1. Fuel upgrading and reforming with metal organic framework

    Eddaoudi, Mohamed; Belmabkhout, Youssef

    2016-01-01

    Systems and methods for separating hydrocarbons on an internal combustion powered vehicle via one or more metal organic frameworks are disclosed. Systems and methods can further include utilizing separated hydrocarbons and exhaust to generate

  2. Improved mechanical stability of HKUST-1 in confined nanospace.

    Casco, M E; Fernández-Catalá, J; Martínez-Escandell, M; Rodríguez-Reinoso, F; Ramos-Fernández, E V; Silvestre-Albero, J

    2015-09-28

    One of the main concerns in the technological application of several metal-organic frameworks (MOFs) relates to their structural instability under pressure (after a conforming step). Here we report for the first time that mechanical instability can be highly improved via nucleation and growth of MOF nanocrystals in the confined nanospace of activated carbons.

  3. Metal organic frameworks for removal of compounds from a fluid

    Eddaoudi, Mohamed

    2016-03-03

    Embodiments provide a method of compound removal from a fluid. The method includes contacting one or more metal organic framework (MOF) compositions with a fluid and sorbing one or more compounds, such as CO2, H2S and condensable hydrocarbons. One or more of CO2, H2S and condensable hydrocarbons can be sorbed simultaneously or in series. The metal organic framework can be an M-soc-MOF.

  4. Ionic Transport Through Metal-Rich Organic Coatings

    2016-08-19

    organic paints, inert metallic layers, and protective oxide layers. 2 Although coatings have been commercially used for many years, the design of new...pigments found in chromates protect the substrate by passivating the metallic surface with an oxide layer. Sacrificial coatings prevent the self...surface, eliminating the components needed for a cathodic reaction to occur. Additionally, organic barrier coatings are protective by preventing

  5. Fuel upgrading and reforming with metal organic framework

    Eddaoudi, Mohamed

    2016-03-31

    Systems and methods for separating hydrocarbons on an internal combustion powered vehicle via one or more metal organic frameworks are disclosed. Systems and methods can further include utilizing separated hydrocarbons and exhaust to generate hydrogen gas for use as fuel. In one aspect, a method for separating hydrocarbons can include contacting a first component containing a first metal organic framework with a flow of hydrocarbons and separating hydrocarbons by size. In certain embodiments, the hydrocarbons can include alkanes.

  6. Metal organic frameworks for removal of compounds from a fluid

    Eddaoudi, Mohamed; Belmabkhout, Youssef

    2016-01-01

    Embodiments provide a method of compound removal from a fluid. The method includes contacting one or more metal organic framework (MOF) compositions with a fluid and sorbing one or more compounds, such as CO2, H2S and condensable hydrocarbons. One or more of CO2, H2S and condensable hydrocarbons can be sorbed simultaneously or in series. The metal organic framework can be an M-soc-MOF.

  7. Solution processed metal oxide thin film hole transport layers for high performance organic solar cells

    Steirer, K. Xerxes; Berry, Joseph J.; Chesin, Jordan P.; Lloyd, Matthew T.; Widjonarko, Nicodemus Edwin; Miedaner, Alexander; Curtis, Calvin J.; Ginley, David S.; Olson, Dana C.

    2017-01-10

    A method for the application of solution processed metal oxide hole transport layers in organic photovoltaic devices and related organic electronics devices is disclosed. The metal oxide may be derived from a metal-organic precursor enabling solution processing of an amorphous, p-type metal oxide. An organic photovoltaic device having solution processed, metal oxide, thin-film hole transport layer.

  8. Reconfigurable electronics using conducting metal-organic frameworks

    Allendorf, Mark D.; Talin, Albert Alec; Leonard, Francois; Stavila, Vitalie

    2017-07-18

    A device including a porous metal organic framework (MOF) disposed between two terminals, the device including a first state wherein the MOF is infiltrated by a guest species to form an electrical path between the terminals and a second state wherein the electrical conductivity of the MOF is less than the electrical conductivity in the first state. A method including switching a porous metal organic framework (MOF) between two terminals from a first state wherein a metal site in the MOF is infiltrated by a guest species that is capable of charge transfer to a second state wherein the MOF is less electrically conductive than in the first state.

  9. Predicting Metal Speciation & Bioavailability via Estimation of Metal-Organic Thermodynamic Properties

    Prasad, A.; Howells, A. E.; Shock, E.

    2017-12-01

    The biological fate of any metal depends on its chemical form in the environment. Arsenic for example, is extremely toxic in the form of inorganic As+3 but completely benign in the organic form of arsenobetaine. Thus, given an exhaustive set of reactions and their equilibrium constants (logK), the bioavailability of any metal can be obtained for blood plasma, hydrothermal fluids or any system of interest. While many data exist for metal-inorganic ligands, logK data covering the temperature range of life for metal-organic complexes are sparse. Hence, we decided to estimate metal-organic logK values from correlations with the commonly available values of ligand pKa. Metal ion specific correlations were made with ligands classified according to their electron donor atoms, denticity and other chemical factors. While this approach has been employed before (Carbonaro et al. 2007, GCA 71, 3958-3968), new correlations were developed that provide estimates even when no metal-organic logK is available. In addition, we have used the same methods to make estimates of metal-organic entropy of association (ΔaS), which can provide logK for any temperature of biological relevance. Our current correlations employ logK and ΔaS data from 30 metal ions (like the biologically relevant Fe+3 & Zn+2) and 74 ligands (like formate and ethylenediamine), which can be expanded to estimate the metal-ligand reaction properties for these 30 metal ions with a possibly limitless number of ligands that may belong to our categories of ligands. With the help of such data, copper speciation was obtained for a defined growth medium for methanotrophs employed by Morton et al. (2000, AEM 66, 1730-1733) that agrees with experimental measurements showing that the free metal ion may not be the bioavailable form in all conditions. These results encourage us to keep filling the gaps in metal-organic logK data and continue finding relationships between biological responses (like metal-accumulation ratios

  10. Functionalised metal-organic frameworks : A novel approach to stabilising single metal atoms

    Szilagyi, P.A.; Rogers, D. M.; Zaiser, I.; Callini, E; Turner, Stuart; Borgschulte, A; Züttel, A.; Geerlings, J.J.C.; Hirscher, M; Dam, B.

    2017-01-01

    We have investigated the potential of metal-organic frameworks for immobilising single atoms of transition metals using a model system of Pd supported on NH2-MIL-101(Cr). Our transmission electron microscopy and in situ Raman spectroscopy results give evidence for the first time that

  11. Metal Complexes for Organic Optoelectronic Applications

    Huang, Liang

    Organic optoelectronic devices have drawn extensive attention by over the past two decades. Two major applications for Organic optoelectronic devices are efficient organic photovoltaic devices(OPV) and organic light emitting diodes (OLED). Organic Solar cell has been proven to be compatible with the low cost, large area bulk processing technology and processed high absorption efficiencies compared to inorganic solar cells. Organic light emitting diodes are a promising approach for display and solid state lighting applications. To improve the efficiency, stability, and materials variety for organic optoelectronic devices, several emissive materials, absorber-type materials, and charge transporting materials were developed and employed in various device settings. Optical, electrical, and photophysical studies of the organic materials and their corresponding devices were thoroughly carried out. In this thesis, Chapter 1 provides an introduction to the background knowledge of OPV and OLED research fields presented. Chapter 2 discusses new porphyrin derivatives- azatetrabenzylporphyrins for OPV and near infrared OLED applications. A modified synthetic method is utilized to increase the reaction yield of the azatetrabenzylporphyrin materials and their photophysical properties, electrochemical properties are studied. OPV devices are also fabricated using Zinc azatetrabenzylporphyrin as donor materials. Pt(II) azatetrabenzylporphyrin were also synthesized and used in near infra-red OLED to achieve an emission over 800 nm with reasonable external quantum efficiencies. Chapter 3, discusses the synthesis, characterization, and device evaluation of a series of tetradentate platinum and palladium complexesfor single doped white OLED applications and RGB white OLED applications. Devices employing some of the developed emitters demonstrated impressively high external quantum efficiencies within the range of 22%-27% for various emitter concentrations. And the palladium complex, i

  12. Trace metals in pelagic organisms from the Mediterranean Sea

    Fowler, S.W.; Oregioni, B.; LaRosa, J.

    1976-01-01

    As a result of current interest in heavy metal pollution in the marine environment much information is accruing on the present levels of metals in certain marine species. By far the majority of the studies have involved elemental analysis of coastal organisms which are relatively easy to collect. However, due to inherent problems in sampling, far less information exists on element concentration in pelagic organisms, species which are important in terms of total marine biomass, their position in the food web, and their ability to concentrate and transport relatively large amounts of metals in various ways. Microplankton and larger zooplanktonic and nektonic species were sampled over a wide geographical range throughout the Mediterranean as well as along selected transects to assess possible gradients in metal concentrations in plankton communities

  13. Reconciling the discrepancies between crystallographic porosity and guest access as exemplified by Zn-HKUST-1.

    Feldblyum, Jeremy I; Liu, Ming; Gidley, David W; Matzger, Adam J

    2011-11-16

    There are several compounds for which there exists a disconnect between porosity as predicted by crystallography and porosity measured by gas sorption analysis. In this paper, the Zn-based analogue of Cu(3)(btc)(2) (HKUST-1), Zn(3)(btc)(2) (Zn-HKUST-1; btc = 1,3,5-benzenetricarboxylate) is investigated. Conventional analysis of Zn-HKUST-1 by powder X-ray diffraction and gas sorption indicates retention of crystalline structure but negligible nitrogen uptake at 77 K. By using positron annihilation lifetime spectroscopy, a densified surface layer preventing the entry of even small molecular species into the crystal framework is revealed. The material is shown to have inherent surface instability after solvent removal, rendering it impermeable to molecular guests irrespective of handling and processing methods. This previously unobserved surface instability may provide insight into the failure of other microporous coordination polymers to exhibit significant porosity despite crystal structures indicative of regular, interconnected, microporous networks.

  14. A Kind of Energy Storage Technology: Metal Organic Frameworks

    Ozturk, Zeynel; Kose, D. A.; Asan, A.; Ozturk, B.

    2016-01-01

    For last fifteen years energy has been transferred by using electricity and as an energy carrier media electricity has some disadvantages like its wire need for transportation and its being non-storable for large amounts. To store more energy safely and for transportation it easily, new storing medias and devices are needed. For easy and safe energy transport there are many technologies and some of these contain hydrogen energy. Metal hydrides, carbon nanotubes, metal organic frameworks (MOFs...

  15. Alkylamine functionalized metal-organic frameworks for composite gas separations

    Long, Jeffrey R.; McDonald, Thomas M.; D'Alessandro, Deanna M.

    2018-01-09

    Functionalized metal-organic framework adsorbents with ligands containing basic nitrogen groups such as alkylamines and alkyldiamines appended to the metal centers and method of isolating carbon dioxide from a stream of combined gases and carbon dioxide partial pressures below approximately 1 and 1000 mbar. The adsorption material has an isosteric heat of carbon dioxide adsorption of greater than -60 kJ/mol at zero coverage using a dual-site Langmuir model.

  16. Inorganic Metal Oxide/Organic Polymer Nanocomposites And Method Thereof

    Gash, Alexander E.; Satcher, Joe H.; Simpson, Randy

    2004-11-16

    A synthetic method for preparation of hybrid inorganic/organic energetic nanocomposites is disclosed herein. The method employs the use of stable metal in organic salts and organic solvents as well as an organic polymer with good solubility in the solvent system to produce novel nanocomposite energetic materials. In addition, fuel metal powders (particularly those that are oxophilic) can be incorporated into composition. This material has been characterized by thermal methods, energy-filtered transmission electron microscopy (EFTEM), N.sub.2 adsoprtion/desorption methods, and Fourier-Transform (FT-IR) spectroscopy. According to these characterization methods the organic polymer phase fills the nanopores of the material, providing superb mixing of the component phases in the energetic nanocomposite.

  17. Organic/metal interfaces. Electronic and structural properties

    Duhm, Steffen

    2008-07-17

    This work addresses several important topics of the field of organic electronics. The focus lies on organic/metal interfaces, which exist in all organic electronic devices. Physical properties of such interfaces are crucial for device performance. Four main topics have been covered: (i) the impact of molecular orientation on the energy levels, (ii) energy level tuning with strong electron acceptors, (iii) the role of thermodynamic equilibrium at organic/ organic homo-interfaces and (iv) the correlation of interfacial electronic structure and bonding distance. To address these issues a broad experimental approach was necessary: mainly ultraviolet photoelectron spectroscopy was used, supported by X-ray photoelectron spectroscopy, metastable atom electron spectroscopy, X-ray diffraction and X-ray standing waves, to examine vacuum sublimed thin films of conjugated organic molecules (COMs) in ultrahigh vacuum. (i) A novel approach is presented to explain the phenomenon that the ionization energy in molecular assemblies is orientation dependent. It is demonstrated that this is due to a macroscopic impact of intramolecular dipoles on the ionization energy in molecular assemblies. Furthermore, the correlation of molecular orientation and conformation has been studied in detail for COMs on various substrates. (ii) A new approach was developed to tune hole injection barriers ({delta}{sub h}) at organic/metal interfaces by adsorbing a (sub-) monolayer of an organic electron acceptor on the metal electrode. Charge transfer from the metal to the acceptor leads to a chemisorbed layer, which reduces {delta}{sub h} to the COM overlayer. This concept was tested with three acceptors and a lowering of {delta}{sub h} of up to 1.2 eV could be observed. (iii) A transition from vacuum-level alignment to molecular level pinning at the homo-interface between a lying monolayer and standing multilayers of a COM was observed, which depended on the amount of a pre-deposited acceptor. The

  18. SEQUESTERING AGENTS FOR ACTIVE CAPS - REMEDIATION OF METALS AND ORGANICS

    Knox, A; Michael Paller, M; Danny D. Reible, D; Xingmao Ma, X; Ioana G. Petrisor, I

    2007-05-10

    This research evaluated organoclays, zeolites, phosphates, and a biopolymer as sequestering agents for inorganic and organic contaminants. Batch experiments were conducted to identify amendments and mixtures of amendments for metal and organic contaminants removal and retention. Contaminant removal was evaluated by calculating partitioning coefficients. Metal retention was evaluated by desorption studies in which residue from the removal studies was extracted with 1 M MgCl{sub 2} solution. The results indicated that phosphate amendments, some organoclays, and the biopolymer, chitosan, were very effective sequestering agents for metals in fresh and salt water. Organoclays were very effective sorbents for phenanthrene, pyrene, and benzo(a)pyrene. Partitioning coefficients for the organoclays were 3000-3500 ml g{sup -1} for benzo(a)pyrene, 400-450 ml g{sup -1} for pyrene, and 50-70 ml g{sup -1} for phenanthrene. Remediation of sites with a mixture of contaminants is more difficult than sites with a single contaminant because metals and organic contaminants have different fate and transport mechanisms in sediment and water. Mixtures of amendments (e.g., organoclay and rock phosphate) have high potential for remediating both organic and inorganic contaminants under a broad range of environmental conditions, and have promise as components in active caps for sediment remediation.

  19. Supramolecular Assembly of Calcium Metal - Organic Frameworks with Structural Transformation

    Liang, P.-Ch.; Liu, H.-K.; Yeh, Ch.-T.; Lin, Ch.-H.; Zima, Vítězslav

    2011-01-01

    Roč. 11, č. 3 (2011), 699-708 ISSN 1528-7483 R&D Projects: GA ČR GA203/08/0208 Institutional research plan: CEZ:AV0Z40500505 Keywords : metal - organic frameworks * calcium * structure Subject RIV: CA - Inorganic Chemistry Impact factor: 4.720, year: 2011

  20. Expanded Organic Building Units for the Construction of Highly Porous Metal-Organic Frameworks

    Kong, G.Q.; Han, Z.D.; He, Y.; Qu, S.; Zhou, W.; Yildirim, T.; Krishna, R.; Zou, C.; Chen, B.; Wu, C.D.

    2013-01-01

    wo new organic building units that contain dicarboxylate sites for their self-assembly with paddlewheel [Cu2(CO2)4] units have been successfully developed to construct two isoreticular porous metal-organic frameworks (MOFs), ZJU-35 and ZJU-36, which have the same tbo topologies (Reticular Chemistry

  1. Quasiparticles and Fermi liquid behaviour in an organic metal

    Kiss, T.; Chainani, A.; Yamamoto, H.M.; Miyazaki, T.; Akimoto, T.; Shimojima, T.; Ishizaka, K.; Watanabe, S.; Chen, C.-T.; Fukaya, A.; Kato, R.; Shin, S.

    2012-01-01

    Many organic metals display exotic properties such as superconductivity, spin-charge separation and so on and have been described as quasi-one-dimensional Luttinger liquids. However, a genuine Fermi liquid behaviour with quasiparticles and Fermi surfaces have not been reported to date for any organic metal. Here, we report the experimental Fermi surface and band structure of an organic metal (BEDT-TTF)3Br(pBIB) obtained using angle-resolved photoelectron spectroscopy, and show its consistency with first-principles band structure calculations. Our results reveal a quasiparticle renormalization at low energy scales (effective mass m*=1.9 me) and ω2 dependence of the imaginary part of the self energy, limited by a kink at ~50 meV arising from coupling to molecular vibrations. The study unambiguously proves that (BEDT-TTF)3Br(pBIB) is a quasi-2D organic Fermi liquid with a Fermi surface consistent with Shubnikov-de Haas results. PMID:23011143

  2. An Ising model for metal-organic frameworks

    Höft, Nicolas; Horbach, Jürgen; Martín-Mayor, Victor; Seoane, Beatriz

    2017-08-01

    We present a three-dimensional Ising model where lines of equal spins are frozen such that they form an ordered framework structure. The frame spins impose an external field on the rest of the spins (active spins). We demonstrate that this "porous Ising model" can be seen as a minimal model for condensation transitions of gas molecules in metal-organic frameworks. Using Monte Carlo simulation techniques, we compare the phase behavior of a porous Ising model with that of a particle-based model for the condensation of methane (CH4) in the isoreticular metal-organic framework IRMOF-16. For both models, we find a line of first-order phase transitions that end in a critical point. We show that the critical behavior in both cases belongs to the 3D Ising universality class, in contrast to other phase transitions in confinement such as capillary condensation.

  3. Increasing the Stability of Metal-Organic Frameworks

    Mathieu Bosch

    2014-01-01

    Full Text Available Metal-organic frameworks (MOFs are a new category of advanced porous materials undergoing study by many researchers for their vast variety of both novel structures and potentially useful properties arising from them. Their high porosities, tunable structures, and convenient process of introducing both customizable functional groups and unsaturated metal centers have afforded excellent gas sorption and separation ability, catalytic activity, luminescent properties, and more. However, the robustness and reactivity of a given framework are largely dependent on its metal-ligand interactions, where the metal-containing clusters are often vulnerable to ligand substitution by water or other nucleophiles, meaning that the frameworks may collapse upon exposure even to moist air. Other frameworks may collapse upon thermal or vacuum treatment or simply over time. This instability limits the practical uses of many MOFs. In order to further enhance the stability of the framework, many different approaches, such as the utilization of high-valence metal ions or nitrogen-donor ligands, were recently investigated. This review details the efforts of both our research group and others to synthesize MOFs possessing drastically increased chemical and thermal stability, in addition to exemplary performance for catalysis, gas sorption, and separation.

  4. Controlling Thermal Expansion: A Metal?Organic Frameworks Route

    Balestra, Salvador R. G.; Bueno-Perez, Rocio; Hamad, Said; Dubbeldam, David; Ruiz-Salvador, A. Rabdel; Calero, Sofia

    2016-01-01

    Controlling thermal expansion is an important, not yet resolved, and challenging problem in materials research. A conceptual design is introduced here, for the first time, for the use of metal?organic frameworks (MOFs) as platforms for controlling thermal expansion devices that can operate in the negative, zero, and positive expansion regimes. A detailed computer simulation study, based on molecular dynamics, is presented to support the targeted application. MOF-5 has been selected as model m...

  5. Molecularly Imprinted Polymer/Metal Organic Framework Based Chemical Sensors

    Zhenzhong Guo

    2016-10-01

    Full Text Available The present review describes recent advances in the concept of molecular imprinting using metal organic frameworks (MOF for development of chemical sensors. Two main strategies regarding the fabrication, performance and applications of recent sensors based on molecularly imprinted polymers associated with MOF are presented: molecularly imprinted MOF films and molecularly imprinted core-shell nanoparticles using MOF as core. The associated transduction modes are also discussed. A brief conclusion and future expectations are described herein.

  6. Breaking Down Chemical Weapons by Metal-Organic Frameworks.

    Mondal, Suvendu Sekhar; Holdt, Hans-Jürgen

    2016-01-04

    Seek and destroy: Filtration schemes and self-detoxifying protective fabrics based on the Zr(IV)-containing metal-organic frameworks (MOFs) MOF-808 and UiO-66 doped with LiOtBu have been developed that capture and hydrolytically detoxify simulants of nerve agents and mustard gas. Both MOFs function as highly catalytic elements in these applications. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. Nano-architecture of metal-organic frameworks

    Milichko, Valentin A.; Zalogina, Anastasiia; Mingabudinova, Leila R.; Vinogradov, Alexander V.; Ubyivovk, Evgeniy; Krasilin, Andrei A.; Mukhin, Ivan; Zuev, Dmitry A.; Makarov, Sergey V.; Pidko, Evgeny A.

    2017-09-01

    Change the shape and size of materials supports new functionalities never found in the sources. This strategy has been recently applied for porous crystalline materials - metal-organic frameworks (MOFs) to create hollow nanoscale structures or mesostructures with improved functional properties. However, such structures are characterized by amorphous state or polycrystallinity which limits their applicability. Here we follow this strategy to create such nano- and mesostructures with perfect crystallinity and new photonics functionalities by laser or focused ion beam fabrication.

  8. Metal organic framework MIL-101 for radioiodine capture and storage

    Assaad, Thaer; Assfour, Bassem

    2017-09-01

    we report on the use of metal organic frameworks(MOFs) for radioiodine recovery and storage. One MOF (namely MIL-101) was prepared and investigated in detail to demonstrate the iodine removal efficiency and capacity of MOFs. The typical sorption kinetics and uptake isotherms were measured using radioactive iodine (123 I) for the first time. Our measurements indicate that MOFs can capture and store radioiodine in very high efficiency and fast kinetics.

  9. Accumulation of trace metals in coastal marine organisms

    Weers, A.W. van; Raaphorst, J.G. van

    1980-01-01

    ECN at Petten carries out a survey on the occurrence of trace metals in coastal marine organisms. The survey is aimed to provide an estimate of concentration factors in local marine organisms for neutron activation products released as low-level liquid radioactive waste into the North Sea. The organisms studied are red and brown seaweed, edible mussels ans shrimp. A summary of the results of analyses of iron, cobalt, zinc, silver and antimony in these organisms is presented. Concentration factors derived from mean stable-element concentrations range from about 50 for Sb in red seaweed and shrimp to about 10 4 for Fe in red seaweed and mussels. The largest variation is shown for zinc in seaweed, which variation is seasonal and most pronounced in brown seaweed. A discussion of the data is presented in relation to data from other West-European coastal areas and to data used for the radiological assessment of deep sea disposal of radioactive waste

  10. Capture of organic iodides from nuclear waste by metal-organic framework-based molecular traps.

    Li, Baiyan; Dong, Xinglong; Wang, Hao; Ma, Dingxuan; Tan, Kui; Jensen, Stephanie; Deibert, Benjamin J; Butler, Joseph; Cure, Jeremy; Shi, Zhan; Thonhauser, Timo; Chabal, Yves J; Han, Yu; Li, Jing

    2017-09-07

    Effective capture of radioactive organic iodides from nuclear waste remains a significant challenge due to the drawbacks of current adsorbents such as low uptake capacity, high cost, and non-recyclability. We report here a general approach to overcome this challenge by creating radioactive organic iodide molecular traps through functionalization of metal-organic framework materials with tertiary amine-binding sites. The molecular trap exhibits a high CH 3 I saturation uptake capacity of 71 wt% at 150 °C, which is more than 340% higher than the industrial adsorbent Ag 0 @MOR under identical conditions. These functionalized metal-organic frameworks also serve as good adsorbents at low temperatures. Furthermore, the resulting adsorbent can be recycled multiple times without loss of capacity, making recyclability a reality. In combination with its chemical and thermal stability, high capture efficiency and low cost, the adsorbent demonstrates promise for industrial radioactive organic iodides capture from nuclear waste. The capture mechanism was investigated by experimental and theoretical methods.Capturing radioactive organic iodides from nuclear waste is important for safe nuclear energy usage, but remains a significant challenge. Here, Li and co-workers fabricate a stable metal-organic framework functionalized with tertiary amine groups that exhibits high capacities for radioactive organic iodides uptake.

  11. Capture of organic iodides from nuclear waste by metal-organic framework-based molecular traps

    Li, Baiyan

    2017-09-01

    Effective capture of radioactive organic iodides from nuclear waste remains a significant challenge due to the drawbacks of current adsorbents such as low uptake capacity, high cost, and non-recyclability. We report here a general approach to overcome this challenge by creating radioactive organic iodide molecular traps through functionalization of metal-organic framework materials with tertiary amine-binding sites. The molecular trap exhibits a high CH3I saturation uptake capacity of 71 wt% at 150 °C, which is more than 340% higher than the industrial adsorbent Ag0@MOR under identical conditions. These functionalized metal-organic frameworks also serve as good adsorbents at low temperatures. Furthermore, the resulting adsorbent can be recycled multiple times without loss of capacity, making recyclability a reality. In combination with its chemical and thermal stability, high capture efficiency and low cost, the adsorbent demonstrates promise for industrial radioactive organic iodides capture from nuclear waste. The capture mechanism was investigated by experimental and theoretical methods.Capturing radioactive organic iodides from nuclear waste is important for safe nuclear energy usage, but remains a significant challenge. Here, Li and co-workers fabricate a stable metal-organic framework functionalized with tertiary amine groups that exhibits high capacities for radioactive organic iodides uptake.

  12. Rapid, Selective Heavy Metal Removal from Water by a Metal-Organic Framework/Polydopamine Composite.

    Sun, Daniel T; Peng, Li; Reeder, Washington S; Moosavi, Seyed Mohamad; Tiana, Davide; Britt, David K; Oveisi, Emad; Queen, Wendy L

    2018-03-28

    Drinking water contamination with heavy metals, particularly lead, is a persistent problem worldwide with grave public health consequences. Existing purification methods often cannot address this problem quickly and economically. Here we report a cheap, water stable metal-organic framework/polymer composite, Fe-BTC/PDA, that exhibits rapid, selective removal of large quantities of heavy metals, such as Pb 2+ and Hg 2+ , from real world water samples. In this work, Fe-BTC is treated with dopamine, which undergoes a spontaneous polymerization to polydopamine (PDA) within its pores via the Fe 3+ open metal sites. The PDA, pinned on the internal MOF surface, gains extrinsic porosity, resulting in a composite that binds up to 1634 mg of Hg 2+ and 394 mg of Pb 2+ per gram of composite and removes more than 99.8% of these ions from a 1 ppm solution, yielding drinkable levels in seconds. Further, the composite properties are well-maintained in river and seawater samples spiked with only trace amounts of lead, illustrating unprecedented selectivity. Remarkably, no significant uptake of competing metal ions is observed even when interferents, such as Na + , are present at concentrations up to 14 000 times that of Pb 2+ . The material is further shown to be resistant to fouling when tested in high concentrations of common organic interferents, like humic acid, and is fully regenerable over many cycles.

  13. Fabrication of hybrid supercapacitor based on rod-like HKUST-1@polyaniline as cathode and reduced graphene oxide as anode

    Jafari, Elnaz Abbasi; Moradi, Morteza; Borhani, Saeed; Bigdeli, Hadise; Hajati, Shaaker

    2018-05-01

    Rod-like HKUST-1 (MOF-199) was hydrothermally synthesized, and the electrochemical capacitance properties of this MOF composited with polyaniline (PANI) were studied. The electrode was characterized by X-ray diffraction technique (XRD), Brunauer, Emmett, and Teller (BET) and scanning electron microscopy (SEM). The electrochemical performance of the HKUST-1 and PANI, as well as HKUST-1/PANI (HP) composite was investigated by cyclic voltammetry and galvanostatic charge-discharge. Pure HKUST-1 showed a low specific capacitance at a current density of 1 A/g, because of its poor conductivity. However, due to the high surface area (190 m2/g) of the rod-like HKUST-1, its composite with PANI led to an improvement in electrochemical performance. The specific capacitance of HP was achieved to be 270 F/g at the current density of 1 A/g, which is much higher than that of HKUST-1 (70 F/g) and PANI (227 F/g). An asymmetric supercapacitor (ASC) was fabricated by using the HP as cathode and rGO nanosheets as anode. This ASC provided a maximum specific power of 7497 W/kg and a specific energy of 6.22 Wh/kg with a wide working potential of 1.5 V and 87% capacity retention after 2000 cycles. Two ASCs connected in series were applied, which without recharging, lightened green and red LEDs up for 3 and 5 min, respectively.

  14. Fabrication of highly co2 selective metal organic framework membrane using liquid phase epitaxy approach

    Eddaoudi, Mohamed

    2016-01-28

    Embodiments include a method of making a metal organic framework membrane comprising contacting a substrate with a solution including a metal ion and contacting the substrate with a solution including an organic ligand, sufficient to form one or more layers of a metal organic framework on a substrate. Embodiments further include a defect-free metal organic framework membrane comprising MSiF6(pyz)2, wherein M is a metal, wherein the thickness of the membrane is less than 1,000 µm, and wherein the metal organic has a growth orientation along the [110] plane relative to a substrate.

  15. Green methods for preparing highly co2 selective and h2s tolerant metal organic frameworks

    Eddaoudi, Mohamed

    2015-12-23

    A green route for preparing a metal organic framework include mixing metal precursor with a ligand precursor to form a solvent-free mixture; adding droplets of water to the mixture; heating the mixture at a first temperature after adding the water; and isolating the metal organic framework material including the metal and the ligand.

  16. Design, Synthesis and Characterization of Functional Metal-Organic Framework Materials

    Alamer, Badriah

    2015-01-01

    are known as Metal Organic Framework (MOFs). This exceptional new family of porous materials is fabricated by linkage of metal ions or clusters and organic linkers via strong bonds. MOFs have been awarded with remarkable interest and widely studied due

  17. Fabrication of highly co2 selective metal organic framework membrane using liquid phase epitaxy approach

    Eddaoudi, Mohamed; Shekhah, Osama; Belmabkhout, Youssef

    2016-01-01

    Embodiments include a method of making a metal organic framework membrane comprising contacting a substrate with a solution including a metal ion and contacting the substrate with a solution including an organic ligand, sufficient to form one

  18. A highly conducting organic metal derived from an organic-transistor material: benzothienobenzothiophene.

    Kadoya, Tomofumi; Ashizawa, Minoru; Higashino, Toshiki; Kawamoto, Tadashi; Kumeta, Shohei; Matsumoto, Hidetoshi; Mori, Takehiko

    2013-11-07

    BTBT ([1]benzothieno[3,2-b][1]benzothiophene) is an organic semiconductor that realizes high mobility in organic transistors. Here we report that the charge-transfer (CT) salt, (BTBT)2PF6, shows a high room-temperature conductivity of 1500 S cm(-1). This compound exhibits a resistivity jump around 150 K, but when it is covered with Apiezon N grease the resistivity jump is suppressed, and the metallic conductivity is maintained down to 60 K. Owing to the very high conductivity, the ESR signal shows a significantly asymmetric Dysonian lineshape (A/B ≅ 3) even at room temperature. Since most organic conductors are based on strong electron donors, it is remarkable that such a weak electron donor as BTBT realizes a stable and highly conducting organic metal.

  19. Metal organic frameworks for the catalytic detoxification of chemical warfare nerve agents

    Hupp, Joseph T.; Farha, Omar K.; Katz, Michael J.; Mondloch, Joseph E.

    2017-04-18

    A method of using a metal organic framework (MOF) comprising a metal ion and an at least bidendate organic ligand to catalytically detoxify chemical warfare nerve agents including exposing the metal-organic-framework (MOF) to the chemical warfare nerve agent and catalytically decomposing the nerve agent with the MOF.

  20. Possibility of a ferromagnetic and conducting metal-organic network

    Mabrouk, Manel; Hayn, Roland; Denawi, Hassan; Ben Chaabane, Rafik

    2018-05-01

    In this paper, we present first principles calculations based on the spin-polarized generalized gradient approximation with on-site Coulomb repulsion term (SGGA + U), to explore the electronic and magnetic properties of the novel planar metal-organic networks TM-Pc and TM-TCNB (where TM means a transition metal of the 3d series: Ti, V, Cr, …, or Zn, Pc - Phthalocyanine, and TCNB - Tetracyanobenzene) as free-standing sheets. This work is an extension of two earlier research works dealing with the Mn (Mabrouk et al., 2015) and Fe (Mabrouk et al., 2017) cases. Our theoretical investigations demonstrate that TM-Pc are more stable than TM-TCNB. Our results unveil that all the TM-Pc frameworks have an insulating behavior with the exception of Mn-Pc which is half-metallic and favor antiferromagnetic order in the case of our magnetic systems except for V-Pc which is ferromagnetic. In contrast, the TM-TCNB networks are metallic at least in one spin direction and exhibit long-range ferromagnetic coupling in case for magnetic structures, which represent ideal candidates and an interesting prospect of unprecedented applications in spintronics. In addition, these results may shed light to achieve a new pathway on further experimental research in molecular spintronics.

  1. Metal-organic frameworks with dynamic interlocked components

    Vukotic, V. Nicholas; Harris, Kristopher J.; Zhu, Kelong; Schurko, Robert W.; Loeb, Stephen J.

    2012-06-01

    The dynamics of mechanically interlocked molecules such as rotaxanes and catenanes have been studied in solution as examples of rudimentary molecular switches and machines, but in this medium, the molecules are randomly dispersed and their motion incoherent. As a strategy for achieving a higher level of molecular organization, we have constructed a metal-organic framework material using a [2]rotaxane as the organic linker and binuclear Cu(II) units as the nodes. Activation of the as-synthesized material creates a void space inside the rigid framework that allows the soft macrocyclic ring of the [2]rotaxane to rotate rapidly, unimpeded by neighbouring molecular components. Variable-temperature 13C and 2H solid-state NMR experiments are used to characterize the nature and rate of the dynamic processes occurring inside this unique material. These results provide a blueprint for the future creation of solid-state molecular switches and molecular machines based on mechanically interlocked molecules.

  2. Thermodynamic screening of metal-substituted MOFs for carbon capture.

    Koh, Hyun Seung; Rana, Malay Kumar; Hwang, Jinhyung; Siegel, Donald J

    2013-04-07

    Metal-organic frameworks (MOFs) have emerged as promising materials for carbon capture applications due to their high CO2 capacities and tunable properties. Amongst the many possible MOFs, metal-substituted compounds based on M-DOBDC and M-HKUST-1 have demonstrated amongst the highest CO2 capacities at the low pressures typical of flue gasses. Here we explore the possibility for additional performance tuning of these compounds by computationally screening 36 metal-substituted variants (M = Be, Mg, Ca, Sr, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Mo, W, Sn, and Pb) with respect to their CO2 adsorption enthalpy, ΔH(T=300K). Supercell calculations based on van der Waals density functional theory (vdW-DF) yield enthalpies in good agreement with experimental measurements, out-performing semi-empirical (DFT-D2) and conventional (LDA & GGA) functionals. Our screening identifies 13 compounds having ΔH values within the targeted thermodynamic window -40 ≤ ΔH ≤ -75 kJ mol(-1): 8 are based on M-DODBC (M = Mg, Ca, Sr, Sc, Ti, V, Mo, and W), and 5 on M-HKUST-1 (M = Be, Mg, Ca, Sr and Sc). Variations in the electronic structure and the geometry of the structural building unit are examined and used to rationalize trends in CO2 affinity. In particular, the partial charge on the coordinatively unsaturated metal sites is found to correlate with ΔH, suggesting that this property may be used as a simple performance descriptor. The ability to rapidly distinguish promising MOFs from those that are "thermodynamic dead-ends" will be helpful in guiding synthesis efforts towards promising compounds.

  3. Thermodynamics of Pore Filling Metal Clusters in Metal Organic Frameworks: Pd in UiO-66

    Vilhelmsen, Lasse; Sholl, David S.

