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Sample records for metal-organic polymeric precursor

  1. 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.

  2. Luminescent Lanthanide Metal Organic Frameworks for cis-Selective Isoprene Polymerization Catalysis

    Samantha Russell

    2015-11-01

    Full Text Available In this study, we are combining two areas of chemistry; solid-state coordination polymers (or Metal-Organic Framework—MOF and polymerization catalysis. MOF compounds combining two sets of different lanthanide elements (Nd3+, Eu3+/Tb3+ were used for that purpose: the use of neodymium was required due to its well-known catalytic properties in dienes polymerization. A second lanthanide, europium or terbium, was included in the MOF structure with the aim to provide luminescent properties. Several lanthanides-based MOF meeting these criteria were prepared according to different approaches, and they were further used as catalysts for the polymerization of isoprene. Stereoregular cis-polyisoprene was received, which in some cases exhibited luminescent properties in the UV-visible range.

  3. Silicon dioxide obtained by Polymeric Precursor Method

    Oliveira, C.T.; Granado, S.R.; Lopes, S.A.; Cavalheiro, A.A.

    2011-01-01

    The Polymeric Precursor Method is able for obtaining several oxide material types with high surface area even obtained in particle form. Several MO 2 oxide types such as titanium, silicon and zirconium ones can be obtained by this methodology. In this work, the synthesis of silicon oxide was monitored by thermal analysis, XRD and surface area analysis in order to demonstrate the influence of the several synthesis and calcining parameters. Surface area values as higher as 370m2/g and increasing in the micropore volume nm were obtained when the material was synthesized by using ethylene glycol as polymerizing agent. XRD analysis showed that the material is amorphous when calcinated at 600°C in despite of the time of calcining, but the material morphology is strongly influenced by the polymeric resin composition. Using Glycerol as polymerizing agent, the pore size increase and the surface area goes down with the increasing in decomposition time, when compared to ethylene glycol. (author)

  4. A novel hybrid metal-organic framework-polymeric monolith for solid-phase microextraction.

    Lin, Chen-Lan; Lirio, Stephen; Chen, Ya-Ting; Lin, Chia-Her; Huang, Hsi-Ya

    2014-03-17

    This study describes the fabrication of a novel hybrid metal-organic framework- organic polymer (MOF-polymer) for use as a stationary phase in fritless solid-phase microextraction (SPME) for validating analytical methods. The MOF-polymer was prepared by using ethylene dimethacrylate (EDMA), butyl methacrylate (BMA), and an imidazolium-based ionic liquid as porogenic solvent followed by microwave-assisted polymerization with the addition of 25 % MOF. This novel hybrid MOF-polymer was used to extract penicillin (penicillin G, penicillin V, oxacillin, cloxacillin, nafcillin, dicloxacillin) under different conditions. Quantitative analysis of the extracted penicillin samples using the MOF-organic polymer for SPME was conducted by using capillary electrochromatography (CEC) coupled with UV analysis. The penicillin recovery was 63-96.2 % with high reproducibility, sensitivity, and reusability. The extraction time with the proposed fabricated SPME was only 34 min. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. 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,

  6. Iron Oxide Doped Alumina-Zirconia Nanoparticle Synthesis by Liquid Flame Spray from Metal Organic Precursors

    Juha-Pekka Nikkanen; Helmi Keskinen; Mikko Aromaa; Mikael Järn; Tomi Kanerva; Erkki Levänen; Jyrki M. Mäkelä; Tapio Mäntylä

    2008-01-01

    The liquid flame spray (LFS) method was used to make iron oxide doped alumina-zirconia nanoparticles. Nanoparticles were generated using a turbulent, high-temperature (Tmax⁡∼3000 K) H2-O2 flame. The precursors were aluminium-isopropoxide, zirconium-n-propoxide, and ferrocene in xylene solution. The solution was atomized into micron-sized droplets by high velocity H2 flow and introduced into the flame where nanoparticles were formed. The particle morphology, size, phase, and chemical compositi...

  7. Iron Oxide Doped Alumina-Zirconia Nanoparticle Synthesis by Liquid Flame Spray from Metal Organic Precursors

    Juha-Pekka Nikkanen

    2008-01-01

    Full Text Available The liquid flame spray (LFS method was used to make iron oxide doped alumina-zirconia nanoparticles. Nanoparticles were generated using a turbulent, high-temperature (Tmax⁡∼3000 K H2-O2 flame. The precursors were aluminium-isopropoxide, zirconium-n-propoxide, and ferrocene in xylene solution. The solution was atomized into micron-sized droplets by high velocity H2 flow and introduced into the flame where nanoparticles were formed. The particle morphology, size, phase, and chemical composition were determined by TEM, XRD, XPS, and N2-adsorption measurements. The collected particulate material consists of micron-sized aggregates with nanosized primary particles. In both doped and undoped samples, tetragonal phase of zirconia was detected in room temperature while alumina was found to be noncrystalline. In the doped powder, Fe was oxidized to Fe2O3. The primary particle size of collected sample was approximately from 6 nm to 40 nm. Doping was observed to increase the specific surface area of the powder from 39 m2/g to 47 m2/g.

  8. Laser-driven coating of vertically aligned carbon nanotubes with manganese oxide from metal organic precursors for energy storage

    Pérez del Pino, A.; György, E.; Alshaikh, I.; Pantoja-Suárez, F.; Andújar, J. L.; Pascual, E.; Amade, R.; Bertran-Serra, E.

    2017-09-01

    Carbon nanotubes-transition metal oxide systems are intensively studied due to their excellent properties for electrochemical applications. In this work, an innovative procedure is developed for the synthesis of vertically aligned multi-walled carbon nanotubes (VACNTs) coated with transition metal oxide nanostructures. VACNTs are grown by plasma enhanced chemical vapor deposition and coated with a manganese-based metal organic precursor (MOP) film based on manganese acetate solution. Subsequent UV pulsed laser irradiation induces the effective heating-decomposition of the MOP leading to the crystallization of manganese oxide nanostructures on the VACNT surface. The study of the morphology, structure and composition of the synthesized materials shows the formation of randomly oriented MnO2 crystals, with few nanometers in size, and to their alignment in hundreds of nm long filament-like structures, parallel to the CNT’s long axis. Electrochemical measurements reveal a significant increase of the specific capacitance of the MnO2-VACNT system (100 F g-1) as compared to the initial VACNT one (21 F g-1).

  9. A peroxidase mimic with atom transfer radical polymerization activity constructed through the grafting of heme onto metal-organic frameworks.

    Jiang, Wei; Pan, Yue; Yang, Jiebing; Liu, Yong; Yang, Yan; Tang, Jun; Li, Quanshun

    2018-07-01

    Atom transfer radical polymerization (ATRP) has been considered to be an efficient strategy for constructing functional macromolecules owing to its simple operation and versatile monomers, and thus it is of great significance to develop ideal catalysts with higher activity and perfect reusability. We constructed a peroxidase mimic through the grafting of heme onto metal-organic frameworks UiO-66-NH 2 (ZrMOF), namely Heme-ZrMOF. After the systematic characterization of structure, the composite Heme-ZrMOF was demonstrated to possess high peroxidase activity using 2,2'-azinobis-(3-ethylbenzthiazoline-6-sulphonate) and 3,3',5,5'-tetramethylbenzidine as substrates. The enzyme mimic was then used as catalysts in the ATRP reactions of different monomers, in which favorable monomer conversion (44.6-98.0%) and product molecular weight (8600-25,600 g/mol) could be obtained. Compared to free heme, Heme-ZrMOF could efficiently achieve the easy separation of heme from the catalytic system and facilitate the ATRP reaction in an aqueous environment to avoid the utilization of organic solvents. In conclusion, the enzyme mimic Heme-ZrMOF could be potentially used as an effective catalyst for preparing well-defined polymers with biomedical applications. Copyright © 2018 Elsevier Inc. All rights reserved.

  10. Graphene nanoribbons synthesized from molecular precursor polymerization on Au(110)

    Massimi, Lorenzo; Ourdjini, Oualid; Della Pia, Ada; Mariani, Carlo; Betti, Maria Grazia [Dipartimento di Fisica, Università di Roma La Sapienza, Piazzale Aldo Moro 2, I - 00185 Roma (Italy); Cavaliere, Emanuele; Gavioli, Luca [i-LAMP & Dipartimento di Matematica e Fisica, Università Cattolica, 25121 Brescia (Italy)

    2015-06-23

    A spectroscopic study of 10,10-dibromo-9,9 bianthracene (DBBA) molecules deposited on the Au(110) surface is presented, by means of ultraviolet and X-ray photoemission, and X-ray absorption spectroscopy. Through a thermally activated procedure, these molecular precursors polymerize and eventually form graphene nanoribbons (GNRs) with atomically controlled shape and width, very important building blocks for several technological applications. The GNRs observed by scanning tunneling microscopy (STM) appear as short segments on top of the gold surface reconstruction, pointing out the delicate balance among surface diffusion and surface corrugation in their synthesis on the Au(110) surface.

  11. Reduced graphene oxide-wrapped MoO3 composites prepared by using metal-organic frameworks as precursor for all-solid-state flexible supercapacitors.

    Cao, Xiehong; Zheng, Bing; Shi, Wenhui; Yang, Jian; Fan, Zhanxi; Luo, Zhimin; Rui, Xianhong; Chen, Bo; Yan, Qingyu; Zhang, Hua

    2015-08-26

    Reduced graphene oxide-wrapped MoO3M (rGO/MoO3 ) is prepared by a novel and simple method that is developed by using a metal-organic framework as the precursor. After a two-step annealing process, the obtained rGO/MoO3 composite is used for a high-performance supercapacitor electrode. Moreover, an all-solid-state flexible supercapacitor is fabricated based on the rGO/MoO3 composite, which shows stable performance under different bending states. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. An evaluation of absorption spectroscopy to monitor YBa2Cu3O7-x precursors for metal organics chemical vapor deposition processing

    Matthew Edward Thomas

    1999-01-01

    Absorption spectroscopy was evaluated as a technique to monitor the metal organics chemical vapor deposition (MOCVD) process for forming YBa 2 Cu 3 O 7-x superconducting coated conductors. Specifically, this study analyzed the feasibility of using absorption spectroscopy to monitor the MOCVD supply vapor concentrations of the organic ligand 2,2,6,6-tetramethyl-3,5-heptanedionate (TMHD) metal chelates of barium, copper, and yttrium. Ba(TMHD) 2 , Cu(TMHD) 2 , and Y(TMHD) 3 compounds have successfully been vaporized in the MOCVD processing technique to form high temperature superconducting ''coated conductors,'' a promising technology for wire fabrication. The absorption study of the barium, copper, and yttrium (TMHD) precursors was conducted in the ultraviolet wavelength region from 200nm to 400nm. To simulate the MOCVD precursor flows the Ba(TMHD) 2 , Cu(TMHD) 2 , and Y(TMHD) 3 complexes were vaporized at vacuum pressures of (0.03--10)Torr. Spectral absorption scans of each precursor were conducted to examine potential measurement wavelengths for determining vapor concentrations of each precursor via Beer's law. The experimental results show that under vacuum conditions the barium, copper, and yttrium (TMHD) precursors begin to vaporize between 90 C and 135 C, which are considerably lower vaporization temperatures than atmospheric thermal gravimetric analyses indicate. Additionally, complete vaporization of the copper and yttrium (TMHD) precursors occurred during rapid heating at temperatures between 145 C and 195 C and after heating at constant temperatures between 90 C and 125 C for approximately one hour, whereas the Ba(TMHD) 2 precursor did not completely vaporize. At constant temperatures, near constant vaporization levels for each precursor were observed for extended periods of time. Detailed spectroscopic scans at stable vaporization conditions were conducted

  13. Comparison of precursors for pulsed metal-organic chemical vapor deposition of HfO2 high-K dielectric thin films

    Teren, Andrew R.; Thomas, Reji; He, Jiaqing; Ehrhart, Peter

    2005-01-01

    Hafnium oxide films were deposited on Si(100) substrates using pulsed metal-organic chemical vapor deposition (CVD) and evaluated for high-K dielectric applications. Three types of precursors were tested: two oxygenated ones, Hf butoxide-dmae and Hf butoxide-mmp, and an oxygen-free one, Hf diethyl-amide. Depositions were carried out in the temperature range of 350-650 deg. C, yielding different microstructures ranging from amorphous to crystalline, monoclinic, films. The films were compared on the basis of growth rate, phase development, density, interface characteristics, and electrical properties. Some specific features of the pulsed injection technique are considered. For low deposition temperatures the growth rate for the amide precursor was significantly higher than for the mixed butoxide precursors. A thickness-dependent amorphous to crystalline phase transition temperature was found for all precursors. There is an increase of the film density along with the deposition temperature from values as low as 5 g/cm 3 at 350 deg. C to values close to the bulk value of 9.7 g/cm 3 at 550 deg. C. Crystallization is observed in the same temperature range for films of typically 10-20 nm thickness. However, annealing studies show that this density increase is not simply related to the crystallization of the films. Similar electrical properties could be observed for all precursors and the dielectric constant of the films reaches values similar to the best values reported for bulk crystalline HfO 2

  14. Anionic PPV polymerization from the sulfinyl precursor route : Block copolymer formation from sequential addition of monomers

    Cosemans, Inge; Vandenbergh, Joke; Voet, Vincent S. D.; Loos, Katja; Lutsen, Laurence; Vanderzande, Dirk; Junkers, Thomas

    2013-01-01

    The sulfinyl precursor route for the synthesis of poly(p-phenylene vinylene) (PPV) materials via an anionic polymerization procedure employing dedicated initiators is evaluated in depth. Reaction kinetics are investigated to gain more control over the polymerization, since polymerization proceeds to

  15. In situ generation of Ni nanoparticles from metal-organic framework precursors and their use for biomass hydrodeoxygenation.

    Čelič, Tadeja Birsa; Grilc, Miha; Likozar, Blaž; Tušar, Nataša Novak

    2015-05-22

    So far, in situ-generated Ni nanoparticles have been reported to be efficient catalysts for tar cracking during wood liquefaction by pyrolysis. Herein, their performance in further bio-oil conversion steps is evaluated. Nanoparticles were generated for the first time from a Ni-containing metal-organic framework, MIL-77, during the hydrotreatment of glycerol-solvolyzed lignocellulosic (LC) biomass. Reactions were conducted at 300 °C and the H2 pressure was 8 MPa in a slurry reactor. The catalytic activity and selectivity of the deoxygenation and hydrocracking reactions for real biomass-derived feedstock using in situ-generated nanoparticles was compared with Ni nanoparticles dispersed on a silica-alumina support (commercial Ni/SiO2 -Al2 O3 catalyst). The mass activity of the in situ-generated nanoparticles for hydrogenolysis was more than ten times higher in comparison to their commercial analogues, and their potential for the use in LC biorefinery is discussed. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. 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.

  17. Growth and characterization of germanium epitaxial film on silicon (001 with germane precursor in metal organic chemical vapour deposition (MOCVD chamber

    Kwang Hong Lee

    2013-09-01

    Full Text Available The quality of germanium (Ge epitaxial film grown directly on a silicon (Si (001 substrate with 6° off-cut using conventional germane precursor in a metal organic chemical vapour deposition (MOCVD system is studied. The growth sequence consists of several steps at low temperature (LT at 400 °C, intermediate temperature ramp (LT-HT of ∼10 °C/min and high temperature (HT at 600 °C. This is followed by post-growth annealing in hydrogen at temperature ranging from 650 to 825 °C. The Ge epitaxial film of thickness ∼ 1 μm experiences thermally induced tensile strain of 0.11 % with a treading dislocation density (TDD of ∼107/cm2 and the root-mean-square (RMS roughness of ∼ 0.75 nm. The benefit of growing Ge epitaxial film using MOCVD is that the subsequent III-V materials can be grown in-situ without the need of breaking the vacuum hence it is manufacturing worthy.

  18. Layered niobate KNb3O8 synthesized by the polymeric precursor method

    Souza, J.K.D. de; Honório, L.M.C.; Torres, S.M.; Santos, I.M.G.; Maia, A.S.; Ferreira, J.M.

    2018-01-01

    The polymeric precursor method was used for the synthesis of KNb 3 O 8 and compared to the solid-state method. The materials were characterized by X-ray diffraction (XRD), infrared spectroscopy, Raman spectroscopy, scanning electron microscopy, and determination of surface area and total pore volume by nitrogen isotherms at 77 K. The material prepared by the polymeric precursor method was single-phase while K 2 Nb 4 O 11 was obtained as secondary phase when the solid state method was used, as evidenced by the XRD patterns and the Raman spectra. The morphology of the materials was significantly altered by the synthesis method, as the KNb 3 O 8 prepared by the polymeric precursor method presented a more porous morphology leading to a higher surface area and pore volume. (author)

  19. Fabrication of a polymeric composite incorporating metal-organic framework nanosheets for solid-phase microextraction of polycyclic aromatic hydrocarbons from water samples

    Wei, Songbo; Lin, Wei; Xu, Jianqiao; Wang, Ying; Liu, Shuqin; Zhu, Fang; Liu, Yuan; Ouyang, Gangfeng

    2017-01-01

    In this contribution, it was discovered that even distribution of a metal-organic framework (MOF) [e.g. copper 1,4-benzenedicarboxylate (CBDC)] within polymeric matrixes (e.g. polyimide) resulted in a high-efficient coating material on the surface of a stainless steel wire (SSW). Consequently, a home-made solid phase microextraction (SPME) fiber was fabricated for fast determination of target analytes in real water samples. Scanning electron microscope images indicated that the coating possessed homogenously porous surface. Coupled with gas chromatography-mass spectrometry (GC-MS) and direct immersion SPME (DI-SPME) technique, the fiber was evaluated through the analysis of five polycyclic aromatic hydrocarbons (PAHs) in aqueous samples. Under optimized extraction and desorption conditions, the established method based on the home-made fiber exhibited good repeatability (4.2–12.7%, n = 6) and reproducibility (0.9–11.7%, n = 3), low limits of detection (LODs, 0.11–2.10 ng L"−"1), low limits of quantification (LOQs, 0.36–6.99 ng L"−"1) and wide linear ranges (20–5000 ng L"−"1). Eventually, the method was proven applicable in the determination of PAHs in real samples, as the recoveries were in a satisfactory range (81.7–116%). - Highlights: • A homogenously porous CBDC@polyimide-coated fiber was fabricated and characterized. • The fiber exhibited highly desired extraction performance towards PAHs. • The fiber was employed for the determination of PAHs in real aqueous samples.

  20. Fabrication of a polymeric composite incorporating metal-organic framework nanosheets for solid-phase microextraction of polycyclic aromatic hydrocarbons from water samples

    Wei, Songbo; Lin, Wei; Xu, Jianqiao [MOE Key Laboratory of Aquatic Product of Safety/KLGHEI of Environment and Energy Chemistry, School of Chemistry, Sun Yat-sen University, Guangzhou 510275 (China); Wang, Ying [School of Pharmacy, Guiyang Medical University, Guiyang 550004 (China); Liu, Shuqin; Zhu, Fang [MOE Key Laboratory of Aquatic Product of Safety/KLGHEI of Environment and Energy Chemistry, School of Chemistry, Sun Yat-sen University, Guangzhou 510275 (China); Liu, Yuan, E-mail: yliu@shou.edu.cn [College of Food Science & Technology, Shanghai Ocean University, Shanghai 201306 (China); Ouyang, Gangfeng, E-mail: cesoygf@mail.sysu.edu.cn [MOE Key Laboratory of Aquatic Product of Safety/KLGHEI of Environment and Energy Chemistry, School of Chemistry, Sun Yat-sen University, Guangzhou 510275 (China)

    2017-06-08

    In this contribution, it was discovered that even distribution of a metal-organic framework (MOF) [e.g. copper 1,4-benzenedicarboxylate (CBDC)] within polymeric matrixes (e.g. polyimide) resulted in a high-efficient coating material on the surface of a stainless steel wire (SSW). Consequently, a home-made solid phase microextraction (SPME) fiber was fabricated for fast determination of target analytes in real water samples. Scanning electron microscope images indicated that the coating possessed homogenously porous surface. Coupled with gas chromatography-mass spectrometry (GC-MS) and direct immersion SPME (DI-SPME) technique, the fiber was evaluated through the analysis of five polycyclic aromatic hydrocarbons (PAHs) in aqueous samples. Under optimized extraction and desorption conditions, the established method based on the home-made fiber exhibited good repeatability (4.2–12.7%, n = 6) and reproducibility (0.9–11.7%, n = 3), low limits of detection (LODs, 0.11–2.10 ng L{sup −1}), low limits of quantification (LOQs, 0.36–6.99 ng L{sup −1}) and wide linear ranges (20–5000 ng L{sup −1}). Eventually, the method was proven applicable in the determination of PAHs in real samples, as the recoveries were in a satisfactory range (81.7–116%). - Highlights: • A homogenously porous CBDC@polyimide-coated fiber was fabricated and characterized. • The fiber exhibited highly desired extraction performance towards PAHs. • The fiber was employed for the determination of PAHs in real aqueous samples.