    2012-01-01

    Metal organic frameworks (MOFs) have experimentally been demonstrated to be capable of supporting isolated transition-metal clusters, but the stability of these clusters with respect to aggregation is unclear. In this letter we use a genetic algorithm together with density functional theory...... calculations to predict the structure of Pd clusters in UiO-66. The cluster sizes examined are far larger than those in any previous modeling studies of metal clusters in MOFs and allow us to test the hypothesis that the physically separated cavities in UiO-66 could stabilize isolated Pd clusters. Our...... calculations show that Pd clusters in UiO-66 are, at best, metastable and will aggregate into connected pore filling structures at equilibrium....

  4. Living Colloidal Metal Particles from Solvated Metal Atoms. Clustering of Metal Atoms in Organic Media 15.

    1986-09-23

    attributed to these solutions, especially toward heart disease. And in 1618 Antoni published Panacea Aurea : Auro Potabile 4 which centered on the...probably a slow process (discussed next under the electrophoresis section ). Electrophoresis: Electrophoresis, the movement of charged particles in...electrical properties. Experimental Section Preparation of a Typical Au-Acetone Colloid The metal atom reactor has been described previo sly. 3 9 ’ 5 9 ’ 6 0

  5. Organic derivatives of lanthanides containing metal in cycle

    Syutkina, O.P.; Rybakova, L.F.; Egorova, E.N.; Sigalov, A.B.; Beletskaya, I.P.

    1983-01-01

    The reaction of 2.2'-dilithium biphenyl with LnBr 3 (Ln=Pr, Sm, Gd, Ho, Yb here bromium atoms are comparatively easily replaced. Previously unknown organic derivatives of lanthanides containing metal in the cycle are obtained. It is established that a successful extraction of the compound requires reaction conditions, such as the use of ether as a solvent with the followinq addition of TGP, the order of addition of reagents. Compounds are extracted in the form of solvates containing TGP melecules. The complexes prepared are coloured, depending on the metal, beige (Pr, Sm) brown (Gd, Yb) and red-brown (Ho). They dissolve readily in TGP moderately in benzen toluene, CCl 4 . When stored their solubility in benzene and CCl 4 decreases considerably, and after 3-2 days, they are practically insoluhle. The compounds prepared are characterized by the elementary analysis, IR and PMR spectra

  6. Xenon Recovery at Room Temperature using Metal-Organic Frameworks

    Elsaidi, Sameh K. [Physical and Computational Science Directorate, Pacific Northwest National Laboratory, Richland WA 99352 USA; Chemistry Department, Faculty of Science, Alexandria University, P. O. Box 426 Ibrahimia Alexandria 21321 Egypt; Ongari, Daniele [Laboratory of Molecular Simulation, Institut des Sciences et Ingeénierie Chimiques, Ecole Polytechnique Fédérale de Lausanne (EPFL), Rue de l' Industrie 17 1951 Sion Valais Switzerland; Xu, Wenqian [X-ray Science Division, Advanced Photon Source, Argonne National Laboratory, Argonne IL 60439 USA; Mohamed, Mona H. [Chemistry Department, Faculty of Science, Alexandria University, P. O. Box 426 Ibrahimia Alexandria 21321 Egypt; Haranczyk, Maciej [IMDEA Materials Institute, c/Eric Kandel 2 28906 Getafe, Madrid Spain; Thallapally, Praveen K. [Physical and Computational Science Directorate, Pacific Northwest National Laboratory, Richland WA 99352 USA

    2017-07-24

    Xenon is known to be a very efficient anesthetic gas but its cost prohibits the wider use in medical industry and other potential applications. It has been shown that Xe recovery and recycle from anesthetic gas mixture can significantly reduce its cost as anesthetic. The current technology uses series of adsorbent columns followed by low temperature distillation to recover Xe, which is expensive to use in medical facilities. Herein, we propose much efficient and simpler system to recover and recycle Xe from simulant exhale anesthetic gas mixture at room temperature using metal organic frameworks. Among the MOFs tested, PCN-12 exhibits unprecedented performance with high Xe capacity, Xe/N2 and Xe/O2 selectivity at room temperature. The in-situ synchrotron measurements suggest the Xe is occupied in the small pockets of PCN-12 compared to unsaturated metal centers (UMCs). Computational modeling of adsorption further supports our experimental observation of Xe binding sites in PCN-12.

  7. Extremely efficient crystallization of HKUST-1 and Keggin-loaded related phases through the epoxide route.

    Oestreicher, Víctor; Jobbágy, Matías

    2017-03-25

    Highly crystalline HKUST-1 and COK-16-like phases were obtained based on a mild in situ alkalinization one-pot epoxide driven method. A slurry composed of finely ground trimesic acid, H 3 BTC, dispersed in a CuCl 2 aqueous solution quantitatively developed well crystallized HKUST-1 after the addition of propylene oxide. The use of solid H 3 BTC ensures a low concentration of free linker, favoring crystalline growth over the precipitation of amorphous or metastable impurities. An extreme space-time yield of 2.1 × 10 5 kg m -3 day -1 was reached, with no linker excess and minimum use of solvent. The method was equally efficient in the achievement of pure NENU/COK-16 phases, containing [PW 12 O 40 ] 3- , [PMo 12 O 40 ] 3- and [SiMo 12 O 40 ] 4- polyoxometalates.

  8. Vacuum-based surface modification of organic and metallic substrates

    Torres, Jessica

    Surface physico-chemical properties play an important role in the development and performance of materials in different applications. Consequently, understanding the chemical and physical processes involved during surface modification strategies is of great scientific and technological importance. This dissertation presents results from the surface modification of polymers, organic films and metallic substrates with reactive species, with the intent of simulating important modification processes and elucidating surface property changes of materials under different environments. The reactions of thermally evaporated copper and titanium with halogenated polytetrafluoroethylene (PTFE) and polyvinyl chloride (PVC) are used to contrast the interaction of metals with polymers. Results indicate that reactive metallization is thermodynamically favored when the metal-halogen bond strength is greater than the carbon-halogen bond strength. X-ray post-metallization treatment results in an increase in metal-halide bond formation due to the production of volatile halogen species in the polymer that react with the metallic overlayer. The reactions of atomic oxygen (AO) and atomic chlorine with polyethylene (PE) and self-assembled monolayers (SAMs) films were followed to ascertain the role of radical species during plasma-induced polymer surface modification. The reactions of AO with X-ray modified SAMs are initially the dominated by the incorporation of new oxygen containing functionality at the vacuum/film interface, leading to the production of volatile carbon containing species such as CO2 that erodes the hydrocarbon film. The reaction of atomic chlorine species with hydrocarbon SAMs, reveals that chlorination introduces C-Cl and C-Cl2 functionalities without erosion. A comparison of the reactions of AO and atomic chlorine with PE reveal a maximum incorporation of the corresponding C-O and C-Cl functionalities at the polymer surface. A novel method to prepare phosphorous

  9. Embedded Librarians in the Classroom: A Case Study at HKUST Library

    Ho, Kevin King-man; Wong, Eunice Sau-ping

    2012-01-01

    The introduction of new 4-year undergraduate program has unprecedented impacts on the curriculum design, pedagogies and student learning styles for higher education institutions in Hong Kong. In order to prepare for this challenging reform, the Hong Kong University of Science and Technology (HKUST) has strategically redeveloped its undergraduate curriculum. The new curriculum also emphasizes the student-centric approach, with new teaching initiatives to enhance students learning and personal ...

  10. Postsynthetic Tuning of Metal-Organic Frameworks for Targeted Applications.

    Islamoglu, Timur; Goswami, Subhadip; Li, Zhanyong; Howarth, Ashlee J; Farha, Omar K; Hupp, Joseph T

    2017-04-18

    Metal-organic frameworks (MOFs) are periodic, hybrid, atomically well-defined porous materials that typically form by self-assembly and consist of inorganic nodes (metal ions or clusters) and multitopic organic linkers. MOFs as a whole offer many intriguing properties, including ultrahigh porosity, tunable chemical functionality, and low density. These properties point to numerous potential applications, including gas storage, chemical separations, catalysis, light harvesting, and chemical sensing, to name a few. Reticular chemistry, or the linking of molecular building blocks into predetermined network structures, has been employed to synthesize thousands of MOFs. Given the vast library of candidate nodes and linkers, the number of potentially synthetically accessible MOFs is enormous. Nevertheless, a powerful complementary approach to obtain specific structures with desired chemical functionality is to modify known MOFs after synthesis. This approach is particularly useful when incorporation of particular chemical functionalities via direct synthesis is challenging or impossible. The challenges may stem from limited stability or solubility of precursors, unwanted secondary reactivity of precursors, or incompatibility of functional groups with the conditions needed for direct synthesis. MOFs can be postsynthetically modified by replacing the metal nodes and/or organic linkers or via functionalization of the metal nodes and/or organic linkers. Here we describe some of our efforts toward the development and application of postsynthetic strategies for imparting desired chemical functionalities in MOFs of known topology. The techniques include methods for functionalizing MOF nodes, i.e., solvent-assisted ligand incorporation (SALI) and atomic layer deposition in MOFs (AIM) as well as a method to replace structural linkers, termed solvent-assisted linker exchange (SALE), also known as postsynthethic exchange (PSE). For each functionalization strategy, we first describe

  11. Insight into the construction of metal-organic polyhedra: Metal-organic cubes as a case study

    Al Kordi, Mohamed; Belof, Jonathan L.; Rivera, Edwin R.; Wojtas, Łukasz; Eddaoudi, Mohamed

    2011-01-01

    Systematic studies were conducted to gain a better understanding of the metal-organic cubes (MOCs) directed assembly and their crystallization under predetermined reaction conditions, i.e. charge and size of metal ions, solvent type, counter anions, pH, and temperature. Four novel metal-organic materials are constructed via solvothermal reactions of different metal ions and 2,2′-(1H-imidazole-4,5-diyl)di-1,4,5,6-tetrahydropyrimidine, namely [Co8(C11N6H15)12]Cl 12·4H2O (1), [Ni4(C11N 6H15)4](NO3)4· 4DMF (2), {Cd(C11N6H15)(NO3) ·DMF}n (3), and [In8(C11N 6H15)12](NO3)12· 4H2O (4). In addition, syntheses and crystal structures for compounds 1(a-f), constructed under deliberately modified reaction conditions of 1, are reported. In compounds 1(a-f), the CoIII-based cationic MOCs crystallize in various packing arrangements in the presence of different counter-ions. Discrete MOCs retain their structural integrity, when crystalline solid was dissolved in water, under various pH (2.03-8.07) and temperatures (298-333 K), as confirmed by solution NMR studies. The assembly of the discrete MOC, from its basic molecular building blocks under mild reaction conditions, is demonstrated and monitored through solution NMR and UV-vis studies. © The Royal Society of Chemistry 2011.

  12. Energy driven self-organization in nanoscale metallic liquid films.

    Krishna, H; Shirato, N; Favazza, C; Kalyanaraman, R

    2009-10-01

    Nanometre thick metallic liquid films on inert substrates can spontaneously dewet and self-organize into complex nanomorphologies and nanostructures with well-defined length scales. Nanosecond pulses of an ultraviolet laser can capture the dewetting evolution and ensuing nanomorphologies, as well as introduce dramatic changes to dewetting length scales due to the nanoscopic nature of film heating. Here, we show theoretically that the self-organization principle, based on equating the rate of transfer of thermodynamic free energy to rate of loss in liquid flow, accurately describes the spontaneous dewetting. Experimental measurements of laser dewetting of Ag and Co liquid films on SiO(2) substrates confirm this principle. This energy transfer approach could be useful for analyzing the behavior of nanomaterials and chemical processes in which spontaneous changes are important.

  13. Semiconductor Metal-Organic Frameworks: Future Low-Bandgap Materials.

    Usman, Muhammad; Mendiratta, Shruti; Lu, Kuang-Lieh

    2017-02-01

    Metal-organic frameworks (MOFs) with low density, high porosity, and easy tunability of functionality and structural properties, represent potential candidates for use as semiconductor materials. The rapid development of the semiconductor industry and the continuous miniaturization of feature sizes of integrated circuits toward the nanometer (nm) scale require novel semiconductor materials instead of traditional materials like silicon, germanium, and gallium arsenide etc. MOFs with advantageous properties of both the inorganic and the organic components promise to serve as the next generation of semiconductor materials for the microelectronics industry with the potential to be extremely stable, cheap, and mechanically flexible. Here, a perspective of recent research is provided, regarding the semiconducting properties of MOFs, bandgap studies, and their potential in microelectronic devices. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. Melt-quenched glasses of metal-organic frameworks

    Bennett, T.D.; Yue, Yuanzheng; Li, P.

    2016-01-01

    Crystalline solids dominate the field of metal−organic frameworks (MOFs), with access to the liquid and glass states of matter usually prohibited by relatively low temperatures of thermal decomposition. In this work, we give due consideration to framework chemistry and topology to expand...... of other MOFs. The glasses formed upon vitrification are chemically and structurally distinct from the three other existing categories of melt-quenched glasses (inorganic nonmetallic, organic, and metallic), and retain the basic metal−ligand connectivity of crystalline MOFs, which connects their mechanical...... the phenomenon of the melting of 3D MOFs, linking crystal chemistry to framework melting temperature and kinetic fragility of the glass-forming liquids. Here we show that melting temperatures can be lowered by altering the chemistry of the crystalline MOF state, which provides a route to facilitate the melting...

  15. Assembly, Structure, and Functionality of Metal-Organic Networks and Organic Semiconductor Layers at Surfaces

    Tempas, Christopher D.

    Self-assembled nanostructures at surfaces show promise for the development of next generation technologies including organic electronic devices and heterogeneous catalysis. In many cases, the functionality of these nanostructures is not well understood. This thesis presents strategies for the structural design of new on-surface metal-organic networks and probes their chemical reactivity. It is shown that creating uniform metal sites greatly increases selectivity when compared to ligand-free metal islands. When O2 reacts with single-site vanadium centers, in redox-active self-assembled coordination networks on the Au(100) surface, it forms one product. When O2 reacts with vanadium metal islands on the same surface, multiple products are formed. Other metal-organic networks described in this thesis include a mixed valence network containing Pt0 and PtII and a network where two Fe centers reside in close proximity. This structure is stable to temperatures >450 °C. These new on-surface assemblies may offer the ability to perform reactions of increasing complexity as future heterogeneous catalysts. The functionalization of organic semiconductor molecules is also shown. When a few molecular layers are grown on the surface, it is seen that the addition of functional groups changes both the film's structure and charge transport properties. This is due to changes in both first layer packing structure and the pi-electron distribution in the functionalized molecules compared to the original molecule. The systems described in this thesis were studied using high-resolution scanning tunneling microscopy, non-contact atomic force microscopy, and X-ray photoelectron spectroscopy. Overall, this work provides strategies for the creation of new, well-defined on-surface nanostructures and adds additional chemical insight into their properties.

  16. Transferable Force Field for Metal–Organic Frameworks from First-Principles: BTW-FF

    2014-01-01

    We present an ab-initio derived force field to describe the structural and mechanical properties of metal–organic frameworks (or coordination polymers). The aim is a transferable interatomic potential that can be applied to MOFs regardless of metal or ligand identity. The initial parametrization set includes MOF-5, IRMOF-10, IRMOF-14, UiO-66, UiO-67, and HKUST-1. The force field describes the periodic crystal and considers effective atomic charges based on topological analysis of the Bloch states of the extended materials. Transferable potentials were developed for the four organic ligands comprising the test set and for the associated Cu, Zn, and Zr metal nodes. The predicted materials properties, including bulk moduli and vibrational frequencies, are in agreement with explicit density functional theory calculations. The modal heat capacity and lattice thermal expansion are also predicted. PMID:25574157

  17. Sulfate Reduction Remediation of a Metals Plume Through Organic Injection

    Phifer, M.A.

    2003-01-01

    Laboratory testing and a field-scale demonstration for the sulfate reduction remediation of an acidic/metals/sulfate groundwater plume at the Savannah River Site has been conducted. The laboratory testing consisted of the use of anaerobic microcosms to test the viability of three organic substrates to promote microbially mediated sulfate reduction. Based upon the laboratory testing, soybean oil and sodium lactate were selected for injection during the subsequent field-scale demonstration. The field-scale demonstration is currently ongoing. Approximately 825 gallons (3,123 L) of soybean oil and 225 gallons (852 L) of 60 percent sodium lactate have been injected into an existing well system within the plume. Since the injections, sulfate concentrations in the injection zone have significantly decreased, sulfate-reducing bacteria concentrations have significantly increased, the pH has increased, the Eh has decreased, and the concentrations of many metals have decreased. Microbially mediated sulfate reduction has been successfully promoted for the remediation of the acidic/metals/sulfate plume by the injection of soybean oil and sodium lactate within the plume

  18. Metal-organic frameworks for adsorption and separation of noble gases

    Allendorf, Mark D.; Greathouse, Jeffery A.; Staiger, Chad

    2017-05-30

    A method including exposing a gas mixture comprising a noble gas to a metal organic framework (MOF), including an organic electron donor and an adsorbent bed operable to adsorb a noble gas from a mixture of gases, the adsorbent bed including a metal organic framework (MOF) including an organic electron donor.

  19. Structural versatility of Metal-organic frameworks: Synthesis and Characterization

    Alsadun, Norah S.

    2017-05-01

    Metal-Organic Frameworks (MOFs), an emerging class of porous crystalline materials, have shown promising properties for diverse applications such as catalysis, gas storage and separation. The high degree of tunability of MOFs vs other solid materials enable the assembly of advanced materials with fascinating properties for specific applications. Nevertheless, the precise control in the construction of MOFs at the molecular level remains challenging. Particularly, the formation of pre-targeted multi-nuclear Molecular Building Block (MBB) precursors to unveil materials with targeted structural characteristics is captivating. The aim of my master project in the continuous quest of the group of Prof. Eddaoudi in exploring different synthetic pathways to control the assembly of Rare Earth (RE) based MOF. After giving a general overview about MOFs, I will discuss in this thesis the results of my work on the use of tri-topic oriented organic carboxylate building units with the aim to explore the assembly/construction of new porous RE based MOFs. In chapter 2 will discuss the assembly of 3-c linkers with RE metals was then evaluated based on symmetry and angularity of the three connected linkers. The focus of chapter 3 is cerium based MOFs and heterometallic system, based on 3-c ligands with different length and symmetry. Overall, the incompatibility of 3-c ligands with the 12-c cuo MBB did not allow to any formation of higher neuclearity (˃6), but it has resulted in affecting the connectivity of the cluster.

  20. Thin films by metal-organic precursor plasma spray

    Schulz, Douglas L.; Sailer, Robert A.; Payne, Scott; Leach, James; Molz, Ronald J.

    2009-01-01

    While most plasma spray routes to coatings utilize solids as the precursor feedstock, metal-organic precursor plasma spray (MOPPS) is an area that the authors have investigated recently as a novel route to thin film materials. Very thin films are possible via MOPPS and the technology offers the possibility of forming graded structures by metering the liquid feed. The current work employs metal-organic compounds that are liquids at standard temperature-pressure conditions. In addition, these complexes contain chemical functionality that allows straightforward thermolytic transformation to targeted phases of interest. Toward that end, aluminum 3,5-heptanedionate (Al(hd) 3 ), triethylsilane (HSi(C 2 H 5 ) 3 or HSiEt 3 ), and titanium tetrakisdiethylamide (Ti(N(C 2 H 5 ) 2 ) 4 or Ti(NEt 2 ) 4 ) were employed as precursors to aluminum oxide, silicon carbide, and titanium nitride, respectively. In all instances, the liquids contain metal-heteroatom bonds envisioned to provide atomic concentrations of the appropriate reagents at the film growth surface, thus promoting phase formation (e.g., Si-C bond in triethylsilane, Ti-N bond in titanium amide, etc.). Films were deposited using a Sulzer Metco TriplexPro-200 plasma spray system under various experimental conditions using design of experiment principles. Film compositions were analyzed by glazing incidence x-ray diffraction and elemental determination by x-ray spectroscopy. MOPPS films from HSiEt 3 showed the formation of SiC phase but Al(hd) 3 -derived films were amorphous. The Ti(NEt 2 ) 4 precursor gave MOPPS films that appear to consist of nanosized splats of TiOCN with spheres of TiO 2 anatase. While all films in this study suffered from poor adhesion, it is anticipated that the use of heated substrates will aid in the formation of dense, adherent films.

  1. Comparison of natural organic acids and synthetic chelates at enhancing phytoextraction of metals from a multi-metal contaminated soil

    Clistenes do Nascimento, Williams A.; Amarasiriwardena, Dula; Xing, Baoshan

    2006-01-01

    Chemically assisted phytoremediation has been developing to induce accumulation of metals by high biomass plants. Synthetic chelates have shown high effectiveness to reach such a goal, but they pose serious drawbacks in field application due to the excessive amount of metals solubilized. We compared the performance of synthetic chelates with naturally occurring low molecular weight organic acids (LMWOA) in enhancing phytoextraction of metals by Indian mustard (Brassica juncea) from multi-metal contaminated soils. Gallic and citric acids were able to induce removal of Cd, Zn, Cu, and Ni from soil without increasing the leaching risk. Net removal of these metals caused by LMWOA can be as much as synthetic chelates. A major reason for this is the lower phytotoxicity of LMWOA. Furthermore, supplying appropriate mineral nutrients increased biomass and metal removal. - Organic acids can be as efficient as synthetic chelates for use in phytoextraction of multi-metal contaminated soils

  2. Metal-organic frameworks based membranes for liquid separation.

    Li, Xin; Liu, Yuxin; Wang, Jing; Gascon, Jorge; Li, Jiansheng; Van der Bruggen, Bart

    2017-11-27

    Metal-organic frameworks (MOFs) represent a fascinating class of solid crystalline materials which can be self-assembled in a straightforward manner by the coordination of metal ions or clusters with organic ligands. Owing to their intrinsic porous characteristics, unique chemical versatility and abundant functionalities, MOFs have received substantial attention for diverse industrial applications, including membrane separation. Exciting research activities ranging from fabrication strategies to separation applications of MOF-based membranes have appeared. Inspired by the marvelous achievements of MOF-based membranes in gas separations, liquid separations are also being explored for the purpose of constructing continuous MOFs membranes or MOF-based mixed matrix membranes. Although these are in an emerging stage of vigorous development, most efforts are directed towards improving the liquid separation efficiency with well-designed MOF-based membranes. Therefore, as an increasing trend in membrane separation, the field of MOF-based membranes for liquid separation is highlighted in this review. The criteria for judicious selection of MOFs in fabricating MOF-based membranes are given. Special attention is paid to rational design strategies for MOF-based membranes, along with the latest application progress in the area of liquid separations, such as pervaporation, water treatment, and organic solvent nanofiltration. Moreover, some attractive dual-function applications of MOF-based membranes in the removal of micropollutants, degradation, and antibacterial activity are also reviewed. Finally, we define the remaining challenges and future opportunities in this field. This Tutorial Review provides an overview and outlook for MOF-based membranes for liquid separations. Further development of MOF-based membranes for liquid separation must consider the demands of strict separation standards and environmental safety for industrial application.

  3. Metal mobilization from metallurgical wastes by soil organic acids.

    Potysz, Anna; Grybos, Malgorzata; Kierczak, Jakub; Guibaud, Gilles; Fondaneche, Patrice; Lens, Piet N L; van Hullebusch, Eric D

    2017-07-01

    Three types of Cu-slags differing in chemical and mineralogical composition (historical, shaft furnace, and granulated slags) and a matte from a lead recovery process were studied with respect to their susceptibility to release Cu, Zn and Pb upon exposure to organic acids commonly encountered in soil environments. Leaching experiments (24-960 h) were conducted with: i) humic acid (20 mg/L) at pH t 0  = 4.4, ii) fulvic acid (20 mg/L) at pH t 0  = 4.4, iii) an artificial root exudates (ARE) (17.4 g/L) solution at pH t 0  = 4.4, iv) ARE solution at pH t 0  = 2.9 and v) ultrapure water (pH t 0  = 5.6). The results demonstrated that the ARE contribute the most to the mobilization of metals from all the wastes analyzed, regardless of the initial pH of the solution. For example, up to 14%, 30%, 24% and 5% of Cu is released within 960 h from historical, shaft furnace, granulated slags and lead matte, respectively, when exposed to the artificial root exudates solution (pH 2.9). Humic and fulvic acids were found to have a higher impact on granulated and shaft furnace slags as compared to the ultrapure water control and increased the release of metals by a factor up to 37.5 (Pb) and 20.5 (Cu) for granulated and shaft furnace slags, respectively. Humic and fulvic acids amplified the mobilization of metals by a maximal factor of 13.6 (Pb) and 12.1 (Pb) for historical slag and lead matte, respectively. The studied organic compounds contributed to different release rates of metallic contaminants from individual metallurgical wastes under the conditions tested. Copyright © 2017 Elsevier Ltd. All rights reserved.

  4. A simple method to prepare self-assembled organic-organic heterobilayers on metal substrates

    L. D. Sun

    2011-06-01

    Full Text Available We demonstrate a self-assembly based simple method to prepare organic-organic heterobilayers on a metal substrate. By either sequential- or co-deposition of para-sexiphenyl (p-6P and pentacene molecules onto the Cu(110 surface in ultrahigh vacuum, p-6P/pentacene/Cu(110 heterobilayer is synthesized at room temperature. The layer sequence of the heterostructure is independent of the growth scenario indicating the p-6P/pentacene/Cu(110 is a self-assembled structure with lowest energy. Besides, the bilayer shows a very high orientational ordering and is thermally stable up to 430K.

  5. A metal-free organic-inorganic aqueous flow battery

    Huskinson, B; Marshak, MP; Suh, C; Er, S; Gerhardt, MR; Galvin, CJ; Chen, XD; Aspuru-Guzik, A; Gordon, RG; Aziz, MJ

    2014-01-08

    As the fraction of electricity generation from intermittent renewable sources-such as solar or wind-grows, the ability to store large amounts of electrical energy is of increasing importance. Solid-electrode batteries maintain discharge at peak power for far too short a time to fully regulate wind or solar power output(1,2). In contrast, flow batteries can independently scale the power (electrode area) and energy (arbitrarily large storage volume) components of the system by maintaining all of the electro-active species in fluid form(3-5). Wide-scale utilization of flow batteries is, however, limited by the abundance and cost of these materials, particularly those using redox-active metals and precious-metal electrocatalysts(6,7). Here we describe a class of energy storage materials that exploits the favourable chemical and electro-chemical properties of a family of molecules known as quinones. The example we demonstrate is ametal-free flow battery based on the redox chemistry of 9,10-anthraquinone-2,7-disulphonic acid (AQDS). AQDS undergoes extremely rapid and reversible two-electron two-proton reduction on a glassy carbon electrode in sulphuric acid. An aqueous flow battery with inexpensive carbon electrodes, combining the quinone/hydroquinone couple with the Br-2/Br- redox couple, yields a peak galvanic power density exceeding 0.6 W cm(-2) at 1.3 A cm(-2). Cycling of this quinone-bromide flow battery showed >99 per cent storage capacity retention per cycle. The organic anthraquinone species can be synthesized from inexpensive commodity chemicals(8). This organic approach permits tuning of important properties such as the reduction potential and solubility by adding functional groups: for example, we demonstrate that the addition of two hydroxy groups to AQDS increases the open circuit potential of the cell by 11% and we describe a pathway for further increases in cell voltage. The use of p-aromatic redox-active organic molecules instead of redox-active metals

  6. Templated synthesis, postsynthetic metal exchange, and properties of a porphyrin-encapsulating metal-organic material

    Zhang, ZhenJie

    2012-01-18

    Reaction of biphenyl-3,4′,5-tricarboxylate (H 3BPT) and CdCl 2 in the presence of meso-tetra(N-methyl-4-pyridyl)porphine tetratosylate (TMPyP) afforded porph@MOM-10, a microporous metal-organic material containing CdTMPyP cations encapsulated in an anionic Cd(II) carboxylate framework, [Cd 6(BPT) 4Cl 4(H 2O) 4]. Porph@MOM-10 is a versatile platform that undergoes exchange to serve as the parent of a series of porph@MOMs that exhibit permanent porosity and heterogeneous catalytic activity. © 2011 American Chemical Society.

  7. Electrocatalytic Metal-Organic Frameworks for Energy Applications.

    Downes, Courtney A; Marinescu, Smaranda C

    2017-11-23

    With the global energy demand expected to increase drastically over the next several decades, the development of a sustainable energy system to meet this increase is paramount. Renewable energy sources can be coupled with electrochemical conversion processes to store energy in chemical bonds. To promote these difficult transformations, electrocatalysts that operate at high conversion rates and efficiency are required. Metal-organic frameworks (MOFs) have emerged as a promising class of materials; however, the insulating nature of MOFs has limited their application as electrocatalysts. The recent development of conductive MOFs has led to several electrocatalytic MOFs that display activity comparable to that of the best-performing heterogeneous catalysts. Although many electrocatalytic MOFs exhibit low activity and stability, the few successful examples highlight the possibility of MOF electrocatalysts as replacements for noble-metal-based catalysts in commercial energy-converting devices. We review herein the use of pristine MOFs as electrocatalysts to facilitate important energy-related reactions. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. Controlling Thermal Expansion: A Metal-Organic Frameworks Route.

    Balestra, Salvador R G; Bueno-Perez, Rocio; Hamad, Said; Dubbeldam, David; Ruiz-Salvador, A Rabdel; Calero, Sofia

    2016-11-22

    Controlling thermal expansion is an important, not yet resolved, and challenging problem in materials research. A conceptual design is introduced here, for the first time, for the use of metal-organic frameworks (MOFs) as platforms for controlling thermal expansion devices that can operate in the negative, zero, and positive expansion regimes. A detailed computer simulation study, based on molecular dynamics, is presented to support the targeted application. MOF-5 has been selected as model material, along with three molecules of similar size and known differences in terms of the nature of host-guest interactions. It has been shown that adsorbate molecules can control, in a colligative way, the thermal expansion of the solid, so that changing the adsorbate molecules induces the solid to display positive, zero, or negative thermal expansion. We analyze in depth the distortion mechanisms, beyond the ligand metal junction, to cover the ligand distortions, and the energetic and entropic effect on the thermo-structural behavior. We provide an unprecedented atomistic insight on the effect of adsorbates on the thermal expansion of MOFs as a basic tool toward controlling the thermal expansion.

  9. Surface nano-architecture of a metal-organic framework.

    Makiura, Rie; Motoyama, Soichiro; Umemura, Yasushi; Yamanaka, Hiroaki; Sakata, Osami; Kitagawa, Hiroshi

    2010-07-01

    The rational assembly of ultrathin films of metal-organic frameworks (MOFs)--highly ordered microporous materials--with well-controlled growth direction and film thickness is a critical and as yet unrealized issue for enabling the use of MOFs in nanotechnological devices, such as sensors, catalysts and electrodes for fuel cells. Here we report the facile bottom-up fabrication at ambient temperature of such a perfect preferentially oriented MOF nanofilm on a solid surface (NAFS-1), consisting of metalloporphyrin building units. The construction of NAFS-1 was achieved by the unconventional integration in a modular fashion of a layer-by-layer growth technique coupled with the Langmuir-Blodgett method. NAFS-1 is endowed with highly crystalline order both in the out-of-plane and in-plane orientations to the substrate, as demonstrated by synchrotron X-ray surface crystallography. The proposed structural model incorporates metal-coordinated pyridine molecules projected from the two-dimensional sheets that allow each further layer to dock in a highly ordered interdigitated manner in the growth of NAFS-1. We expect that the versatility of the solution-based growth strategy presented here will allow the fabrication of various well-ordered MOF nanofilms, opening the way for their use in a range of important applications.

  10. Xenon Recovery at Room Temperature using Metal-Organic Frameworks

    Elsaidi, Sameh K. [Physical and Computational Science Directorate, Pacific Northwest National Laboratory, Richland WA 99352 USA; Chemistry Department, Faculty of Science, Alexandria University, P. O. Box 426 Ibrahimia Alexandria 21321 Egypt; Ongari, Daniele [Laboratory of Molecular Simulation, Institut des Sciences et Ingeénierie Chimiques, Ecole Polytechnique Fédérale de Lausanne (EPFL), Rue de l' Industrie 17 1951 Sion Valais Switzerland; Xu, Wenqian [X-ray Science Division, Advanced Photon Source, Argonne National Laboratory, Argonne IL 60439 USA; Mohamed, Mona H. [Chemistry Department, Faculty of Science, Alexandria University, P. O. Box 426 Ibrahimia Alexandria 21321 Egypt; Haranczyk, Maciej [IMDEA Materials Institute, c/Eric Kandel 2 28906 Getafe, Madrid Spain; Thallapally, Praveen K. [Physical and Computational Science Directorate, Pacific Northwest National Laboratory, Richland WA 99352 USA

    2017-07-24

    Xenon is known to be a very efficient anesthetic gas but its cost prohibits the wider use in medical industry and other potential applications. It has been shown that Xe recovery and recycle from anesthetic gas mixture can significantly reduce its cost as anesthetic. The current technology uses series of adsorbent columns followed by low temperature distillation to recover Xe, which is expensive to use in medical facilities. Herein, we propose much efficient and simpler system to recover and recycle Xe from simulant exhale anesthetic gas mixture at room temperature using metal organic frameworks. Among the MOFs tested, PCN-12 exhibits unprecedented performance with high Xe capacity, Xe/O2, Xe/N2 and Xe/CO2 selectivity at room temperature. The in-situ synchrotron measurements suggest the Xe is occupied in the small pockets of PCN-12 compared to unsaturated metal centers (UMCs). Computational modeling of adsorption further supports our experimental observation of Xe binding sites in PCN-12.

  11. Enzyme-MOF (metal-organic framework) composites.

    Lian, Xizhen; Fang, Yu; Joseph, Elizabeth; Wang, Qi; Li, Jialuo; Banerjee, Sayan; Lollar, Christina; Wang, Xuan; Zhou, Hong-Cai

    2017-06-06

    The ex vivo application of enzymes in various processes, especially via enzyme immobilization techniques, has been extensively studied in recent years in order to enhance the recyclability of enzymes, to minimize enzyme contamination in the product, and to explore novel horizons for enzymes in biomedical applications. Possessing remarkable amenability in structural design of the frameworks as well as almost unparalelled surface tunability, Metal-Organic Frameworks (MOFs) have been gaining popularity as candidates for enzyme immobilization platforms. Many MOF-enzyme composites have achieved unprecedented results, far outperforming free enzymes in many aspects. This review summarizes recent developments of MOF-enzyme composites with special emphasis on preparative techniques and the synergistic effects of enzymes and MOFs. The applications of MOF-enzyme composites, primarily in transferation, catalysis and sensing, are presented as well. The enhancement of enzymatic activity of the composites over free enzymes in biologically incompatible conditions is emphasized in many cases.

  12. Phosphorus organic extragents and sorbents of radioactive a heavy metals

    Trofimov, B.A.; Gusarova, N.K.; Malysheva, S.F.; Sukhov, B.G.

    2002-01-01

    A fundamentally new method for activation of phosphorus in heterogenous super-base media including the conditions of mechanical, ultrasonic and X-ray activation, opening up a new way to C-P bond formation is developed. The method is opens principally new possibilities for direct atom-economic synthesis of previously unknown or difficult to obtain organophosphorus compounds (primary, secondary, tertiary phosphines and phosphine oxides) from elemental phosphorus and orga-nyl halides, electrophilic alkenes, acetylenes and oxiranes. Thus, the phosphothion and phosphorylation of organic compounds with elemental phosphorus, phosphines and phosphine oxides opens the principal new approach to the synthesis of specific and selective extra-gents, sorbents and complex-forming agents which can be used in the processes of purification and disinfecting of soil and water from radioactive and heavy metals

  13. Ordered macro-microporous metal-organic framework single crystals

    Shen, Kui; Zhang, Lei; Chen, Xiaodong; Liu, Lingmei; Zhang, Daliang; Han, Yu; Chen, Junying; Long, Jilan; Luque, Rafael; Li, Yingwei; Chen, Banglin

    2018-01-01

    We constructed highly oriented and ordered macropores within metal-organic framework (MOF) single crystals, opening up the area of three-dimensional–ordered macro-microporous materials (that is, materials containing both macro- and micropores) in single-crystalline form. Our methodology relies on the strong shaping effects of a polystyrene nanosphere monolith template and a double-solvent–induced heterogeneous nucleation approach. This process synergistically enabled the in situ growth of MOFs within ordered voids, rendering a single crystal with oriented and ordered macro-microporous structure. The improved mass diffusion properties of such hierarchical frameworks, together with their robust single-crystalline nature, endow them with superior catalytic activity and recyclability for bulky-molecule reactions, as compared with conventional, polycrystalline hollow, and disordered macroporous ZIF-8.

  14. Catalysis by metal-organic frameworks: fundamentals and opportunities.

    Ranocchiari, Marco; van Bokhoven, Jeroen Anton

    2011-04-14

    Crystalline porous materials are extremely important for developing catalytic systems with high scientific and industrial impact. Metal-organic frameworks (MOFs) show unique potential that still has to be fully exploited. This perspective summarizes the properties of MOFs with the aim to understand what are possible approaches to catalysis with these materials. We categorize three classes of MOF catalysts: (1) those with active site on the framework, (2) those with encapsulated active species, and (3) those with active sites attached through post-synthetic modification. We identify the tunable porosity, the ability to fine tune the structure of the active site and its environment, the presence of multiple active sites, and the opportunity to synthesize structures in which key-lock bonding of substrates occurs as the characteristics that distinguish MOFs from other materials. We experience a unique opportunity to imagine and design heterogeneous catalysts, which might catalyze reactions previously thought impossible.

  15. Gas sorption properties of microporous metal organic frameworks

    Lee, JeongYong; Li Jing; Jagiello, Jacek

    2005-01-01

    A low-temperature gas sorption study has been carried out on four three-dimensional microporous metal organic framework (MMOF) structures and two two-dimensional layered structures. The pore characteristics are analyzed based on the argon adsorption-desorption isotherms at 87 K. The results from hydrogen sorption experiments conducted at 77 and 87 K show that all MMOFs have a relatively high hydrogen uptake, with adsorbed hydrogen densities falling in the range of liquid hydrogen. Isosteric heats of hydrogen adsorption data calculated based on the Clausius-Clapeyron equation are consistent with these observations, indicating strong sorbent-sorbate interactions. - Graphical abstract: Hydrogen adsorption isotherms measured at 77 and 87 K

  16. Ordered macro-microporous metal-organic framework single crystals

    Shen, Kui

    2018-01-16

    We constructed highly oriented and ordered macropores within metal-organic framework (MOF) single crystals, opening up the area of three-dimensional-ordered macro-microporous materials (that is, materials containing both macro- and micropores) in single-crystalline form. Our methodology relies on the strong shaping effects of a polystyrene nanosphere monolith template and a double-solvent-induced heterogeneous nucleation approach. This process synergistically enabled the in situ growth of MOFs within ordered voids, rendering a single crystal with oriented and ordered macro-microporous structure. The improved mass diffusion properties of such hierarchical frameworks, together with their robust single-crystalline nature, endow them with superior catalytic activity and recyclability for bulky-molecule reactions, as compared with conventional, polycrystalline hollow, and disordered macroporous ZIF-8.

  17. Designing Kitaev Spin Liquids in Metal-Organic Frameworks

    Yamada, Masahiko G.; Fujita, Hiroyuki; Oshikawa, Masaki

    2017-08-01

    Kitaev's honeycomb lattice spin model is a remarkable exactly solvable model, which has a particular type of spin liquid (Kitaev spin liquid) as the ground state. Although its possible realization in iridates and α -RuCl3 has been vigorously discussed recently, these materials have substantial non-Kitaev direct exchange interactions and do not have a spin liquid ground state. We propose metal-organic frameworks (MOFs) with Ru3 + (or Os3 + ), forming the honeycomb lattice as promising candidates for a more ideal realization of Kitaev-type spin models, where the direct exchange interaction is strongly suppressed. The great flexibility of MOFs allows generalization to other three-dimensional lattices for the potential realization of a variety of spin liquids, such as a Weyl spin liquid.

  18. Ordered macro-microporous metal-organic framework single crystals

    Shen, Kui; Zhang, Lei; Chen, Xiaodong; Liu, Lingmei; Zhang, Daliang; Han, Yu; Chen, Junying; Long, Jilan; Luque, Rafael; Li, Yingwei; Chen, Banglin

    2018-01-01

    We constructed highly oriented and ordered macropores within metal-organic framework (MOF) single crystals, opening up the area of three-dimensional-ordered macro-microporous materials (that is, materials containing both macro- and micropores) in single-crystalline form. Our methodology relies on the strong shaping effects of a polystyrene nanosphere monolith template and a double-solvent-induced heterogeneous nucleation approach. This process synergistically enabled the in situ growth of MOFs within ordered voids, rendering a single crystal with oriented and ordered macro-microporous structure. The improved mass diffusion properties of such hierarchical frameworks, together with their robust single-crystalline nature, endow them with superior catalytic activity and recyclability for bulky-molecule reactions, as compared with conventional, polycrystalline hollow, and disordered macroporous ZIF-8.

  19. In situ synthesis of metal-organic frameworks in a porous polymer monolith as the stationary phase for capillary liquid chromatography.

    Yang, Shengchao; Ye, Fanggui; Zhang, Cong; Shen, Shufen; Zhao, Shulin

    2015-04-21

    In this study, HKUST-1 was synthesized in situ on the porous polymer monolith as the stationary phase for capillary liquid chromatography (cLC). The unique carboxyl functionalized poly(methacrylic acid-co-ethylene dimethacrylate) (poly(MAA-co-EDMA)) monolith was used as a support to directly grow HKUST-1 by a controlled layer-by-layer self-assembly strategy. X-ray diffraction, scanning electron microscopy, energy dispersive X-ray spectrometry, and Fourier transform infrared spectroscopy of the resulting HKUST-1-poly(MAA-co-EDMA) monoliths indicated that HKUST-1 was successfully grafted onto the pore surface of the poly(MAA-co-EDMA) monolith. The column performance of HKUST-1-poly(MAA-co-EDMA) monoliths for the separation of various small molecules, such as benzenediols, xylenes, ethylbenzenes, and styrenes, was evaluated. The chromatographic performance was found to improve with increasing HKUST-1 density, and the column efficiencies and resolutions of HKUST-1-poly(MAA-co-EDMA) monoliths were 18 320-19 890 plates m(-1) and 1.62-6.42, respectively, for benzenediols. The HKUST-1-poly(MAA-co-EDMA) monolith displayed enhanced resolution for the separation of positional isomers when compared to the traditional C18 and HKUST-1 incorporated polymer monoliths. Hydrophobic, π-π, and hydrogen bonding interactions within the HKUST-1-poly(MAA-co-EDMA) monolith were observed in the separation of small molecules. The results showed that the HKUST-1-poly(MAA-co-EDMA) monoliths are promising stationary phases for cLC.

  20. Metal-directed topological diversity of three fluorescent metal-organic frameworks based on a new tetracarboxylate strut

    Lou, Xinhua

    2013-01-01

    Three d- or p-block metal ions based metal-organic frameworks (MOFs) were isolated by employing a new tetracarboxylate linker, featuring unusual flu, self-interpenetrated lvt and new (3,5)-c topological nets, respectively. Interesting photoluminescent properties of these solid-state materials were also observed. © 2013 The Royal Society of Chemistry.

  1. New metal-organic nanomaterials synthesized by laser irradiation of organic liquids

    Kuzmin, Stanislav L.; Wesolowski, Michal J.; Duley, Walter W. [Department of Physics and Astronomy, University of Waterloo, 200 University Avenue West, Waterloo, ON N2L 3G1 (Canada)

    2014-03-31

    A new type of metal-organic composition consisting of clusters of nanoparticles has been synthesised by laser irradiation of metallocene/benzene solutions. The metallocene molecules in this reaction become the source of the metal. Exposure to high-energy femtosecond laser pulses dehydrogenate benzene molecules and initiate the high-temperature high-pressure conditions that results in the synthesis of new materials. Irradiation experiments have been carried out on ferrocene/benzene and on other solutions. With ferrocene the synthesis of a new compound has been confirmed by X-ray powder diffraction as the peaks detected do not correspond to any known substance in the Crystallography Open Database. Theoretical simulation of the periodic structure of this new carbide predicts that it has hexagonal symmetry and a unit cell with a = 3.2A and c =2.8A. The exact structure is still uncertain but may be determined from scanning tunneling microscope (STM) studies.

  2. Electronic properties of metal-organic and organic-organic interfaces studied by photoemission and photoabsorption spectroscopy

    Molodtsova, Olga

    2006-07-01

    In this work systematic studies of the organic semiconductor CuPc have been presented. In general the investigation can be devided in three parts. In the first one we have studied the electronic structure of clean CuPc thin film. The next two parts are devoted to organic-organic and metal-organic interface formation, where one of the interface components is CuPc thin film. The main results of this thesis are: - The electronic structure of the pristine organic semiconductor CuPc has been obtained by a combination of conventional and resonant photoemission, near-edge X-ray absorption, as well as by theoretical ab initio quantum-chemical calculations. The contributions of different atomic species as well as sites of the CuPc molecule to the electronic DOS has been established. A combined experimental and theoretical study of the unoccupied electronic density of states of CuPc was presented. - The electronic properties of the organic heterointerfaces between fullerite and pristine copper phthalocyanine were studied. Both interfaces, CuPc/C{sub 60} and C{sub 60}/CuPc, were found to be non-reactive with pronounced shifts of the vacuum level pointing to the formation of an interfacial dipole mainly at the CuPc side of the heterojunctions. The dipole values are close to the difference of the work functions of the two materials. Important interface parameters and hole-injection barriers were obtained. The sequence of deposition does not influence the electronic properties of the interfaces. - CuPc doped with potassium was studied by means of photoemission and photoabsorption spectroscopy. A detailed analysis of the core-level PE spectra allows one to propose possible lattice sites, which harbor the potassium ions. The films prepared in this thesis showed no finite electronic density of states at the Fermi level. - Two stages of the In/CuPc interface formation have been distinguished. The low-coverage stage is characterized by a strong diffusion of the In atoms into the

  3. Metal Deposition from Organic Solutions for Microelectronic Applications

    Dahlgren, E

    2001-01-01

    ... plating in aqueous solutions. This process was also shown to be capable of producing selectively deposited seed layers only on exposed reactive metal surfaces for subsequent electroless and electrolytic metal depositions...

  4. Design, synthesis and characterization of metal organic frameworks

    Eddaoudi, Mohamed; Xue, Dongxu; Luebke, Ryan; Guillerm, Vincent; Peedikakkal, Abdul Malik Puthan; Adil, Karim; Weselinski, Lukasz Jan

    2015-01-01

    A molecular building block composition can include a metal ion component; and a ligand component including a core including at least one functional group associated with the metal ion component and the core.

  5. Design, synthesis and characterization of metal organic frameworks

    Eddaoudi, Mohamed

    2015-12-03

    A molecular building block composition can include a metal ion component; and a ligand component including a core including at least one functional group associated with the metal ion component and the core.

  6. Electronic self-organization in layered transition metal dichalcogenides

    Ritschel, Tobias

    2015-10-30

    The interplay between different self-organized electronically ordered states and their relation to unconventional electronic properties like superconductivity constitutes one of the most exciting challenges of modern condensed matter physics. In the present thesis this issue is thoroughly investigated for the prototypical layered material 1T-TaS{sub 2} both experimentally and theoretically. At first the static charge density wave order in 1T-TaS{sub 2} is investigated as a function of pressure and temperature by means of X-ray diffraction. These data indeed reveal that the superconductivity in this material coexists with an inhomogeneous charge density wave on a macroscopic scale in real space. This result is fundamentally different from a previously proposed separation of superconducting and insulating regions in real space. Furthermore, the X-ray diffraction data uncover the important role of interlayer correlations in 1T-TaS{sub 2}. Based on the detailed insights into the charge density wave structure obtained by the X-ray diffraction experiments, density functional theory models are deduced in order to describe the electronic structure of 1T-TaS{sub 2} in the second part of this thesis. As opposed to most previous studies, these calculations take the three-dimensional character of the charge density wave into account. Indeed the electronic structure calculations uncover complex orbital textures, which are interwoven with the charge density wave order and cause dramatic differences in the electronic structure depending on the alignment of the orbitals between neighboring layers. Furthermore, it is demonstrated that these orbital-mediated effects provide a route to drive semiconductor-to-metal transitions with technologically pertinent gaps and on ultrafast timescales. These results are particularly relevant for the ongoing development of novel, miniaturized and ultrafast devices based on layered transition metal dichalcogenides. The discovery of orbital textures

  7. Ionic behavior of organic-inorganic metal halide perovskite based metal-oxide-semiconductor capacitors.

    Wang, Yucheng; Zhang, Yuming; Pang, Tiqiang; Xu, Jie; Hu, Ziyang; Zhu, Yuejin; Tang, Xiaoyan; Luan, Suzhen; Jia, Renxu

    2017-05-24

    Organic-inorganic metal halide perovskites are promising semiconductors for optoelectronic applications. Despite the achievements in device performance, the electrical properties of perovskites have stagnated. Ion migration is speculated to be the main contributing factor for the many unusual electrical phenomena in perovskite-based devices. Here, to understand the intrinsic electrical behavior of perovskites, we constructed metal-oxide-semiconductor (MOS) capacitors based on perovskite films and performed capacitance-voltage (C-V) and current-voltage (I-V) measurements of the capacitors. The results provide direct evidence for the mixed ionic-electronic transport behavior within perovskite films. In the dark, there is electrical hysteresis in both the C-V and I-V curves because the mobile negative ions take part in charge transport despite frequency modulation. However, under illumination, the large amount of photoexcited free carriers screens the influence of the mobile ions with a low concentration, which is responsible for the normal C-V properties. Validation of ion migration for the gate-control ability of MOS capacitors is also helpful for the investigation of perovskite MOS transistors and other gate-control photovoltaic devices.

  8. Photoreactivity of Metal-Organic Frameworks in Aqueous Solutions: Metal Dependence of Reactive Oxygen Species Production.

    Liu, Kai; Gao, Yanxin; Liu, Jing; Wen, Yifan; Zhao, Yingcan; Zhang, Kunyang; Yu, Gang

    2016-04-05

    Promising applications of metal-organic frameworks (MOFs) in various fields have raised concern over their environmental fate and safety upon inevitable discharge into aqueous environments. Currently, no information regarding the transformation processes of MOFs is available. Due to the presence of repetitive π-bond structure and semiconductive property, photochemical transformations are an important fate process that affects the performance of MOFs in practical applications. In the current study, the generation of reactive oxygen species (ROS) in isoreticular MIL-53s was studied. Scavengers were employed to probe the production of (1)O2, O2(•-), and •OH, respectively. In general, MIL-53(Cr) and MIL-53(Fe) are dominated by type I and II photosensitization reactions, respectively, and MIL-53(Al) appears to be less photoreactive. The generation of ROS in MIL-53(Fe) may be underestimated due to dismutation. Further investigation of MIL-53(Fe) encapsulated diclofenac transformation revealed that diclofenac can be easily transformed by MIL-53(Fe) generated ROS. However, the cytotoxicity results implied that the ROS generated from MIL-53s have little effect on the viability of the human hepatocyte (HepG2) cell line. These results suggest that the photogeneration of ROS by MOFs may be metal-node dependent, and the application of MIL-53s as drug carriers needs to be carefully considered due to their high photoreactivity.

  9. Study of the electronic properties of organic molecules within a metal-molecule-metal junction

    Lambert, Mathieu

    2003-01-01

    This ph-D thesis is about electronic transport through organic molecules inserted in a metal molecule-metal junction. We describe first a simple process to prepare sub-3 nm gaps by controllable breakage (under an electrical stress) of gold wires lithographed on a SiO 2 Si substrate at low temperature (4.2 K). We show that the involved mechanism is thermally assisted electromigration. We observe that current-voltage (I-V) characteristics of resulting electrodes are stable up to ∼5 V. which gives access to the well-known Fowler-Nordheim regime in the I-V, allowing an accurate characterisation of the gap size. The average gap is found lo be between 1.5 nm in width and 2.5 eV in height. Molecules and nanoparticles have then been inserted in the junction in the case of nanoparticles for example. The resulting IV clearly shows the suppression of electrical current at low bias known as Coulomb blockade. Characteristic of single-electron tunnelling through nanometer-sized structures, finally we fabricated a single-electron tunneling device based on Au nanoparticles connected to the electrodes via terthiophene (T3) molecule. We use the silicon substrate, separated from the planar structure by a silicon oxide of 200 nm, as an electrostatic gate and observed clear current modulation with possible signature of the transport properties of the terthiophene molecules. (author) [fr

  10. Organ- and species-specific accumulation of metals in two land snail species (Gastropoda, Pulmonata)

    Boshoff, Magdalena, E-mail: magdalena.boshoff@ua.ac.be [University of Antwerp, Systemic Physiological and Ecotoxicological Research, Groenenborgerlaan 171, B-2020 Antwerp (Belgium); Jordaens, Kurt [Royal Museum for Central Africa (JEMU), Leuvensesteenweg 13, B-3080 Tervuren (Belgium); University of Antwerp, Evolutionary Ecology Group, Groenenborgerlaan 171, B-2020 Antwerp (Belgium); Backeljau, Thierry [University of Antwerp, Evolutionary Ecology Group, Groenenborgerlaan 171, B-2020 Antwerp (Belgium); Royal Belgian Institute of Natural Sciences (JEMU), Vautierstraat 29, B-1000 Brussels (Belgium); Lettens, Suzanna [Research Institute for Nature and Forest (INBO), Kliniekstraat 25, B-1070 Brussels (Belgium); Tack, Filip [Ghent University, Laboratory of Analytical Chemistry and Applied Ecochemistry, Coupure Links 265, B-9000 Ghent (Belgium); Vandecasteele, Bart [Institute for Agricultural and Fisheries Research (ILVO), Burg van Gansberghelaan 109, B-9820 Merelbeke (Belgium); De Jonge, Maarten; Bervoets, Lieven [University of Antwerp, Systemic Physiological and Ecotoxicological Research, Groenenborgerlaan 171, B-2020 Antwerp (Belgium)

    2013-04-01

    In order to evaluate the usefulness of terrestrial gastropods as bioindicators there is a need for studies that simultaneously compare (1) concentrations of metals in reference and polluted plots, (2) species within the same polluted habitat, (3) metal accumulation patterns in different organs and (4) metal accumulation patterns in relation to soil physicochemical properties. This study aims to assess metal accumulation patterns in two land snail species. Instead of analyzing an organism as a whole, investigating the partitioning of metals in different organs can provide information on the actual toxicological relevant fractions. Therefore, concentrations of Ag, Cd, Cr, Cu, Ni and Zn were examined in five different organs of Cepaea nemoralis, as well as in the foot and the body of Succinea putris. Snails were sampled at four polluted dredged sediment disposal localities and three adjacent less polluted reference plots situated along waterways in Flanders, Belgium. Due to the small size and problematic dissection of S. putris only the concentrations in the foot of both species could be compared. For this reason only, C. nemoralis can be described as a better bioindicator species that allows a far more detailed analysis of organ metal accumulation. This study showed that organs other than the digestive gland may be involved in the immobilization and detoxification of metals. Furthermore, pH, soil fractionation (clay %, silt %, sand %) and organic matter, correlate with metal accumulation in organs. However, most often the soil metal concentrations did not correlate with the concentrations found in snail organs. Metal concentrations in organs of both species (1) differed among polluted plots but rarely between polluted and reference plots within a locality, (2) were organ-specific (digestive gland > foot > albumen gland = spermoviduct = ovotestis), (3) were species-specific and (4) depended on the metal type (high Cd and Cu concentrations were observed in the

  11. Transformation of metal-organic framework to polymer gel by cross-linking the organic ligands preorganized in metal-organic framework.

    Ishiwata, Takumi; Furukawa, Yuki; Sugikawa, Kouta; Kokado, Kenta; Sada, Kazuki

    2013-04-10

    Until now, seamless fusion of metal-organic frameworks (MOFs) and covalently cross-linked polymer gels (PG) at molecular level has been extremely rare, since these two matters have been regarded as opposite, that is, hard versus soft. In this report, we demonstrate transformation of cubic MOF crystals to PG via inner cross-linking of the organic linkers in the void space of MOF, followed by decomposition of the metal coordination. The obtained PG behaved as a polyelectrolyte gel, indicating the high content of ionic groups inside. Metal ions were well adsorbed in the PG due to its densely packed carboxylate groups. A chimera-type hybrid material consisting of MOF and PG was obtained by partial hydrolysis of resulting cross-linked MOF. The shape of resulting PG network well reflected the crystal structure of MOF employed as a template. Our results will connect the two different network materials that have been ever studied in the two different fields to provide new soft and hard hybrid materials, and the unique copolymerization in the large void space of the MOF will open a new horizon toward "ideal network polymers" never prepared before now.

  12. Three-dimensional metal-intercalated covalent organic frameworks for near-ambient energy storage

    Gao, Fei; Ding, Zijing; Meng, Sheng

    2013-01-01

    A new form of nanoporous material, metal intercalated covalent organic framework (MCOF) is proposed and its energy storage property revealed. Employing density functional and thermodynamical analysis, we find that stable, chemically active, porous materials could form by stacking covalent organic framework (COF) layers with metals as a gluing agent. Metal acts as active sites, while its aggregation is suppressed by a binding energy significantly larger than the corresponding cohesive energy of bulk metals. Two important parameters, metal binding and metal-metal separation, are tuned by selecting suitable building blocks and linkers when constructing COF layers. Systematic searches among a variety of elements and organic molecules identify Ca-intercalated COF with diphenylethyne units as optimal material for H2 storage, reaching a striking gravimetric density ~ 5 wt% at near-ambient conditions (300 K, 20 bar), in comparison to < 0.1 wt% for bare COF-1 under the same condition. PMID:23698018

  13. Self-aligned metallization on organic semiconductor through 3D dual-layer thermal nanoimprint

    Jung, Y; Cheng, X

    2014-01-01

    High-resolution patterning of metal structures on organic semiconductors is important to the realization of high-performance organic transistors for organic integrated circuit applications. The traditional shadow mask technique has a limited resolution, precluding sub-micron metal structures on organic semiconductors. Thus organic transistors cannot benefit from scaling into the deep sub-micron region to improve their dc and ac performances. In this work, we report an efficient multiple-level metallization on poly (3-hexylthiophene) (P3HT) with a deep sub-micron lateral gap. By using a 3D nanoimprint mold in a dual-layer thermal nanoimprint process, we achieved self-aligned two-level metallization on P3HT. The 3D dual-layer thermal nanoimprint enables the first metal patterns to have suspending side-wings that can clearly define a distance from the second metal patterns. Isotropic and anisotropic side-wing structures can be fabricated through two different schemes. The process based on isotropic side-wings achieves a lateral-gap in the order of 100 nm (scheme 1). A gap of 60 nm can be achieved from the process with anisotropic side-wings (scheme 2). Because of the capability of nanoscale metal patterning on organic semiconductors with high overlay accuracy, this self-aligned metallization technique can be utilized to fabricate high-performance organic metal semiconductor field-effect transistor. (paper)

  14. Metal-organic frameworks for lithium ion batteries and supercapacitors

    Ke, Fu-Sheng; Wu, Yu-Shan; Deng, Hexiang

    2015-01-01

    Porous materials have been widely used in batteries and supercapacitors attribute to their large internal surface area (usually 100–1000 m 2 g −1 ) and porosity that can favor the electrochemical reaction, interfacial charge transport, and provide short diffusion paths for ions. As a new type of porous crystalline materials, metal-organic frameworks (MOFs) have received huge attention in the past decade due to their unique properties, i.e. huge surface area (up to 7000 m 2 g −1 ), high porosity, low density, controllable structure and tunable pore size. A wide range of applications including gas separation, storage, catalysis, and drug delivery benefit from the recent fast development of MOFs. However, their potential in electrochemical energy storage has not been fully revealed. Herein, the present mini review appraises recent and significant development of MOFs and MOF-derived materials for rechargeable lithium ion batteries and supercapacitors, to give a glimpse into these potential applications of MOFs. - Graphical abstract: MOFs with large surface area and high porosity can offer more reaction sites and charge carriers diffusion path. Thus MOFs are used as cathode, anode, electrolyte, matrix and precursor materials for lithium ion battery, and also as electrode and precursor materials for supercapacitors. - Highlights: • MOFs have potential in electrochemical area due to their high porosity and diversity. • We summarized and compared works on MOFs for lithium ion battery and supercapacitor. • We pointed out critical challenges and provided possible solutions for future study

  15. PZT Films Fabricated by Metal Organic Decomposition Method

    Sobolev, Vladimir; Ishchuk, Valeriy

    2014-03-01

    High quality lead zirconate titanate films have been fabricated on different substrates by metal organic decomposition method and their ferroelectric properties have been investigated. Main attention was paid to studies of the influence of the buffer layer with conditional composition Pb1.3(Zr0.5Ti0.5) O3 on the properties of Pb(Zr0.5Ti0.5) O3 films fabricated on the polycrystalline titanium and platinum substrates. It is found that in the films on the Pt substrate (with or without the buffer layer) the dependencies of the remanent polarization and the coercivity field on the number of switching cycles do not manifest fatigue up to 109 cycles. The remanent polarization dependencies for films on the Ti substrate with the buffer layer containing an excess of PbO demonstrate an fundamentally new feature that consists of a remanent polarization increase after 108 switching cycles. The increase of remanent polarization is about 50% when the number of cycles approaches 1010, while the increase of the coercivity field is small. A monotonic increase of dielectric losses has been observed in all cases.

  16. Metal-organic frameworks for lithium ion batteries and supercapacitors

    Ke, Fu-Sheng; Wu, Yu-Shan; Deng, Hexiang, E-mail: hdeng@whu.edu.cn

    2015-03-15

    Porous materials have been widely used in batteries and supercapacitors attribute to their large internal surface area (usually 100–1000 m{sup 2} g{sup −1}) and porosity that can favor the electrochemical reaction, interfacial charge transport, and provide short diffusion paths for ions. As a new type of porous crystalline materials, metal-organic frameworks (MOFs) have received huge attention in the past decade due to their unique properties, i.e. huge surface area (up to 7000 m{sup 2} g{sup −1}), high porosity, low density, controllable structure and tunable pore size. A wide range of applications including gas separation, storage, catalysis, and drug delivery benefit from the recent fast development of MOFs. However, their potential in electrochemical energy storage has not been fully revealed. Herein, the present mini review appraises recent and significant development of MOFs and MOF-derived materials for rechargeable lithium ion batteries and supercapacitors, to give a glimpse into these potential applications of MOFs. - Graphical abstract: MOFs with large surface area and high porosity can offer more reaction sites and charge carriers diffusion path. Thus MOFs are used as cathode, anode, electrolyte, matrix and precursor materials for lithium ion battery, and also as electrode and precursor materials for supercapacitors. - Highlights: • MOFs have potential in electrochemical area due to their high porosity and diversity. • We summarized and compared works on MOFs for lithium ion battery and supercapacitor. • We pointed out critical challenges and provided possible solutions for future study.

  17. Laser assisted anticancer activity of benzimidazole based metal organic nanoparticles.

    Praveen, P A; Ramesh Babu, R; Balaji, P; Murugadas, A; Akbarsha, M A

    2018-03-01

    Recent studies showed that the photothermal therapy can be effectively used for the targeted cancerous cells destruction. Hence, in the present study, benzimidazole based metal organic complex nanoparticles, dichloro cobalt(II) bis-benzimidazole (Co-BMZ) and dichloro copper(II) bis-benzimidazole (Cu-BMZ), were synthesized by reprecipitation method and their anti-cancer activity by means of photothermal effect has been studied. Transmission electron microscopy analysis shows that the particle size of Cu-BMZ is ∼100 nm and Co-BMZ is in the range between 100 and 400 nm. Zeta potential analysis ensures the stability of the synthesized nanoparticles. It is found that the nonlinear absorption of the nanoparticles increases with increase in laser power intensity. Phototoxicity of human lung cancer (A549) and the normal mouse embryonic fibroblast (NIH-3T3) cells was studied using a 650 nm laser. Even though both the cell lines were affected by laser irradiation, A549 cells show higher cell destruction and lower IC 50 values than the normal cells. Docking studies were used to analyse the interaction site and the results showed that the Cu-BMZ molecules have higher dock score than the Co-BMZ molecules. The obtained results indicate that Cu-BMZ samples have lesser particle size, higher nonlinear absorption and higher interaction energy than the Co-BMZ samples. Copyright © 2018 Elsevier B.V. All rights reserved.

  18. Fabrication of metal organic framework materials using a layer-by-layer spin coating approach

    Eddaoudi, Mohamed; Shekhah, Osama

    2016-01-01

    Embodiments describe a method of depositing an MOF, including depositing a metal solution onto a substrate, spinning the substrate sufficient to spread the metal solution, depositing an organic ligand solution onto the substrate and spinning the substrate sufficient to spread the organic ligand solution and form a MOF layer.

  19. Metal-organic frameworks at interfaces of hybrid perovskite solar cells for enhanced photovoltaic properties.

    Shen, Deli; Pang, Aiying; Li, Yafeng; Dou, Jie; Wei, Mingdeng

    2018-01-31

    In this study, metal-organic frameworks, as an interfacial layer, were introduced into perovskite solar cells (PSCs) for the first time. An interface modified with the metal-organic framework ZIF-8 efficiently enhanced perovskite crystallinity and grain sizes, and the photovoltaic performance of the PSCs was significantly improved, resulting in a maximum PCE of 16.99%.

  20. Fabrication of metal organic framework materials using a layer-by-layer spin coating approach

    Eddaoudi, Mohamed

    2016-03-17

    Embodiments describe a method of depositing an MOF, including depositing a metal solution onto a substrate, spinning the substrate sufficient to spread the metal solution, depositing an organic ligand solution onto the substrate and spinning the substrate sufficient to spread the organic ligand solution and form a MOF layer.

  1. Small-angle X-ray scattering documents the growth of metal-organic frameworks

    Goesten, M.G.; Stavitski, I.; Juan-Alcañiz, J.; Martinez-Joaristi, A.; Petukhov, A.V.; Kapteijn, F.; Gascon, J.

    2013-01-01

    We present a combined in situ small- and wide-angle scattering (SAXS/WAXS) study on the crystallization of two topical metal-organic frameworks synthesized from similar metal and organic precursors: NH2-MIL-53(Al) and NH2-MIL-101(Al). A thorough analysis of SAXS data reveals the most important

  2. A study on the photocatalytic reaction of the metals and organics

    Na, Jeong Won; Cho, Young Hyun; Seong, Ki Woong; Kim, Yong Ik; Kang, Hee [Korea Atomic Energy Research Institute, Taejon (Korea, Republic of)

    1995-12-01

    TiO{sub 2}-based photocatalytic reactions in organometallic solution the form of metal(iron and copper)-EDTA complexes in order to examine the metal removal behavior were performed. Photocatalysis technology that have the ability to remove both organics and metal can be applied to efficiently treat the radioactive organic waste in the basis of appropriate process development. 10 tabs., 21 figs. (Author).

  3. A study on the photocatalytic reaction of the metals and organics

    Na, Jeong Won; Cho, Young Hyun; Seong, Ki Woong; Kim, Yong Ik; Kang, Hee

    1995-12-01

    TiO 2 -based photocatalytic reactions in organometallic solution the form of metal(iron and copper)-EDTA complexes in order to examine the metal removal behavior were performed. Photocatalysis technology that have the ability to remove both organics and metal can be applied to efficiently treat the radioactive organic waste in the basis of appropriate process development. 10 tabs., 21 figs. (Author)

  4. Room temperature synthesis of free-standing HKUST-1 membranes from copper hydroxide nanostrands for gas separation.

    Mao, Yiyin; shi, Li; Huang, Hubiao; Cao, Wei; Li, Junwei; Sun, Luwei; Jin, Xianda; Peng, Xinsheng

    2013-06-25

    Large scale, robust, well intergrown free-standing HKUST-1 membranes were converted from copper hydroxide nanostrand free-standing films in 1,3,5-benzenetricarboxylic acid water-ethanol solution at room temperature, and explored for gas separation. The truncated crystals are controllable and favorable for the dense intergrowth.

  5. Metal Organic Frameworks: Explorations and Design Strategies for MOF Synthesis

    AbdulHalim, Rasha

    2016-11-27

    Metal-Organic Frameworks (MOFs) represent an emerging new class of functional crystalline solid-state materials. In the early discovery of this now rapidly growing class of materials significant challenges were often encountered. However, MOFs today, with its vast structural modularity, reflected by the huge library of the available chemical building blocks, and exceptional controlled porosity, stand as the most promising candidate to address many of the overbearing societal challenges pertaining to energy and environmental sustainability. A variety of design strategies have been enumerated in the literature which rely on the use of predesigned building blocks paving the way towards potentially more predictable structures. The two major design strategies presented in this work are the molecular building block (MBB) and supermolecular building block (SBB) -based approaches for the rationale assembly of functional MOF materials with the desired structural features. In this context, we targeted two highly connected MOF platforms, namely rht-MOF and shp-MOF. These two MOF platforms are classified based on their topology, defined as the underlying connectivity of their respective net, as edge transitive binodal nets; shp being (4,12)-connected net and rht being (3,24)-connected net. These highly connected nets were deliberately targeted due to the limited number of possible nets for connecting their associated basic building units. Two highly porous materials were designed and successfully constructed; namely Y-shp-MOF-5 and rht-MOF-10. The Y-shp-MOF-5 features a phenomenal water stability with an exquisite behavior when exposed to water, positioning this microporous material as the best adsorbent for moisture control applications. The shp-MOF platform proved to be modular to ligand functionalization and thus imparting significant behavioral changes when hydrophilic and hydrophobic functionalized ligands were introduced on the resultant MOF. On the other hand, rht

  6. HKUST-1 as a Heterogeneous Catalyst for the Synthesis of Vanillin.

    Yépez, Rebeca; Illescas, Juan F; Gijón, Paulina; Sánchez-Sánchez, Manuel; González-Zamora, Eduardo; Santillan, Rosa; Álvarez, J Raziel; Ibarra, Ilich A; Aguilar-Pliego, Julia

    2016-07-23

    Vanillin (4-hydoxy-3-methoxybenzaldehyde) is the main component of the extract of vanilla bean. The natural vanilla scent is a mixture of approximately 200 different odorant compounds in addition to vanillin. The natural extraction of vanillin (from the orchid Vanilla planifolia, Vanilla tahitiensis and Vanilla pompon) represents only 1% of the worldwide production and since this process is expensive and very long, the rest of the production of vanillin is synthesized. Many biotechnological approaches can be used for the synthesis of vanillin from lignin, phenolic stilbenes, isoeugenol, eugenol, guaicol, etc., with the disadvantage of harming the environment since these processes use strong oxidizing agents and toxic solvents. Thus, eco-friendly alternatives on the production of vanillin are very desirable and thus, under current investigation. Porous coordination polymers (PCPs) are a new class of highly crystalline materials that recently have been used for catalysis. HKUST-1 (Cu3(BTC)2(H2O)3, BTC = 1,3,5-benzene-tricarboxylate) is a very well known PCP which has been extensively studied as a heterogeneous catalyst. Here, we report a synthetic strategy for the production of vanillin by the oxidation of trans-ferulic acid using HKUST-1 as a catalyst.

  7. Influence of dissimilatory metal reduction on fate of organic and metal contaminants in the subsurface

    Lovley, Derek R.; Anderson, Robert T.