  1. Silicon dioxide obtained by Polymeric Precursor Method; Obtencao de dioxido de silicio pelo Metodo dos Precursores Polimericos

    Oliveira, C.T.; Granado, S.R.; Lopes, S.A.; Cavalheiro, A.A., E-mail: cinthia_quimica@hotmail.com [Universidade Estadual de Mato Grosso do Sul (CPTREN/UEMS), Navirai, MS (Brazil). Centro de Pesquisas Tecnologicas em Recursos Naturais

    2011-07-01

    The Polymeric Precursor Method is able for obtaining several oxide material types with high surface area even obtained in particle form. Several MO{sub 2} oxide types such as titanium, silicon and zirconium ones can be obtained by this methodology. In this work, the synthesis of silicon oxide was monitored by thermal analysis, XRD and surface area analysis in order to demonstrate the influence of the several synthesis and calcining parameters. Surface area values as higher as 370m2/g and increasing in the micropore volume nm were obtained when the material was synthesized by using ethylene glycol as polymerizing agent. XRD analysis showed that the material is amorphous when calcinated at 600°C in despite of the time of calcining, but the material morphology is strongly influenced by the polymeric resin composition. Using Glycerol as polymerizing agent, the pore size increase and the surface area goes down with the increasing in decomposition time, when compared to ethylene glycol. (author)

  2. Tin dioxide nanostructured thin films obtained through polymeric precursor method

    Marcelo Antônio Dal Santos

    2012-11-01

    Full Text Available Tin dioxide (SnO2 nanostructured thin films with low proportion of defects and low roughness were produced through the systematic control of temperature and viscosity of the precursor solutions used for thin films deposition. These solutions were obtained through the citrate method and the films were deposited through the ‘dip-coating’ technique on glass substrate and after thermal treatment at 470ºC/4h, they were characterized both structurally and morphologically through the X-ray diffractometry, optic microscopy, scanning electronic microscopy, atomic force microscopy, X-ray fluorescence, UV-Vis absorption spectroscopy and X-ray excited photoelectrons spectroscopy. The film thickness was obtained through scanning electronic microscopy of the films cross-section and correlated to the proportion of Sn and Si obtained through X-ray fluorescence. X-ray diffractometry of the films revealed the presence of peaks corresponding to the SnO2 crystalline phase, overlapping a wide peak between 20 and 30º (2?, characteristic of the glass substrate. Optic microscopy, Scanning electronic microscopy and atomic force microscopy revealed homogeneous films, with low roughness, suitable to several applications such as sensors and transparent electrodes. It could be observed through the UV-Vis absorption analysis that the films presented high optical transparency and ‘band gap’ energy 4.36 eV. The X-ray excited photoelectron spectroscopy confirmed the presence of SnO2, as well as traces of the elements present in the glass substrate and residual carbon from the thermal treatment of the films.

  3. Processing and characterization of yttrium-stabilized zirconia thin films on polyimide from aqueous polymeric precursors

    Gorman, B.P.; Anderson, H.U.

    2004-01-01

    Low-temperature deposition of dense, nanocrystalline yttrium-stabilized zirconia (YSZ) thin films on polyimide (PI) substrates is illustrated using an aqueous polymeric precursor spin-coating technique. The polymeric precursor uses low-cost materials, is water-soluble and the viscosity and cation concentrations can be easily adjusted in order to vary the film thickness from 0.02 to 0.3 μm. Due to the use of water as the solvent in the YSZ precursor and the hydrophobic nature of the PI surface, surface modification processes were utilized in order to improve the wetting characteristics. Surface modification of PI substrates using wet chemical and oxygen plasma techniques led to a decrease in the precursor contact angle, and ultimately allowed for uniform film formation on both bulk and thin film PI substrates. Scanning electron microscopy, transmission electron microscopy and UV/Vis absorption illustrate that near full-density nanocrystalline thin films of YSZ can be produced at temperatures as low as 350 deg. C. Thermogravimetric analyses illustrate that the PI substrate does not undergo any weight loss up to these temperatures

  4. Nano structured TiO2 thin films by polymeric precursor method

    Stroppa, Daniel Grando; Giraldi, Tania Regina; Leite, Edson Roberto; Varela, Jose Arana; Longo, Elson

    2008-01-01

    This work focuses in optimizing setup for obtaining TiO 2 thin films by polymeric precursor route due to its advantages on stoichiometric and morphological control. Precursor stoichiometry, synthesis pH, solids concentration and rotation speed at deposition were optimized evaluating thin films morphology and thickness. Thermogravimetry and NMR were applied for precursor's characterization and AFM, XRD and ellipsometry for thin films evaluation. Results showed successful attainment of homogeneous nanocrystalline anatase TiO 2 thin films with outstanding control over morphological characteristics, mean grain size of 17 nm, packing densities between 57 and 75%, estimated surface areas of 90 m 2 /g and monolayers thickness within 20 and 128 nm. (author)

  5. NiTiO3 powders obtained by polymeric precursor method: Synthesis and characterization

    Lopes, K.P.; Cavalcante, L.S.; Simoes, A.Z.; Varela, J.A.; Longo, E.; Leite, E.R.

    2009-01-01

    Nickel titanate (NiTiO 3 ) powders were synthesized by the polymeric precursor method after thermal treatment at different temperatures for 2 h in air atmosphere. The decomposition of the precursors was monitored by differential scanning calorimetry and thermogravimetric analysis. The NiTiO 3 powders presented a reduction in the specific surface area and increase of the average particle size with the evolution of the temperature. The structural evolution of NiTiO 3 phase was accompanied by X-ray diffraction and Fourier transform Raman spectroscopy. By scanning electron microscopy was revealed the agglomerated nature of very fine particles of NiTiO 3 powders annealed from 600 to 1000 deg. C

  6. Methods of forming single source precursors, methods of forming polymeric single source precursors, and single source precursors and intermediate products formed by such methods

    Fox, Robert V.; Rodriguez, Rene G.; Pak, Joshua J.; Sun, Chivin; Margulieux, Kelsey R.; Holland, Andrew W.

    2012-12-04

    Methods of forming single source precursors (SSPs) include forming intermediate products having the empirical formula 1/2{L.sub.2N(.mu.-X).sub.2M'X.sub.2}.sub.2, and reacting MER with the intermediate products to form SSPs of the formula L.sub.2N(.mu.-ER).sub.2M'(ER).sub.2, wherein L is a Lewis base, M is a Group IA atom, N is a Group IB atom, M' is a Group IIIB atom, each E is a Group VIB atom, each X is a Group VIIA atom or a nitrate group, and each R group is an alkyl, aryl, vinyl, (per)fluoro alkyl, (per)fluoro aryl, silane, or carbamato group. Methods of forming polymeric or copolymeric SSPs include reacting at least one of HE.sup.1R.sup.1E.sup.1H and MER with one or more substances having the empirical formula L.sub.2N(.mu.-ER).sub.2M'(ER).sub.2 or L.sub.2N(.mu.-X).sub.2M'(X).sub.2 to form a polymeric or copolymeric SSP. New SSPs and intermediate products are formed by such methods.

  7. Methods of forming single source precursors, methods of forming polymeric single source precursors, and single source precursors formed by such methods

    Fox, Robert V.; Rodriguez, Rene G.; Pak, Joshua J.; Sun, Chivin; Margulieux, Kelsey R.; Holland, Andrew W.

    2014-09-09

    Methods of forming single source precursors (SSPs) include forming intermediate products having the empirical formula 1/2{L.sub.2N(.mu.-X).sub.2M'X.sub.2}.sub.2, and reacting MER with the intermediate products to form SSPs of the formula L.sub.2N(.mu.-ER).sub.2M'(ER).sub.2, wherein L is a Lewis base, M is a Group IA atom, N is a Group IB atom, M' is a Group IIIB atom, each E is a Group VIB atom, each X is a Group VIIA atom or a nitrate group, and each R group is an alkyl, aryl, vinyl, (per)fluoro alkyl, (per)fluoro aryl, silane, or carbamato group. Methods of forming polymeric or copolymeric SSPs include reacting at least one of HE.sup.1R.sup.1E.sup.1H and MER with one or more substances having the empirical formula L.sub.2N(.mu.-ER).sub.2M'(ER).sub.2 or L.sub.2N(.mu.-X).sub.2M'(X).sub.2 to form a polymeric or copolymeric SSP. New SSPs and intermediate products are formed by such methods.

  8. Ultrasound-assisted synthesis of nano-structured Zinc(II)-based metal-organic frameworks as precursors for the synthesis of ZnO nano-structures.

    Bigdeli, Fahime; Ghasempour, Hosein; Azhdari Tehrani, Alireza; Morsali, Ali; Hosseini-Monfared, Hassan

    2017-07-01

    A 3D, porous Zn(II)-based metal-organic framework {[Zn 2 (oba) 2 (4-bpmn)]·(DMF) 1.5 } n (TMU-21), (4-bpmn=N,N'-Bis-pyridin-4-ylmethylene-naphtalene-1,5-diamine, H 2 oba=4,4'-oxybis(benzoic acid)) with nano-rods morphology under ultrasonic irradiation at ambient temperature and atmospheric pressure was prepared and characterized by scanning electron microscopy. Sonication time and concentration of initial reagents effects on the size and morphology of nano-structured MOFs were studied. Also {[Zn 2 (oba) 2 (4-bpmn)] (TMU-21) and {[Zn 2 (oba) 2 (4-bpmb)] (TMU-6), 4-bpmb=N,N'-(1,4-phenylene)bis(1-(pyridin-4-yl)methanimine) were easily prepared by mechanochemical synthesis. Nanostructures of Zinc(II) oxide were obtained by calcination of these compounds and their de-solvated analogue as activated MOFs, at 550°C under air atmosphere. As a result of that, different Nanostructures of Zinc(II) oxide were obtained. The ZnO nanoparticles were characterized by powder X-ray diffraction (XRD), scanning electron microscopy (SEM) and FT-IR spectroscopy. Copyright © 2016 Elsevier B.V. All rights reserved.

  9. Preparation and evaluation of open-tubular capillary columns modified with metal-organic framework incorporated polymeric porous layer for liquid chromatography.

    Zhu, Manman; Zhang, Lingyi; Chu, Zhanying; Wang, Shulei; Chen, Kai; Zhang, Weibing; Liu, Fan

    2018-07-01

    An open tubular capillary liquid phase chromatographic column (1 m × 25 µm i.d.× 375 µm o.d.) was prepared by incorporating metal organic framework particles modified with vancomycin directly into zwitterionic polymer coating synthesized by the copolymerization of [2-(methacryloyloxy)ethyl]dimethyl-(3-sulfopropyl) ammonium hydroxide and N,N'-methylenebisacrylamide. The incorporation of IRMOF-3 (isoreticular metal organic framework-3) particles improved selectivity of zwitterionic polymer coating with absolute column efficiency reaching 79900 plates for p-xylene. Besides strong hydrophilic interaction, the separation of neutral, basic, and acidic compounds demonstrates that π-π stacking interaction and the coordination effect of unsaturated Zn 2+ of MOF also contribute to separation of various analytes. The RSD values (run-to-run, day-to-day, column-to-column, n = 3) of retention time of neutral compounds were less than 0.71%, 0.69% and 3.08% respectively, suggesting good repeatability. In addition, the column was applied to the analysis of the trypsin digest of bovine serum albumin, revealing the potential in separating biological samples. Copyright © 2018 Elsevier B.V. All rights reserved.