    Dissimilatory Fe(III)-reducing microorganisms have the ability to destroy organic contaminants under anaerobic conditions by oxidizing them to carbon dioxide. Some Fe(III)-reducing microorganisms can also reductively dechlorinate chlorinated contaminants. Fe(III)-reducing microorganisms can reduce a variety of contaminant metals and convert them from soluble forms to forms that are likely to be immobilized in the subsurface. Studies in petroleum-contaminated aquifers have demonstrated that Fe(III)-reducing microorganisms can be effective agents in removing aromatic hydrocarbons from groundwater under anaerobic conditions. Laboratory studies have demonstrated the potential for Fe(III)-reducing microorganisms to remove uranium from contaminated groundwaters. The activity of Fe(III)-reducing microorganisms can be stimulated in several ways to enhance organic contaminant oxidation and metal reduction. Molecular analyses in both field and laboratory studies have demonstrated that microorganisms of the genus Geobacter become dominant members of the microbial community when Fe(III)-reducing conditions develop as the result of organic contamination, or when Fe(III) reduction is artificially stimulated. These results suggest that further understanding of the ecophysiology of Geobacter species would aid in better prediction of the natural attenuation of organic contaminants under anaerobic conditions and in the design of strategies for the bioremediation of subsurface metal contamination. Des micro-organismes simulant la réduction du fer ont la capacité de détruire des polluants organiques dans des conditions anérobies en les oxydant en dioxyde de carbone. Certains micro-organismes réducteurs de fer peuvent aussi dé-chlorer par réduction des polluants chlorés. Des micro-organismes réducteurs de fer peuvent réduire tout un ensemble de métaux polluants et les faire passer de formes solubles à des formes qui sont susceptibles d'être immobilisées dans le milieu

  8. The concept of mixed organic ligands in metal-organic frameworks: design, tuning and functions.

    Yin, Zheng; Zhou, Yan-Ling; Zeng, Ming-Hua; Kurmoo, Mohamedally

    2015-03-28

    The research on metal-organic frameworks (MOFs) has been developing at an extraordinary pace in its two decades of existence, as judged by the exponential growth of novel structures and the constant expansion of its applicability and research scope. A major part of the research and its success are due to the vital role of the concept of mixed organic ligands in the design, tuning and functions. This perspective, therefore, reviews the recent advances in MOFs based on this concept, which is generally based on employing a small polydentate ligand (here labelled as "nodal ligand") to form either clusters, rods or layers, which are then connected by a second ditopic linker ligand to form the framework. The structures of the materials can be grouped into the following three categories: layer-spacer (usually known as pillared-layer), rod-spacer, and cluster-spacer based MOFs. Depending on the size and geometry of the spacer ligands, interpenetrations of frameworks are occasionally found. These MOFs show a wide range of properties such as (a) crystal-to-crystal transformations upon solvent modifications, post-synthetic metal exchange or ligand reactions, (b) gas sorption, solvent selectivity and purification, (c) specific catalysis, (d) optical properties including colour change, luminescence, non-linear optic, (e) short- and long range magnetic ordering, metamagnetism and reversible ground-state modifications and (f) drug and iodine carriers with controlled release. In the following, we will highlight the importance of the above concept in the design, tuning, and functions of a selection of existing MOFs having mixed organic ligands and their associated structures and properties. The results obtained so far using this concept look very promising for fine-tuning the pore size and shape for selective adsorption and specificity in catalytic reactions, which appears to be one way to propel the advances in the application and commercialization of MOFs.

  9. Surface stress and large-scale self-organization at organic-metal interfaces

    Pollinger, Florian

    2009-01-22

    The role of elastic interactions, particularly for the self-organized formation of periodically faceted interfaces, was investigated in this thesis for archetype organic-metal interfaces. The cantilever bending technique was applied to study the change of surface stress upon formation of the interface between 3,4,9,10-perylene-tetracarboxylic-dianhydride (PTCDA) and Ag(111). The main focus of this work was on the investigation of the formation of the long-range ordered, self-organized faceted PTCDA/Ag(10 8 7) interface. Reciprocal space maps of this interface were recorded both by spot profile analysis low energy electron diffraction (SPA-LEED) and low energy electron microscopy (LEEM) in selected area LEED mode. Complementary to the reciprocal data, also microscopic real-space LEEM data were used to characterize the morphology of this interface. Six different facet faces ((111), (532), (743), (954), (13 9 5), and (542)) were observed for the preparation path of molecular adsorption on the substrate kept at 550 K. Facet-sensitive dark-field LEEM localized these facets to grow in homogeneous areas of microscopic extensions. The temperature-dependence of the interface formation was studied in a range between 418 K and 612 K in order to learn more about the kinetics of the process. Additional steeper facets of 27 inclination with respect to the (111) surface were observed in the low temperature regime. Furthermore, using facet-sensitive dark-field LEEM, spatial and size distributions of specific facets were studied for the different temperatures. Moreover, the facet dimensions were statistically analyzed. The total island size of the facets follows an exponential distribution, indicating a random growth mode in absence of any mutual facet interactions. While the length distribution of the facets also follows an exponential distribution, the width distribution is peaked, reflecting the high degree of lateral order. This anisotropy is temperature-dependent and occurs

  10. Metal organic frameworks as a drug delivery system for flurbiprofen.

    Al Haydar, Muder; Abid, Hussein Rasool; Sunderland, Bruce; Wang, Shaobin

    2017-01-01

    Metal organic frameworks (MOFs) have attracted more attention in the last decade because of a suitable pore size, large surface area, and high pore volume. Developing biocompatible MOFs such as the MIL family as a drug delivery system is possible. Flurbiprofen (FBP), a nonsteroidal anti-inflammatory agent, is practically insoluble in aqueous solution, and, therefore, needs suitable drug delivery systems. Different biocompatible MOFs such as Ca-MOF and Fe-MILs (53, 100, and 101) were synthesized and employed for FBP delivery. A sample of 50 mg of each MOF was mixed and stirred for 24 h with 10 mL of 5 mg FBP in acetonitrile (40%) in a sealed container. The supernatant of the mixture after centrifuging was analyzed by high-performance liquid chromatography to determine the loaded quantity of FBP on the MOF. The overnight-dried solid material after centrifuging the mixture was analyzed for loading percent using X-ray diffraction, Fourier-transform infrared spectroscopy, scanning electron microscopy, nuclear magnetic resonance, and FBP release profile. The loading values of FBP were achieved at 10.0%±1%, 20%±0.8%, 37%±2.3%, and 46%±3.1% on Ca-MOF, Fe-MIL-53, Fe-MIL-101, and Fe-MIL-100, respectively. The FBP release profiles were investigated in a phosphate buffer solution at pH 7.4. The total release of the FBP after 2 days was obtained at 72.9, 75.2, 78.3, and 90.3% for Ca-MOF, Fe-MIL-100, Fe-MIL-53, and Fe-MIL-101, respectively. The MOFs are shown to be a promising drug delivery option for FBP with a significant loading percent and relatively prolonged drug release.

  11. Anisotropic thermal expansion in a metal-organic framework.

    Madsen, Solveig Røgild; Lock, Nina; Overgaard, Jacob; Iversen, Bo Brummerstedt

    2014-06-01

    Ionothermal reaction between Mn(II)(acetate)2·4H2O and 1,3,5-benzenetricarboxylic acid (H3BTC) in either of the two ionic liquids 1-ethyl-3-methylimidazolium bromide (EMIMBr) and 1-ethyl-3-methylimidazolium tosylate (EMIMOTs) resulted in the formation of the new metal-organic framework (MOF) EMIM[Mn(II)BTC] (BTC = 1,3,5-benzenetricarboxylate). The compound crystallizes in the orthorhombic space group Pbca with unit-cell parameters of a = 14.66658 (12), b = 12.39497 (9), c = 16.63509 (14) Å at 100 K. Multi-temperature single-crystal (15-340 K) and powder X-ray diffraction studies (100-400 K) reveal strongly anisotropic thermal expansion properties. The linear thermal expansion coefficients, αL(l), attain maximum values at 400 K along the a- and b-axis, with αL(a) = 115 × 10(-6) K(-1) and αL(b) = 75 × 10(-6) K(-1). At 400 K a negative thermal expansion coefficient of -40 × 10(-6) K(-1) is observed along the c-axis. The thermal expansion is coupled to a continuous deformation of the framework, which causes the structure to expand in two directions. Due to the rigidity of the linker, the expansion in the ab plane causes the network to contract along the c-axis. Hirshfeld surface analysis has been used to describe the interaction between the framework structure and the EMIM cation that resides within the channel. This reveals a number of rather weak interactions and one governing hydrogen-bonding interactions.

  12. Ultrafast rotation in an amphidynamic crystalline metal organic framework.

    Vogelsberg, Cortnie S; Uribe-Romo, Fernando J; Lipton, Andrew S; Yang, Song; Houk, K N; Brown, Stuart; Garcia-Garibay, Miguel A

    2017-12-26

    Amphidynamic crystals are an emergent class of condensed phase matter designed with a combination of lattice-forming elements linked to components that display engineered dynamics in the solid state. Here, we address the design of a crystalline array of molecular rotors with inertial diffusional rotation at the nanoscale, characterized by the absence of steric or electronic barriers. We solved this challenge with 1,4-bicyclo[2.2.2]octane dicarboxylic acid (BODCA)-MOF, a metal-organic framework (MOF) built with a high-symmetry bicyclo[2.2.2]octane dicarboxylate linker in a Zn 4 O cubic lattice. Using spin-lattice relaxation 1 H solid-state NMR at 29.49 and 13.87 MHz in the temperature range of 2.3-80 K, we showed that internal rotation occurs in a potential with energy barriers of 0.185 kcal mol -1 These results were confirmed with 2 H solid-state NMR line-shape analysis and spin-lattice relaxation at 76.78 MHz obtained between 6 and 298 K, which, combined with molecular dynamics simulations, indicate that inertial diffusional rotation is characterized by a broad range of angular displacements with no residence time at any given site. The ambient temperature rotation of the bicyclo[2.2.2]octane (BCO) group in BODCA-MOF constitutes an example where engineered rotational dynamics in the solid state are as fast as they would be in a high-density gas or in a low-density liquid phase.

  13. Ultrafast rotation in an amphidynamic crystalline metal organic framework

    Vogelsberg, Cortnie S.; Uribe-Romo, Fernando J.; Lipton, Andrew S.; Yang, Song; Houk, K. N.; Brown, Stuart; Garcia-Garibay, Miguel A.

    2017-12-11

    Amphidynamic crystals are an emergent class of condensed phase matter designed with a combination of lattice-forming elements linked to components that display engineered dynamics in the solid state. Here, we address the design of a crystalline array of molecular rotors with inertial diffusional rotation at the nanoscale, characterized by the absence of steric or electronic barriers. We solved this challenge with 1,4-bicyclo[2.2.2]octane dicarboxylic acid (BODCA)-MOF, a metal-organic framework (MOF) built with a high-symmetry bicyclo[2.2.2]octane dicarboxylate linker in a Zn4O cubic lattice. Using spin-lattice relaxation 1H solid-state NMR at 29.49 and 13.87 MHz in the temperature range of 2.3–80 K, we showed that internal rotation occurs in a potential with energy barriers of 0.185 kcal mol-1. These results were confirmed with 2H solid-state NMR line-shape analysis and spin-lattice relaxation at 76.78 MHz obtained between 6 and 298 K, which, combined with molecular dynamics simulations, indicate that inertial diffusional rotation is characterized by a broad range of angular displacements with no residence time at any given site. The ambient temperature rotation of the bicyclo[2.2.2]octane (BCO) group in BODCA-MOF constitutes an example where engineered rotational dynamics in the solid state are as fast as they would be in a high-density gas or in a low-density liquid phase.

  14. Fresh organic matter of municipal solid waste enhances phytoextraction of heavy metals from contaminated soil

    Salati, S.; Quadri, G.; Tambone, F. [Dipartimento di Produzione Vegetale, Universita degli Studi di Milano, Via Celoria 2, 20133 Milano (Italy); Adani, F., E-mail: fabrizio.adani@unimi.i [Dipartimento di Produzione Vegetale, Universita degli Studi di Milano, Via Celoria 2, 20133 Milano (Italy)

    2010-05-15

    In this study, the ability of the organic fraction of municipal solid wastes (OFMSW) to enhance heavy metal uptake of maize shoots compared with ethylenediamine disuccinic acid (EDDS) was tested on soil contaminated with heavy metals. Soils treated with OFMSW and EDDS significantly increased the concentration of heavy metals in maize shoots (increments of 302%, 66%, 184%, 169%, and 23% for Cr, Cu, Ni, Zn, and Pb with respect to the control and increments of 933%, 482%, 928%, 428%, and 5551% for soils treated with OFMSW and EDDS, respectively). In soil treated with OFMSW, metal uptake was favored because of the high presence of dissolved organic matter (DOM) (41.6x than soil control) that exhibited ligand properties because of the high presence of carboxylic acids. Because of the toxic effect of EDDS on maize plants, soil treated with OFMSW achieved the highest extraction of total heavy metals. - Organic fraction of MSW affects the bioavailability of heavy metals in soil.

  15. Fresh organic matter of municipal solid waste enhances phytoextraction of heavy metals from contaminated soil

    Salati, S.; Quadri, G.; Tambone, F.; Adani, F.

    2010-01-01

    In this study, the ability of the organic fraction of municipal solid wastes (OFMSW) to enhance heavy metal uptake of maize shoots compared with ethylenediamine disuccinic acid (EDDS) was tested on soil contaminated with heavy metals. Soils treated with OFMSW and EDDS significantly increased the concentration of heavy metals in maize shoots (increments of 302%, 66%, 184%, 169%, and 23% for Cr, Cu, Ni, Zn, and Pb with respect to the control and increments of 933%, 482%, 928%, 428%, and 5551% for soils treated with OFMSW and EDDS, respectively). In soil treated with OFMSW, metal uptake was favored because of the high presence of dissolved organic matter (DOM) (41.6x than soil control) that exhibited ligand properties because of the high presence of carboxylic acids. Because of the toxic effect of EDDS on maize plants, soil treated with OFMSW achieved the highest extraction of total heavy metals. - Organic fraction of MSW affects the bioavailability of heavy metals in soil.

  16. Enhancing Skin Permeation of Biphenylacetic Acid (BPA) Using Salt Formation with Organic and Alkali Metal Bases

    PAWAR, Vijay; NAIK, Prashant; GIRIDHAR, Rajani; YADAV, Mange Ram

    2014-01-01

    In the present study, a series of organic and alkali metal salts of biphenylacetic acid (BPA) have been prepared and evaluated in vitro for percutaneous drug delivery. The physicochemical properties of BPA salts were determined using solubility measurements, DSC, and IR. The DSC thermogram and FTIR spectra confirmed the salt formation with organic and alkali metal bases. Among the series, salts with organic amines (ethanolamine, diethanolamine, triethanol-amine, and diethylamine) had lowered ...

  17. Bi–Mn mixed metal organic oxide: A novel 3d-6p mixed metal coordination network

    Shi, Fa-Nian; Rosa Silva, Ana; Bian, Liang

    2015-01-01

    A new terminology of metal organic oxide (MOO) was given a definition as a type of coordination polymers which possess the feature of inorganic connectivity between metals and the direct bonded atoms and show 1D, 2D or 3D inorganic sub-networks. One such compound was shown as an example. A 3d-6p (Mn–Bi. Named MOOMnBi) mixed metals coordination network has been synthesized via hydrothermal method. The new compound with the molecular formula of [MnBi 2 O(1,3,5-BTC) 2 ] n (1,3,5-BTC stands for benzene-1,3,5-tricarboxylate) was characterized via single crystal X-ray diffraction technique that revealed a very interesting 3-dimensional (3D) framework with Bi 4 O 2 (COO) 12 clusters which are further connected to Mn(COO) 6 fragments into a 2D MOO. The topology study indicates an unprecedented topological type with the net point group of (4 13 .6 2 )(4 13 .6 8 )(4 16 .6 5 )(4 18 .6 10 )(4 22 .6 14 )(4 3 ) corresponding to 3,6,7,7,8,9-c hexa-nodal net. MOOMnBi shows catalytic activity in the synthesis of (E)-α,β-unsaturated ketones. - Graphical abstract: This metal organic framework (MOF) is the essence of a 2D metal organic oxide (MOO). - Highlights: • New concept of metal organic oxide (MOO) was defined and made difference from metal organic framework. • New MOO of MOOMnBi was synthesized by hydrothermal method. • Crystal structure of MOOMnBi was determined by single crystal X-ray analysis. • The catalytic activity of MOOMnBi was studied showing reusable after 2 cycles

  18. Bi–Mn mixed metal organic oxide: A novel 3d-6p mixed metal coordination network

    Shi, Fa-Nian, E-mail: fshi@ua.pt [School of Science, Shenyang University of Technology, 110870 Shenyang (China); Department of Chemistry, CICECO, University of Aveiro, 3810-193 Aveiro (Portugal); Rosa Silva, Ana [Department of Chemistry, CICECO, University of Aveiro, 3810-193 Aveiro (Portugal); Bian, Liang [Key Laboratory of Functional Materials and Devices for Special Environments, Chinese Academy of Sciences, Urumqi 830011, Xinjiang (China)

    2015-05-15

    A new terminology of metal organic oxide (MOO) was given a definition as a type of coordination polymers which possess the feature of inorganic connectivity between metals and the direct bonded atoms and show 1D, 2D or 3D inorganic sub-networks. One such compound was shown as an example. A 3d-6p (Mn–Bi. Named MOOMnBi) mixed metals coordination network has been synthesized via hydrothermal method. The new compound with the molecular formula of [MnBi{sub 2}O(1,3,5-BTC){sub 2}]{sub n} (1,3,5-BTC stands for benzene-1,3,5-tricarboxylate) was characterized via single crystal X-ray diffraction technique that revealed a very interesting 3-dimensional (3D) framework with Bi{sub 4}O{sub 2}(COO){sub 12} clusters which are further connected to Mn(COO){sub 6} fragments into a 2D MOO. The topology study indicates an unprecedented topological type with the net point group of (4{sup 13}.6{sup 2})(4{sup 13}.6{sup 8})(4{sup 16}.6{sup 5})(4{sup 18}.6{sup 10})(4{sup 22}.6{sup 14})(4{sup 3}) corresponding to 3,6,7,7,8,9-c hexa-nodal net. MOOMnBi shows catalytic activity in the synthesis of (E)-α,β-unsaturated ketones. - Graphical abstract: This metal organic framework (MOF) is the essence of a 2D metal organic oxide (MOO). - Highlights: • New concept of metal organic oxide (MOO) was defined and made difference from metal organic framework. • New MOO of MOOMnBi was synthesized by hydrothermal method. • Crystal structure of MOOMnBi was determined by single crystal X-ray analysis. • The catalytic activity of MOOMnBi was studied showing reusable after 2 cycles.

  19. Using biochar for remediation of soils contaminated with heavy metals and organic pollutants.

    Zhang, Xiaokai; Wang, Hailong; He, Lizhi; Lu, Kouping; Sarmah, Ajit; Li, Jianwu; Bolan, Nanthi S; Pei, Jianchuan; Huang, Huagang

    2013-12-01

    Soil contamination with heavy metals and organic pollutants has increasingly become a serious global environmental issue in recent years. Considerable efforts have been made to remediate contaminated soils. Biochar has a large surface area, and high capacity to adsorb heavy metals and organic pollutants. Biochar can potentially be used to reduce the bioavailability and leachability of heavy metals and organic pollutants in soils through adsorption and other physicochemical reactions. Biochar is typically an alkaline material which can increase soil pH and contribute to stabilization of heavy metals. Application of biochar for remediation of contaminated soils may provide a new solution to the soil pollution problem. This paper provides an overview on the impact of biochar on the environmental fate and mobility of heavy metals and organic pollutants in contaminated soils and its implication for remediation of contaminated soils. Further research directions are identified to ensure a safe and sustainable use of biochar as a soil amendment for remediation of contaminated soils.

  20. Chemoselective single-site Earth-abundant metal catalysts at metal–organic framework nodes

    Manna, Kuntal; Ji, Pengfei; Lin, Zekai; Greene, Francis X.; Urban, Ania; Thacker, Nathan C.; Lin, Wenbin (UC)

    2016-08-30

    Earth-abundant metal catalysts are critically needed for sustainable chemical synthesis. Here we report a simple, cheap and effective strategy of producing novel earth-abundant metal catalysts at metal–organic framework (MOF) nodes for broad-scope organic transformations. The straightforward metalation of MOF secondary building units (SBUs) with cobalt and iron salts affords highly active and reusable single-site solid catalysts for a range of organic reactions, including chemoselective borylation, silylation and amination of benzylic C–H bonds, as well as hydrogenation and hydroboration of alkenes and ketones. Our structural, spectroscopic and kinetic studies suggest that chemoselective organic transformations occur on site-isolated, electron-deficient and coordinatively unsaturated metal centres at the SBUs via σ-bond metathesis pathways and as a result of the steric environment around the catalytic site. MOFs thus provide a novel platform for the development of highly active and affordable base metal catalysts for the sustainable synthesis of fine chemicals.

  1. Current-Voltage Characteristics of the Metal / Organic Semiconductor / Metal Structures: Top and Bottom Contact Configuration Case

    Šarūnas MEŠKINIS

    2013-03-01

    Full Text Available In present study five synthesized organic semiconductor compounds have been used for fabrication of the planar metal / organic semiconductor / metal structures. Both top electrode and bottom electrode configurations were used. Current-voltage (I-V characteristics of the samples were investigated. Effect of the hysteresis of the I-V characteristics was observed for all the investigated samples. However, strength of the hysteresis was dependent on the organic semiconductor used. Study of I-V characteristics of the top contact Al/AT-RB-1/Al structures revealed, that in (0 – 500 V voltages range average current of the samples measured in air is only slightly higher than current measured in nitrogen ambient. Deposition of the ultra-thin diamond like carbon interlayer resulted in both decrease of the hysteresis of I-V characteristics of top contact Al/AT-RB-1/Al samples. However, decreased current and decreased slope of the I-V characteristics of the samples with diamond like carbon interlayer was observed as well. I-V characteristic hysteresis effect was less pronounced in the case of the bottom contact metal/organic semiconductor/metal samples. I-V characteristics of the bottom contact samples were dependent on electrode metal used.DOI: http://dx.doi.org/10.5755/j01.ms.19.1.3816

  2. Artificial organs: recent progress in metals and ceramics.

    Nomura, Naoyuki

    2010-04-01

    The superior properties and novel functions of biomaterials, including metals and ceramics commonly used as implants and medical devices, have been the focus of a number of recent papers. New functions have been explored in metastable beta-Ti alloys, Ni-free Co-Cr-Mo alloys, Mg alloys, and other materials. In addition, porous metals and ceramics with sophisticated structures have been studied as scaffolds for regenerative medicine. In this review, recent advances in bioceramics, metallic biomaterials, and their composites are discussed in terms of their material properties and morphology.

  3. Organic matter and heavy metals in grey-water sludge

    2010-01-08

    Jan 8, 2010 ... metal loads comparable to Danish sewage sludge, and it exceeds the Danish quality criteria for ... The hydraulic retention time (HRT) of the whole plant is .... sludge will contain an important part of the XOCs which were.

  4. Distribution of Heavy Metals in Organs of Freshwater Fishes from ...

    MBI

    2015-12-24

    Dec 24, 2015 ... indicate that the concentrations of the heavy metals in the samples are generally well above the respective recommended ... weathering processes on rocks and soils (Babel and. Opiso ..... Source apportionment of suspended.

  5. Metal organic frameworks as a drug delivery system for flurbiprofen

    AL Haydar M

    2017-09-01

    Full Text Available Muder AL Haydar,1,2 Hussein Rasool Abid,3,4 Bruce Sunderland,2 Shaobin Wang5,6 1Pharmaceutics Department, College of the Pharmacy, University of Kerbala, Kerbala, Iraq; 2Pharmaceutics Department, School of Pharmacy, Faculty of Health Sciences, Curtin University, Perth, WA, Australia; 3Department of Chemical Engineering, Curtin University, Perth, WA, Australia; 4College of Applied Medical Sciences, University of Kerbala, Kerbala, Iraq; 5School of Pharmacy, Faculty of Health Sciences, Curtin University, Perth, WA, Australia; 6Department of Chemical Engineering, School of Chemical and Petroleum Engineering, Faculty of Science and Engineering, Curtin University, Perth, WA, Australia Background: Metal organic frameworks (MOFs have attracted more attention in the last decade because of a suitable pore size, large surface area, and high pore volume. Developing biocompatible MOFs such as the MIL family as a drug delivery system is possible. Purpose: Flurbiprofen (FBP, a nonsteroidal anti-inflammatory agent, is practically insoluble in aqueous solution, and, therefore, needs suitable drug delivery systems. Different biocompatible MOFs such as Ca-MOF and Fe-MILs (53, 100, and 101 were synthesized and employed for FBP delivery. Patients and methods: A sample of 50 mg of each MOF was mixed and stirred for 24 h with 10 mL of 5 mg FBP in acetonitrile (40% in a sealed container. The supernatant of the mixture after centrifuging was analyzed by high-performance liquid chromatography to determine the loaded quantity of FBP on the MOF. The overnight-dried solid material after centrifuging the mixture was analyzed for loading percent using X-ray diffraction, Fourier-transform infrared spectroscopy, scanning electron microscopy, nuclear magnetic resonance, and FBP release profile. Results: The loading values of FBP were achieved at 10.0%±1%, 20%±0.8%, 37%±2.3%, and 46%±3.1% on Ca-MOF, Fe-MIL-53, Fe-MIL-101, and Fe-MIL-100, respectively. The FBP release

  6. Construction of acylhydrazidate-extended metal-organic frameworks.

    Wang, Yan-Ning; Yang, Qing-Feng; Li, Guang-Hua; Zhang, Ping; Yu, Jie-Hui; Xu, Ji-Qing

    2014-08-14

    Under hydrothermal conditions, the reactions of Ba(2+)/Zn(2+), aromatic polycarboxylic acids and N2H4 with or without oxalic acid were carried out, affording four new acylhydrazidate-extended metal-organic frameworks (MOFs) [Ba(pmdh)] (pmdh = pyromellitdihydrazidate) 1, [Ba(sdpth)(H2O)2]·0.5H2O (sdpth = 4,4'-sulfoyldiphthalhydrazidate) 2, [Ba2(cpth)2(H2O)2] (cpth = 4-carboxylphthalhydrazidate) 3 and [Zn2(pdh)2(ox)]·H2O (ox = oxalate, pdh = pyridine-2,3-dicarboxylhydrazidate) 4. The acylhydrazidate molecules pmdh, sdpth, cpth and pdh in compounds 1-4 derived from the hydrothermal in situ acylation of N2H4 with aromatic polycarboxylic acids. X-ray single-crystal diffraction analysis revealed that (i) in compound 1, the pmdh I molecules link the Ba(2+) ions into a two-dimensional (2D) layer with a (4,4) topology, and then the pmdh II molecules extend these layers into a three-dimensional (3D) network; (ii) in compound 2, the sdpth molecules link the Ba(2+) ions to form a one-dimensional (1D) square tube. Interestingly, the tubes are further linked into a 3D supramolecular network via the N-H···O interactions, creating synchronously big channels; (iii) in compound 3, the cpth I molecules link the Ba1 ions into a 3D network with a (10,3) topology. Ba2 and cpth II are distributed on the channels; (iv) in compound 4, Zn(2+) and pdh aggregate to form two types of Zn4(pdh)4 clusters. The ox molecules act as the secondary linkers, extending the Zn4(pdh)4 secondary building units (SBUs) into a 3D network with a 6(6) topology. The photoluminescence analysis indicates that compounds 3 and 4 emit green light with maxima at 495 nm for 3 (λ(ex) = 397 nm), and 522 nm for 4 (λ(ex) = 395 nm), respectively. At 77 K, the activated 2 and 4 can adsorb N2 in amounts of 58.31 cm(3) g(-1) for 2 and 38.38 cm(3) g(-1) for 4, respectively.

  7. Facile synthesis of Fe3O4/g-C3N4/HKUST-1 composites as a novel biosensor platform for ochratoxin A.

    Hu, Shuisheng; Ouyang, Wenjun; Guo, Longhua; Lin, Zhenyu; Jiang, Xiaohua; Qiu, Bin; Chen, Guonan

    2017-06-15

    A fluorescent biosensor for ochratoxin A was fabricated on the basis of a new nanocomposite (Fe 3 O 4 /g-C 3 N 4 /HKUST-1 composites). Fe 3 O 4 /g-C 3 N 4 /HKUST-1 was synthesized in this work for the first time, which combined HKUST-1 with g-C 3 N 4 to improve its chemical stability. Fe 3 O 4 /g-C 3 N 4 /HKUST-1 composites have strong adsorption capacity for dye-labeled aptamer and are able to completely quench the fluorescence of the dye through the photoinduced electron transfer (PET) mechanism. In the presence of ochratoxin A (OTA), it can bind with the aptamer with high affinity, causing the releasing of the dye-labeled aptamer from the Fe 3 O 4 /g-C 3 N 4 /HKUST-1 and therefore results in the recovery of fluorescence. The fluorescence intensity of the biosensor has a linear relationship with the OTA concentration in the range of 5.0-160.0ng/mL. The LOD of sensor is 2.57ng/mL (S/N=3). This fluorescence sensor based on the Fe 3 O 4 /g-C 3 N 4 /HKUST-1 composites has been applied to detect OTA in corn with satisfying results. Copyright © 2016. Published by Elsevier B.V.

  8. Charge transfer and injection barrier at the metal-organic interfaces

    Yan, Li

    2002-09-01

    The metal-organic interface plays a critical role in determining the functionality and performance of many innovative organic based devices. It has attracted extensive research interests in recent years. This thesis presents investigations of the electronic structures of organic materials, such as tris-(8-hydroxyquinoline) aluminum (Alq3) and copper phthalocyanine (CuPc), during their interface formation with metals. The characterization is accomplished by X-ray and ultraviolet photoelectron spectroscopes (XPS and UPS) and inverse photoelectron spectroscopy (IPES). As discussed herein, both occupied and unoccupied electronic states at the interfaces are carefully examined in different aspects. In Chapter 4, the charge transfer and chemical reaction at various metal/Alq3 interfaces are investigated using XPS and UPS to study the electron injection into the Alga film. Electron transfer from the low work function metal and Al/LiF(CsF) bilayer to the Alga has been observed. The role of the dielectric and possible chemistry at the interface are discussed in comparison of the low work function metals. Further in Chapter 5, the origin of the metal-interface dipole and the estimation of charge injection barrier is explored using several organic materials. A thermodynamic equilibrium model is extended to explain the relation between the charge transfer process ad the interface dipole. Further, in Chapter 6 the combination of XPS, UPS and IPES detailed the evolution of both occupied and unoccupied energy states during the alkali metal doping. The energy gap modification in organic due to metal doping is observed directly for the spectra. Chapter 7 provides stability study of the organic thin films under x-ray and UV light. The results verify the usability of UPS and XPS for the organic materials used in the thesis. Chapter 7 also shows the secondary ion mass spectroscopy results of metal diffusion in organic thin films.

  9. Synthesis of Pd and Rh metal nanoparticles in the interlayer space of organically modified montmorillonite

    Patel, Hasmukh A.; Bajaj, Hari C.; Jasra, Raksh Vir

    2008-01-01

    This study reports the synthesis of palladium and rhodium metal nanoparticles supported on montmorillonite (MMT) and partially organically modified MMT (POMM) using tetraamine palladium and hexaamine rhodium complex as precursor for palladium and rhodium respectively. The synthesized nanoparticles were characterized by powder X-ray diffraction PXRD and TEM. The PXRD study shows characteristic crystallographic planes for Pd and Rh metal and confirm the formation of metal nanoparticles in MMT and POMM. The TEM images reveal the effect of organic modification of MMT on decreasing particle size of Pd and Rh metal. The Pd and Rh metal nanoparticles are agglomerated in pristine MMT while nanoparticles are well dispersed in POMM. ICP-AES analysis was carried out to estimate quantitative amount of Pd and Rh metal in MMT and POMM

  10. Chelation in metal intoxication. V. Lowering of manganese content in poisoned rat organs

    Tandon, S K; Mathur, A K

    1976-01-01

    Metal chelation has been considered useful in the management of manganese poisoning to a considerable extent. Our own studies in this direction have shown that some polyaminocarboxylic acids and a few amino acids are effective in not only removing manganese from the vital organs of experimentally poisoned animals but also in restoring certain metal induced biochemical and histological changes in such organs. Further, the success of p-aminosalicylic acid (PAS), a chemotherapeutic agent for tuberculosis, in manganese mobilization has led us to examine some other structurally related compounds together with a few other possible metal binding agents for their ability to remove excess metal from the organs, their sub-cellular fractions and blood cells of manganese administered rats and to investigate if there exists any relationship between the structure of such compounds and their metal mobilizing capacity. The present communication deals with the results of these investigations.

  11. ENHANCEMENT OF ACIDITY AND CATALYTIC ACTIVITY OF ALUMINA BASED METAL ORGANIC FRAMEWORK (MIL-53 Al)

    Yilmaz, Esra; Sert, Emine; Atalay, Ferhan Sami

    2017-01-01

    Metal organic frameworks are highly porous materials which are formed bycombination of metal precursor and salts as inorganic part and ligand asorganic part. They have many advantages such as low density, high surface area,tunable pore size and high porosity. Due to peculiar features, such asunsaturated metal active sites, high surface area and easily functionalization,its usage as catalyst are promising.  The MIL-53(Al) structure contains chains of transcorner-sharing [AlO4(OH)2] oc...

  12. Final Report for Project ''Role of Metal Bioavailability in In Situ Bioremediation of Metal and Organic Co-Contaminated Sites''; FINAL

    Raina M. Maier

    2002-01-01

    A large proportion of hazardous waste sites are co-contaminated with organics and various metals. Such co-contaminated sites are difficult to bioremediate due to the nature of the mixed contaminants. Specifically, the presence of a co-contaminating metal imposes increased stress on indigenous populations already impacted by organic contaminant stress. The overall objective of this research is to investigate the effect of varying metal bioavailability on microbial populations and biodegradation of organics to allow a better understanding of how optimize remediation of co-contaminated sites. The hypothesis for this project is that metal bioavailability is not directly correlated with metal stress imposed on microbial populations that are degrading organics in soil and that further understanding of the relationship between metal bioavailability and metal stress is required for successful treatment of sites contaminated with mixtures of organics and metals. The specific objectives to be addressed to accomplish this goal are: (1) To determine the influence of metal bioavailability in soil microcosms co-contaminated with organics and metals on degradation of the organic contaminants and on mechanisms of metal resistance and (2) To determine the efficacy of different bioremediation strategies for co-contaminated soils based on metal bioavailability

  13. Highly reproducible alkali metal doping system for organic crystals through enhanced diffusion of alkali metal by secondary thermal activation.

    Lee, Jinho; Park, Chibeom; Song, Intek; Koo, Jin Young; Yoon, Taekyung; Kim, Jun Sung; Choi, Hee Cheul

    2018-05-16

    In this paper, we report an efficient alkali metal doping system for organic single crystals. Our system employs an enhanced diffusion method for the introduction of alkali metal into organic single crystals by controlling the sample temperature to induce secondary thermal activation. Using this system, we achieved intercalation of potassium into picene single crystals with closed packed crystal structures. Using optical microscopy and Raman spectroscopy, we confirmed that the resulting samples were uniformly doped and became K 2 picene single crystal, while only parts of the crystal are doped and transformed into K 2 picene without secondary thermal activation. Moreover, using a customized electrical measurement system, the insulator-to-semiconductor transition of picene single crystals upon doping was confirmed by in situ electrical conductivity and ex situ temperature-dependent resistivity measurements. X-ray diffraction studies showed that potassium atoms were intercalated between molecular layers of picene, and doped samples did not show any KH- nor KOH-related peaks, indicating that picene molecules are retained without structural decomposition. During recent decades, tremendous efforts have been exerted to develop high-performance organic semiconductors and superconductors, whereas as little attention has been devoted to doped organic crystals. Our method will enable efficient alkali metal doping of organic crystals and will be a resource for future systematic studies on the electrical property changes of these organic crystals upon doping.

  14. Inelastic neutron scattering of H{sub 2} adsorbed in HKUST-1

    Liu, Y. [Department of Materials and Engineering, University of Maryland, College Park, MD 20742 (United States); NIST Center for Neutron Research, 100 Bureau Drive, Gaithersburg, MD 20899-8562 (United States); Brown, C.M. [NIST Center for Neutron Research, 100 Bureau Drive, Gaithersburg, MD 20899-8562 (United States); Indiana University Cyclotron Facility, Indiana University, 2401 Milo B. Sampson Lane, Bloomington, IN 47408 (United States)], E-mail: craig.brown@nist.gov; Neumann, D.A. [NIST Center for Neutron Research, 100 Bureau Drive, Gaithersburg, MD 20899-8562 (United States); Peterson, V.K.; Kepert, C.J. [School of Chemistry, University of Sydney, NSW 2006 (Australia)

    2007-10-31

    A series of inelastic neutron scattering (INS) investigations of hydrogen adsorbed in activated HKUST-1 (Cu{sub 3}(1,3,5-benzenetricarboxylate){sub 2}) result in INS spectra with rich features, even at very low loading (<1.0 H{sub 2}:Cu). The distinct inelastic features in the spectra show that there are three binding sites that are progressively populated when the H{sub 2} loading is less than 2.0 H{sub 2}:Cu, which is consistent with the result obtained from previous neutron powder diffraction experiments. The temperature dependence of the INS spectra reveals the relative binding enthalpies for H{sub 2} at each site.

  15. Hydrolytically stable fluorinated metal-organic frameworks for energy-efficient dehydration

    Cadiau, Amandine; Belmabkhout, Youssef; Adil, Karim; Bhatt, Prashant; Pillai, Renjith S.; Shkurenko, Aleksander; Martineau-Corcos, Charlotte; Maurin, Guillaume; Eddaoudi, Mohamed

    2017-01-01

    fluorinated metal-organic framework, AlFFIVE-1-Ni (KAUST-8), with a periodic array of open metal coordination sites and fluorine moieties within the contracted square-shaped one-dimensional channel. This material selectively removed water vapor from gas

  16. Determination of elemental composition of metals using ambient organic mass spectrometry

    Shiea, Christopher [Department of Medical Laboratory Science and Biotechnology, Kaohsiung Medical University, 100 Shih-Chuan 1st Rd, Kaohsiung 807, Taiwan (China); Huang, Yeou-Lih [Department of Medical Laboratory Science and Biotechnology, Kaohsiung Medical University, 100 Shih-Chuan 1st Rd, Kaohsiung 807, Taiwan (China); Department of Chemistry, National Sun Yat-Sen University, 70 Lien-Hai Rd, Kaohsiung 804, Taiwan (China); Cheng, Sy-Chyi; Chen, Yi-Lun [Department of Chemistry, National Sun Yat-Sen University, 70 Lien-Hai Rd, Kaohsiung 804, Taiwan (China); Shiea, Jentaie, E-mail: jetea@mail.nsysu.edu.tw [Department of Chemistry, National Sun Yat-Sen University, 70 Lien-Hai Rd, Kaohsiung 804, Taiwan (China); Department of Medicinal and Applied Chemistry, Kaohsiung Medical University, 100 Shih-Chuan 1st Rd, Kaohsiung 807, Taiwan (China)

    2017-05-22

    Conventional inorganic mass spectrometric (MS) analysis of metals can require time-consuming and tedious sample preparation. We thus report the novel and direct characterization of metals in solid samples using an organic MS technique known as electrospray laser desorption ionization mass spectrometry (ELDI/MS). No sample pretreatment was needed, and results were rapidly obtained due to the ambient and laser-based nature of ELDI/MS. Metals from samples were desorbed and ionized by laser irradiation, after which they reacted with EDTA and then post-ionized and detected as metal-EDTA complexes. Aluminum, copper, iron, lead, nickel, and zinc from plates, foils, and coins were characterized in seconds. This study demonstrates that an ESI/MS system can be easily modified to analyze metal elements in solids by involving a chelating agent, indicating a potentially promising development in MS towards the analysis of metals using organic MS. - Highlights: • “Organic MS” was utilized as “inorganic MS” to detect metal ions in solid samples. • Element ions desorbed by laser irradiation rapidly reacted with a chelating reagent before they were detected by MS. • Elemental composition of metals was determined by this “Organic MS” method.

  17. Green methods for preparing highly co2 selective and h2s tolerant metal organic frameworks

    Eddaoudi, Mohamed; Shekhah, Osama; Belmabkhout, Youssef

    2015-01-01

    A green route for preparing a metal organic framework include mixing metal precursor with a ligand precursor to form a solvent-free mixture; adding droplets of water to the mixture; heating the mixture at a first temperature after adding the water

  18. Determination of elemental composition of metals using ambient organic mass spectrometry

    Shiea, Christopher; Huang, Yeou-Lih; Cheng, Sy-Chyi; Chen, Yi-Lun; Shiea, Jentaie

    2017-01-01

    Conventional inorganic mass spectrometric (MS) analysis of metals can require time-consuming and tedious sample preparation. We thus report the novel and direct characterization of metals in solid samples using an organic MS technique known as electrospray laser desorption ionization mass spectrometry (ELDI/MS). No sample pretreatment was needed, and results were rapidly obtained due to the ambient and laser-based nature of ELDI/MS. Metals from samples were desorbed and ionized by laser irradiation, after which they reacted with EDTA and then post-ionized and detected as metal-EDTA complexes. Aluminum, copper, iron, lead, nickel, and zinc from plates, foils, and coins were characterized in seconds. This study demonstrates that an ESI/MS system can be easily modified to analyze metal elements in solids by involving a chelating agent, indicating a potentially promising development in MS towards the analysis of metals using organic MS. - Highlights: • “Organic MS” was utilized as “inorganic MS” to detect metal ions in solid samples. • Element ions desorbed by laser irradiation rapidly reacted with a chelating reagent before they were detected by MS. • Elemental composition of metals was determined by this “Organic MS” method.

  19. Heavy metal pollution in sediment from Sisimiut, Greenland. Adsorption to organic matter and fine particles

    Ottosen, Lisbeth M.; Villumsen, Arne

    2006-01-01

    . The pollution could be linked to human activities in Sisimiut, a link that have not been investigated previously in Greenland. Except from the most polluted samples there was good correlation between heavy metal concentration and organic matter. Also some relation between fine fraction and heavy metal...

  20. Complexation with dissolved organic matter and solubility control of heavy metals in sandy soil

    Weng, L.; Temminghoff, E.J.M.; Lofts, S.; Tipping, E.; Riemsdijk, van W.H.

    2002-01-01

    The complexation of heavy metals with dissolved organic matter (DOM) in the environment influences the solubility and mobility of these metals. In this paper, we measured the complexation of Cu, Cd, Zn, Ni, and Pb with DOM in the soil solution at pH 3.7-6.1 using a Donnan membrane technique. The

  1. Surface modification and functionalization of metal and metal oxide nanoparticles by organic ligands

    Neouze, M.A.; Schubert, U.S.

    2008-01-01

    Metal or metal oxide nanoparticles possess unique features compared to equivalent larger-scale materials. For applications, it is often necessary to stabilize or functionalize such nanoparticles. Thus, modification of the surface of nanoparticles is an important chemical challenge. In this survey,

  2. Compositions and methods of making and using metal-organic framework compositions

    Mohideen, Mohamed Infas Haja; Adil, Karim; Belmabkhout, Youssef; Eddaoudi, Mohamed; Bhatt, Prashant M.

    2017-01-01

    Embodiments of the present disclosure include a metal-organic framework (MOF) composition comprising one or more metal ions, a plurality of organic ligands, and a solvent, wherein the one or more metal ions associate with the plurality of organic ligands sufficient to form a MOF with kag topology. Embodiments of the present disclosure further include a method of making a MOF composition comprising contacting one or more metal ions with a plurality of organic ligands in the presence of a solvent, sufficient to form a MOF with kag topology, wherein the solvent comprises water only. Embodiments of the present disclosure also describe a method of capturing chemical species from a fluid composition comprising contacting a MOF composition with kag topology and pore size of about 3.4Å to 4.8Å with a fluid composition comprising two or more chemical species and capturing one or more captured chemical species from the fluid composition.

  3. Metal-organic Materials (moms) For Co2 Adsorption And Methods Of Using Moms

    Eddaoudi, Mohamed

    2015-06-11

    Embodiments of the present disclosure provide for metal-organic materials (MOMs), systems that exhibit permanent porosity and using hydrophobic MOMs to separate components in a gas, methods of separating CO.sub.2 from a gas, and the like.

  4. Fully solution-processed organic solar cells on metal foil substrates

    Gaynor, Whitney; Lee, Jung-Yong; Peumans, Peter

    2009-01-01

    We demonstrate fully solution-processed organic photovoltaic cells on metal foil substrates with power conversion efficiencies similar to those obtained in devices on transparent substrates. The cells are based on the regioregular poly- (3

  5. Metal-Organic Frameworks: Building Block Design Strategies for the Synthesis of MOFs.

    Luebke, Ryan

    2014-01-01

    A significant and ongoing challenge in materials chemistry and furthermore solid state chemistry is to design materials with the desired properties and characteristics. The field of Metal-Organic Frameworks (MOFs) offers several strategies

  6. The levels of certain heavy metals in marine organisms from Aguada Bay (Goa)

    Singbal, S.Y.S.; George, M.D.; Topgi, R.S.; Noronha, R.J.

    The levels of manganese, iron, cobalt, nickel, copper, zinc and mercury have been measured in marine organisms from Aguada Bay which is one of the major fishing zones in Goa, India. The concentration of metals varied from species to species...

  7. Synthesis of Thin Film Composite Metal-Organic Frameworks Membranes on Polymer Supports

    Barankova, Eva

    2017-01-01

    Since the discovery of size-selective metal-organic frameworks (MOF) researchers have tried to manufacture them into gas separation membranes. ZIF-8 became the most studied MOF for membrane applications mainly because of its simple synthesis, good

  8. Rapidly assessing the activation conditions and porosity of metal-organic frameworks using thermogravimetric analysis.

    McDonald, Thomas M; Bloch, Eric D; Long, Jeffrey R

    2015-03-25

    A methodology utilizing a thermogravimetric analyzer to monitor propane uptake following incremental increases of the temperature is demonstrated as a means of rapidly identifying porous materials and determining the optimum activation conditions of metal-organic frameworks.

  9. Compositions and methods of making and using metal-organic framework compositions

    Mohideen, Mohamed Infas Haja

    2017-05-04

    Embodiments of the present disclosure include a metal-organic framework (MOF) composition comprising one or more metal ions, a plurality of organic ligands, and a solvent, wherein the one or more metal ions associate with the plurality of organic ligands sufficient to form a MOF with kag topology. Embodiments of the present disclosure further include a method of making a MOF composition comprising contacting one or more metal ions with a plurality of organic ligands in the presence of a solvent, sufficient to form a MOF with kag topology, wherein the solvent comprises water only. Embodiments of the present disclosure also describe a method of capturing chemical species from a fluid composition comprising contacting a MOF composition with kag topology and pore size of about 3.4Å to 4.8Å with a fluid composition comprising two or more chemical species and capturing one or more captured chemical species from the fluid composition.

  10. Metal-organic Materials (moms) For Co2 Adsorption And Methods Of Using Moms

    Eddaoudi, Mohamed; Zaworotko, Michael J.; Nugent, Patrick; Burd, Stephen D.; Luebke, Ryan; Belmabkhout, Youssef; Shekhah, Osama

    2015-01-01

    Embodiments of the present disclosure provide for metal-organic materials (MOMs), systems that exhibit permanent porosity and using hydrophobic MOMs to separate components in a gas, methods of separating CO.sub.2 from a gas, and the like.

  11. Metal-organic materials (MOMs) for adsorption of polarizable gases and methods of using MOMs

    Zaworotko, Michael; Mohamed, Mona H.; Elsaidi, Sameh

    2017-06-14

    Embodiments of the present disclosure provide for multi-component metal-organic materials (MOMs), systems including the MOM, systems for separating components in a gas, methods of separating polarizable gases from a gas mixture, and the like.

  12. Vapor phase coatings of metals and organics for laser fusion target applications

    Simonsic, G.A.; Powell, B.W.

    Techniques for applying a variety of metal and organic coatings to 50- to 500 μm diameter glass micro-balloons are discussed. Coating thicknesses vary from 1- to 10 μm. Physical vapor deposition (PVD), chemical vapor deposition (CVD), and electrolytic and electroless plating are some of the techniques being evaluated for metal deposition. PVD and glow discharge polymerization are being used for the application of organic coatings. (U.S.)

  13. Baltic Metal - metallisektori koostööorgan / Endel Soon

    Soon, Endel

    2004-01-01

    Ilmunud ka: EAKL Teataja : Narodnaja Gazeta, märts, nr. 3, 2004, lk. 4. Riias toimus Balti- ja Põhjamaade metalliala ametiühinguorganisatsioonide esindajate ühisnõupidamine. Kirjutati alla Baltimaade metallisektori koostööorgani Baltic Metal moodustamise leping

  14. Heavy Metals and Organic Pollutants in Sediments of Dar es ...

    The Florida criteria (MacDonald 1993) for assessment of pollution of tropical marine sediments was adopted in oredr to evaluate the extent of pollution in Dar es Salaam harbour sediments. The Florida criteria is one of the established references for sediment quality assessment. Heavy metals that had concentrations above ...

  15. Identification of metal-tolerant organisms isolated from the ...

    2011-01-28

    Jan 28, 2011 ... To whom all correspondence should be addressed. ☎ +27 21 460-9095; ... mostly as biofilm communities attached to surfaces; microbial biofilms exhibit high ... 1) in a 10 ℓ plastic container and transported at 4°C. Metal concentrations .... using Blastn from the National Centre for Biotechnology. Information ...

  16. The relevance of metal organic frameworks (MOFs) in inorganic ...

    nal design.3 The assemblage of the many components in a MOF structure ... in a short span of time. This approach .... single-crystal to-single-crystal (SCSC) transformation ..... The exchanges through the carboxylate bridges linking the metal ...

  17. Bridging-ligand-substitution strategy for the preparation of metal-organic polyhedra

    Li, Jian-Rong; Zhou, Hong-Cai

    2010-10-01

    Metal-organic polyhedra-discrete molecular architectures constructed through the coordination of metal ions and organic linkers-have recently attracted considerable attention due to their intriguing structures, their potential for a variety of applications and their relevance to biological self-assembly. Several synthetic routes have been investigated to prepare these complexes. However, to date, these preparative methods have typically been based on the direct assembly of metal ions and organic linkers. Although these routes are convenient, it remains difficult to find suitable reaction conditions or to control the outcome of the assembly process. Here, we demonstrate a synthetic strategy based on the substitution of bridging ligands in soluble metal-organic polyhedra. The introduction of linkers with different properties from those of the initial metal-organic polyhedra can thus lead to new metal-organic polyhedra with distinct properties (including size and shape). Furthermore, partial substitution can also occur and form mixed-ligand species that may be difficult to access by means of other approaches.

  18. Methane storage mechanism in the metal-organic framework Cu3(btc)2: An in situ neutron diffraction study

    Getzschmann, J.; Senkovska, I.; Wallacher, D.; Tovar, M.; Fairen-Jimenez, D.; Düren, T.; van Baten, J.M.; Krishna, R.; Kaskel, S.

    2010-01-01

    The adsorption of deutero-methane (CD4) in Cu3(btc)2 (HKUST-1) was investigated at 77 K using high-resolution neutron powder diffraction. Rietveld refinement of the neutron data revealed a sequential filling of the rigid framework at distinct preferred adsorption sites, and showed the importance of

  19. Copper Benzenetricarboxylate Metal-Organic Framework Nucleation Mechanisms on Metal Oxide Powders and Thin Films formed by Atomic Layer Deposition.

    Lemaire, Paul C; Zhao, Junjie; Williams, Philip S; Walls, Howard J; Shepherd, Sarah D; Losego, Mark D; Peterson, Gregory W; Parsons, Gregory N

    2016-04-13

    Chemically functional microporous metal-organic framework (MOF) crystals are attractive for filtration and gas storage applications, and recent results show that they can be immobilized on high surface area substrates, such as fiber mats. However, fundamental knowledge is still lacking regarding initial key reaction steps in thin film MOF nucleation and growth. We find that thin inorganic nucleation layers formed by atomic layer deposition (ALD) can promote solvothermal growth of copper benzenetricarboxylate MOF (Cu-BTC) on various substrate surfaces. The nature of the ALD material affects the MOF nucleation time, crystal size and morphology, and the resulting MOF surface area per unit mass. To understand MOF nucleation mechanisms, we investigate detailed Cu-BTC MOF nucleation behavior on metal oxide powders and Al2O3, ZnO, and TiO2 layers formed by ALD on polypropylene substrates. Studying both combined and sequential MOF reactant exposure conditions, we find that during solvothermal synthesis ALD metal oxides can react with the MOF metal precursor to form double hydroxy salts that can further convert to Cu-BTC MOF. The acidic organic linker can also etch or react with the surface to form MOF from an oxide metal source, which can also function as a nucleation agent for Cu-BTC in the mixed solvothermal solution. We discuss the implications of these results for better controlled thin film MOF nucleation and growth.

  20. Selective fluorescence sensors for detection of nitroaniline and metal Ions based on ligand-based luminescent metal-organic frameworks

    Yu, Zongchao; Wang, Fengqin; Lin, Xiangyi; Wang, Chengmiao; Fu, Yiyuan; Wang, Xiaojun; Zhao, Yongnan; Li, Guodong

    2015-01-01

    Metal-organic frameworks (MOFs) are porous crystalline materials with high potential for applications in fluorescence sensors. In this work, two solvent-induced Zn(II)–based metal-organic frameworks, Zn_3L_3(DMF)_2 (1) and Zn_3L_3(DMA)_2(H_2O)_3 (2) (L=4,4′-stilbenedicarboxylic acid), were investigated as selective sensing materials for detection of nitroaromatic compounds and metal ions. The sensing experiments show that 1 and 2 both exhibit selective fluorescence quenching toward nitroaniline with a low detection limit. In addition, 1 exhibits high selectivity for detection of Fe"3"+ and Al"3"+ by significant fluorescence quenching or enhancement effect. While for 2, it only exhibits significant fluorescence quenching effect for Fe"3"+. The results indicate that 1 and 2 are both promising fluorescence sensors for detecting and recognizing nitroaniline and metal ions with high sensitivity and selectivity. - Graphical abstract: Two MOFs have been selected as the fluorescence sensing materials for selectively sensing mitroaromatic compounds and metal ions. The high selectivity makes them promising fluorescence sensors for detecting and recognizing nitroaniline and Fe"3"+ or Al"3"+.

  1. Functionalized metal organic frameworks for effective capture of radioactive organic iodides

    Li, Baiyan

    2017-06-27

    Highly efficient capture of radioactive organic iodides (ROIs) from off-gas mixtures remains a substantial challenge for nuclear waste treatment. Current materials utilized for ROI sequestration suffer from low capacity, high cost (e.g. use of noble metals), and poor recyclability. Recently, we have developed a new strategy to tackle this challenge by functionalizing MOF materials with tertiary amines to create molecular traps for the effective capture and removal of ROIs (e.g. radioactive methyl iodide) from nuclear wastes. To further enhance the uptake capacity and performance of CH3I capture by ROI molecular traps, herein, we carry out a systematic study to investigate the effect of different amine molecules on ROI capture. The results demonstrate a record-high CH3I saturation uptake capacity of 80% for MIL-101-Cr-DMEDA at 150 °C, which is 5.3 times that of Ag0@MOR (15 wt%), a leading adsorbent material for capturing ROIs during nuclear fuel reprocessing. Furthermore, the CH3I decontamination factors (DFs) for MIL-101-Cr-DMEDA are as high as 5000 under simulated reprocessing conditions, largely exceeding that of facility regulatory requirements (DF = 3000). In addition, MIL-101-Cr-DMEDA can be recycled without loss of capacity, illustrating yet another advantage compared to known industrial adsorbents, which are typically of a

  2. New biodegradable organic-soluble chelating agents for simultaneous removal of heavy metals and organic pollutants from contaminated media

    Ullmann, Amos; Brauner, Neima; Vazana, Shlomi; Katz, Zhanna; Goikhman, Roman; Seemann, Boaz; Marom, Hanit; Gozin, Michael

    2013-01-01

    Highlights: • New soil remediation process using phase transition of partially miscible solvents. • Design and synthesis of new bio-degradable, organic soluble chelating agents. • Feasibility tests of the process on authentically polluted sediments and sludge. • Simultaneous removal of toxic metals and organic pollutants was demonstrated. -- Abstract: Advanced biodegradable and non-toxic organic chelators, which are soluble in organic media, were synthesized on the basis of the S,S-ethylenediamine-disuccinate (S,S-EDDS) ligand. The modifications suggested in this work include attachment of a lipophilic hydrocarbon chain (“tail”) to one or both nitrogen atoms of the S,S-EDDS. The new ligands were designed and evaluated for application in the Sediments Remediation Phase Transition Extraction (SR-PTE) process. This novel process is being developed for the simultaneous removal of both heavy metals and organic pollutants from contaminated soils, sediments or sludge. The new chelators were designed to bind various target metal ions, to promote extraction of these ions into organic solvents. Several variations of attached tails were synthesized and tested. The results for one of them, N,N′-bis-dodecyl-S,S-EDDS (C24-EDDS), showed that the metal-ligand complexes are concentrated in the organic-rich phase in the Phase Transition Extraction process (more than 80%). Preliminary applications of the SR-PTE process with the C24-EDDS ligand were conducted also on actually contaminated sludge (field samples). The extraction of five toxic metals, namely, Cd, Cu, Ni, Pb and Zn was examined. In general, the extraction performance of the new ligand was not less than that of S,S-EDDS when a sufficient ligand-to-extracted ion ratio (about 4:1 was applied

  3. New biodegradable organic-soluble chelating agents for simultaneous removal of heavy metals and organic pollutants from contaminated media

    Ullmann, Amos, E-mail: Ullmann@eng.tau.ac.il [Faculty of Engineering, School of Mechanical Engineering, Tel Aviv University, Tel Aviv 69978 (Israel); Brauner, Neima; Vazana, Shlomi; Katz, Zhanna [Faculty of Engineering, School of Mechanical Engineering, Tel Aviv University, Tel Aviv 69978 (Israel); Goikhman, Roman [The Hebrew University of Jerusalem, The Robert H. Smith, Faculty of Agriculture, Food and Environment, Rehovot (Israel); Seemann, Boaz; Marom, Hanit [School of Chemistry, Faculty of Exact Sciences, Tel Aviv University, Tel Aviv 69978 (Israel); Gozin, Michael, E-mail: cogozin@gmail.com [School of Chemistry, Faculty of Exact Sciences, Tel Aviv University, Tel Aviv 69978 (Israel)

    2013-09-15

    Highlights: • New soil remediation process using phase transition of partially miscible solvents. • Design and synthesis of new bio-degradable, organic soluble chelating agents. • Feasibility tests of the process on authentically polluted sediments and sludge. • Simultaneous removal of toxic metals and organic pollutants was demonstrated. -- Abstract: Advanced biodegradable and non-toxic organic chelators, which are soluble in organic media, were synthesized on the basis of the S,S-ethylenediamine-disuccinate (S,S-EDDS) ligand. The modifications suggested in this work include attachment of a lipophilic hydrocarbon chain (“tail”) to one or both nitrogen atoms of the S,S-EDDS. The new ligands were designed and evaluated for application in the Sediments Remediation Phase Transition Extraction (SR-PTE) process. This novel process is being developed for the simultaneous removal of both heavy metals and organic pollutants from contaminated soils, sediments or sludge. The new chelators were designed to bind various target metal ions, to promote extraction of these ions into organic solvents. Several variations of attached tails were synthesized and tested. The results for one of them, N,N′-bis-dodecyl-S,S-EDDS (C24-EDDS), showed that the metal-ligand complexes are concentrated in the organic-rich phase in the Phase Transition Extraction process (more than 80%). Preliminary applications of the SR-PTE process with the C24-EDDS ligand were conducted also on actually contaminated sludge (field samples). The extraction of five toxic metals, namely, Cd, Cu, Ni, Pb and Zn was examined. In general, the extraction performance of the new ligand was not less than that of S,S-EDDS when a sufficient ligand-to-extracted ion ratio (about 4:1 was applied.

  4. Multirate delivery of multiple therapeutic agents from metal-organic frameworks

    Alistair C. McKinlay

    2014-12-01

    Full Text Available The highly porous nature of metal-organic frameworks (MOFs offers great potential for the delivery of therapeutic agents. Here, we show that highly porous metal-organic frameworks can be used to deliver multiple therapeutic agents—a biologically active gas, an antibiotic drug molecule, and an active metal ion—simultaneously but at different rates. The possibilities offered by delivery of multiple agents with different mechanisms of action and, in particular, variable timescales may allow new therapy approaches. Here, we show that the loaded MOFs are highly active against various strains of bacteria.

  5. Enhanced Emission by Accumulated Charges at Organic/Metal Interfaces Generated during the Reverse Bias of Organic Light Emitting Diodes

    Soichiro Nozoe

    2017-10-01

    Full Text Available A high frequency rectangular alternating voltage was applied to organic light emitting diodes (OLEDs with the structure ITO/TPD/Alq3/Al and ITO/CoPc/Alq3/Al, where ITO is indium-tin-oxide, TPD is 4,4′-bis[N-phenyl-N-(m-tolylamino]biphenyl, CoPc is cobalt phthalocyanine, and Alq3 is Tris(8-quinolinolatoaluminum, and the effect on emission of the reverse bias was examined. The results reveal that the emission intensity under an alternating reverse-forward bias is greater than that under an alternating zero-forward bias. The difference in the emission intensity (∆I increased both for decreasing frequency and increasing voltage level of the reverse bias. In particular, the change in emission intensity was proportional to the voltage level of the reverse bias given the same frequency. To understand ΔI, this paper proposes a model in which an OLED works as a capacitor under reverse bias, where positive and negative charges accumulate on the metal/organic interfaces. In this model, the emission enhancement that occurs during the alternating reverse-forward bias is rationalized as a result of the charge accumulation at the organic/metal interfaces during the reverse bias, which possibly modulates the vacuum level shifts at the organic/metal interfaces to reduce both the hole injection barrier at the organic/ITO interface and the electron injection barrier at the organic/Al interface under forward bias.

  6. Plasmonically sensitized metal-oxide electron extraction layers for organic solar cells.

    Trost, S; Becker, T; Zilberberg, K; Behrendt, A; Polywka, A; Heiderhoff, R; Görrn, P; Riedl, T

    2015-01-16

    ZnO and TiOx are commonly used as electron extraction layers (EELs) in organic solar cells (OSCs). A general phenomenon of OSCs incorporating these metal-oxides is the requirement to illuminate the devices with UV light in order to improve device characteristics. This may cause severe problems if UV to VIS down-conversion is applied or if the UV spectral range (λ work, silver nanoparticles (AgNP) are used to plasmonically sensitize metal-oxide based EELs in the vicinity (1-20 nm) of the metal-oxide/organic interface. We evidence that plasmonically sensitized metal-oxide layers facilitate electron extraction and afford well-behaved highly efficient OSCs, even without the typical requirement of UV exposure. It is shown that in the plasmonically sensitized metal-oxides the illumination with visible light lowers the WF due to desorption of previously ionosorbed oxygen, in analogy to the process found in neat metal oxides upon UV exposure, only. As underlying mechanism the transfer of hot holes from the metal to the oxide upon illumination with hν < Eg is verified. The general applicability of this concept to most common metal-oxides (e.g. TiOx and ZnO) in combination with different photoactive organic materials is demonstrated.

  7. Molecular Speciation of Trace Metal Organic Complexes in the Pacific Ocean

    Repeta, D.; Boiteau, R. M.; Bundy, R. M.; Babcock-Adams, L.

    2017-12-01

    Microbial production across approximately one third of the surface ocean is limited by extraordinarily low (picomolar) concentrations of dissolved iron, essentially all of which is complexed to strong organic ligands of unknown composition. Other biologically important trace metals (cobalt, copper, zinc, nickel) are also complexed to strong organic ligands, which again have not been extensively characterized. Nevertheless, organic ligands exert a strong influence on metal bioavailability and toxicity. For example, amendment experiments using commercially available siderophores, organic compounds synthesized by microbes to facilitate iron uptake, show these ligands can both facilitate or impede iron uptake depending on the siderophore composition and available uptake pathways. Over the past few years we have developed analytical techniques using high pressure liquid chromatography interfaced with inductively coupled plasma and electrospray ionization mass spectrometry to identify and quantify trace metal organic complexes in laboratory cultures of marine microbes and in seawater. We found siderophores to be widely distributed in the ocean, particularly in regions characterized by low iron concentrations. We also find chemically distinct complexes of copper, zinc, colbalt and nickel that we have yet to fully characterize. We will discuss some of our recent work on trace metal organic speciation in seawater and laboratory cultures, and outline future efforts to better understand the microbial cycling of trace metal organic complexes in the sea.

  8. Fresh organic matter of municipal solid waste enhances phytoextraction of heavy metals from contaminated soil.

    Salati, S; Quadri, G; Tambone, F; Adani, F

    2010-05-01

    In this study, the ability of the organic fraction of municipal solid wastes (OFMSW) to enhance heavy metal uptake of maize shoots compared with ethylenediamine disuccinic acid (EDDS) was tested on soil contaminated with heavy metals. Soils treated with OFMSW and EDDS significantly increased the concentration of heavy metals in maize shoots (increments of 302%, 66%, 184%, 169%, and 23% for Cr, Cu, Ni, Zn, and Pb with respect to the control and increments of 933%, 482%, 928%, 428%, and 5551% for soils treated with OFMSW and EDDS, respectively). In soil treated with OFMSW, metal uptake was favored because of the high presence of dissolved organic matter (DOM) (41.6x than soil control) that exhibited ligand properties because of the high presence of carboxylic acids. Because of the toxic effect of EDDS on maize plants, soil treated with OFMSW achieved the highest extraction of total heavy metals. Copyright 2009 Elsevier Ltd. All rights reserved.

  9. Role of organic amendments on enhanced bioremediation of heavy metal(loid) contaminated soils.

    Park, Jin Hee; Lamb, Dane; Paneerselvam, Periyasamy; Choppala, Girish; Bolan, Nanthi; Chung, Jae-Woo

    2011-01-30

    As land application becomes one of the important waste utilization and disposal practices, soil is increasingly being seen as a major source of metal(loid)s reaching food chain, mainly through plant uptake and animal transfer. With greater public awareness of the implications of contaminated soils on human and animal health there has been increasing interest in developing technologies to remediate contaminated sites. Bioremediation is a natural process which relies on soil microorganisms and higher plants to alter metal(loid) bioavailability and can be enhanced by addition of organic amendments to soils. Large quantities of organic amendments, such as manure compost, biosolid and municipal solid wastes are used as a source of nutrients and also as a conditioner to improve the physical properties and fertility of soils. These organic amendments that are low in metal(loid)s can be used as a sink for reducing the bioavailability of metal(loid)s in contaminated soils and sediments through their effect on the adsorption, complexation, reduction and volatilization of metal(loid)s. This review examines the mechanisms for the enhanced bioremediation of metal(loid)s by organic amendments and discusses the practical implications in relation to sequestration and bioavailability of metal(loid)s in soils. Copyright © 2010 Elsevier B.V. All rights reserved.

  10. Fabrication of metallic nanomasks by transfer of self-organized nanodot patterns from semiconductor material into thin metallic layers

    Bobek, T.; Kurz, H.

    2007-01-01

    The basic understanding of the formation of highly regular nanostructures during ion erosion of amorphous GaSb layers is revised. The essential physical parameters for the formation of the highly regular dot pattern are discussed. Numerical modelling based on the stabilized isotropic Kuramoto-Sivashinsky equation is presented and discussed. The experimental part of this contribution presents the successful pattern transfer into metallic buried thin layers as well as into Silicon underlayers. The critical conditions for this transfer technique are discussed. Application potential of using this self-organization scheme for the generation of highly regular patterns in ferromagnetic metal layers as well as in crystalline silicon is estimated

  11. Surfactant biocatalyst for remediation of recalcitrant organics and heavy metals

    Brigmon, Robin L [North Augusta, SC; Story, Sandra [Greenville, SC; Altman, Denis [Evans, GA; Berry, Christopher J [Aiken, SC

    2009-01-06

    Novel strains of isolated and purified bacteria have been identified which have the ability to degrade petroleum hydrocarbons including a variety of PAHs. Several isolates also exhibit the ability to produce a biosurfactant. The combination of the biosurfactant-producing ability along with the ability to degrade PAHs enhances the efficiency with which PAHs may be degraded. Additionally, the biosurfactant also provides an additional ability to bind heavy metal ions for removal from a soil or aquatic environment.

  12. Design, Synthesis and Characterization of Functional Metal-Organic Framework Materials

    Alamer, Badriah

    2015-06-01

    Over the past few decades, vast majority of industrial and academic research throughout the world has witnessed the emergence of materials that can serve as ideal candidates for potential utility in desired applications, and these materials are known as Metal Organic Framework (MOFs). This exceptional new family of porous materials is fabricated by linkage of metal ions or clusters and organic linkers via strong bonds. MOFs have been awarded with remarkable interest and widely studied due to their inherent structural methodology (e.g. use of various metals, expanded library of organic building blocks with different geometry and functionality particularly frameworks designed from carboxylate organic linkers) and unquestionably unique structural and chemical features for many practical applications. (i.e. gas storage/separation, catalysis, drug delivery etc). Simply, metal organic frameworks epitomize the beauty of porous chemical structures. From a design perspective, the introduction of the Molecular Building Block (MBB) approach is actively being pursued pathway by researchers toward the construction of MOFs by employing inorganic building blocks and organic linkers and taking advantage of not only their multiple coordination modes and geometries but also the way in which they are reticulated to generate final framework. In this thesis, research studies will be directed toward (i) the investigation of the relationship between experimental parameters and synthesis of well-known fcu –MOF, (ii) rational design and synthesis of new rare earth (RE) based MOFs, (ii) isoreticular materials based on particular MBB ([M3O(RCO2)6]), M= p-and d-block metals, and (iv) zeolite- like metal organic framework assembled from single-metal ion based MBB ([MN2(CO2)4]) via 2-, 3-,and 4-connected organic linkers. Consequently, the porosity, chemical and thermal stability, and gas sorption properties will be evaluated and detailed.

  13. Nanocrystals of [Cu3(btc)2] (HKUST-1): a combined time-resolved light scattering and scanning electron microscopy study.

    Zacher, Denise; Liu, Jianing; Huber, Klaus; Fischer, Roland A

    2009-03-07

    The formation of [Cu(3)(btc)(2)] (HKUST-1; btc = 1,3,5-benzenetricarboxylate) nanocrystals from a super-saturated mother solution at room temperature was monitored by time-resolved light scattering (TLS); the system is characterized by a rapid growth up to a size limit of 200 nm within a few minutes, and the size and shape of the crystallites were also determined by scanning electron microscopy (SEM).

  14. Model potential for the description of metal/organic interface states

    Armbrust, Nico; Schiller, Frederik; Güdde, Jens; Höfer, Ulrich

    2017-01-01

    We present an analytical one-dimensional model potential for the description of electronic interface states that form at the interface between a metal surface and flat-lying adlayers of π-conjugated organic molecules. The model utilizes graphene as a universal representation of these organic adlayers. It predicts the energy position of the interface state as well as the overlap of its wave function with the bulk metal without free fitting parameters. We show that the energy of the interface state depends systematically on the bond distance between the carbon backbone of the adayers and the metal. The general applicability and robustness of the model is demonstrated by a comparison of the calculated energies with numerous experimental results for a number of flat-lying organic molecules on different closed-packed metal surfaces that cover a large range of bond distances. PMID:28425444

  15. Metal-organic frameworks: structure, properties, methods of synthesis and characterization

    Butova, V V; Soldatov, M A; Guda, A A; Lomachenko, K A; Lamberti, C

    2016-01-01

    This review deals with key methods of synthesis and characterization of metal-organic frameworks (MOFs). The modular structure affords a wide variety of MOFs with different active metal sites and organic linkers. These compounds represent a new stage of development of porous materials in which the pore size and the active site structure can be modified within wide limits. The set of experimental methods considered in this review is sufficient for studying the short-range and long-range order of the MOF crystal structure, determining the morphology of samples and elucidating the processes that occur at the active metal site in the course of chemical reactions. The interest in metal-organic frameworks results, first of all, from their numerous possible applications, ranging from gas separation and storage to chemical reactions within the pores. The bibliography includes 362 references

  16. Studies on selected organic-metal interactions of importance in the environment

    Mason, Ian.

    1995-10-01

    This research project investigated the interaction between natural organics acids and selected metal ions. The aims of the project was to provide quantitative data on the speciation of metal ions when placed in systems containing natural organic acids. It was envisaged that such data will assist in the risk assessment of the Drigg low level waste site in Cumbria. The formation and complexing ability of these natural organic acids is discussed and the classing of these acids into high molecular weight organic acids and low molecular weight organic acids. Initial investigations used a potentiometric technique to study the interaction between nickel and europium and selected low molecular weight organic acids which were thought to occur in significant concentrations in soils and groundwaters. These experiments confirmed existing critically assessed literature values, and provided an experimental methodology for further 'in-house' measurement of such values. In addition, studies were also performed on systems containing two competing organic acids. (author)

  17. Heavy metals content in reproductive organs of small mammals inhabiting in condition of chronic chemical exposure

    Mukhacheva, S.V.; Davydova, Yu.A.

    2008-01-01

    In this research by example of bank vole the heavy metals concentrations (cadmium, copper and zinc) in reproductive organs of small mammals inhabiting in condition of environmental pollution with wastes from copper-smelting industry have been considered. The levels of radionuclides accumulation in testes, seminal vesicle and ovaries of voles with radionuclide concentration in others organs and tissues of animals have been compared.

  18. Lanthanide-Based Metal Organic Frameworks: Synthetic Strategies and Catalytic Applications

    Pagis, C.; Ferbinteanu, M.; Rothenberg, G.; Grecea, S.