  10. Synthesis of encapsulated pigments based on Fe, Co and Si by route of polymeric precursors

    Macedo, D.S.S.M.; Macedo Neto, O.C.; Paskocimas, C.A.; Varela, M.L.N.

    2012-01-01

    The objective is to apply the polymeric precursor method to obtain encapsulated pigments, the basis of oxides of iron and cobalt deposited on silica. The method has advantages such as reduction of time and reproducibility in the conventional methods, and also improves optical properties, thermal stability and morphology. The synthesis was based on the dissolution of the citric acid (complexing agent), addition of oxides of iron and cobalt (ions chromophores) polymerization of ethylene glycol and silica coating. The mixture was pre-calcined to form the precursor powder was analyzed by TG and DTA. Was then split, and calcined at different temperatures (700 ° C - 900 ° C) and analyzed by BET, DRX, MEV and UV-Visible. The pigments were stable thermally, with surface area ranging between 3,09 and 7,65 m² / g, formation of crystalline phases of cobalt ferrite (CoFe 2 O 4 ) and Cristobalite (SiO 2 ) and agglomerates of particles slightly rounded. (author)

  11. Synthesis of polymeric fluorinated sol–gel precursor for fabrication of superhydrophobic coating

    Li, Qianqian; Yan, Yuheng; Yu, Miao; Song, Botao; Shi, Suqing; Gong, Yongkuan

    2016-01-01

    Graphical abstract: - Highlights: • A polymeric fluorinated sol–gel precursor PFT is designed to fabricate superhydrophobic coatings. • The superhydrophobicity could be governed by the concentration of PFT. • Bio-mimicking self-cleaning property similar to lotus leaves could also be achieved. - Abstract: A fluorinated polymeric sol–gel precursor (PFT) is synthesized by copolymerization of 2,3,4,5,5,5-hexafluoro-2,4-bis(trifluorinated methyl)pentyl methacrylate (FMA) and 3-methacryloxypropyltrimethoxysilane (TSMA) to replace the expensive long chain fluorinated alkylsilanes. The fluorinated silica sol is prepared by introducing PFT as co-precursor of tetraethyl orthosilicate (TEOS) in the sol–gel process with ammonium hydroxide as catalyst, which is then used to fabricate superhydrophobic coating on glass substrate through a simple dip-coating method. The effects of PFT concentrations on the chemical structure of the formed fluorinated silica, the surface chemical composition, surface morphology, wetting and self-cleaning properties of the resultant fluorinated silica coatings were studied by using X-ray powder diffraction (XRD), Fourier transform infrared spectrometer (FTIR), X-ray photoelectron spectrophotometer (XPS), scanning electron microscopy (SEM) and water contact angle measurements (WCA). The results show that the fluorinated silica sols are successfully obtained. The size and size distribution of the fluorinated silica particles are found greatly dependent on the concentration of PFT, which play a crucial role in the surface morphology of the corresponding fluorinated silica coatings. The suitable PFT concentration added in the sol–gel stage, i.e. for F-sol-1 and F-sol-2, is helpful to achieve both the low surface energy and multi-scaled microstructures, leading to the formation of the superhydrophobic coatings with bio-mimicking self-cleaning property similar to lotus leaves.

  12. Er:YAB nanoparticles and vitreous thin films by the polymeric precursor method

    Maia, Lauro J. Q., E-mail: lauro@if.sc.usp.b [Universidade de Sao Paulo, Grupo Crescimento de Cristais e Materiais Ceramicos, Departamento de Fisica e Ciencia dos Materiais, Instituto de Fisica de Sao Carlos (Brazil); Ibanez, Alain; Ortega, Luc [Laboratoire de Cristallographie CNRS associe a l' Universite Joseph Fourier et a l' INPG (France); Mastelaro, Valmor R.; Hernandes, Antonio C. [Universidade de Sao Paulo, Grupo Crescimento de Cristais e Materiais Ceramicos, Departamento de Fisica e Ciencia dos Materiais, Instituto de Fisica de Sao Carlos (Brazil)

    2008-12-15

    The synthesis of Y{sub 0.9}Er{sub 0.1}Al{sub 3}(BO{sub 3}){sub 4} crystalline powders and vitreous thin films were studied. Precursor solutions were obtained using a modified polymeric precursor method using d-sorbitol as complexant agent. The chemical reactions were described. Y{sub 0.9}Er{sub 0.1}Al{sub 3}(BO{sub 3}){sub 4} composition presents good thermal stability with regard to crystallization. The Y{sub 0.9}Er{sub 0.1}Al{sub 3}(BO{sub 3}){sub 4} crystallized phase can be obtained at 1,150 {sup o}C, in agreement with other authors. Crack- and porosity-free films were obtained with very small grain size and low RMS roughness. The films thickness revealed to be linearly dependent on precursor solution viscosity, being the value of 25 mPa s useful to prepare high-quality amorphous multi-layers (up to {approx} 800 nm) at 740 {sup o}C during 2 h onto silica substrates by spin coating with a gyrset technology.

  13. Synthesis and characterization of Al2O3 obtained from the polymeric precursor method using glycerin as a poly alcohol

    Elicker, C.; Gaier, M.; Almeida, S.R.; Vieiraaa, B.M.; Ratmann, C.W.R.; Pereira, C.M.P. de; Cava, S.S.; Egea, J.J.

    2014-01-01

    In this study, calcium aluminate was synthesized using glycerin to replace ethylene glycol in the polymeric precursor method. The resulting resin was pre-calcined in a muffle at 300 °C for 2 h and the resulting material was calcined at 900 °C for 2 h. The powders were analyzed by XRD, SEM and EDX, TEM, Micro-Raman and IR. The results demonstrated the possibility of using glycerin as an alternative to ethylene glycol in the polymeric precursor method. (author)

  14. High-pressure synthesis of CuBa2Ca3Cu4O10+δ superconductor from precursors prepared by a polymerized complex method

    Aoba, Tomoya; Bizen, Takeshi; Suzuki, Tsuneo; Nakayama, Tadachika; Suematsu, Hisayuki; Niihara, Koichi; Katsumata, Tetsuhiro; Inaguma, Yoshiyuki

    2011-01-01

    Samples of a CuBa 2 Ca 3 Cu 4 O 10+ δ superconductor were synthesized under a high pressure of 5 GPa at 1100-1200degC for 30 min using precursors produced by solid-state reaction and polymerized complex methods. Compared with the precursors prepared by the solid-state reaction method, the precursors produced by the polymerized complex method have low grain sizes. The superconductive transition temperature of the samples prepared using precursors made by the polymerized complex method was found to be 113 K. The volume fractions of the superconducting phase in the samples prepared using precursors made by the solid-state reaction and polymerized complex methods were 49 and 36%, respectively. From these results, precursors made by the polymerized complex method can be used in the high-pressure synthesis of superconductors similarly to those made by the solid-state reaction method. (author)

  15. The effect of Nb doping on ferroelectric properties of PZT thin films prepared from polymeric precursors

    Souza, E.C.F.; Simoes, A.Z.; Cilense, M.; Longo, E.; Varela, J.A.

    2004-01-01

    Pure and Nb doped PbZr 0.4 Ti 0.6 O 3 thin films was prepared by the polymeric precursor method and deposited by spin coating on Pt/Ti/SiO 2 /Si (100) substrates and annealed at 700 deg. C. The films are oriented in (1 1 0) and (1 0 0) direction. The electric properties of PZT thin films show strong dependence of the crystallographic orientation. The P-E hysteresis loops for the thin film with composition PbZr 0.39 Ti 0.6 Nb 0.1 O 3 showed good saturation, with values for coercive field (E c ) equal to 60 KV cm -1 and for remanent polarization (P r ) equal to 20 μC cm -2 . The measured dielectric constant (ε) is 1084 for this film. These results show good potential for application in FERAM

  16. 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:

  17. Nanocystalline ZnO films prepared via polymeric precursor method (Pechini)

    Sanchez, C.; Doria, J.; Paucar, C.; Hernandez, M. [Laboratorio de Materiales Ceramicos y Vitreos, Universidad Nacional de Colombia, Sede Medellin, A.A. 568, Medellin (Colombia); Mosquera, A.; Rodriguez, J.E. [Grupo CYTEMAC, Universidad del Cauca, Calle 5 No 4-70, Popayan (Colombia); Gomez, A. [Departamento de Ingenieria de Materiales, Universidad Nacional de Colombia, sede Medellin, A.A. 568, Medellin (Colombia); Baca, E. [Grupo de Ingenieria de Nuevos Materiales, Universidad del Valle, A.A. 25360 Cali (Colombia); Moran, O., E-mail: omoranc@unal.edu.c [Laboratorio de Materiales Ceramicos y Vitreos, Universidad Nacional de Colombia, Sede Medellin, A.A. 568, Medellin (Colombia)

    2010-09-01

    The polymeric precursor method (Pechini) was employed to prepare high-quality nanocrystalline zinc oxide (ZnO) films. Briefly, the process started off with the preparation of a coating solution by the Pechini process followed by a coating of the glass substrates by a dip-coating technique and subsequent heat-treatment of the as-deposited films up to 550 {sup o}C for 30 min. The Rietveld profile analysis of the X-ray diffraction (XRD) spectra revealed the wuerzite structure as expected for ZnO with a P6{sub 3}mc symmetry. No additional peaks were observed that would correspond to any secondary crystalline phase. The average crystallites size was 20 nm as calculated by Sherrer's equation. UV-vis spectroscopy showed sharp ultraviolet absorption edges at {approx}380 nm. The absorption edge analysis yielded optical band gap energy of 3.24 eV with electronic transition of the direct transition type. The Fourier transform infrared (FTIR) analysis showed asymmetric and symmetric stretching modes of the carboxyl group (C=O). Scanning electron microscope (SEM) analysis revealed a crack-free surface morphology indicating that coating of the amorphous glass substrates was homogeneous on large surface areas. The temperature dependent conductivity featured a typical semiconducting-like behavior with resistivity approaching 3x10{sup -1} {Omega} cm at 220 K.

  18. Nanogravimetric studies of tungsten oxide thin films obtained by the polymeric precursor method

    Fernandes, V.C.; Santos, M.C.; Bulhoes, L.O.S.