    2016-01-01

    This short critical review outlines the main synthetic strategies used in the designed synthesis of lanthanide-based metal organic frameworks (Ln-MOFs). It explains the impact of the choice of organic linker on the final network topology, and it highlights the applications of Ln-MOFs in the

  19. Electrospray droplet exposure to organic vapors: metal ion removal from proteins and protein complexes.

    DeMuth, J Corinne; McLuckey, Scott A

    2015-01-20

    The exposure of aqueous nanoelectrospray droplets to various organic vapors can dramatically reduce sodium adduction on protein ions in positive ion mass spectra. Volatile alcohols, such as methanol, ethanol, and isopropanol lead to a significant reduction in sodium ion adduction but are not as effective as acetonitrile, acetone, and ethyl acetate. Organic vapor exposure in the negative ion mode, on the other hand, has essentially no effect on alkali ion adduction. Evidence is presented to suggest that the mechanism by which organic vapor exposure reduces alkali ion adduction in the positive mode involves the depletion of alkali metal ions via ion evaporation of metal ions solvated with organic molecules. The early generation of metal/organic cluster ions during the droplet desolvation process results in fewer metal ions available to condense on the protein ions formed via the charged residue mechanism. These effects are demonstrated with holomyoglobin ions to illustrate that the metal ion reduction takes place without detectable protein denaturation, which might be revealed by heme loss or an increase in charge state distribution. No evidence is observed for denaturation with exposure to any of the organic vapors evaluated in this work.

  20. City, (from Point of Organic Pollutants and Heavy Metals

    Sajad Mazlomi

    2014-03-01

    Full Text Available Background: In this study quality and quantity characteristics wastewater of hospitals, clinics and health centers of Arak city and the potential impacts of them on Arak wastewater plant investigated. Methods: In this cross-sectional  study, which done during 2011-2012, the quantity and quality  of wastewater via point of COD,BOD5, pH, TKN, PO4and also heavy metals in the hospitals, clinics and health center of Arak were studied. Then, the effects of these pollutants as equal to person on wastewater convey system and wastewater treatment plant were assisted. Results: Monitoring of BOD5, TKN, and PO4 indicated that the daily disposal rate of these pollutants were equal 778.14, 102.7, and 53.6 kg/d, respectively, which equal to 15763, 51351, and 6700 person, respectively. The average water consumption of these centers was equal to 8.2l/s, and the estimated measure of produced wastewater was6.14 l/s. Also, after analysis the measure of heavy metals, Hg production (99.331 g/d was more than other heavy metals, and the next rank was related to Zn (41.96 g/d and Ag (41.96g/d, respectively. Conclusion: Although existence pretreatment process units can help to decrease the side effects of produced wastewater, this kind of wastewater needs complete treatment. Discharge of this kind wastewater to absorption trenches led to adverse health impacts in future. Therefore, a construction separate wastewater treatment plants and proper operation of these systems can reduce ecosystem impacts of wastewater discharges.

  1. Structure of the Buried Metal-Molecule Interface in Organic Thin Film Devices

    Hansen, Christian Rein; Sørensen, Thomas Just; Glyvradal, Magni

    2009-01-01

    By use of specular X-ray reflectivity (XR) the structure of a metal-covered organic thin film device is measured with angstrom resolution. The model system is a Langmuir-Blodgett (LB) film, sandwiched between a silicon substrate and a top electrode consisting of 25 Å titanium and 100 Å aluminum....... By comparison of XR data for the five-layer Pb2+ arachidate LB film before and after vapor deposition of the Ti/Al top electrode, a detailed account of the structural damage to the organic film at the buried metal-molecule interface is obtained. We find that the organized structure of the two topmost LB layers...

  2. 40 CFR 60.33b - Emission guidelines for municipal waste combustor metals, acid gases, organics, and nitrogen oxides.

    2010-07-01

    ... combustor metals, acid gases, organics, and nitrogen oxides. 60.33b Section 60.33b Protection of Environment... Constructed on or Before September 20, 1994 § 60.33b Emission guidelines for municipal waste combustor metals, acid gases, organics, and nitrogen oxides. (a) The emission limits for municipal waste combustor metals...

  3. 40 CFR 62.14103 - Emission limits for municipal waste combustor metals, acid gases, organics, and nitrogen oxides.

    2010-07-01

    ... combustor metals, acid gases, organics, and nitrogen oxides. 62.14103 Section 62.14103 Protection of... combustor metals, acid gases, organics, and nitrogen oxides. (a) The emission limits for municipal waste combustor metals are specified in paragraphs (a)(1) through (a)(3) of this section. (1) The owner or...

  4. Metal-ion interactions and the structural organization of Sepia eumelanin.

    Liu, Yan; Simon, John D

    2005-02-01

    The structural organization of melanin granules isolated from ink sacs of Sepia officinalis was examined as a function of metal ion content by scanning electron microscopy and atomic force microscopy. Exposing Sepia melanin granules to ethelenediaminetetraacetic acid (EDTA) solution or to metal salt solutions changed the metal content in the melanin, but did not alter granular morphology. Thus ionic forces between the organic components and metal ions in melanin are not required to sustain the natural morphology once the granule is assembled. However, when aqueous suspensions of Sepia melanin granules of varying metal content are ultra-sonicated, EDTA-washed and Fe-saturated melanin samples lose material to the solution more readily than the corresponding Ca(II) and Mg(II)-loaded samples. The solubilized components are found to be 5,6-dihydroxyindole-2-carboxylic acid (DHICA)-rich constituents. Associated with different metal ions, Na(I), Ca(II) and Mg(II) or Fe(III), these DHICA-rich entities form distinct two-dimensional aggregation structures when dried on the flat surface of mica. The data suggest multiply-charged ions play an important role in assisting or templating the assembly of the metal-free organic components to form the three-dimensional substructure distributed along the protein scaffold within the granule.

  5. Micronutrient metal speciation is controlled by competitive organic chelation in grassland soils

    Boiteau, Rene M.; Shaw, Jared B.; Pasa Tolic, Ljiljana; Koppenaal, David W.; Jansson, Janet K.

    2018-05-01

    Many elements are scarcely soluble in aqueous conditions found in high pH environments, such as calcareous grassland soils, unless complexed to strong binding organic ligands. To overcome this limitation, some plants and microbes produce chelators that solubilize micronutrient metals such as Fe, Ni, Cu, and Zn from mineral phases. These complexes are taken up by organisms via specific membrane receptors, thereby differentially impacting the bioavailability of these metals to the plant and microbial community. Although the importance of these chelation strategies for individual organisms has been well established, little is known about which pathways coexist within rhizosphere microbiomes or how they interact and compete for metal binding. Identifying these metallo-organic species within natural ecosystems has remained a formidable analytical challenge due to the vast diversity of compounds and poorly defined metabolic processes in complex soil matrix. Herein, we employed recently developed liquid chromatography (LC) mass spectrometry (MS) methods to characterize the speciation of water-soluble dissolved trace elements (Fe, Ni, Cu, and Zn) from Kansas Prairie soil. Both plant and fungal chelators were identified, revealing compound-specific patterns of chelation to biologically essential metals. Numerous metabolites typically implicated in plant iron acquisition and homeostasis, including mugineic acids, deoxymugineic acid, nicotianamine, and hydroxynicotianamine, dominated the speciation of divalent metals such as Ni, Cu, and Zn (2-57 pmol / g soil). In contrast, the fungal siderophore ferricrocine bound comparatively more trivalent Fe (9pmol / g soil). These results define biochemical pathways that underpin the regulation of metals in the grassland rhizosphere. They also raise new questions about the competition of these compounds for metal binding and their bioavailability to different members of the rhizosphere population. Even small structural differences

  6. Versatile Surface Functionalization of Metal-Organic Frameworks through Direct Metal Coordination with a Phenolic Lipid Enables Diverse Applications

    Zhu, Wei [Univ. of New Mexico, Albuquerque, NM (United States); Xiang, Guolei [Univ. of Cambridge (United Kingdom); Shang, Jin [Univ. of Hong Kong (China); Guo, Jimin [Univ. of New Mexico, Albuquerque, NM (United States); Motevalli, Benyamin [Monash Univ., Clayton, VIC (Australia); Durfee, Paul [Univ. of New Mexico, Albuquerque, NM (United States); Agola, Jacob Ongudi [Univ. of New Mexico, Albuquerque, NM (United States); Coker, Eric N. [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States); Brinker, C. Jeffrey [Univ. of New Mexico, Albuquerque, NM (United States); Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)

    2018-02-22

    Here, a novel strategy for the versatile functionalization of the external surface of metal-organic frameworks (MOFs) has been developed based on the direct coordination of a phenolic-inspired lipid molecule DPGG (1,2-dipalmitoyl-sn-glycero-3-galloyl) with metal nodes/sites surrounding MOF surface. X-ray diffraction and Argon sorption analysis prove that the modified MOF particles retain their structural integrity and porosity after surface modification. Density functional theory calculations reveal that strong chelation strength between the metal sites and the galloyl head group of DPGG is the basic prerequisite for successful coating. Due to the pH-responsive nature of metal-phenol complexation, the modification process is reversible by simple washing in weak acidic water, showing an excellent regeneration ability for water-stable MOFs. Moreover, the colloidal stability of the modified MOFs in the nonpolar solvent allows them to be further organized into 2 dimensional MOF or MOF/polymer monolayers by evaporation-induced interfacial assembly conducted on an air/water interface. Lastly, the easy fusion of a second functional layer onto DPGG-modified MOF cores, enabled a series of MOF-based functional nanoarchitectures, such as MOFs encapsulated within hybrid supported lipid bilayers (so-called protocells), polyhedral core-shell structures, hybrid lipid-modified-plasmonic vesicles and multicomponent supraparticles with target functionalities, to be generated. for a wide range of applications.

  7. A Metal Chelating Porous Polymeric Support: The Missing Link for a Defect-free Metal-Organic Framework Composite Membrane

    Barankova, Eva

    2017-02-06

    Since the discovery of size-selective metal-organic frameworks (MOFs), researchers have tried to incorporate these materials into gas separation membranes. Impressive gas selectivities were found, but these MOF membranes were mostly made on inorganic supports, which are generally too bulky and expensive for industrial gas separation. Forming MOF layers on porous polymer supports is industrially attractive but technically challenging. Two features to overcome these problems are described: 1) a metal chelating support polymer to bind the MOF layer, and 2) control of MOF crystal growth by contra-diffusion, aiming at a very thin nanocrystalline MOF layer. Using a metal chelating polythiosemicarbazide (PTSC) support and adjusting the metal and organic ligand concentrations carefully, a very compact ZIF-8 (ZIF=zeolitic imidazolate framework) layer was produced that displayed interference colors because of its smooth surface and extreme thinness-within the range of visible light. High performances were measured in terms of hydrogen/propane (8350) and propylene/propane (150) selectivity.

  8. Entrapment of metal clusters in metal-organic framework channels by extended hooks anchored at open metal sites.

    Zheng, Shou-Tian; Zhao, Xiang; Lau, Samuel; Fuhr, Addis; Feng, Pingyun; Bu, Xianhui

    2013-07-17

    Reported here are the new concept of utilizing open metal sites (OMSs) for architectural pore design and its practical implementation. Specifically, it is shown here that OMSs can be used to run extended hooks (isonicotinates in this work) from the framework walls to the channel centers to effect the capture of single metal ions or clusters, with the concurrent partitioning of the large channel spaces into multiple domains, alteration of the host-guest charge relationship and associated guest-exchange properties, and transfer of OMSs from the walls to the channel centers. The concept of the extended hook, demonstrated here in the multicomponent dual-metal and dual-ligand system, should be generally applicable to a range of framework types.

  9. Contrary interfacial exciton dissociation at metal/organic interface in regular and reverse configuration organic solar cells

    Wu, Bo; Wu, Zhenghui; Tam, Hoi Lam; Zhu, Furong, E-mail: frzhu@hkbu.edu.hk [Department of Physics, Institute of Advanced Materials, and Institute of Research and Continuing Education (Shenzhen), Hong Kong Baptist University, 224 Waterloo Road, Kowloon Tong, NT (Hong Kong)

    2014-09-08

    An opposite interfacial exciton dissociation behavior at the metal (Al)/organic cathode interface in regular and inverted organic solar cells (OSCs) was analyzed using transient photocurrent measurements. It is found that Al/organic contact in regular OSCs, made with the blend layer of poly[[4,8-bis[(2-ethylhexyl)oxy]benzo[1,2-b:4,5-b′]dithiophene-2,6-diyl] -[3-fluoro-2-[(2-ethylhexyl)carbonyl]thieno[3,4-b]-thiophenediyl

  10. Spectrographic determination of metallic impurities in organic coolants for nuclear reactors

    Martin Munoz, M.; Alvarez Gonzalez, F.

    1969-01-01

    A spectrochemical method for determining metallic impurities in organic coolants for nuclear reactors is given. The organic matter in solid samples is eliminated by controlled distillation and dry ashing in the presence of magnesium oxide as carrier. Liquid, samples are vacuum distillated. The residue is analyzed by carrier distillation and by total burning techniques. The analytical results are discussed and compared with those obtained destroying the organic matter without carrier and using the copper spark technique. (Author) 12 refs

  11. Organic-inorganic nanosystems designed for multiple metal corrosion inhibition

    Stockley, Robert

    This research focuses on the refinement and discovery of environmentally friendly coatings of metals with increased durability and longer lifetimes as the goal. In the pursuit of an ideal, such as environmentally friendly coatings or "green chemistry," there are many obstacles that must be overcome. This is particularly true in the case of protecting magnesium and its alloys. The relatively low open circuit potential of magnesium makes it highly susceptible to galvanic corrosion when in contact with other metals. It is also easily oxidized when exposed to air or humid conditions and forms a loose hydroxide/oxide layer (Mg(OH)2/MgO). However, for all of its problems, the advantages to using magnesium far outweigh the disadvantages; if and only if, its natural tendency to corrode can be adequately controlled. Magnesium has a high strength to weight ratio, similar to that of glass, making it ideal for a vast array of commercial applications. Magnesium has a high electromagnetic shielding effect (-52.34 dB at 2.45/ GHz for AZ31), making it applicable not only to aircraft instrumentation, but structure as well, due to its low density (d = 1.48 g/cm3). The list of applications for magnesium and its alloys is extensive. Our research has provided insights into the prevention of magnesium corrosion and the applications of "green chemistry" to a metal used across a multitude of industries. Specifically, excellent results were obtained for the electrochemical impedance spectroscopy of LZ91 (magnesium alloy) which demonstrated an impedance of 1.0 x 1010 Ohms to 1.0 x 1011 Ohms. These results suggest our coatings display a pure capacitance behavior in the Bode plot. According to ASTM B117 testing (salt fog testing) the coating on LZ91 panels reached 120 hours, a period considered to be the equivalent of five years of real world conditions, without appreciable corrosion. The possible mechanism for this corrosion protection will also be discussed. These advancements are

  12. SIMULTANEOUS DESTRUCTION OF ORGANICS AND STABILIZATION OF METALS IN SOILS

    The Sulchem Process reacts the material being treated with elemental sulfur at elevated temperatures in an inert reactor system. Organic hydrocarbons react with the sulfur to form an inert fine solid of carbon and sulfur, hydrogen sulfide gas, and modest amounts of carbon disulfi...

  13. Rapid, sensitive, and selective fluorescent DNA detection using iron-based metal-organic framework nanorods: Synergies of the metal center and organic linker.

    Tian, Jingqi; Liu, Qian; Shi, Jinle; Hu, Jianming; Asiri, Abdullah M; Sun, Xuping; He, Yuquan

    2015-09-15

    Considerable recent attention has been paid to homogeneous fluorescent DNA detection with the use of nanostructures as a universal "quencher", but it still remains a great challenge to develop such nanosensor with the benefits of low cost, high speed, sensitivity, and selectivity. In this work, we report the use of iron-based metal-organic framework nanorods as a high-efficient sensing platform for fluorescent DNA detection. It only takes about 4 min to complete the whole "mix-and-detect" process with a low detection limit of 10 pM and a strong discrimination of single point mutation. Control experiments reveal the remarkable sensing behavior is a consequence of the synergies of the metal center and organic linker. This work elucidates how composition control of nanostructures can significantly impact their sensing properties, enabling new opportunities for the rational design of functional materials for analytical applications. Copyright © 2015 Elsevier B.V. All rights reserved.

  14. Influence of Organic Matter - Mineral Interfacial Reactions on Metal(loid) Speciation and Bioaccessibility

    Chorover, J.; Kong, S.; Root, R. A.; Thomas, A.

    2015-12-01

    Bioaccessibility of contaminant metals in geomedia is often measured on the basis of kinetic release to solution during in vitro reaction with biofluid simulants. We postulate that development of a predictive-mechanistic understanding of bioaccessibility requires knowledge of metal(loid) molecular speciation upon sample introduction, as well as its change over the course of the in vitro reaction. Our results - including data from batch, column, mesocosm and field studies pertaining to arsenic, lead, and zinc contaminated materials - indicate the strong influence of organic matter and associated biological activity on metal(loid) speciation in mine tailings and related model systems. Furthermore, presence/absence of organic matter during bioassays affects the kinetics of metal(loid) release into biofluid simulants through multiple mechanisms.

  15. Interpretation of complexometric titration data: An intercomparison of methods for estimating models of trace metal complexation by natural organic ligands

    Pižeta, I.; Sander, S.G.; Hudson, R.J.M.; Omanovic, D.; Baars, O.; Barbeau, K.A.; Buck, K.N.; Bundy, R.M.; Carrasco, G.; Croot, P.L.; Garnier, C.; Gerringa, L.J.A.; Gledhill, M.; Hirose, K.; Kondo, Y.; Laglera, L.M.; Nuester, J.; Rijkenberg, M.J.A.; Takeda, S.; Twining, B.S.; Wells, M.

    2015-01-01

    With the common goal of more accurately and consistently quantifying ambient concentrations of free metal ions and natural organic ligands in aquatic ecosystems, researchers from 15 laboratories that routinely analyze trace metal speciation participated in an intercomparison of statistical methods

  16. Bioaccumulation of heavy metals in organs of fresh water fish Cyprinus carpio (Common carp)

    Vinodhini, R.; Narayanan, M.

    2008-01-01

    The objective of the present study is to determine the bioaccumulation of heavy metals in various organs of the fresh water fish exposed to heavy metal contaminated water system. The experimental fish was exposed to Cr. Ni, Cd and Pb at sublethal concentrations for periods of 32 days. The elements Cd, Pb, Ni and Cr were assayed using Shimadzu AA 6200 atomic absorption spectrophotometry and the results were given as μg/g dry wt. The accumulation of heavy metal gradually increases in liver during the heavy metal exposure period. All the results were statistically significant at p Pb > Ni > Cr and Pb > Cd > Ni > Cr. Similarly, in case of kidney and flesh tissues, the order was Pb > Cd > Cr > Ni and Pb > Cr > Cd > Ni. In all heavy metals, the bioaccumulation of lead and cadmium proportion was significantly increased in the tissues of Cyprinus carpio (Common carp)

  17. Modular assembly of metal-organic super-containers incorporating calixarenes

    Wang, Zhenqiang; Dai, Feng-Rong

    2018-01-16

    A new strategy to design container molecules is presented. Sulfonylcalix[4]arenes, which are synthetic macrocyclic containers, are used as building blocks that are combined with various metal ions and tricarboxylate ligands to construct metal-organic `super-containers` (MOSCs). These MOSCs possess both endo and exo cavities and thus mimic the structure of viruses. The synthesis of MOSCs is highly modular, robust, and predictable.

  18. High index of refraction films for dielectric mirrors prepared by metal-organic chemical vapor deposition

    Brusasco, R.M.

    1989-01-01

    A wide variety of metal oxides with high index of refraction can be prepared by Metal-Organic Chemical Vapor Deposition. We present some recent optical and laser damage results on oxide films prepared by MOCVD which could be used in a multilayer structure for highly reflecting (HR) dielectric mirror applications. The method of preparation affects both optical properties and laser damage threshold. 10 refs., 8 figs., 4 tabs

  19. Phase-coherent electron transport through metallic atomic-sized contacts and organic molecules

    Pauly, F.

    2007-02-02

    This work is concerned with the theoretical description of systems at the nanoscale, in particular the electric current through atomic-sized metallic contacts and organic molecules. In the first part, the characteristic peak structure in conductance histograms of different metals is analyzed within a tight-binding model. In the second part, an ab-initio method for quantum transport is developed and applied to single-atom and single-molecule contacts. (orig.)

  20. Mechanisms of Heavy Metal Sequestration in Soils: Plant-Microbe Interactions and Organic Matter Aging

    Teresa W.-M. Fan; Richard M. Higashi; David Crowley; Andrew N. Lane: Teresa A. Cassel; Peter G. Green

    2004-12-31

    For stabilization of heavy metals at contaminated sites, the three way interaction among soil organic matter (OM)-microbes-plants, and their effect on heavy metal binding is critically important for long-term sustainability, a factor that is poorly understood at the molecular level. Using a soil aging system, the humification of plant matter such as wheat straw was probed along with the effect on microbial community on soil from the former McClellan Air Force Base.

  1. Structural Origins of Scintillation: Metal Organic Frameworks as a Nanolaboratory

    2016-06-01

    adsorption of fluorphores within their pores, form exciplexes similar to those found in solution-based systems and can these serve as a tool to control the...selected due to their ability to form luminescent exciplexes with electron-accepting organic chromophores. Incorporation of these guests within the...and W2×(A4), exciplex , where W and A terms describe the peak weighting factors and amplitudes. The intensities were determined from the integrated

  2. Metal-organic frameworks and their applications in catalysis; Redes metalorganicas e suas aplicacoes em catalise

    Ramos, Andre Luis Dantas, E-mail: aldramos@ufs.br [Universidade Federal de Sergipe (UFSE), Sao Cristovao, SE (Brazil). Departamento de Engenharia Quimica; Tanase, Stefania; Rothenberg, Gadi [Van' t Hoff Institute for Molecular Sciences, University of Amsterdam, Amsterdam (Netherlands)

    2014-07-01

    Metal-organic frameworks (MOFs) form a new class of materials with well-defined yet tunable properties. These are crystalline, highly porous and exhibit strong metal-ligand interactions. Importantly, their physical and chemical properties, including pore size, pore structure, acidity, and magnetic and optical characteristics, can be tailored by choosing the appropriate ligands and metal precursors. Here we review the key aspects of synthesis and characterization of MOFs, focusing on lanthanide-based and vanadium-based materials. We also outline some of their applications in catalysis and materials science. (author)

  3. Effects of heavy metals (other than mercury) on marine and estuarine organisms

    Bryan, G W

    1971-01-01

    Heavy metals such as copper, zinc and lead are normal constituents of marine and estuarine environments. When additional quantities are introduced from industrial wastes or sewage they enter the biogeochemical cycle and, as a result of being potentially toxic, may interfere with the ecology of a particular environment. In different marine organisms, the behavior of heavy metals is described in terms of their absorption, storage, excretion and regulation when different concentrations are available in the environment. At higher concentrations, the detrimental effects of heavy metals become apparent and their different toxic effects and factors affecting them are also described. 78 references, 9 figures, 4 tables.

  4. Tunable photoluminescent metal-organic-frameworks and method of making the same

    Nenoff, Tina M.; Sava Gallis, Dorina Florentina; Rohwer, Lauren E.S.

    2017-08-22

    The present disclosure is directed to new photoluminescent metal-organic frameworks (MOFs). The newly developed MOFs include either non rare earth element (REE) transition metal atoms or limited concentrations of REE atoms, including: Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, Y, Ru, Ag, Cd, Sn, Sb, Ir, Pb, Bi, that are located in the MOF framework in site isolated locations, and have emission colors ranging from white to red, depending on the metal concentration levels and/or choice of ligand.

  5. The impact of the Fermi-Dirac distribution on charge injection at metal/organic interfaces.

    Wang, Z B; Helander, M G; Greiner, M T; Lu, Z H

    2010-05-07

    The Fermi level has historically been assumed to be the only energy-level from which carriers are injected at metal/semiconductor interfaces. In traditional semiconductor device physics, this approximation is reasonable as the thermal distribution of delocalized states in the semiconductor tends to dominate device characteristics. However, in the case of organic semiconductors the weak intermolecular interactions results in highly localized electronic states, such that the thermal distribution of carriers in the metal may also influence device characteristics. In this work we demonstrate that the Fermi-Dirac distribution of carriers in the metal has a much more significant impact on charge injection at metal/organic interfaces than has previously been assumed. An injection model which includes the effect of the Fermi-Dirac electron distribution was proposed. This model has been tested against experimental data and was found to provide a better physical description of charge injection. This finding indicates that the thermal distribution of electronic states in the metal should, in general, be considered in the study of metal/organic interfaces.

  6. Lymphoid Aggregates That Resemble Tertiary Lymphoid Organs Define a Specific Pathological Subset in Metal-on-Metal Hip Replacements

    Barone, Francesca; Hardie, Debbie L.; Matharu, Gulraj S.; Davenport, Alison J.; Martin, Richard A.; Grant, Melissa; Mosselmans, Frederick; Pynsent, Paul; Sumathi, Vaiyapuri P.; Addison, Owen; Revell, Peter A.; Buckley, Christopher D.

    2013-01-01

    Aseptic lymphocyte-dominated vasculitis-associated lesion (ALVAL) has been used to describe the histological lesion associated with metal-on-metal (M-M) bearings. We tested the hypothesis that the lymphoid aggregates, associated with ALVAL lesions resemble tertiary lymphoid organs (TLOs). Histopathological changes were examined in the periprosthetic tissue of 62 M-M hip replacements requiring revision surgery, with particular emphasis on the characteristics and pattern of the lymphocytic infiltrate. Immunofluorescence and immunohistochemistry were used to study the classical features of TLOs in cases where large organized lymphoid follicles were present. Synchrotron X-ray fluorescence (XRF) measurements were undertaken to detect localisation of implant derived ions/particles within the samples. Based on type of lymphocytic infiltrates, three different categories were recognised; diffuse aggregates (51%), T cell aggregates (20%), and organised lymphoid aggregates (29%). Further investigation of tissues with organised lymphoid aggregates showed that these tissues recapitulate many of the features of TLOs with T cells and B cells organised into discrete areas, the presence of follicular dendritic cells, acquisition of high endothelial venule like phenotype by blood vessels, expression of lymphoid chemokines and the presence of plasma cells. Co-localisation of implant-derived metals with lymphoid aggregates was observed. These findings suggest that in addition to the well described general foreign body reaction mediated by macrophages and a T cell mediated type IV hypersensitivity response, an under-recognized immunological reaction to metal wear debris involving B cells and the formation of tertiary lymphoid organs occurs in a distinct subset of patients with M-M implants. PMID:23723985

  7. Metal Speciation in Landfill Leachates with a Focus on the Influence of Organic Matter

    F Claret; C Tournassat; C Crouzet; E Gaucher; T Schäfer; G Braibant; D Guyonnet

    2011-12-31

    This study characterizes the heavy-metal content in leachates collected from eight landfills in France. In order to identify heavy metal occurrence in the different size fractions of leachates, a cascade filtration protocol was applied directly in the field, under a nitrogen gas atmosphere to avoid metal oxidation. The results of analyses performed on the leachates suggest that most of the metals are concentrated in the <30 kDa fraction, while lead, copper and cadmium show an association with larger particles. Initial speciation calculations, without considering metal association with organic matter, suggest that leachate concentrations in lead, copper, nickel and zinc are super-saturated with respect to sulphur phases. Speciation calculations that account for metal complexation with organic matter, considered as fulvic acids based on C1(s) NEXAFS spectroscopy, show that this mechanism is not sufficient to explain such deviation from equilibrium conditions. It is therefore hypothesized that the deviation results also from the influence of biological activity on the kinetics of mineral phase precipitation and dissolution, thus providing a dynamic system. The results of chemical analyses of sampled fluids are compared with speciation calculations and some implications for the assessment of metal mobility and natural attenuation in a context of landfill risk assessment are discussed.

  8. Evaluation of Trichoptera as an indicator organism for environmental pollution by heavy metals

    Aizawa, Shoichi; Tsunoda, Kin-ichi; Akatsuka, Masayoshi; Inoue, Sadao; Akaiwa, Hideo

    1994-01-01

    A method of analysis for heavy metals in trichopteran larvae by AAS was established to evaluate this aquatic insect as an indicator organism for environmental pollution by heavy metals. A wet digestion method with nitric acid and hydrogen peroxide was found to be suitable for the decomposition of trichopteran larva samples. No serious variation in heavy metal contents was found in individual samples collected from one sampling point. A weak negative correlation was observed between the body length and the heavy metal contents of trichopteran larvae. In addition, the heavy metal content of trichopteran larvae seems to show a seasonal fluctuation. Trichopteran larvae in the Watarase River, which has abandoned copper and manganese mines along its upper stream, show an enriched heavy metal content as compared with those in other non-polluted rivers. Moreover, this aquatic insect in the Kiryu River also shows enrichment of manganese due to abandoned manganese mines situated upstream. These facts suggest that the trichopteran larva in a useful indicator organism for environmental pollution by heavy metals. (author)

  9. Comparative studies of metals in fish organs, sediments and water from Nigerian fresh water fish ponds

    Ipinmoroti, K.O.; Oshodi, A.A.; Owolabi, R.A.

    1997-01-01

    Fish samples (Illisha africana) were collected from six man-made fish pond in Edo and Ondo states, Nigeria. Some organs of the fish sediment and water from the fish habitat were analysed for Cd, Pb, Hg, Ca, Fe, Zn, Cu and Cr, Physico-chemical properties of water samples from the ponds were also re-corded. The concentration of the metals varied in the sediment water as well as in different organs of the fish. However, chromium was absent in all the samples. The descending order of metal concentration in fish organs was: gills intestine, head and muscle. To avoid harmful accumulation of these metals in the human system, the gills and the intestine should preferably be discarded while processing fish for consumption. The head with a relatively high concentration of calcium might be useful in feed formulation. (author)

  10. Enhancing Skin Permeation of Biphenylacetic Acid (BPA) Using Salt Formation with Organic and Alkali Metal Bases.

    Pawar, Vijay; Naik, Prashant; Giridhar, Rajani; Yadav, Mange Ram

    2015-01-01

    In the present study, a series of organic and alkali metal salts of biphenylacetic acid (BPA) have been prepared and evaluated in vitro for percutaneous drug delivery. The physicochemical properties of BPA salts were determined using solubility measurements, DSC, and IR. The DSC thermogram and FTIR spectra confirmed the salt formation with organic and alkali metal bases. Among the series, salts with organic amines (ethanolamine, diethanolamine, triethanolamine, and diethylamine) had lowered melting points while the alkali metal salt (sodium) had a higher melting point than BPA. The in vitro study showed that salt formation improves the physicochemical properties of BPA, leading to improved permeability through the skin. Amongst all the prepared salts, ethanolamine salt (1b) showed 7.2- and 5.4-fold higher skin permeation than the parent drug at pH 7.4 and 5.0, respectively, using rat skin.

  11. Highly stable [mambf6-n(o/h2o)n(ligand)2(solvent)x]n metal organic frameworks

    Eddaoudi, Mohamed

    2016-10-13

    Provided herein are metal organic frameworks having high selectivity and stability in the present of gases and vapors including H2S, H2O, and CO2. Metal organic frameworks can comprise metal nodes and N-donor organic ligands. Further provided are methods of making metal organic frameworks.

  12. Facile growth of a single-crystal pattern: a case study of HKUST-1.

    Li, Shaozhou; Lu, Guang; Huang, Xiao; Li, Hai; Sun, Yinghui; Zhang, Hua; Chen, Xiaodong; Huo, Fengwei

    2012-12-18

    In order to fabricate metal-organic framework (MOF) based devices, it is desirable to precisely position high-quality and mono-sized MOF crystals on supports. In this work, we demonstrate a facile solution procedure for the fabrication of oriented and monodispersed single-crystal MOF pattern. We expect that such capability will expand the scope of applications of MOFs to advanced fields.

  13. Leakage radiation spectroscopy of organic/dielectric/metal systems

    Fiutowski, Jacek; Kawalec, Tomasz; Kostiučenko, Oksana

    2014-01-01

    side of a hemisphere fused silica prism with an index matching liquid was illuminated under normal incidence by a He-Cd 325 nm laser. Two orthogonal linear polarizations were used both parallel and perpendicular to the detection plane. Spectrally resolved leakage radiation was observed on the opposite......Leakage radiation spectroscopy of organic para-Hexaphenylene (p-6P) molecules has been performed in the spectral range 420-675 nm which overlaps with the p-6P photoluminescence band. The p-6P was deposited on 40 nm silver (Ag) films on BK7 glass, covered with SiO2 layers. The SiO2 layer thickness...

  14. Nanostructural self-organization and dynamic adaptation of metal-polymer tribosystems

    Mashkov, Yu. K.

    2017-02-01

    The results of investigating the effect of nanosize modifiers of a polymer matrix on the nanostructural self-organization of polymer composites and dynamic adaptation of metal-polymer tribosystems, which considerably affect the wear resistance of polymer composite materials, have been analyzed. It has been shown that the physicochemical nanostructural self-organization processes are developed in metal-polymer tribosystems with the formation of thermotropic liquid-crystal structures of the polymer matrix, followed by the transition of the system to the stationary state with a negative feedback that ensures dynamic adaptation of the tribosystem to given operating conditions.

  15. Force-Field Prediction of Materials Properties in Metal-Organic Frameworks

    2016-01-01

    In this work, MOF bulk properties are evaluated and compared using several force fields on several well-studied MOFs, including IRMOF-1 (MOF-5), IRMOF-10, HKUST-1, and UiO-66. It is found that, surprisingly, UFF and DREIDING provide good values for the bulk modulus and linear thermal expansion coefficients for these materials, excluding those that they are not parametrized for. Force fields developed specifically for MOFs including UFF4MOF, BTW-FF, and the DWES force field are also found to provide accurate values for these materials’ properties. While we find that each force field offers a moderately good picture of these properties, noticeable deviations can be observed when looking at properties sensitive to framework vibrational modes. This observation is more pronounced upon the introduction of framework charges. PMID:28008758

  16. Organic-inorganic perovskites containing trivalent metal halide layers: the templating influence of the organic cation layer.

    Mitzi, D B

    2000-12-25

    Thin sheetlike crystals of the metal-deficient perovskites (H2AEQT)M2/3I4 [M = Bi or Sb; AEQT = 5,5"'-bis-(aminoethyl)-2,2':5',2'':5'',2'''-quaterthiophene] were formed from slowly cooled ethylene glycol/2-butanol solutions containing the bismuth(III) or antimony(III) iodide and AEQT.2HI salts. Each structure was refined in a monoclinic (C2/m) subcell, with the lattice parameters a = 39.712(13) A, b = 5.976(2) A, c = 6.043(2) A, beta = 92.238(5) degrees, and Z = 2 for M = Bi and a = 39.439(7) A, b = 5.952(1) A, c = 6.031(1) A, beta = 92.245(3) degrees, and Z = 2 for M = Sb. The trivalent metal cations locally adopt a distorted octahedral coordination, with M-I bond lengths ranging from 3.046(1) to 3.218(3) A (3.114 A average) for M = Bi and 3.012(1) to 3.153(2) A (3.073 A average) for M = Sb. The new organic-inorganic hybrids are the first members of a metal-deficient perovskite family consisting of (Mn+)2/nV(n-2)/nX4(2-) sheets, where V represents a vacancy (generally left out of the formula) and the metal cation valence, n, is greater than 2. The organic layers in the AEQT-based organic-inorganic hybrids feature edge-to-face aromatic interactions among the rigid, rodlike quaterthiophene moieties, which may help to stabilize the unusual metal-deficient layered structures.

  17. Micronutrient metal speciation is driven by competitive organic chelation in grassland soils.

    Boiteau, R.; Shaw, J. B.; Paša-Tolić, L.; Koppenaal, D.; Jansson, J.

    2017-12-01

    Many elements are scarcely soluble in aqueous conditions found in high pH environments, such as calcareous grassland soils, unless complexed to strong binding organic ligands. To overcome this limitation, some plants and microbes produce chelators that solubilize micronutrient metals such as Fe, Ni, Cu, and Zn from mineral phases. These complexes are taken up by organisms via specific membrane receptors, thereby differentially impacting the bioavailability of these metals to the plant and microbial community. Although the importance of these chelation strategies for individual organisms has been well established, little is known about which pathways coexist within rhizosphere microbiomes or how they interact and compete for metal binding. Identifying these metallo-organic species within natural ecosystems has remained a formidable analytical challenge due to the vast diversity of compounds and poorly defined metabolic processes in complex soil matrix. Herein, we employed recently developed liquid chromatography (LC) mass spectrometry (MS) methods to characterize the speciation of water-soluble dissolved trace elements (Fe, Ni, Cu, and Zn) from Kansas Prairie soil. Both plant and fungal chelators were identified, revealing compound-specific patterns of chelation to biologically essential metals. Numerous metabolites typically implicated in plant iron acquisition and homeostasis, including mugineic acids, deoxymugineic acid, nicotianamine, and hydroxynicotianamine, dominated the speciation of divalent metals such as Ni, Cu, and Zn (2-57 pmol / g soil). In contrast, the fungal siderophore ferricrocine bound comparatively more trivalent Fe (9pmol / g soil). These results define biochemical pathways that underpin the regulation of metals in the grassland rhizosphere. They also raise new questions about the competition of these compounds for metal binding and their bioavailability to different members of the rhizosphere population.

  18. Speciation and Distribution of Trace Metals and Organic Matter in Marine Lake as In Situ Laboratory

    Mlakar, M.; Fiket, Ž.; Cuculić, V.; Cukrov, N.; Geček, S.

    2016-02-01

    Marine lakes are unique, isolated marine systems, also recognized as in situ "laboratories" in which geochemical processes on a different scale compared to the open sea, can be observed. Impact of organic matter cycling on distribution of trace metals in the marine lake Mir, located on Dugi Otok Island, in the central part of the eastern Adriatic Sea, was investigated. Intense spatial and seasonal variations of physico-chemical parameters and organic matter concentrations in the water column of the Lake are governed predominantly by natural processes. Enhanced oxygen consumption in the Lake during summer season, high organic carbon concentrations and low redox potential result in occasional occurrence of anoxic conditions in the bottom layers. Speciation modelling showed that dissolved trace metals Cu, Pb and Zn, are mostly bound to organic matter, while Cd, Co and Ni are present predominantly as free ions and inorganic complexes. Trace metals removal from the water column and their retention in the sediment was found to depend on the nature of the relationship between specific metal and high proportion of organic matter (up to 9%) and inorganic phases, Fe-oxyhydroxydes or biogenic calcite. Surrounding karstic background, with occasional occurrences of red soil characterize deposited sediments as coarse grained and carbonate rich, whose elemental composition is affected by bathymetry of the basin and overall biological production.

  19. Rational design of metal-organic electronic devices: A computational perspective

    Chilukuri, Bhaskar

    Organic and organometallic electronic materials continue to attract considerable attention among researchers due to their cost effectiveness, high flexibility, low temperature processing conditions and the continuous emergence of new semiconducting materials with tailored electronic properties. In addition, organic semiconductors can be used in a variety of important technological devices such as solar cells, field-effect transistors (FETs), flash memory, radio frequency identification (RFID) tags, light emitting diodes (LEDs), etc. However, organic materials have thus far not achieved the reliability and carrier mobility obtainable with inorganic silicon-based devices. Hence, there is a need for finding alternative electronic materials other than organic semiconductors to overcome the problems of inferior stability and performance. In this dissertation, I research the development of new transition metal based electronic materials which due to the presence of metal-metal, metal-pi, and pi-pi interactions may give rise to superior electronic and chemical properties versus their organic counterparts. Specifically, I performed computational modeling studies on platinum based charge transfer complexes and d 10 cyclo-[M(mu-L)]3 trimers (M = Ag, Au and L = monoanionic bidentate bridging (C/N~C/N) ligand). The research done is aimed to guide experimental chemists to make rational choices of metals, ligands, substituents in synthesizing novel organometallic electronic materials. Furthermore, the calculations presented here propose novel ways to tune the geometric, electronic, spectroscopic, and conduction properties in semiconducting materials. In addition to novel material development, electronic device performance can be improved by making a judicious choice of device components. I have studied the interfaces of a p-type metal-organic semiconductor viz cyclo-[Au(mu-Pz)] 3 trimer with metal electrodes at atomic and surface levels. This work was aimed to guide the device

  20. Modulate Organic-Metal Oxide Heterojunction via [1,6] Azafulleroid for Highly Efficient Organic Solar Cells.

    Li, Chang-Zhi; Huang, Jiang; Ju, Huanxin; Zang, Yue; Zhang, Jianyuan; Zhu, Junfa; Chen, Hongzheng; Jen, Alex K-Y

    2016-09-01

    By creating an effective π-orbital hybridization between the fullerene cage and the aromatic anchor (addend), the azafulleroid interfacial modifiers exhibit enhanced electronic coupling to the underneath metal oxides. High power conversion efficiency of 10.3% can be achieved in organic solar cells using open-cage phenyl C61 butyric acid methyl ester (PCBM)-modified zinc oxide layer. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. The addition of organic carbon and nitrate affects reactive transport of heavy metals in sandy aquifers

    Satyawali, Yamini

    2011-04-01

    Organic carbon introduction in the soil to initiate remedial measures, nitrate infiltration due to agricultural practices or sulphate intrusion owing to industrial usage can influence the redox conditions and pH, thus affecting the mobility of heavy metals in soil and groundwater. This study reports the fate of Zn and Cd in sandy aquifers under a variety of plausible in-situ redox conditions that were induced by introduction of carbon and various electron acceptors in column experiments. Up to 100% Zn and Cd removal (from the liquid phase) was observed in all the four columns, however the mechanisms were different. Metal removal in column K1 (containing sulphate), was attributed to biological sulphate reduction and subsequent metal precipitation (as sulphides). In the presence of both nitrate and sulphate (K2), the former dominated the process, precipitating the heavy metals as hydroxides and/or carbonates. In the presence of sulphate, nitrate and supplemental iron (Fe(OH)3) (K3), metal removal was also due to precipitation as hydroxides and/or carbonates. In abiotic column, K4, (with supplemental iron (Fe(OH)3), but no nitrate), cation exchange with soil led to metal removal. The results obtained were modeled using the reactive transport model PHREEQC-2 to elucidate governing processes and to evaluate scenarios of organic carbon, sulphate and nitrate inputs. © 2010 Elsevier B.V.

  2. Impact of metal and anion substitutions on the hydrogen storage properties of M-BTT metal-organic frameworks.

    Sumida, Kenji; Stück, David; Mino, Lorenzo; Chai, Jeng-Da; Bloch, Eric D; Zavorotynska, Olena; Murray, Leslie J; Dincă, Mircea; Chavan, Sachin; Bordiga, Silvia; Head-Gordon, Martin; Long, Jeffrey R

    2013-01-23

    Microporous metal-organic frameworks are a class of materials being vigorously investigated for mobile hydrogen storage applications. For high-pressure storage at ambient temperatures, the M(3)[(M(4)Cl)(3)(BTT)(8)](2) (M-BTT; BTT(3-) = 1,3,5-benzenetristetrazolate) series of frameworks are of particular interest due to the high density of exposed metal cation sites on the pore surface. These sites give enhanced zero-coverage isosteric heats of adsorption (Q(st)) approaching the optimal value for ambient storage applications. However, the Q(st) parameter provides only a limited insight into the thermodynamics of the individual adsorption sites, the tuning of which is paramount for optimizing the storage performance. Here, we begin by performing variable-temperature infrared spectroscopy studies of Mn-, Fe-, and Cu-BTT, allowing the thermodynamics of H(2) adsorption to be probed experimentally. This is complemented by a detailed DFT study, in which molecular fragments representing the metal clusters within the extended solid are simulated to obtain a more thorough description of the structural and thermodynamic aspects of H(2) adsorption at the strongest binding sites. Then, the effect of substitutions at the metal cluster (metal ion and anion within the tetranuclear cluster) is discussed, showing that the configuration of this unit indeed plays an important role in determining the affinity of the framework toward H(2). Interestingly, the theoretical study has identified that the Zn-based analogs would be expected to facilitate enhanced adsorption profiles over the compounds synthesized experimentally, highlighting the importance of a combined experimental and theoretical approach to the design and synthesis of new frameworks for H(2) storage applications.

  3. The structure of organic langmuir films on liquid metal surfaces

    Kraack, H.; Deutsch, M.; Ocko, B.M.; Pershan, P.S.

    2003-01-01

    Langmuir films (LFs) on water have long been studied for their interest for basic science and their numerous applications in chemistry, physics, materials science and biology. We present here A-resolution synchrotron X-ray studies of the structure of stearic acid LFs on a liquid mercury surface. At low coverage, ≥110 A 2 /mol, a 2D gas phase of flat-lying molecules is observed. At high coverage, ≤23 A 2 /mol, two different hexatic phases of standing-up molecules are observed. At intermediate coverage, 52≤A≤110 A 2 /mol, novel single- and double-layered phases of flat-lying molecular dimers are found, exhibiting a 1D in-layer order. Such flat-lying phases were not hitherto observed in any LF. Measurements on LFs of fatty acids of other chain lengths indicate that this structure is generic to chain molecules on mercury, although the existence of some of the flat-lying phases, and the observed phase sequence, depend on the chain length. Organic LFs on Hg, and in particular the new flat-lying phases, should provide a broader nano-structural tunability range for molecular electronic device construction than most solid-supported self-assembled monolayers used at present

  4. White organic light-emitting diodes with 4 nm metal electrode

    Lenk, Simone; Schwab, Tobias; Schubert, Sylvio; Müller-Meskamp, Lars; Leo, Karl; Reineke, Sebastian [Institut für Angewandte Photophysik, Technische Universität Dresden, George-Bähr-Straße 1, 01069 Dresden (Germany); Gather, Malte C. [Institut für Angewandte Photophysik, Technische Universität Dresden, George-Bähr-Straße 1, 01069 Dresden (Germany); Organic Semiconductor Centre, SUPA, School of Physics and Astronomy, University of St Andrews, North Haugh, St Andrews KY16 9SS (United Kingdom)

    2015-10-19

    We investigate metal layers with a thickness of only a few nanometers as anode replacement for indium tin oxide (ITO) in white organic light-emitting diodes (OLEDs). The ultrathin metal electrodes prove to be an excellent alternative that can, with regard to the angular dependence and efficiency of the OLED devices, outperform the ITO reference. Furthermore, unlike ITO, the thin composite metal electrodes are readily compatible with demanding architectures (e.g., top-emission or transparent OLEDs, device unit stacking, etc.) and flexible substrates. Here, we compare the sheet resistance of both types of electrodes on polyethylene terephthalate for different bending radii. The electrical performance of ITO breaks down at a radius of 10 mm, while the metal electrode remains intact even at radii smaller than 1 mm.

  5. White organic light-emitting diodes with 4 nm metal electrode

    Lenk, Simone; Schwab, Tobias; Schubert, Sylvio; Müller-Meskamp, Lars; Leo, Karl; Gather, Malte C.; Reineke, Sebastian

    2015-10-01

    We investigate metal layers with a thickness of only a few nanometers as anode replacement for indium tin oxide (ITO) in white organic light-emitting diodes (OLEDs). The ultrathin metal electrodes prove to be an excellent alternative that can, with regard to the angular dependence and efficiency of the OLED devices, outperform the ITO reference. Furthermore, unlike ITO, the thin composite metal electrodes are readily compatible with demanding architectures (e.g., top-emission or transparent OLEDs, device unit stacking, etc.) and flexible substrates. Here, we compare the sheet resistance of both types of electrodes on polyethylene terephthalate for different bending radii. The electrical performance of ITO breaks down at a radius of 10 mm, while the metal electrode remains intact even at radii smaller than 1 mm.

  6. Inorganic-Organic Coating via Molecular Layer Deposition Enables Long Life Sodium Metal Anode.

    Zhao, Yang; Goncharova, Lyudmila V; Zhang, Qian; Kaghazchi, Payam; Sun, Qian; Lushington, Andrew; Wang, Biqiong; Li, Ruying; Sun, Xueliang

    2017-09-13

    Metallic Na anode is considered as a promising alternative candidate for Na ion batteries (NIBs) and Na metal batteries (NMBs) due to its high specific capacity, and low potential. However, the unstable solid electrolyte interphase layer caused by serious corrosion and reaction in electrolyte will lead to big challenges, including dendrite growth, low Coulombic efficiency and even safety issues. In this paper, we first demonstrate the inorganic-organic coating via advanced molecular layer deposition (alucone) as a protective layer for metallic Na anode. By protecting Na anode with controllable alucone layer, the dendrites and mossy Na formation have been effectively suppressed and the lifetime has been significantly improved. Moreover, the molecular layer deposition alucone coating shows better performances than the atomic layer deposition Al 2 O 3 coating. The novel design of molecular layer deposition protected Na metal anode may bring in new opportunities to the realization of the next-generation high energy-density NIBs and NMBs.

  7. Direct conversion of radioactive and chemical waste containing metals, ceramics, amorphous solids, and organics to glass

    Forsberg, C.W.; Beahm, E.C.; Parker, G.W.

    1994-01-01

    The Glass Material Oxidation and Dissolution System (CMODS) is a new process for direct conversion of radioactive, mixed, and chemical wastes to glass. The wastes can be in the chemical forms of metals, ceramics, amorphous solids, and organics. GMODS destroys organics and it incorporates heavy metals and radionuclides into a glass. Processable wastes may include miscellaneous spent fuels (SF), SF hulls and hardware, plutonium wastes in different forms, high-efficiency particulate air (HEPA) filters, ion-exchange resins, failed equipment, and laboratory wastes. Thermodynamic calculations indicate theoretical feasibility. Small-scale laboratory experiments (< 100 g per test) have demonstrated chemical laboratory feasibility for several metals. Additional work is needed to demonstrate engineering feasibility

  8. CFA-7: an interpenetrated metal-organic framework of the MFU-4 family.

    Schmieder, Phillip; Grzywa, Maciej; Denysenko, Dmytro; Hambach, Manuel; Volkmer, Dirk

    2015-08-07

    The novel interpenetrated metal-organic framework CFA-7 (Coordination Framework Augsburg University-7), [Zn5Cl4(tqpt)3], has been synthesized containing the organic linker {H2-tqpt = 6,6,14,14-tetramethyl-6,14-dihydroquinoxalino[2,3-b]phenazinebistriazole}. Reaction of H2-tqpt and anhydrous ZnCl2 in N,N-dimethylformamide (DMF) yields CFA-7 as pseudo-cubic crystals. CFA-7 serves as precursor for the synthesis of isostructural frameworks with redox-active metal centers, which is demonstrated by postsynthetic metal exchange of Zn(2+) by different M(2+) (M = Co, Ni, Cu) ions. The novel framework is robust upon solvent removal and has been structurally characterized by single-crystal X-ray diffraction, TGA and IR spectroscopy, as well as gas sorption (Ar, CO2 and H2).

  9. Magnetic phase transition induced by electrostatic gating in two-dimensional square metal-organic frameworks

    Wang, Yun-Peng; Li, Xiang-Guo; Liu, Shuang-Long; Fry, James N.; Cheng, Hai-Ping

    2018-03-01

    We investigate theoretically magnetism and magnetic phase transitions induced by electrostatic gating of two-dimensional square metal-organic framework compounds. We find that electrostatic gating can induce phase transitions between homogeneous ferromagnetic and various spin-textured antiferromagnetic states. Electronic structure and Wannier function analysis can reveal hybridizations between transition-metal d orbitals and conjugated π orbitals in the organic framework. Mn-containing compounds exhibit a strong d -π hybridization that leads to partially occupied spin-minority bands, in contrast to compounds containing transition-metal ions other than Mn, for which electronic structure around the Fermi energy is only slightly spin split due to weak d -π hybridization and the magnetic interaction is of the Ruderman-Kittel-Kasuya-Yosida type. We use a ferromagnetic Kondo lattice model to understand the phase transition in Mn-containing compounds in terms of carrier density and illuminate the complexity and the potential to control two-dimensional magnetization.

  10. Influence of organic matter transformations on the bioavailability of heavy metals in a sludge base compost

    Molina, M. J.; Ingelmo, F.; Soriano, M. D.; Gallardo, A.; Lapena, L.

    2009-01-01

    The agricultural use of anaerobically digested sewage sludge (ADSS) as stable, mature compost implies knowing its total content in heavy metals and their bioavailability. since the chemical form of the metal in the sewage sludge-based compost depends on the effect of stabilization and maturation of the organic material during composting, the objective of this work was to examine the relationships between the changes in the organic matter content and humus fractions, and the bioavailability of heavy metals in a mixture of ADSS and wood chips (70:30 on wet basis) with an initial C/N ratio of 30.4, during its aerobic batch composting at 30 degree centigrade of external temperature in an open type lab-scale reactor with-out lixiviation. (Author)

  11. Applications of Total Scattering & Pair Distribution Function Analysis in Metal-Organic Framework Materials

    Xu, Hui; Birgisson, Steinar; Sommer, Sanna

    structure. At the same time, there is an ongoing debate on whether the SBU is present prior, or during MOF crystallization in MOF chemistry. However, little is known about MOFs formation mechanism. Currently techniques to study the in situ MOF formation process mainly focused on after......-crystallization process, for example in situ XRD and SAXS/WAXS study on MOF formation. However, the pre-crystallization process in the early stage of MOF formation is still unexplored. In this project, total scattering and PDF study will be carried out to explore the MOF formation process in early stage. This includes......Metal-Organic Frameworks (MOFs) is constructed by metal-oxide nodes and organic ligands. The formation of different structures of metal-oxide nodes (also called secondary building units, SBU) is crucial for MOF final structures, because the connectivity of SBU greatly influence the final MOF...

  12. Influence of organic matter transformations on the bioavailability of heavy metals in a sludge base compost

    Molina, M. J.; Ingelmo, F.; Soriano, M. D.; Gallardo, A.; Lapena, L.

    2009-07-01

    The agricultural use of anaerobically digested sewage sludge (ADSS) as stable, mature compost implies knowing its total content in heavy metals and their bioavailability. since the chemical form of the metal in the sewage sludge-based compost depends on the effect of stabilization and maturation of the organic material during composting, the objective of this work was to examine the relationships between the changes in the organic matter content and humus fractions, and the bioavailability of heavy metals in a mixture of ADSS and wood chips (70:30 on wet basis) with an initial C/N ratio of 30.4, during its aerobic batch composting at 30 degree centigrade of external temperature in an open type lab-scale reactor with-out lixiviation. (Author)

  13. Metal-doped organic foam and method of making same. [Patent application

    Rinde, J.A.

    Organic foams having a low density and very small cell size and method for producing same in either a metal-loaded or unloaded (nonmetal loaded) form are described. Metal-doped foams are produced by soaking a polymer gel in an aqueous solution of desired metal salt, soaking the gel successively in a solvent series of decreasing polarity to remove water from the gel and replace it with a solvent of lower polarity with each successive solvent in the series being miscible with the solvents on each side and being saturated with the desired metal salt, and removing the last of the solvents from the gel to produce the desired metal-doped foam having desired density cell size, and metal loading. The unloaded or metal-doped foams can be utilized in a variety of applications requiring low density, small cell size foam. For example, rubidium-doped foam made in accordance with the invention has utility in special applications, such as in x-ray lasers.

  14. Performance Monitoring: Evaluating an Organic Carbon-Limestone PRB for Treatment of Heavy Metals and Acidity

    Since 2004, researchers from the U.S. EPA National Risk Management Research Laboratory (NRMRL) have annually evaluated performance of an organic carbon-limestone permeable reactive barrier (PRB) system installed in 2003 by EPA Region 6 at the Delatte Metals Superfund site in Ponc...

  15. Lime treatment of liquid waste containing heavy metals, radionuclides and organics

    DuPont, A.

    1990-01-01

    This paper reports on lime treatment of liquid waste containing heavy metals, radio nuclides and organics. Lime is wellknown for its use in softening drinking water the treatment of municipal wastewaters. It is becoming important in the treatment of industrial wastewater and liquid inorganic hazardous waste; however, there are many questions regarding the use of lime for the treatment of liquid hazardous waste

  16. Anchoring of organic molecules to a metal surface: HtBDC on Cu(110)

    Schunack, M.; Petersen, L.; Kuhnle, A.

    2001-01-01

    The interaction of largish molecules with metal surfaces has been studied by combining the imaging and manipulation capabilities of the scanning tunneling microscope (STM). At the atomic scale, the STM results directly reveal that the adsorption of a largish organic molecule can induce...

  17. Hydrogen storage for fuel cell applications: Challenges, opportunities and prospects for metal-organic frameworks

    Langmi, Henrietta W

    2013-07-01

    Full Text Available and release, and cycle life of the materials. In the past decade, there has been growing interest in metal organic frameworks (MOFs) as hydrogen storage materials and significant progress has been made in this regard. The challenges, opportunities...

  18. On-board co2 capture and storage with metal organic framework

    Eddaoudi, Mohamed; Belmabkhout, Youssef; Shekhah, Osama

    2016-01-01

    In general, this disclosure describes method of capturing and storing CO2 on a vehicle. The method includes contacting an vehicle exhaust gas with one or more of a first metal organic framework (MOF) composition sufficient to separate CO2 from

  19. Lipase-supported metal-organic framework bioreactor catalyzes warfarin synthesis.

    Liu, Wan-Ling; Yang, Ni-Shin; Chen, Ya-Ting; Lirio, Stephen; Wu, Cheng-You; Lin, Chia-Her; Huang, Hsi-Ya

    2015-01-02

    A green and sustainable strategy synthesizes clinical medicine warfarin anticoagulant by using lipase-supported metal-organic framework (MOF) bioreactors (see scheme). These findings may be beneficial for future studies in the industrial production of chemical, pharmaceutical, and agrochemical precursors. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  20. Effect of Ocean Acidification on Organic and Inorganic Speciation of Trace Metals.

    Stockdale, Anthony; Tipping, Edward; Lofts, Stephen; Mortimer, Robert J G

    2016-02-16

    Rising concentrations of atmospheric carbon dioxide are causing acidification of the oceans. This results in changes to the concentrations of key chemical species such as hydroxide, carbonate and bicarbonate ions. These changes will affect the distribution of different forms of trace metals. Using IPCC data for pCO2 and pH under four future emissions scenarios (to the year 2100) we use a chemical speciation model to predict changes in the distribution of organic and inorganic forms of trace metals. Under a scenario where emissions peak after the year 2100, predicted free ion Al, Fe, Cu, and Pb concentrations increase by factors of up to approximately 21, 2.4, 1.5, and 2.0 respectively. Concentrations of organically complexed metal typically have a lower sensitivity to ocean acidification induced changes. Concentrations of organically complexed Mn, Cu, Zn, and Cd fall by up to 10%, while those of organically complexed Fe, Co, and Ni rise by up to 14%. Although modest, these changes may have significance for the biological availability of metals given the close adaptation of marine microorganisms to their environment.

  1. Gas Phase Sensing of Alcohols by Metal Organic Framework-Polymer Composite Materials

    Sachdeva, S.; Koper, S.J.H.; Sabetghadam Esfahani, A.; Soccol, Dimitri; Gravesteijn, Dirk J.; Kapteijn, F.; Sudholter, E.J.R.; Gascon Sabate, J.; de Smet, L.C.P.M.

    2017-01-01

    Affinity layers play a crucial role in chemical sensors for the selective and sensitive detection of analytes. Here, we report the use of composite affinity layers containing Metal Organic Frameworks (MOFs) in a polymeric matrix for sensing purposes. Nanoparticles of NH2-MIL-53(Al)

  2. Gas Phase Sensing of Alcohols by Metal Organic Framework-Polymer Composite Materials

    Sachdeva, Sumit; Koper, Sander J.H.; Sabetghadam, Anahid; Soccol, Dimitri; Gravesteijn, Dirk J.; Kapteijn, Freek; Sudhölter, Ernst J.R.; Gascon, Jorge; Smet, De Louis C.P.M.

    2017-01-01

    Affinity layers play a crucial role in chemical sensors for the selective and sensitive detection of analytes. Here, we report the use of composite affinity layers containing Metal Organic Frameworks (MOFs) in a polymeric matrix for sensing purposes. Nanoparticles of NH2-MIL-53(Al) were dispersed in

  3. Gas phase sensing of alcohols by Metal Organic Framework – polymer composite materials

    Sachdeva, S.; Koper, Sander J.H.; Sabetghadam, Anahid; Soccol, D.; Gravesteijn, Dirk J; Kapteijn, Freek; Sudholter, Ernst J.R.; Gascon, Jorge; de Smet, Louis C.P.M.

    2017-01-01

    Affinity layers play a crucial role in chemical sensors for the selective and sensitive detection of analytes. Here, we report the use of composite affinity layers containing Metal Organic Frameworks (MOFs) in a polymeric matrix for sensing purposes. Nanoparticles of NH2-MIL-53(Al) were dispersed in

  4. Metal organic framework synthesis in the presence of surfactants : Towards hierarchical MOFs?

    Seoane, B.; Dikhtiarenko, A.; Mayoral, A.; Tellez, C.; Coronas, J.; Kapteijn, F.; Gascon, J.

    2015-01-01

    The effect of synthesis pH and H2O/EtOH molar ratio on the textural properties of different aluminium trimesate metal organic frameworks (MOFs) prepared in the presence of the well-known cationic surfactant cetyltrimethylammonium bromide (CTAB) at 120 °C was studied with the purpose of obtaining a

  5. Metal-Organic Frameworks as Active Materials in Electronic Sensor Devices.

    Campbell, Michael G; Dincă, Mircea

    2017-05-12

    In the past decade, advances in electrically conductive metal-organic frameworks (MOFs) and MOF-based electronic devices have created new opportunities for the development of next-generation sensors. Here we review this rapidly-growing field, with a focus on the different types of device configurations that have allowed for the use of MOFs as active components of electronic sensor devices.

  6. Review of metal concentrations in Southern African coastal waters, sediments and organisms

    Hennig, HF-KO

    1985-08-01

    Full Text Available be highly correlated in one species, while other metals are not. For example in this review bivalves show no clear accumulation trend when one is attempting to establish baseline levels for zinc. Whelk species on the other hand show less inter-organism...

  7. Identifying sources of metal exposure in organic and conventional dairy farming.

    López-Alonso, M; Rey-Crespo, F; Herrero-Latorre, C; Miranda, M

    2017-10-01

    In humans the main route of exposure to toxic metals is through the diet, and there is therefore a clear need for this source of contamination to be minimized, particularly in food of animal origin. For this purpose, the various sources of toxic metals in livestock farming (which vary depending on the production system) must be taken into account. The objectives of the present study were to establish the profile of metal exposure in dairy cattle in Spain and to determine, by chemometric (multivariate statistical) analysis, any differences between organic and conventional systems. Blood samples from 522 cows (341 from organic farms and 181 from conventional farms) were analysed by inductively coupled plasma mass spectrometry to determine the concentrations of 14 elements: As, Cd, Co, Cr, Cu, Fe, Hg, I, Mn, Mo, Ni, Pb, Se and Zn. In conventional systems the generally high and balanced trace element concentrations in the mineral-supplemented concentrate feed strongly determined the metal status of the cattle. However, in organic systems, soil ingestion was an important contributing factor. Our results demonstrate that general information about the effects of mineral supplementation in conventional farming cannot be directly extrapolated to organic farming and special attention should be given to the contribution of ingestion of soil during grazing and/or ingestion of soil contaminated forage. Copyright © 2017 Elsevier Ltd. All rights reserved.

  8. Methane storage in porous solids: From Activated Carbons to Metal Organic Frameworks

    Ramos-Fernández, E. V.

    2014-01-01

    [EN]This paper reviews the most promising Metal Organic frameworks for storing natural gas. I discuss the features that make these materials promising for the application. Furthermore, it also indicates how these materials are evaluated and what requirements need to fulfil for being finally applied.

  9. Light-enhanced acid catalysis over a metal-organic framework.

    Xu, Caiyun; Sun, Keju; Zhou, Yu-Xiao; Ma, Xiao; Jiang, Hai-Long

    2018-03-06

    A Brønsted acid-functionalized metal-organic framework (MOF), MIL-101-SO 3 H, was prepared for acid-engaged esterification reactions. Strikingly, for the first time, the MOF exhibits significantly light-enhanced activity and possesses excellent activity and recyclability, with even higher activity than H 2 SO 4 under light irradiation.

  10. Separation of polar compounds using a flexible metal-organic framework

    Motkuri, R.K.; Thallapally, P.K.; Annapureddy, H.V.R.; Dang, L.X.; Krishna, R.; Nune, S.K.; Fernandez, C.A.; Liu, J.; McGrail, B.P.

    2015-01-01

    A flexible metal-organic framework constructed from a flexible linker is shown to possess the capability of separating mixtures of polar compounds (propanol isomers) by exploiting the differences in the saturation capacities of the constituents. Transient breakthrough simulations show that these

  11. Assembly of a water-insoluble strontium metal-organic framework with luminescent properties

    Lo, S.-H.; Liu, H.-K.; Zhan, J.-X.; Lin, W.-Ch.; Kao, Ch.-Ch.; Lin, Ch.-H.; Zima, Vítězslav

    2011-01-01

    Roč. 14, č. 10 (2011), 1602-1605 ISSN 1387-7003 R&D Projects: GA ČR GA203/08/0208 Institutional research plan: CEZ:AV0Z40500505 Keywords : structure * strontium * metal -organic Subject RIV: CA - Inorganic Chemistry Impact factor: 1.972, year: 2011

  12. Catalytic behavior of metal-organic frameworks and zeolites: Rationalization and comparative analysis

    Opanasenko, Maksym

    2015-01-01

    Roč. 243, APR 2015 (2015), s. 2-9 ISSN 0920-5861 R&D Projects: GA ČR GA14-07101S Institutional support: RVO:61388955 Keywords : Metal -organic frameworks * Zeolites * heterogeneous catalysis Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 4.312, year: 2015

  13. Nematodes as sentinels of heavy metals and organic toxicants in the soil

    Ekschmitt, K.; Korthals, G.W.

    2006-01-01

    Field and laboratory research has repeatedly shown that free-living soil nematodes differ in their sensitivity to soil pollution. In this paper, we analyze whether nematode genera proved sensitive or tolerant toward heavy metals and organic pollutants in six long-term field experiments. We discuss

  14. Microporous metal-organic framework with potential for carbon dioxide capture at ambient conditions

    Xiang, S.C.; He, Y.; Zhang, Z.; Wu, H.; Zhou, W.; Krishna, R.; Chen, B.

    2012-01-01

    Carbon dioxide capture and separation are important industrial processes that allow the use of carbon dioxide for the production of a range of chemical products and materials, and to minimize the effects of carbon dioxide emission. Porous metal-organic frameworks are promising materials to achieve

  15. Tetrathiafulvalene S-oxide: a Potential Donor Impurity in the Organic Metal TTF-TCNQ

    Carlsen, Lars; Bechgaard, Klaus; Jacobsen, Claus Schelde

    1979-01-01

    Tetrathiafulvalene S-oxide, which because of its size similarity with tetrathiafulvalene is a potential ‘donor impurity’ in the organic metal TTF–TCNQ, was prepared and characterized spectroscopically. Experiments in which tetrathiafulvalene S-oxide was purposely doped into TTF–TCNQ indicate, how...

  16. Investigation of buried metal-organic interface with photoelectron spectroscopy (PES)

    Vrdoljak, Pavo; Schoell, Achim; Reinert, Friedrich [Universitaet Wuerzburg, Experimentelle Physik II, 97074 Wuerzburg (Germany); Umbach, Eberhard [Forschungszentrum Karlsruhe, 76021 Karlsruhe (Germany)

    2008-07-01

    Metal-organic interfaces are of crucial importance for electronic devices since they influence the layer morphology, the electronic structure at contacts, and the charge carrier transport. Various investigations have addressed this issue from the viewpoint of surface science, applying model systems with thin organic films on flat (single crystalline or amorphous) metal substrates. The contacts in electronic devices, however, can be very different. This is mainly due to the morphological roughness of the interface in case of a metal top contact deposited on an organic layer and the possible influence on the electronic structure. In case of real contacts also interdiffusion has to be taken into account. However, surface sensitive techniques such as photoelectron spectroscopy (PES) and atomic force microscopy (AFM) can not immediately access the buried interface. To tackle this problem we have applied and optimised a lift-off technique which allows the removal of the metal top-contact in the UHV and analyse the interface between the contact and the organic film. We present first PES and AFM results of Au contacts deposited on PTCDA layers.

  17. Hybrid Glasses from Strong and Fragile Metal-Organic Framework Liquids

    Bennett, T.D.; Tan, J.C.; Yue, Yuanzheng

    2015-01-01

    Hybrid glasses connect the emerging field of metal-organic frameworks (MOFs) with the glass formation, amorphization and melting processes of these chemically versatile systems. Though inorganic zeolites collapse around the glass transition and melt at higher temperatures, the relationship betwee...

  18. Simultaneous removal of metals and organic compounds from a heavily polluted soil

    Szpyrkowicz, L.; Radaelli, M.; Bertini, S.; Daniele, S.; Casarin, F.

    2007-01-01

    The paper describes the results of treatment of soil samples, deriving from a dismissed industrial site, contaminated with several metals: Hg, Ni, Co, Zn, Pb, Cu, Cr, As and organic substances. The soil was subjected to remediation based on a process in which an oxidising leaching agent was produced electrochemically in-line in an undivided electrochemical cell reactor equipped with a Ti/Pt-Ir anode and a stainless steel cathode. Leaching of the soil samples was performed under dynamic conditions using a leaching column. A subsequent regeneration of the leaching solution, which consisted in electrodeposition of metals and electro-oxidation of organic substances, was carried out in a packed-bed reactor equipped with a centrally positioned graphite rod, serving as an anode, and stainless steel three-dimensional filling as a cathode. The study was focused on how and to which extent the metals present in the soil, as organic complexes, can be solubilised and how the process rates are impacted by the solution pH and other process variables. Data obtained under non-oxidising conditions, typically adopted for leaching of metals, are compared with the performance of chlorine-enriched leaching solutions. The results obtained under various conditions are also discussed in terms of the total organic carbon (TOC) removal from the water phase

  19. Metal-Organic Frameworks For Adsorption Driven Energy Transformation : From Fundamentals To Applications

    De Lange, M.F.

    2015-01-01

    A novel class of materials, i.e. Metal-Organic Frameworks (MOFs), has successfully been developed that is extremely suited for application in heat pumps and chillers. They have a superior performance over commercial sorbents and may potentially contribute to considerable energy savings worldwide.

  20. From metal-organic squares to porous zeolite-like supramolecular assemblies

    Wang, Shuang

    2010-12-29

    We report the synthesis, structure, and characterization of two novel porous zeolite-like supramolecular assemblies, ZSA-1 and ZSA-2, having zeolite gis and rho topologies, respectively. The two compounds were assembled from functional metal-organic squares (MOSs) via directional hydrogen-bonding interactions and exhibited permanent microporosity and thermal stability up to 300 °C. © 2010 American Chemical Society.

  1. Anthraquinone with Tailored Structure for Nonaqueous Metal-Organic Redox Flow Battery

    Wang, Wei; Xu, Wu; Cosimbescu, Lelia; Choi, Daiwon; Li, Liyu; Yang, Zhenguo

    2012-06-08

    A nonaqueous, hybrid metal-organic redox flow battery based on tailored anthraquinone structure is demonstrated to have an energy efficiency of {approx}82% and a specific discharge energy density similar to aqueous redox flow batteries, which is due to the significantly improved solubility of anthraquinone in supporting electrolytes.

  2. The role of dissolved organic matter in adsorbing heavy metals in clay-rich soils

    Refaey, Y.; Jansen, B.; El-Shater, A.H.; El-Haddad, A.A.; Kalbitz, K.

    2014-01-01

    Adsorption of tested heavy metals on Egyptian soils was large in all situations tested and follows the order: Cu >> Ni ≈ Zn. Copper was influenced by the timing of dissolved organic matter addition more than Ni and Zn. Specific binding mechanisms (inner-sphere complexes) dominated the affinity of Cu

  3. Anthraquinone with tailored structure for a nonaqueous metal-organic redox flow battery.

    Wang, Wei; Xu, Wu; Cosimbescu, Lelia; Choi, Daiwon; Li, Liyu; Yang, Zhenguo

    2012-07-07

    A nonaqueous, hybrid metal-organic redox flow battery based on tailored anthraquinone structure is demonstrated to have an energy efficiency of ~82% and a specific discharge energy density similar to those of aqueous redox flow batteries, which is due to the significantly improved solubility of anthraquinone in supporting electrolytes.

  4. Stepwise transformation of the molecular building blocks in a porphyrin-encapsulating metal-organic material

    Zhang, ZhenJie; Wojtas, Łukasz; Eddaoudi, Mohamed; Zaworotko, Michael J.