    2007-01-01

    In this work, the intercalation/de-intercalation process of Li + ions in the tungsten oxide matrix was investigated. The reaction mechanism involved was also investigated. The WO 3 films, prepared by the polymeric precursor method, were deposited on a Pt covered quartz crystal using the dip-coating technique. The electrolyte was 0.1 mol L -1 LiClO 4 in acetonitrile. The morphology and structure of the deposit was accomplished by scanning electron microscopy and X-ray diffraction, respectively. In the electrochemical quartz crystal nanobalance results, it was observed that the mass transport as well as the kinetic processes involved are facilitated in the films cycled at lower potential sweep-rates. The mass variation data as a function of the charge variations in the anodic and cathodic regions indicate the participation of solvent molecules (acetonitrile) during the Li + ion intercalation/de-intercalation process. This was confirmed by the development of a model of the species flux as a function of the potential

  19. Low-temperature synthesis, structural and magnetic properties of self-dopant LaMnO{sub 3+δ} nanoparticles from a metal-organic polymeric precursor

    Ahmad, Tokeer, E-mail: tahmad3@jmi.ac.in [Nanochemistry Laboratory, Department of Chemistry, Jamia Millia Islamia, New Delhi 110025 (India); Lone, Irfan H.; Ubaidullah, Mohd. [Nanochemistry Laboratory, Department of Chemistry, Jamia Millia Islamia, New Delhi 110025 (India); Coolhan, Kelsey [Department of Physics and Astronomy, Rowan University, 201 Mullica Hill Road, Glassboro, NJ 08028 (United States)

    2013-11-15

    Graphical abstract: Monophasic and highly crystalline Self-dopant LaMnO{sub 3+δ} nanoparticles (72 nm) have been successfully synthesized at low temperature (773 K) by metal citrate complex method based on Pechini-type reaction route which showed ferromagnetic interaction. Surface areas of LaMnO{sub 3+δ} nanoparticles were found to be 157.4 and 153 m{sup 2} g{sup −1} for the samples annealed at 773 K and 1173 K, respectively. - Highlights: • Self-dopant LaMnO{sub 3+δ} nanoparticles using Pechini-type reaction route at 773 K. • Size range varies from 72 to 80 nm. • Surface area varies from 153 to 157 m{sup 2} g{sup −1}. • Extensive characterization using sophisticated techniques. - Abstract: Self-dopant LaMnO{sub 3+δ} nanoparticles have been successfully synthesized by metal citrate complex method based on Pechini-type reaction route, at low temperature (773 K). Powder X-ray diffraction and transmission electron microscope revealed pure and nanostructured phase of LaMnO{sub 3+δ} (δ = 0.125) with an average grain size of ∼72 nm (773 K) and ∼80 nm (1173 K). DC-magnetization measurements under an applied magnetic field of H = ±60 kOe showed an increase in the magnetization with the increase of calcination temperature. Ferromagnetic nature shown by non-stoichiometric LaMnO{sub 3+δ} was verified by well-defined hysteresis loop with large remanent magnetization (M{sub r}) and coercive field (H{sub c}). Surface areas of LaMnO{sub 3+δ} nanoparticles were found to be 157.4 and 153 m{sup 2} g{sup −1} for the samples annealed at 773 K and 1173 K, respectively.

  20. Study of hafnium (IV) oxide nanoparticles synthesized by polymerized complex and polymer precursor derived sol-gel methods

    Ramos-Gonzá lez, R.; Garcí a-Cerda, L. A.; Alshareef, Husam N.; Gnade, Bruce E.; Quevedo-Ló pez, Manuel Angel Quevedo

    2010-01-01

    This work reports the preparation and characterization of hafnium (IV) oxide (HfO2) nanoparticles grown by derived sol-gel routes that involves the formation of an organic polymeric network. A comparison between polymerized complex (PC) and polymer precursor (PP) methods is presented. For the PC method, citric acid (CA) and ethylene glycol (EG) are used as the chelating and polymerizable reagents, respectively. In the case of PP method, poly(acrylic acid) (PAA) is used as the chelating reagent. In both cases, different precursor gels were prepared and the hafnium (IV) chloride (HfCl4) molar ratio was varied from 0.1 to 1.0 for the PC method and from 0.05 to 0.5 for the PP method. In order to obtain the nanoparticles, the precursors were heat treated at 500 and 800 °C. The thermal characterization of the precursor gels was carried out by thermogravimetric analysis (TGA) and the structural and morphological characterization by X-ray diffraction (XRD) and transmission electron microscopy (TEM). The XRD patterns of the samples obtained by both methods shows the formation of HfO2 at 500 °C with monoclinic crystalline phase. The PC method exhibited also the cubic phase. Finally, the HfO2 nanoparticles size (4 to 11 nm) was determined by TEM and XRD patterns. © (2010) Trans Tech Publications.

  1. Study of hafnium (IV) oxide nanoparticles synthesized by polymerized complex and polymer precursor derived sol-gel methods

    Ramos-González, R.

    2010-03-01

    This work reports the preparation and characterization of hafnium (IV) oxide (HfO2) nanoparticles grown by derived sol-gel routes that involves the formation of an organic polymeric network. A comparison between polymerized complex (PC) and polymer precursor (PP) methods is presented. For the PC method, citric acid (CA) and ethylene glycol (EG) are used as the chelating and polymerizable reagents, respectively. In the case of PP method, poly(acrylic acid) (PAA) is used as the chelating reagent. In both cases, different precursor gels were prepared and the hafnium (IV) chloride (HfCl4) molar ratio was varied from 0.1 to 1.0 for the PC method and from 0.05 to 0.5 for the PP method. In order to obtain the nanoparticles, the precursors were heat treated at 500 and 800 °C. The thermal characterization of the precursor gels was carried out by thermogravimetric analysis (TGA) and the structural and morphological characterization by X-ray diffraction (XRD) and transmission electron microscopy (TEM). The XRD patterns of the samples obtained by both methods shows the formation of HfO2 at 500 °C with monoclinic crystalline phase. The PC method exhibited also the cubic phase. Finally, the HfO2 nanoparticles size (4 to 11 nm) was determined by TEM and XRD patterns. © (2010) Trans Tech Publications.

  2. UV and VUV characteristics of (YGd)2O3:Eu phosphor particles prepared by spray pyrolysis from polymeric precursors

    Kim, E.J.; Kang, Y.C.; Park, H.D.; Ryu, S.K.

    2003-01-01

    Red-emitting (YGd) 2 O 3 :Eu phosphor particles, with high luminescence efficiency under vacuum ultraviolet (VUV) and ultraviolet (UV) excitation, were prepared by a large-scale spray pyrolysis process. To control the morphology of phosphor particles under severe preparation conditions, spray solution with polymeric precursors were introduced in spray pyrolysis. The prepared (YGd) 2 O 3 :Eu phosphor particles had spherical shape and filled morphology even after post-treatment irrespective of Gd/Y ratio. In the case of solution with polymeric precursors, long polymeric chains formed by esterification reaction in a hot tubular reactor; the droplets turned into viscous gel, which retarded the precipitation of nitrate salts and promoted the volume precipitation of droplets. The brightness of (YGd) 2 O 3 :Eu phosphor particles increased with increasing gadolinium content, and the Gd 2 O 3 :Eu phosphor had the highest luminescence intensity under UV and VUV excitation. The maximum peak intensity of Gd 2 O 3 :Eu phosphor particles under UV and VUV were 118 and 110% of the commercial Y 2 O 3 :Eu phosphor particles, respectively

  3. 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).

  4. 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).

  5. 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.

  6. 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.

  7. Ferrimagnetism and spin excitation in a Ni–Mn partially inverted spinel prepared using a modified polymeric precursor method

    Ferreira, Rafael A. [Programa de Pos-Graduação em Ciência e Tecnologia de Materiais (POSMAT), Universidade Estadual Paulista, Faculdade de Ciências, Caixa Postal 473, 17033-360 Bauru, São Paulo (Brazil); Institut des Sciences Chimiques de Rennes – UMR 6226, Université de Rennes 1, F-35042 Rennes (France); Tedesco, Julio C.G.; Birk, Jonas O. [The Niels Bohr Institute, University of Copenhagen, DK-2100 Copenhagen (Denmark); Kalceff, Walter, E-mail: wkalceff@uts.edu.au [School of Physics and Advanced Materials, University of Technology Sydney (UTS), P.O. Box 123, Broadway, NSW 2007 (Australia); Yokaichiya, Fabiano [Laboratório Nacional de Luz Síncrotron (LNLS), Caixa Postal 6192, CEP 13083-970 Campinas, São Paulo (Brazil); Comissao Nacional de Energia Nuclear (CNEN), Instituto de Pesquisas Energeticas e Nucleares (IPEN), Reactor Multiproposito Brasileiro - RMB, Avenida Lineo Prestes 2242, Bloco A, Cidade Universitaria Armando Salles de Oliveira, Sao Paulo (Brazil); Rasmussen, Nina [The Niels Bohr Institute, University of Copenhagen, DK-2100 Copenhagen (Denmark); Peña, Octavio [Institut des Sciences Chimiques de Rennes – UMR 6226, Université de Rennes 1, F-35042 Rennes (France); Henry, Paul F. [European Spallation Source ESS AB, Box 176, 22100 Lund (Sweden); Simeoni, Giovanna G. [Heinz Maier-Leibnitz Zentrum (MLZ) and Physics Department, Technische Universität München, Lichtenbergstr. 1, 85748 Garching (Germany); Bordallo, Heloisa N. [The Niels Bohr Institute, University of Copenhagen, DK-2100 Copenhagen (Denmark); European Spallation Source ESS AB, Box 176, 22100 Lund (Sweden); and others

    2014-07-01

    We demonstrate that a Ni–Mn oxide partially inverted spinel (Ni{sub 1−ν}Mn{sub ν})[Ni{sub ν}Mn{sub 2−ν}]O{sub 4} having inversion degree ν ≈ 0.8 and produced by a modified polymeric precursor method exhibits behaviour previously reported only in monophased samples. The structure of the specimen was determined using Rietveld analysis of X-ray and neutron powder diffraction data, showing that at room temperature the material crystallizes in the Fd3{sup ¯}m space group with a lattice constant a = 8.392 Å. Combining magnetization measurements with neutron powder diffraction, we show that the magnetic structure of this spinel is associated with the interplay between the ferromagnetic and antiferromagnetic lattices which coexist due to the cations' presence on both tetrahedral and octahedral sites. Our analysis of the neutron diffraction data confirms the postulated magnetic structure involving a star-like moment arrangement, arising from competition for the B (octahedral) spinel sites by the Ni and Mn cations. Finally, we show that strong magnetic fluctuations are observed in the inelastic neutron scattering data. - Highlights: • Ni–Mn oxide partially-inverted spinel made by modified polymeric precursor method. • Magnetic measurements showed a ferrimagnetic and a parasitic magnetic transition. • NPD revealed a magnetic structure consistent with a star-like moment arrangement. • INS measurements indicated four distinct temperature-dependent magnetic regimes.

  8. Structural and morphological characterization of TiO2-ZrO2 powders obtained by the polymeric precursors method

    Ribeiro, M.A.; Gama, L.; Bispo, A.; Neiva, L.S.; Bernardi, M.I.B.; Kiminami, R.H.G.A.

    2010-01-01

    This work aims to characterize the structure and morphology of TiO 2 -ZrO 2 powders obtained by polymeric precursor method. For this we studied the following compositions: 0.25, 0.5 and 0.75 moles of Zr and calcined at 800 deg C for one hour. The powders obtained were characterized by XRD, SEM and nitrogen adsorption (BET). The analysis of X-ray diffraction showed that the powders had a phase of TiO 2 in the anatase form and a tetragonal phase of ZrO 2 . The crystallite size was between 8, 13 and 11 nm respectively. The analysis of scanning electron microscopy showed the growth of ZrO 2 nanoparticles and that these comprise spherical agglomerates of less than 100 nm. Particle size determined by the BET ranging 28.1-29.5 nm, showing thereby the character of nanosized powders. (author)

  9. Effect of the calcining temperature on the porosity of the titanium dioxide powders obtained by Polymeric Precursor Method

    Silva, D.W.; Granado, S.R.; Ciola, R.A.; Cavalheiro, A.A.

    2011-01-01

    Ceramics materials obtained by Polymeric Precursor Method exhibit mechanisms of the pore formation and elimination dependents on the decomposition kinetics of the residual organic matter of the polyester. The mechanism of pore elimination seems to occur by disrupting of the wall among the pores because it leads to the consequent pore coalescence and increasing in pore volume, which posses higher pore diameters. In this case, it was observed that the porosity decreasing occurs by pore wall moving after that the residual organic matter is eliminated from the pore inside. The pore diameter associated to the highest volume desorption occurred for the material obtained after calcining at 450°C is approximately 1,7 nm, what seems to be related to the amorphous carbon accumulated inside the pores, once that the pore volume decreases more effectively for the material obtained by calcining at 550°C, making the maximum volume situates at 2,0 nm. (author)

  10. Polymeric precursors method for obtaining pigments based on Inorganic oxides of chromium and iron deposited on TiO2

    Silva, Everlania M. da; Galvao, Sheila B.; Paskocimas, C.A.

    2011-01-01

    The case study was the use of chromium oxides and iron, as a precursor in the synthesis of inorganic pigments. The synthesis was based on the dissolution of citric acid as a complexing agent, addition of metal oxides, such as ion chromophores; polymerization with ethylene glycol and doping with titanium oxide. Going through pre-calcination, breakdown, calcination at different temperatures (700, 900 and 1100 deg C resulting in pigments: green for pigment and chromium deposited on TiO2, orange for iron on TiO2. The thermal analysis (TG and DTA), evaluated their thermal decompositions, the XRD revealed the formation of crystalline phases such as iron titanate and chrome titanate; SEM showed the formation of hexagonal particles for both oxides. Under the different analysis, one can see the potential stability of pigments and powders, can be proposed its use as pigments in polymers. (author)

  11. 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.

  12. The role of hydroperoxides as a precursor in the radiation-induced graft polymerization of methyl methacrylate to ultra-high molecular weight polyethylene

    Enomoto, Ichiro, E-mail: enomoto.ichiro@iri-tokyo.j [Tokyo Metropolitan Industrial Technology Research Institute, KFC bldg., 12F, 1-6-1, Yokoami, Sumida-ku, Tokyo 130-0015 (Japan); School of Engineering, The University of Tokyo, 7-3-1, Hongo, Bunkyo-ku, Tokyo 113-8656 (Japan); Katsumura, Yosuke [School of Engineering, The University of Tokyo, 7-3-1, Hongo, Bunkyo-ku, Tokyo 113-8656 (Japan); Advanced Science Research Center, Japan Atomic Energy Agency, 2-4 Shirakata Shirane, Tokai-mura, Ibaraki 319-1195 (Japan); Kudo, Hisaaki [School of Engineering, The University of Tokyo, 7-3-1, Hongo, Bunkyo-ku, Tokyo 113-8656 (Japan); Sekiguchi, Masayuki [Tokyo Metropolitan Industrial Technology Research Institute, KFC bldg., 12F, 1-6-1, Yokoami, Sumida-ku, Tokyo 130-0015 (Japan)

    2010-06-15

    A graft polymerization of methyl methacrylate (MMA) to ultra-high molecular weight polyethylene (UHMWPE) with Co-60 gamma-ray irradiation in air at room temperature has been carried out. The grafting yields were measured as a function of the storage time (elapsed time from the end of irradiation to the start of grafting), and it was found that the yields reach at the maximum values at around several days since the end of irradiation. In order to clarify the precursor of the graft polymerization, changes of the radical yields and the carbonyl groups were measured as a function of storage time with ESR and microscopic FT-IR, respectively. From the similarities between the depth profiles of the hydroperoxide formation and the grafting products, it was concluded that the hydroperoxides can be main precursors of the grafting of the radiation-induced polymerization of MMA to UHMWPE under the given conditions.

  13. The role of hydroperoxides as a precursor in the radiation-induced graft polymerization of methyl methacrylate to ultra-high molecular weight polyethylene

    Enomoto, Ichiro; Katsumura, Yosuke; Kudo, Hisaaki; Sekiguchi, Masayuki

    2010-01-01

    A graft polymerization of methyl methacrylate (MMA) to ultra-high molecular weight polyethylene (UHMWPE) with Co-60 γ-ray irradiation in air at room temperature has been carried out. The grafting yields were measured as a function of the storage time (elapsed time from the end of irradiation to the start of grafting), and it was found that the yields reach at the maximum values at around several days since the end of irradiation. In order to clarify the precursor of the graft polymerization, changes of the radical yields and the carbonyl groups were measured as a function of storage time with ESR and microscopic FT-IR, respectively. From the similarities between the depth profiles of the hydroperoxide formation and the grafting products, it was concluded that the hydroperoxides can be main precursors of the grafting of the radiation-induced polymerization of MMA to UHMWPE under the given conditions.

  14. Redox polymerization of acrylonitrile-methyl acrylate-fumaronitrile terpolymer as precursor for carbon fiber

    Jamil, S.N.A.M.; Rusli Daik; Ahmad, I.

    2010-01-01

    Synthesis of acrylonitrile (AN) with methyl acrylate and fumaronitrile as comonomer and termonomer respectively, were carried out by redox polymerization using sodium bisulfite (SBS) and potassium persulphate (KPS) as initiator at 40 degree Celsius. The effect of methyl acrylate (MA) and fumaronitrile (FN) on the glass transition temperature (T g ) and stabilization temperature has been studied by Differential Scanning Calorimetry (DSC). The degradation behavior and char yield were obtained by Thermogravimetric Analysis. The T g of poly (AN/ MA) copolymers were found to be lower (∼70 degree Celsius) as compared with polyacrylonitrile (PAN) (210 degree Celsius). However, by incorporating MA into PAN system, the char yield reduced significantly. It was found that FN reduced the initial cyclization temperature of poly (AN/ MA/ FN) terpolymer to ∼230 degree Celsius as compared with poly(AN/ MA) copolymer (∼260 degree Celsius). In addition, FN reduced the heat liberation per unit time during the stabilization process that consequently reduced the emission of volatile group during this process. Thereby, the char yield of poly(AN/ MA/ FN) 90/ 4/ 6 terpolymer is higher at 51 % as compared with poly(AN/ MA) 90/ 10 copolymer (45 %). (author)

  15. Surface modification of blood-contacting biomaterials by plasma-polymerized superhydrophobic films using hexamethyldisiloxane and tetrafluoromethane as precursors

    Hsiao, Chaio-Ru [Department of Materials Science and Engineering, Feng Chia University, No. 100, Wenhwa Rd., Seatwen District, Taichung City 40724, Taiwan (China); Lin, Cheng-Wei [Department of Dental Technology and Materials Science, Central Taiwan University of Science and Technology, No. 666, Buzih Rd., Beitun District, Taichung City 40601, Taiwan (China); Chou, Chia-Man, E-mail: cmchou@vghtc.gov.tw [Department of Surgery, Taichung Veterans General Hospital, No. 1650, Sec. 4, Taiwan Boulevard, Seatwen District, Taichung City 40705, Taiwan (China); Department of Medicine, National Yang-Ming University, No. 155, Sec. 2, Linong Street, Beitou District, Taipei City 11221, Taiwan (China); Chung, Chi-Jen, E-mail: cjchung@seed.net.tw [Department of Dental Technology and Materials Science, Central Taiwan University of Science and Technology, No. 666, Buzih Rd., Beitun District, Taichung City 40601, Taiwan (China); He, Ju-Liang [Department of Materials Science and Engineering, Feng Chia University, No. 100, Wenhwa Rd., Seatwen District, Taichung City 40724, Taiwan (China)

    2015-08-15

    Highlights: • Biomaterials modified by nanoparticle-containing plasma polymerized films. • A superhydrophoic film was obtained, and the properties of the coating were examined. • In vitro blood compatibility tests revealed neither platelet adhesion nor fibrinogen adsorption. • Surface modification technology of medical devices: non-cytotoxic and no blood clot formation. - Abstract: This paper proposes a plasma polymerization system that can be used to modify the surface of the widely used biomaterial, polyurethane (PU), by employing low-cost hexamethyldisiloxane (HMDSO) and tetrafluoromethane (CF{sub 4}) as precursors; this system features a pulsed-dc power supply. Plasma-polymerized HMDSO/CF{sub 4} (pp-HC) with coexisting micro- and nanoscale morphology was obtained as a superhydrophobic coating material by controlling the HMDSO/CF{sub 4} (f{sub H}) monomer flow ratio. The developed surface modification technology can be applied to medical devices, because it is non-cytotoxic and has favorable hemocompatibility, and no blood clots form when the device surface direct contacts. Experimental results reveal that the obtained pp-HC films contained SiO{sub x} nanoparticles randomly dispersed on the micron-scale three-dimensional network film surface. The −CF functional group, −CF{sub 2} bonding, and SiO{sub x} were detected on the film surface. The maximal water contact angle of the pp-HC coating was 161.2°, apparently attributable to the synergistic effect of the coexisting micro- and nanoscale surface morphology featuring a low surface-energy layer. The superhydrophobic and antifouling characteristics of the coating were retained even after it was rubbed 20 times with a steel wool tester. Results of in vitro cytotoxicity, fibrinogen adsorption, and platelet adhesion tests revealed favorable myoblast cell proliferation and the virtual absence of fibrinogen adsorption and platelet adhesion on the pp-HC coated specimens. These quantitative findings imply