    2013-01-01

    When immersed in solutions containing Cu(II) cations, the microporous metal-organic material P11 ([Cd4(BPT)4]·[Cd(C 44H36N8)(S)]·[S], BPT = biphenyl-3,4′,5-tricarboxylate) undergoes a transformation of its [Cd 2(COO)6]2- molecular building blocks

  5. Exploiting large-pore metal-organic frameworks for separations through entropic molecular mechanisms

    Torres-Knoop, A.; Dubbeldam, D.

    2015-01-01

    We review the molecular mechanisms behind adsorption and the separations of mixtures in metal-organic frameworks and zeolites. Separation mechanisms can be based on differences in the affinity of the adsorbate with the framework and on entropic effects. To develop next-generation adsorbents, the

  6. Metal-Organic Frameworks with d-f Cyanide Bridges: Structural Diversity, Bonding Regime, and Magnetism

    Ferbinteanu, M.; Cimpoesu, F.; Tanase, S.; Cheng, P.

    2015-01-01

    We present a selection of metal-organic frameworks based on d-f and f-f linkages, discussing their structural features and properties from experimental and theoretical viewpoints. We give an overview of our own synthetic and modeling methodologies, highlighting the complexity of the

  7. Metal organic frameworks as precursors for the manufacture of advanced catalytic materials

    Oar-Arteta Gonzalez, L.; Wezendonk, T.A.; Sun, X.; Kapteijn, F.; Gascon Sabate, J.

    The use of metal organic frameworks as hard templates for the preparation of heterogeneous catalysts is thoroughly reviewed. In this critical article, the main factors to consider when using a MOF as a sacrificial template are first discussed. Then, the existing literature on the topic is reviewed,

  8. Modulated synthesis of zirconium-metal organic framework (Zr-MOF) for hydrogen storage applications

    Ren, Jianwei

    2014-01-01

    Full Text Available A modulated synthesis of Zr-metal organic framework (Zr-MOF) with improved ease of handling and decreased reaction time is reported to yield highly crystalline Zr-MOF with well-defined octahedral shaped crystals for practical hydrogen storage...

  9. Theoretical study of adsorption of organic phosphines on transition metal surfaces

    Lou, Shujie; Jiang, Hong

    2018-04-01

    The adsorption properties of organic phosphines on transition metal (TM) surfaces (Fe, Co, Ni, Cu, Ru, Rh, Pd, Ag, Ir, Pt, and Au) have been studied to explore the possibility of building novel heterogeneous chiral catalytic systems based on organic phosphines. Preferred adsorption sites, adsorption energies and surface electronic structures of a selected set of typical organic phosphines adsorbed on TM surfaces are calculated with density-functional theory to obtain a systematic understanding on the nature of adsorption interactions. All organic phosphines considered are found to chemically adsorb on these TM surfaces with the atop site as the most preferred one, and the TM-P bond is formed via the lone-pair electrons of the P atom and the directly contacted TM atom. These findings imply that it is indeed possible to build heterogeneous chiral catalytic systems based on organic phosphines adsorbed on TM surfaces, which, however, requires a careful design of molecular structure of organic phosphines.

  10. Scalable room-temperature conversion of copper(II) hydroxide into HKUST-1 (Cu3 (btc)2).

    Majano, Gerardo; Pérez-Ramírez, Javier

    2013-02-20

    Copper(II) hydroxide is converted directly to HKUST-1 (Cu(3) (btc)(2) ) after only 5 min at room-temperature in aqueous ethanolic solution without the need of additional solvents. Scale up to the kilogram scale does not influence porous properties yielding pure-phase product with a remarkable total surface area exceeding 1700 m(2) g(-1) featuring aggregates of nanometer-sized crystals (<600 nm) and extremely high space-time yields. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. Occurrence of antibiotic and metal resistance in bacteria from organs of river fish

    Pathak, S.P.; Gopal, K.

    2005-01-01

    Bacterial populations in some organs, viz., liver, spleen, kidney, gill, and arborescent organ of the catfish Clarias batrachus were enumerated followed by determination of resistance for antibiotics and metals. The total viable counts in these organs, observed, were 2.24x10 4 , 2.08x10 4 , 1.44x10 4 , 1.23x10 4 , and 6.40x10 3 colony-forming units/mL, respectively. The random bacterial isolates from these fish organs showed resistance in decreasing order for colistin (98%), ampicillin (82%), gentamycin (34%), carbenicillin (28%), tetracyline (20%), streptomycin (12%), and ciprofloxacin (02%). Most of the isolates exhibited an increasing order of tolerance for the metals (μg/mL) copper (100), lead (200), manganese (400), cadmium (200), and chromium (50), with minimum inhibitory concentration (MIC) ranging from <50 to 1600 μg/mL. These observations indicate that the significant occurrence of bacterial population in organs of fish with high incidence of resistance for antibiotics and metals may pose risk to fish fauna and public health

  12. Recent advances in metal-organic frameworks and covalent organic frameworks for sample preparation and chromatographic analysis.

    Wang, Xuan; Ye, Nengsheng

    2017-12-01

    In the field of analytical chemistry, sample preparation and chromatographic separation are two core procedures. The means by which to improve the sensitivity, selectivity and detection limit of a method have become a topic of great interest. Recently, porous organic frameworks, such as metal-organic frameworks (MOFs) and covalent organic frameworks (COFs), have been widely used in this research area because of their special features, and different methods have been developed. This review summarizes the applications of MOFs and COFs in sample preparation and chromatographic stationary phases. The MOF- or COF-based solid-phase extraction (SPE), solid-phase microextraction (SPME), gas chromatography (GC), high-performance liquid chromatography (HPLC) and capillary electrochromatography (CEC) methods are described. The excellent properties of MOFs and COFs have resulted in intense interest in exploring their performance and mechanisms for sample preparation and chromatographic separation. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  13. Pristine Metal-Organic Frameworks and their Composites for Energy Storage and Conversion.

    Liang, Zibin; Qu, Chong; Guo, Wenhan; Zou, Ruqiang; Xu, Qiang

    2017-11-22

    Metal-organic frameworks (MOFs), a new class of crystalline porous organic-inorganic hybrid materials, have recently attracted increasing interest in the field of energy storage and conversion. Herein, recent progress of MOFs and MOF composites for energy storage and conversion applications, including photochemical and electrochemical fuel production (hydrogen production and CO 2 reduction), water oxidation, supercapacitors, and Li-based batteries (Li-ion, Li-S, and Li-O 2 batteries), is summarized. Typical development strategies (e.g., incorporation of active components, design of smart morphologies, and judicious selection of organic linkers and metal nodes) of MOFs and MOF composites for particular energy storage and conversion applications are highlighted. A broad overview of recent progress is provided, which will hopefully promote the future development of MOFs and MOF composites for advanced energy storage and conversion applications. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. Interface properties of Fe/MgO/Cu-phthalocyanine metal-insulator-organic semiconductor structures

    Lee, Nyunjong; Bae, Yujeong; Kim, Taehee; Ito, Eisuke; Hara, Masahiko

    2014-01-01

    Hybrid interface structures consisting of organic copper-phthalocyanine (CuPc) and ferromagnetic metal Fe(001) with and without a MgO(001) cover were investigated by using surface sensitive techniques of X-ray photoemission spectroscopy and ultraviolet photoemission spectroscopy. A systematic study of the energy level alignment at the interfaces was carried out. For the hybrid interfaces considered here, our results indicate that the insertion of an artificially-grown ultra-thin oxide layer MgO(001) can prevent Femi level pinning and induce a rather large interface dipole, thereby resulting in remarkable CuPc Fermi level shifts when the thickness of the CuPc film is less than 3 nm. This study provides a better understanding of spin filtering in MgO-based organic spin devices and a new way to alter the interface electronic structure of metal/organic semiconductor hybrid systems.

  15. Metal-organic extended 2D structures: Fe-PTCDA on Au(111)

    Alvarez, Lucia; Caillard, Renaud; MartIn-Gago, Jose A; Mendez, Javier; Pelaez, Samuel; Serena, Pedro A

    2010-01-01

    In this work we combine organic molecules of 3,4,9,10-perylenetetracarboxylic dianhydride (PTCDA) with iron atoms on an Au (111) substrate in ultra-high vacuum conditions at different temperatures. By means of scanning tunnelling microscopy (STM) we study the formation of stable 2D metal-organic structures. We show that at certain growth conditions (temperature, time and coverage) stable 'ladder-like' nanostructures are obtained. These are the result of connecting together two metal-organic chains through PTCDA molecules placed perpendicularly, as rungs of a ladder. These structures, stable up to 450 K, can be extended in a 2D layer covering the entire surface and presenting different rotation domains. STM images at both polarities show a contrast reversal between the two molecules at the unit cell. By means of density functional theory (DFT) calculations, we confirm the stability of these structures and that their molecular orbitals are placed separately at the different molecules.

  16. Metal-organic frameworks for the removal of toxic industrial chemicals and chemical warfare agents.

    Bobbitt, N Scott; Mendonca, Matthew L; Howarth, Ashlee J; Islamoglu, Timur; Hupp, Joseph T; Farha, Omar K; Snurr, Randall Q

    2017-06-06

    Owing to the vast diversity of linkers, nodes, and topologies, metal-organic frameworks can be tailored for specific tasks, such as chemical separations or catalysis. Accordingly, these materials have attracted significant interest for capture and/or detoxification of toxic industrial chemicals and chemical warfare agents. In this paper, we review recent experimental and computational work pertaining to the capture of several industrially-relevant toxic chemicals, including NH 3 , SO 2 , NO 2 , H 2 S, and some volatile organic compounds, with particular emphasis on the challenging issue of designing materials that selectively adsorb these chemicals in the presence of water. We also examine recent research on the capture and catalytic degradation of chemical warfare agents such as sarin and sulfur mustard using metal-organic frameworks.

  17. The trace metals accumulation in marine organisms of the southeastern Adriatic coast, Montenegro

    Joksimovic Danijela

    2012-01-01

    Full Text Available The concentration and accumulation of trace metals (Co, Ni, As, Cd, Pb and Hg were measured in sea water, sediments and marine organisms in the coastline of the Montenegro. The obtained results of trace metals in seagrass and mussels were compared with those found in the water column and sediment. Sampling was performed in the fall of 2005 at five locations in the Montenegrin coastline, Sveta Stasija, Herceg Novi, Zanjice, Budva and Bar, which present different levels and sources of human impact. The heavy metals analyses in seawater, sediment, P. oceanica and M. galloprovincialis identified the harbor of Bar as the most Hg-contaminated site, Zanjice as the most As contaminated and Sveta Stasija as the most Pb-contaminated areas of the Montenegrin coastal area. This study showed that P. oceanica may have a greater bioaccumulation capacity than M. galloprovincialis for the considered metals, except for As and Hg, and both organisms may reflect contamination in the water column and in the sediment. For the first time, seagrass P. oceanica and M. galloprovincialis were employed as metal bioindicators for the southeastern Adriatic. The results of this study could serve as a baseline in the future for the assessment of anthropogenic effects in this marine ecosystem.

  18. Capture of organic iodides from nuclear waste by metal-organic framework-based molecular traps

    Li, Baiyan; Dong, Xinglong; Wang, Hao; Ma, Dingxuan; Tan, Kui; Jensen, Stephanie; Deibert, Benjamin J.; Butler, Joseph; Cure, Jeremy; Shi, Zhan; Thonhauser, Timo; Chabal, Yves J.; Han, Yu; Li, Jing

    2017-01-01

    capture from nuclear waste. The capture mechanism was investigated by experimental and theoretical methods.Capturing radioactive organic iodides from nuclear waste is important for safe nuclear energy usage, but remains a significant challenge. Here, Li

  19. Functionalized metal organic frameworks for effective capture of radioactive organic iodides

    Li, Baiyan; Dong, Xinglong; Wang, Hao; Ma, Dingxuan; Tan, Kui; Shi, Zhan; Chabal, Yves J.; Han, Yu; Li, Jing

    2017-01-01

    Highly efficient capture of radioactive organic iodides (ROIs) from off-gas mixtures remains a substantial challenge for nuclear waste treatment. Current materials utilized for ROI sequestration suffer from low capacity, high cost (e.g. use of noble

  20. Metal organic framework absorbent platforms for removal of co2 and h2s from natural gas

    Belmabkhout, Youssef; Eddaoudi, Mohamed; Adil, Karim; Cadiau, Amandine; Bhatt, Prashant M.

    2016-01-01

    Provided herein are metal organic frameworks comprising metal nodes and N-donor organic ligands which have high selectivity and stability in the present of gases and vapors including H2S, H2O, and CO2. Methods include capturing one or more of H2S, H2O, and CO2 from fluid compositions, such as natural gas.

  1. Metal organic framework absorbent platforms for removal of co2 and h2s from natural gas

    Belmabkhout, Youssef

    2016-10-13

    Provided herein are metal organic frameworks comprising metal nodes and N-donor organic ligands which have high selectivity and stability in the present of gases and vapors including H2S, H2O, and CO2. Methods include capturing one or more of H2S, H2O, and CO2 from fluid compositions, such as natural gas.

  2. Bioleaching of heavy metals from soil using fungal-organic acids : bench scale testing

    Cathum, S.J.; Ousmanova, D.; Somers, A.; Punt, M. [SAIC Canada, Ottawa, ON (Canada); Brown, C.E. [Environment Canada, Ottawa, ON (Canada). Emergencies Engineering Division]|[Environment Canada, Ottawa, ON (Canada). Environmental Technology Centre

    2006-07-01

    The ability of fungi to solubilize metals from solid materials may present new opportunities in environmental remediation. This paper presented details of a bench scale experiment that evaluated the leaching of heavy metals from contaminated soil using in situ fungal-generated organic acids. Rice was used as the growing media for organic acid production by A. foetidus. The cultivated fungus was placed on large pieces of potato-dextrose agar (PDA) plates and suspended in 5 L of sterilized water. The cooked rice was inoculated by pouring the 5 L spore suspension over the rice layer. Soil was obtained from a soil pile impacted with heavy metals at a private industrial site and augmented with Pb-contaminated soil. A polyethylene tub was used with a drain pipe leading to a leachate vessel. Crushed stone was spread over the bottom of the tub to assist leachate drainage. Approximately 45 kg of the contaminated soil was spread evenly over the stone layer to a depth of 10 cm. The concentrated spore suspension was sprinkled over the rice. Each week the leachate collection vessel was removed from the bioleaching system and the fine soil particles were allowed to settle. A control was run using the contaminated soil and solid substrate without fungus. Growth of A. foetidus was observed in both control experiment and test experiment after a period of 35 days. The pH of the leachate was measured as the fungal growth progressed. The process was assessed using ICP Mass Spectroscopy and electron spectroscopy, which showed that approximately 65 g of heavy metals were mobilized from 45 kg of soil, and that the biological leaching process resulted in greater mobilization of heavy metals relative to the control experiment. It was concluded that organic acids generated by A. foetidus were capable of leaching heavy metals from the soil. 30 refs., 4 tabs., 15 figs.

  3. Risk assessment of metals and PAHs for receptor organisms in differently polluted areas in Slovenia.

    Al Sayegh Petkovšek, Samar; Kopušar, Nataša; Tome, Davorin; Kryštufek, Boris

    2015-11-01

    Samples from receptor organisms (small mammals, passerine birds) and their food sources (herbaceous plants, leaves and fruits of wood plants, earthworms) were collected during 2011-2014 from the vicinity of a former lead smelter, from the vicinity of the largest Slovenian thermal power plant, from along a state road and also from a reference area. The samples were then analysed to determine the degree of contamination with the metals (Pb, Cd, Zn, Hg, Cu, Mo) and with polycyclic aromatic hydrocarbons (PAHs). This study provides the first data on metal and PAH exposure to small mammals and passerine birds in southeast Europe, focussing on the transfer of metals and PAHs through the food chain and on risk assessment for differently polluted areas in Slovenia. The results indicate that: (i) earthworms and herbaceous plants (especially roots) can be a source of metal exposure for organisms higher in the food chain; (ii) a risk from Pb and Cd (HQ > 1) in the vicinity of the former lead smelter exists for Myodes glareolus feeding in part on roots and for Apodemus flavicollis and Parus major feeding in part on earthworms; and (iii) mean Pb and Cd concentrations in the liver of small mammal species inhabiting the vicinity of the lead smelter reach effect concentrations in a significant proportion of the specimens (Pb: 40%, Cd: 67%); (iv) the results for P. major confirm that the study area is exposed to Pb, Cd, Hg; (v) metals contribute the major part of the total risk for receptor organisms from vicinity of lead smelter. On the contrary, the risk of PAHs for small mammals trapped close to the state road is insignificant. We can summarize, that the hazards experienced by the local ecosystem due to metal exposure may persist for decades in the vicinity of large emission sources (especially smelters). Copyright © 2015 Elsevier B.V. All rights reserved.

  4. Effects of ultrasound on properties of ni-metal organic framework nanostructures

    Abbas Pardakhty

    2016-10-01

    Full Text Available Objective(s: According to the unique properties of magnetic nanoparticles, Nickel Metal-Organic Frameworks (MOF was synthesized successfully by ultrasound irradiation. Metal-organic frameworks (MOFs are organic–inorganic hybrid extended networks that are constructed via covalent linkages between metal ions/metal clusters and organic ligands called a linker. Materials and Methods: The nanoparticles were synthesized by Ultrasound  Method Under a synthesis conditions, All chemicals were used as received without further purification. Scanning electron microscopy (SEM images were obtained on LEO- 1455VP equipped with an energy dispersive X-ray spectroscopy at university of Kashan in Iran. Transition electron microscopy (TEM images were obtained on EM208 Philips transmission electron microscope with an accelerating voltage of 200 kV. Results: Results showed that Ni-MOF synthesized by this method, had smaller particle size distribution and It was found that the different kinds of ligand leads to preparation products with different morphologies and textural properties. Moreover, ultrasound irradiation method has significant effect on microstructures of as-synthesized MOFs and can improve their textural properties compared to method without using hydrothermal route.The XRD patterns of the samples obtained from ultrasound irradiation was well matched with that of as-prepared Ni-MOF by solvothermal method. Conclusion: This rapid method of ultrasonic radiation as compared to the classical solvothermal synthesis, showed promising results in terms of size distribution, surface area, pore diameter and pore volume.

  5. Metal immobilization by sludge-derived biochar: roles of mineral oxides and carbonized organic compartment.

    Zhang, Weihua; Huang, Xinchen; Jia, Yanming; Rees, Frederic; Tsang, Daniel C W; Qiu, Rongliang; Wang, Hong

    2017-04-01

    Pyrolyzing sludge into biochar is a potentially promising recycling/disposal solution for municipal wastewater sludge, and the sludge-derived biochar (SDBC) presents an excellent sorbent for metal immobilization. As SDBC is composed of both mineral oxides and carbonized organic compartment, this study therefore compared the sorption behaviour of Pb and Zn on SDBC to those of individual and mixture of activated carbon (AC) and amorphous aluminium oxide (Al 2 O 3 ). Batch experiments were conducted at 25 and 45 °C, and the metal-loaded sorbents were artificially aged in the atmosphere for 1-60 days followed by additional sorption experiments. The Pb sorption was generally higher than Zn sorption, and the co-presence of Pb reduced Zn sorption on each studied sorbent. Higher sorption capacities were observed at 45 °C than 25 °C for SDBC and AC, while the opposite was shown for Al 2 O 3 , indicating the significance of temperature-dependent diffusion processes in SDBC and AC. Nevertheless, metal sorption was more selective on Al 2 O 3 that showed a greater affinity towards Pb over Zn under competition, correlating with the reducible fraction of sequential extraction. Furthermore, significant amounts of Pb and Zn were additionally sorbed on SDBC following 30-day ageing. The X-ray diffraction revealed the formation of metal-phosphate precipitates, while the X-ray photoelectron spectroscopy showed a larger quantity of metal-oxygen bonding after 30-day ageing of metal-loaded SDBC. The results may imply favourable long-term transformation and additional sorption capacity of SDBC. In conclusion, SDBC resembles the sorption characteristics of both organic and mineral sorbents in different aspects, presenting an appropriate material for metal immobilization during soil amendment.

  6. A review of metal (Pb and Zn) sensitive and pH tolerant bioassay organisms for risk screening of metal-contaminated acidic soils

    Chapman, E.Emily V.; Dave, Göran; Murimboh, John D.

    2013-01-01

    To improve risk estimates at the screening stage of Ecological Risk Assessment (ERA), short duration bioassays tailored to undisturbed soil cores from the contaminated site could be useful. However, existing standardized bioassays use disturbed soil samples and often pH sensitive organisms. This is a problem as naturally acidic soils are widespread. Changing soil properties to suit the test organism may change metal bioavailability, leading to erroneous risk estimates. For bioassays in undisturbed soil cores to be effective, species able to withstand natural soil properties must be identified. This review presents a critical examination of bioassay species' tolerance of acidic soils and sensitivity to metal contaminants such as Pb and Zn. Promising organisms include; Dendrobaena octaedra, Folsomia candida, Caenorhabditis elegans, Oppia nitens, Brassica rapa, Trifolium pratense, Allium cepa, Quercus rubra and Acer rubrum. The MetSTICK test and the Bait lamina test were also identified as suitable microorganism tests. -- Highlights: •Risk screening of metal contaminated soils should consider metal bioavailability. •Metal bioavailability is dependent on soil properties such as pH. •Many standardized bioassay organisms are sensitive to acidic soils. •This review identifies acid tolerant and metal sensitive bioassays and species. •The identified tests can improve risk screening of acidic metal contaminated soil. -- This review identifies bioassay species able to withstand naturally acidic soils while being sensitive to metal contaminants

  7. Metal-Organic Framework-Derived Materials for Sodium Energy Storage.

    Zou, Guoqiang; Hou, Hongshuai; Ge, Peng; Huang, Zhaodong; Zhao, Ganggang; Yin, Dulin; Ji, Xiaobo

    2018-01-01

    Recently, sodium-ion batteries (SIBs) are extensively explored and are regarded as one of the most promising alternatives to lithium-ion batteries for electrochemical energy conversion and storage, owing to the abundant raw material resources, low cost, and similar electrochemical behavior of elemental sodium compared to lithium. Metal-organic frameworks (MOFs) have attracted enormous attention due to their high surface areas, tunable structures, and diverse applications in drug delivery, gas storage, and catalysis. Recently, there has been an escalating interest in exploiting MOF-derived materials as anodes for sodium energy storage due to their fast mass transport resulting from their highly porous structures and relatively simple preparation methods originating from in situ thermal treatment processes. In this Review, the recent progress of the sodium-ion storage performances of MOF-derived materials, including MOF-derived porous carbons, metal oxides, metal oxide/carbon nanocomposites, and other materials (e.g., metal phosphides, metal sulfides, and metal selenides), as SIB anodes is systematically and completely presented and discussed. Moreover, the current challenges and perspectives of MOF-derived materials in electrochemical energy storage are discussed. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. Application of cryptogams as monitoring organisms of metal air pollution in Denmark

    Rasmussen, L; Pilegaard, K; Gydesen, H

    1980-01-01

    A reviewing statement of the use of bryophytes and lichens as biologically monitoring organisms of metal air pollution in Denmark is given with comments on the difficulties of the different methods. On the basis of presented investigations the advantages of the application of epiphytically growing bryophytes over epigeically growing species are discussed. It is concluded that epiphytes are more effective accumulators of the metals with the highest binding affinity, e.g., Cu, Fe, Pb, than epigeically growing species. Furthermore, the specific habitat conditions for epiphytes give a higher degree of comparability between different sampling sites, although epiphytes still are dependent on the existence of a suitable phorophyte on the site.

  9. On-board co2 capture and storage with metal organic framework

    Eddaoudi, Mohamed

    2016-03-17

    In general, this disclosure describes method of capturing and storing CO2 on a vehicle. The method includes contacting an vehicle exhaust gas with one or more of a first metal organic framework (MOF) composition sufficient to separate CO2 from the exhaust gas, contacting the separated CO2 with one or more of a second MOF composition sufficient to store the CO2 and wherein the one or more first MOF composition comprises one or more SIFSIX-n-M MOF and wherein M is a metal and n is 2 or 3. Embodiments also describe an apparatus or system for capturing and storing CO2 onboard a vehicle.

  10. Heavy metal and Pb isotopic compositions of aquatic organisms in the Pearl River Estuary, South China

    Ip, C.C.M.; Li, X.D.; Zhang, G.; Wong, C.S.C.; Zhang, W.L.

    2005-01-01

    The accumulation of trace metals in aquatic organisms may lead to serious health problems through the food chain. The present research project aims to study the accumulation and potential sources of trace metals in aquatic organisms of the Pearl River Estuary (PRE). Four groups of aquatic organisms, including fish, crab, shrimp, and shellfish, were collected in the PRE for trace metal and Pb isotopic analyses. The trace metal concentrations in the aquatic organism samples ranged from 0.01 to 2.10 mg/kg Cd, 0.02 to 4.33 mg/kg Co, 0.08 to 4.27 mg/kg Cr, 0.15 to 77.8 mg/kg Cu, 0.17 to 31.0 mg/kg Ni, 0.04 to 30.7 mg/kg Pb, and 8.78 to 86.3 mg/kg Zn (wet weight). High concentrations of Cd were found in crab, shrimp and shellfish samples, while high concentration of Pb was found in fish. In comparison with the baseline reference values in other parts of the world, fish in the PRE had the highest elevated trace metals. The results of Pb isotopic compositions indicated that the bioaccumulation of Pb in fish come from a wide variety of food sources and/or exposure pathways, particularly the anthropogenic inputs. - Relative high concentrations of Cd were found in crab, shrimp and shellfish samples while high concentration of Pb was found in fish, particularly from the anthropogenic inputs

  11. Bioavailability of Heavy Metals in Soil: Impact on Microbial Biodegradation of Organic Compounds and Possible Improvement Strategies

    Olaniran, Ademola O.; Balgobind, Adhika; Pillay, Balakrishna

    2013-01-01

    Co-contamination of the environment with toxic chlorinated organic and heavy metal pollutants is one of the major problems facing industrialized nations today. Heavy metals may inhibit biodegradation of chlorinated organics by interacting with enzymes directly involved in biodegradation or those involved in general metabolism. Predictions of metal toxicity effects on organic pollutant biodegradation in co-contaminated soil and water environments is difficult since heavy metals may be present in a variety of chemical and physical forms. Recent advances in bioremediation of co-contaminated environments have focussed on the use of metal-resistant bacteria (cell and gene bioaugmentation), treatment amendments, clay minerals and chelating agents to reduce bioavailable heavy metal concentrations. Phytoremediation has also shown promise as an emerging alternative clean-up technology for co-contaminated environments. However, despite various investigations, in both aerobic and anaerobic systems, demonstrating that metal toxicity hampers the biodegradation of the organic component, a paucity of information exists in this area of research. Therefore, in this review, we discuss the problems associated with the degradation of chlorinated organics in co-contaminated environments, owing to metal toxicity and shed light on possible improvement strategies for effective bioremediation of sites co-contaminated with chlorinated organic compounds and heavy metals. PMID:23676353

  12. Bioavailability of Heavy Metals in Soil: Impact on Microbial Biodegradation of Organic Compounds and Possible Improvement Strategies

    Balakrishna Pillay

    2013-05-01

    Full Text Available Co-contamination of the environment with toxic chlorinated organic and heavy metal pollutants is one of the major problems facing industrialized nations today. Heavy metals may inhibit biodegradation of chlorinated organics by interacting with enzymes directly involved in biodegradation or those involved in general metabolism. Predictions of metal toxicity effects on organic pollutant biodegradation in co-contaminated soil and water environments is difficult since heavy metals may be present in a variety of chemical and physical forms. Recent advances in bioremediation of co-contaminated environments have focussed on the use of metal-resistant bacteria (cell and gene bioaugmentation, treatment amendments, clay minerals and chelating agents to reduce bioavailable heavy metal concentrations. Phytoremediation has also shown promise as an emerging alternative clean-up technology for co-contaminated environments. However, despite various investigations, in both aerobic and anaerobic systems, demonstrating that metal toxicity hampers the biodegradation of the organic component, a paucity of information exists in this area of research. Therefore, in this review, we discuss the problems associated with the degradation of chlorinated organics in co-contaminated environments, owing to metal toxicity and shed light on possible improvement strategies for effective bioremediation of sites co-contaminated with chlorinated organic compounds and heavy metals.

  13. Feasibility of biochar manufactured from organic wastes on the stabilization of heavy metals in a metal smelter contaminated soil.

    Abdelhafez, Ahmed A; Li, Jianhua; Abbas, Mohamed H H

    2014-12-01

    The main objectives of the current study were to evaluate the potential effects of biochar derived from sugar cane bagasse (SC-BC) and orange peel (OP-BC) on improving the physicochemical properties of a metal smelter contaminated soil, and determining its potentiality for stabilizing Pb and As in soil. To achieve these goals, biochar was produced in a small-scale biochar producing plant, and an incubation experiment was conducted using a silt loam metal-contaminated soil treated with different application rates of biochar (0-10% w/w). The obtained results showed that, the addition of SC-BC and OP-BC increased significantly the soil aggregate stability, water-holding capacity, cation exchange capacity, organic matter and N-status in soil. SC-BC considerably decreased the solubility of Pb to values lower than the toxic regulatory level of the toxicity characteristics leaching procedure extraction (5 mg L(-1)). The rise in soil pH caused by biochar application, and the increase of soil organic matter transformed the labile Pb into less available fractions i.e. "Fe-Mn oxides" and "organic" bound fractions. On the other hand, As was desorbed from Fe-Mn oxides, which resulted in greater mobility of As in the treated soil. We concluded that SC-BC and OP-BC could be used successfully for remediating soils highly contaminated with Pb. However, considerable attention should be paid when using it in soil contaminated with As. Copyright © 2014 Elsevier Ltd. All rights reserved.

  14. Organic Metals

    Andersen, Jan Rud; Craven, R. A.; Weidenborner, J. E.

    1977-01-01

    Replacement of the sulphur atoms in the charge transfer salt tetrathiafulvalene (TTF)–2,5-diethyltetracyano-p-quinodimethane (DETCNQ) with selenium yields the isostructural and better conducting analogue tetraselenafulvalene (TSeF)–DETCNQ, in which the Peierls transition temperature is decreased....

  15. Homochiral metal-organic frameworks and their application in chromatography enantioseparations.

    Peluso, Paola; Mamane, Victor; Cossu, Sergio

    2014-10-10

    The last frontier in the chiral stationary phases (CSPs) field for chromatography enantioseparations is represented by homochiral metal-organic frameworks (MOFs), a class of organic-inorganic hybrid materials built from metal-connecting nodes and organic-bridging ligands. The modular nature of these materials allows to design focused structures by combining properly metal, organic ligands and rigid polytopic spacers. Intriguingly, chiral ligands introduce molecular chirality in the MOF-network as well as homochirality in the secondary structure of materials (such as homohelicity) producing homochiral nets in a manner mimicking biopolymers (proteins, polysaccharides) which are characterized by a definite helical sense associated with the chirality of their building blocks (amino acids or sugars). Nowadays, robust and flexible materials characterized by high porosity and surface area became available by using preparative procedures typical of the so-called reticular synthesis. This review focuses on recent developments in the synthesis and applications of homochiral MOFs as supports for chromatography enantioseparations. Indeed, despite this field is in its infancy, interesting results have been produced and a critical overview of the 12 reported applications for gas chromatography (GC) and high-performance liquid chromatography (HPLC) can orient the reader approaching the field. Mechanistic aspects are shortly discussed and a view regarding future trends in this field is provided. Copyright © 2014 Elsevier B.V. All rights reserved.

  16. Synergistic extraction of transition metal cations from aqueous media by two separated organic phases

    Goldberg, I.

    1991-12-01

    We have therefore initiated novel approaches to the study of the mechanism of the synergistic extraction of metal ions by means of two separated organic phases, which are brought in contact with the same aqueous phase. The present work is concerned with the extraction of transition metals and actinides ions from nitric acid by chelating agents e.g., HTTA thenoyltrifluoroacetone in a diluent - the first organic phase, and by natural donor, e.g., TBP, tri-butyl phosphate in a diluent the second organic phase. The adduct formation was studied by means of spectrochemical and radiochemical methods. In the first approach the aqueous phase was attacked with both organic phases simultanously (the static or parallel extraction). In this method organic phase are separated one from the other. It was shown that even in the absence of mixing, synergism is observed under this experimental conditions. The results indicate, that adduct formation occurs in both organic phases. Nevertheless the enhanchment of extraction in the TBP phase is by far greater than that in the HTTA containing phase. This approach has one disadvatage, viz., the experiments are very time consuming, a typical experiment requiring over 10 days. In order to overcome this difficulty, the following experiments were carried out: the aqueous phase were first shaken with diluent containing an anionic ligand and the phases were allowed to separate. Then the aqueous solution were shaken with diluent containing a netural donor and the phase again were allowed to separate. The concentration of the metal ions in all the phases were determined. The experiments were repeated with an other diluent replacing the first diluent in one or both organic phases. In this way eight sequences of experiments were carried out for each concentration set chosen. The results thus point out that this experimental approach open new possibilities to investigate the mechanism and the kinetics of synergistic extraction processes. (author) the

  17. Effect of pendant isophthalic acid moieties on the adsorption properties of light hydrocarbons in HKUST-1-like tbo -MOFs: Application to methane purification and storage

    Belmabkhout, Youssef; Mouttaki, Hasnaa; Eubank, Jarrod F.; Guillerm, Vincent; Eddaoudi, Mohamed

    2014-01-01

    Equilibrium adsorption of methane (CH4), C2+ gases (ethane (C2H6), ethylene (C2H4), propane (C3H8), and propylene (C3H6)), and carbon dioxide (CO2) was measured on a series of tbo-MOFs (topological analogues of the prototypical MOF, HKUST-1

  18. Mechanically stable, hierarchically porous Cu3(btc)2 (HKUST-1) monoliths via direct conversion of copper(II) hydroxide-based monoliths.

    Moitra, Nirmalya; Fukumoto, Shotaro; Reboul, Julien; Sumida, Kenji; Zhu, Yang; Nakanishi, Kazuki; Furukawa, Shuhei; Kitagawa, Susumu; Kanamori, Kazuyoshi

    2015-02-28

    The synthesis of highly crystalline macro-meso-microporous monolithic Cu3(btc)2 (HKUST-1; btc(3-) = benzene-1,3,5-tricarboxylate) is demonstrated by direct conversion of Cu(OH)2-based monoliths while preserving the characteristic macroporous structure. The high mechanical strength of the monoliths is promising for possible applications to continuous flow reactors.

  19. Chemical Engineering of Photoactivity in Heterometallic Titanium-Organic Frameworks by Metal Doping.

    Castells-Gil, Javier; Padial, Natalia M; Almora-Barrios, Neyvis; Albero, Josep; Ruiz-Salvador, A Rabdel; González-Platas, Javier; García, Hermenegildo; Martí-Gastaldo, Carlos

    2018-06-06

    We report a new family of titanium-organic frameworks that enlarges the limited number of crystalline, porous materials available for this metal. They are chemically robust and can be prepared as single crystals at multi-gram scale from multiple precursors. Their heterometallic structure enables engineering of their photoactivity by metal doping rather than by linker functionalization. Compared to other methodologies based on the post-synthetic metallation of MOFs, our approach is well-fitted for controlling the positioning of dopants at an atomic level to gain more precise control over the band-gap and electronic properties of the porous solid. Changes in the band-gap are also rationalized with computational modelling and experimentally confirmed by photocatalytic H 2 production. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  20. Mechanically and electrically robust metal-mask design for organic CMOS circuits

    Shintani, Michihiro; Qin, Zhaoxing; Kuribara, Kazunori; Ogasahara, Yasuhiro; Hiromoto, Masayuki; Sato, Takashi

    2018-04-01

    The design of metal masks for fabricating organic CMOS circuits requires the consideration of not only the electrical property of the circuits, but also the mechanical strength of the masks. In this paper, we propose a new design flow for metal masks that realizes coanalysis of the mechanical and electrical properties and enables design exploration considering the trade-off between the two properties. As a case study, we apply a “stitching technique” to the mask design of a ring oscillator and explore the best design. With this technique, mask patterns are divided into separate parts using multiple mask layers to improve the mechanical strength at the cost of high resistance of the vias. By a numerical experiment, the design trade-off of the stitching technique is quantitatively analyzed, and it is demonstrated that the proposed flow is useful for the exploration of the designs of metal masks.