  16. Development of plurimetallic electrocatalysts prepared by decomposition of polymeric precursors for EtOH/O{sub 2} fuel cell

    Palma, Livia M.; Almeida, Thiago S.; Andrade, Adalgisa R. de, E-mail: ardandra@ffclrp.usp.br [Departamento de Quimica, Faculdade de Filosofia, Ciencias e Letras de Ribeirao Preto, Universidade de Sao Paulo, Ribeirao Preto, SP (Brazil)

    2012-03-15

    This work aimed to develop plurimetallic electrocatalysts composed of Pt, Ru, Ni, and Sn supported on C by decomposition of polymeric precursors (DPP), at a constant metal:carbon ratio of 40:60 wt.%, for application in direct ethanol fuel cell (DEFC). The obtained nanoparticles were physico-chemically characterized by X-ray diffraction (XRD) and energy dispersive X-ray spectroscopy (EDX). XRD results revealed a face-centered cubic crystalline Pt with evidence that Ni, Ru, and Sn atoms were incorporated into the Pt structure. Electrochemical characterization of the nanoparticles was accomplished by cyclic voltammetry (CV) and chronoamperometry (CA) in slightly acidic medium (0.05 mol L{sup -1}H{sub 2}SO{sub 4}), in the absence and presence of ethanol. Addition of Sn to PtRuNi/C catalysts significantly shifted the ethanol and CO onset potentials toward lower values, thus increasing the catalytic activity, especially for the quaternary composition Pt{sub 64}Sn{sub 15}Ru{sub 13}Ni{sub 8}/C. Electrolysis of ethanol solutions at 0.4 V vs. RHE allowed determination of acetaldehyde and acetic acid as the main reaction products. The presence of Ru in alloys promoted formation of acetic acid as the main product of ethanol oxidation. The Pt{sub 64}Sn{sub 15}Ru{sub 13}Ni{sub 8}/C catalyst displayed the best performance for DEFC. (author)

  17. Ethanol electrooxidation using Ti/(RuO2)(x) Pt(1-x) electrodes prepared by the polymeric precursor method

    Freitas, R.G.; Marchesi, L.F.Q.P.; Forim, M.R.; Pereira, E.C. [Departamento de Quimica, Universidade Federal de Sao Carlos, Sao Carlos, SP (Brazil); Bulhoes, L.O.S [CENIP, Centro Universitario Central Paulista, Sao Carlos, SP (Brazil); Santos, M.C. [LEMN, Centro de Ciencias Naturais e Humanas, Universidade Federal do ABC, Santo Andre, SP (Brazil); Oliveira, R.T.S., E-mail: robson@icbn.uftm.edu.br [Instituto de Ciencias Biologicas e Naturais, Universidade Federal do Triangulo Mineiro, Uberaba, MG (Brazil)

    2011-09-15

    This work describes a detailed study of the ethanol electrooxidation on Ti/(RuO{sub 2}){sub (x)}Pt{sub (1-x)} electrodes using several compositions prepared by the polymeric precursor method. The results obtained using cyclic voltammetry and chronoamperometry showed that the best composition of Ti/(RuO{sub 2}){sub (x)}Pt{sub (1-x)} electrodes for CO and ethanol oxidation processes is Ti/(RuO{sub 2}){sub 0.50}Pt{sub 0.50}. On this electrode composition the onset of CO and the ethanol oxidation occurred at 380 mV and 220 mV more negative than on Ti/Pt, respectively. Besides, there was an increase of 2.5-fold in the current density for ethanol electrooxidation under constant potential polarization. The Ti/(RuO{sub 2}){sub 0.50}Pt{sub 0.50}. electrodes produced lower amount of acetic acid compared to Ti/Pt and polycrystalline Pt electrodes using in situ HPLC spectrometric analysis. Also, a non common product from ethanol oxidation could be observed on higher RuO{sub 2} loads: ethyl acetate. Finally, the impedance data showed that Ti/(RuO{sub 2}){sub 0.50}Pt{sub 0.50}. electrode composition had the smallest charge transfer resistance for ethanol oxidation among those compositions investigated. (author)

  18. Development of plurimetallic electrocatalysts prepared by decomposition of polymeric precursors for EtOH/O2 fuel cell

    Palma, Livia M.; Almeida, Thiago S.; Andrade, Adalgisa R. de

    2012-01-01

    This work aimed to develop plurimetallic electrocatalysts composed of Pt, Ru, Ni, and Sn supported on C by decomposition of polymeric precursors (DPP), at a constant metal:carbon ratio of 40:60 wt.%, for application in direct ethanol fuel cell (DEFC). The obtained nanoparticles were physico-chemically characterized by X-ray diffraction (XRD) and energy dispersive X-ray spectroscopy (EDX). XRD results revealed a face-centered cubic crystalline Pt with evidence that Ni, Ru, and Sn atoms were incorporated into the Pt structure. Electrochemical characterization of the nanoparticles was accomplished by cyclic voltammetry (CV) and chronoamperometry (CA) in slightly acidic medium (0.05 mol L -1 H 2 SO 4 ), in the absence and presence of ethanol. Addition of Sn to PtRuNi/C catalysts significantly shifted the ethanol and CO onset potentials toward lower values, thus increasing the catalytic activity, especially for the quaternary composition Pt 64 Sn 15 Ru 13 Ni 8 /C. Electrolysis of ethanol solutions at 0.4 V vs. RHE allowed determination of acetaldehyde and acetic acid as the main reaction products. The presence of Ru in alloys promoted formation of acetic acid as the main product of ethanol oxidation. The Pt 64 Sn 15 Ru 13 Ni 8 /C catalyst displayed the best performance for DEFC. (author)

  19. Activity, Performance, and Durability for the Reduction of Oxygen in PEM Fuel Cells, of Fe/N/C Electrocatalysts Obtained from the Pyrolysis of Metal-Organic-Framework and Iron Porphyrin Precursors

    Yang, Lijun; Larouche, Nicholas; Chenitz, Régis; Zhang, Gaixia; Lefèvre, Michel; Dodelet, Jean-Pol

    2015-01-01

    Graphical abstract: TOC After a first decay common to all electrocatalysts, only NC Por-0.8 -1150 Ar + NH3 shows an improvement in durability attributable to a decrease in water flooding its catalytic sites, particularly those located in micropores. - Abstract: Fe/N/C type catalysts have been produced by ballmilling ZIF-8 (a metal-organic-framework) and a chloroiron-tetramethoxyporphyrin (ClFeTMPP). The resulting material was first pyrolyzed in Ar at temperatures ranging from 850 to 1150 °C, then in NH 3 at 950 °C in order to produce two series of catalysts: the Ar and the Ar + NH 3 ones. They were labeled NC Por-x-T Ar or NC Por-x-T Ar + NH 3 , where x is the nominal Fe loading in wt% and T is the temperature of the first pyrolysis in Ar. At 80 °C in H 2 /O 2 fuel cell, the most active and performing catalyst is NC Por-0.8-1050 Ar + NH 3 . All NC Por-0.8-T Ar + NH 3 catalysts with T comprised between 850 and 1050 °C display the same instability behavior. The only catalyst showing an improvement in durability is NC Por-0.8-1150 Ar + NH 3 . It is proposed that the drastic change in durability upon increasing the first pyrolysis temperature, from 1050 to 1150 °C in Ar, is attributable to an important decrease in the heteroatom content (a drop of 32% for both N and O atoms) of the catalyst upon graphitization, reducing the hydrophilic character of its carbonaceous support and decreasing the possibility of water flooding its catalytic sites, particularly the sites located in micropores

  20. Role of hydrogen in Sb film deposition and characterization of Sb and GexSby films deposited by cyclic plasma enhanced chemical vapor deposition using metal-organic precursors

    Kim, Hyung Keun; Jung, Jin Hwan; Choi, Doo Jin

    2012-01-01

    To meet increasing demands for chemical vapor deposition methods for high performance phase-change memory, cyclic plasma enhanced chemical vapor deposition of Sb and Ge x Sb y phase-change films and characterization of their properties were performed. Two cycle sequences were designed to investigate the role of hydrogen gas as a reduction gas during Sb film deposition. Hydrogen gas was not introduced into the reaction chamber during the purge step in cycle sequence A and was introduced during the purge step for cycle sequence B. The role of hydrogen gas was investigated by comparing the results obtained from these two cycle sequences and was concluded to exert an effect by a combination of precursor decomposition, surface maintenance as a hydrogen termination agent, and surface etching. These roles of hydrogen gas are discussed through consideration of changes in deposition rates, the oxygen concentration on the surface of the Sb film, and observations of film surface morphology. Based on these results, Ge x Sb y phase-change films were deposited with an adequate flow rate of hydrogen gas. The Ge and Sb composition of the film was controlled with the designed cycle sequences. A strong oxygen affinity for Ge was observed during the X-ray photoelectron spectroscopy analysis of Sb 3d, Sb 4d, and Ge 3d orbitals. Based on the XPS results, the ratios of Ge to Sb were calculated to be Ge 0.32 Sb 0.68 , Ge 0.38 Sb 0.62 , Ge 0.44 Sb 0.56 , Ge 0.51 Sb 0.49 and Ge 0.67 Sb 0.33 for the G1S7, G1S3, G1S2, G1S1, and G2S1 cycles, respectively. Crystal structures of Sb, Ge, and the GeSb metastable phase were observed with various Ge x Sb y film compositions. Sb crystallinity decreased with respect to Ge crystallinity by increasing the Ge fraction. A current–voltage curve was introduced, and an electro-switching phenomenon was clearly generated at a typical voltage, V th . V th values increased in conjunction with an increased proportion of Ge. The Sb crystallinity decrease and V

  1. 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

  2. Synthesis by the polymeric precursor method and characterization of undoped and Sn, Cr and V-doped ZrTiO4

    Rodrigues de Lucena, Poty; Pessoa-Neto, Osmundo Dantas; Garcia dos Santos, Ieda Maria; Souza, Antonio Gouveia; Longo, Elson; Varela, Jose Arana

    2005-01-01

    In this work, zirconium titanate doped with 0.1, 0.2, and 0.4-bar mole% of tin, chromium and vanadium was synthesized by the polymeric precursors method and characterized by thermal analysis (TG/DTA), X-ray diffraction (XRD), nitrogen adsorption and scanning electronic microscopy (SEM). The powder presented two mass losses attributed to the exit of water and to the pyrolysis of the organic material. The surface area reduction observed from 500-bar o C indicates the beginning of the sintering process. All the dopants led to changes in the lattice parameters and to the decrease of both crystallite size and particle size

  3. 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.

  4. TiO{sub 2} synthesized by the method of polymeric precursor (Pechini): structure of the intermediate resine; TiO{sub 2} sintetizado por el metodo de precursor polimerico (Pechini): estructura de la resina intermedia

    Vargas, M. A.; Granco, Y.; Ochoa, Y.; Ortegon, Y.; Rodriguez Paez, J. E.

    2011-07-01

    In this work, the polymeric precursor method (Pechini method) was used to synthesize titanium dioxide. This process allowed a bigger control on the purity of the oxide and the crystalline phase present in the material. In this case, the principal phase was anatase. The resine obtained in this process was characterized using NMR and IR spectroscopy to determine their structure. With this information we proposed a resine structure model. To finish the process, the resin was thermally treated to obtain TiO{sub 2}. This oxide was characterized using different techniques: ray-X diffraction (RDX) and electron microscopy (TEM and SEM). The results indicated that the TiO{sub 2} anatase phase can be obtained at 450 degree centigrade with a particle size <100nm. (Author) 10 refs.

  5. Effect of the calcining temperature on the porosity of the titanium dioxide powders obtained by Polymeric Precursor Method; Efeito da temperatura de calcinacao na porosidade de pos de dioxido de titanio obtidos pelo Metodo dos Precursores Polimericos

    Silva, D.W.; Granado, S.R.; Ciola, R.A.; Cavalheiro, A.A., E-mail: douglas_levis@hotmail.com [Universidade Estadual de Mato Grosso do Sul (CPTREN/UEMS), Navirai, MS (Brazil). Centro de Pesquisas Tecnologicas em Recursos Naturais

    2011-07-01

    Ceramics materials obtained by Polymeric Precursor Method exhibit mechanisms of the pore formation and elimination dependents on the decomposition kinetics of the residual organic matter of the polyester. The mechanism of pore elimination seems to occur by disrupting of the wall among the pores because it leads to the consequent pore coalescence and increasing in pore volume, which posses higher pore diameters. In this case, it was observed that the porosity decreasing occurs by pore wall moving after that the residual organic matter is eliminated from the pore inside. The pore diameter associated to the highest volume desorption occurred for the material obtained after calcining at 450°C is approximately 1,7 nm, what seems to be related to the amorphous carbon accumulated inside the pores, once that the pore volume decreases more effectively for the material obtained by calcining at 550°C, making the maximum volume situates at 2,0 nm. (author)

  6. 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)

  7. 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

  8. 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

  9. Microstructural study of Ce1-xGdxO2-δ (x = 0.1 and 0.2) nano crystallized powders synthesized by the polymeric precursor method

    Cela, B.; Macedo, D.A.; Souza, G.L.; Paskocimas, C.A.; Martinelli, A.E.; Nascimento, R.M.

    2009-01-01

    Gadolinia-doped ceria powders (Ce 1-x Gd x O 2-δ ) were prepared with substitution of 10 and 20% of the dopant element by the polymeric precursor method. This method makes possible the attainment of homogeny powder in molecular level, ideal to application in Solid Oxide Fuel Cell (SOFC) component. In this work, the particulated materials were calcinated in a range from 500 °C to 900 °C and structurally characterized by X-Ray Diffraction (XRD). The sintering behaviors of the compact samples were determined by dilatometric analyses. The results showed the method efficiency to attain monophasic nanopowder with cubic crystalline structure starting at 700 °C. The crystallite average size and crystalline parameter were determined by the Rietveld refinement method. (author)

  10. Catalytic oxidation of n-hexane promoted by Ce1−xCuxO2 catalysts prepared by one-step polymeric precursor method

    Araújo, Vinícius D.; Lima, Maurício M. de; Cantarero, Andrés; Bernardi, Maria I.B.; Bellido, Jorge D.A.; Assaf, Elisabete M.; Balzer, Rosana; Probst, Luiz F.D.; Fajardo, Humberto V.

    2013-01-01

    Ceria-supported copper catalysts (Ce 1−x Cu x O 2 , with x (mol) = 0, 0.01, 0.03, 0.05 and 0.10) were prepared in one step through the polymeric precursor method. The textural properties of the catalysts were investigated by X-ray diffraction (XRD), Rietveld refinement, N 2 -physisorption (BET surface area), electron paramagnetic resonance (EPR), UV–visible diffuse reflectance and photoluminescence spectroscopies and temperature-programmed reduction (TPR). In a previous study ceria-supported copper catalysts were found to be efficient in the preferential oxidation of CO. In this study, we extended the catalytic application of Ce 1−x Cu x O 2 systems to n-hexane oxidation and it was verified that the catalysts were highly efficient in the proposed reaction. The best performance (up to 95% conversion) was observed for the catalysts with low copper loads (Ce 0.97 Cu 0.03 O 2 and Ce 0.99 Cu 0.01 O 2 , respectively). The physicochemical characterizations revealed that these behaviors could be attributed to the copper species present in the catalysts and the interaction between CuO and CeO 2 , which vary according to the copper content. - Highlights: • Synthesis of CuO/CeO2 catalysts by the one-step polymeric precursor method. • 95% n-hexane conversion on Ce0.97Cu0.03O2 catalyst. • Redox properties play a key role in the catalytic performance

  11. 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.

  12. Synthesis and characterization of Al{sub 2}O{sub 3} obtained from the polymeric precursor method using glycerin as a poly alcohol; Sintese e caracterizacao de Al{sub 2}O{sub 3} obtida por meio do metodo dos precursores polimericos utilizando glicerina como polialcool

    Elicker, C.; Gaier, M.; Almeida, S.R.; Vieiraaa, B.M.; Ratmann, C.W.R.; Pereira, C.M.P. de; Cava, S.S. [Universidade Federal de Pelotas (UFPel), Pelotas, RS (Brazil); Egea, J.J. [Consejo Superior de Investigaciones Cientificas, Madrid (Spain)

    2014-07-01

    In this study, calcium aluminate was synthesized using glycerin to replace ethylene glycol in the polymeric precursor method. The resulting resin was pre-calcined in a muffle at 300 °C for 2 h and the resulting material was calcined at 900 °C for 2 h. The powders were analyzed by XRD, SEM and EDX, TEM, Micro-Raman and IR. The results demonstrated the possibility of using glycerin as an alternative to ethylene glycol in the polymeric precursor method. (author)

  13. 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.

  14. 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.

  15. 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

  16. Synthesis and characterization of SnO2 doped with fluorine by the technique of polymeric precursors

    Pereira, Gilberto J.; Lopes, Rafael Ialago

    2016-01-01

    The present work deals with the synthesis of tin dioxide powders doped with fluorine and chlorine anions to evaluate the influence of these on the physico-chemical properties of SnO2, as well as to verify if the dopant does not make a solid solution with the material and its possible use as sintering additive. The samples were synthesized by Pechini method (polymer precursors) with tin oxalate as a source not contaminated with chlorine of this metal. Specific surface area characterization (BET method) and X-ray diffractometry (XRD) show that doping reduces the particle size of SnO2, being more effective at lower dopant levels. The dilatometry of the doped powders shows a reduction in the beginning and end temperatures of the sintering of the tin dioxide when compared with values in the literature

  17. 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.

  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. Enhanced CO2 Adsorption by Nitrogen-Doped Graphene Oxide Sheets (N-GOs Prepared by Employing Polymeric Precursors

    Abdulaziz Ali Alghamdi

    2018-04-01

    Full Text Available Nitrogen-doped graphene oxide sheets (N-GOs are prepared by employing N-containing polymers such as polypyrrole, polyaniline, and copolymer (polypyrrole-polyaniline doped with acids such as HCl, H2SO4, and C6H5-SO3-K, which are activated using different concentrations of KOH and carbonized at 650 °C; characterized using SEM, TEM, BET, TGA-DSC, XRD, and XPS; and employed for the removal of environmental pollutant CO2. The porosity of the N-GOs obtained were found to be in the range 1–3.5 nm when the KOH employed was in the ratio of 1:4, and the XRD confirmed the formation of the layered like structure. However, when the KOH employed was in the ratio of 1:2, the pore diameter was found to be in the range of 50–200 nm. The SEM and TEM analysis reveal the porosity and sheet-like structure of the products obtained. The nitrogen-doped graphene oxide sheets (N-GOs prepared by employing polypyrrole doped with C6H5-SO3-K were found to possess a high surface area of 2870 m2/g. The N-GOs displayed excellent CO2 capture property with the N-GOs; PPy/Ar-1 displayed ~1.36 mmol/g. The precursor employed, the dopant used, and the activation process were found to affect the adsorption property of the N-GOs obtained. The preparation procedure is simple and favourable for the synthesis of N-GOs for their application as adsorbents in greenhouse gas removal and capture.

  20. Synthesis of ZrO2-8%CeO2 and ZrO2-8%Y2O3 by polymeric precursors route

    Macedo, D.A.; Macedo, M.C.; Melo, D.M.A.; Nascimento, R.M.; Rabelo, A.A.

    2006-01-01

    The stabilization of zirconia in the cubical and tetragonal structures comes gaining importance because of its excellent thermal stability, chemical resistance, mechanical properties and oxygen conductivity. Its main applications include electrolytes of high temperature fuel cells, sensors of oxygen and electrochemical reactors. In this work the polymeric precursors route was used to synthesize ZrO 2 -8 mol% Y 2 O 3 and ZrO 2 -8 mol%CeO 2 . In this process the dopant concentration, besides making possible the stabilization of distinct structures, influences in the morphologic characteristics of the powders synthesized. The characterization of the powders was carried through X-ray diffraction for existing phases verification and average crystallite size, thermogravimetric analysis, specific surface area measures, particles size distribution by laser scattering and the powder morphology was observed using scanning electronic microscopy. The powder only calcined at 700 deg C had presented of average crystallite size of 6,77 nm for ZrO 2 -8%Y 2 O 3 and 7,14 nm for ZrO 2 -CeO 2 . (author)

  1. Structural, morphological and thermal properties of La1-xSrxMnO3 (x = 0.15 and 0.22) prepared by the polymeric precursor method

    Macedo, D.A; Cela, B.; Carvalho, W.M.; Martinelli, A.E.; Nascimento, R.M.; Paskocimas, C.A.

    2009-01-01

    Strontium-doped lanthanum manganite (La1 -x Sr x MnO 3 or LSM) is traditionally the most used material for cathodes in high temperature solid oxide fuel cell (800 deg C). This material shows excellent electrocatalytic activity for oxygen reduction and is chemical and thermal stable with the yttria-stabilized zirconia electrolyte (YSZ). In this work La 0.85 Sr 0.15 MnO 3 (LSM 15) and La 0.78 Sr 0.22 MnO 3 (LSM 22) were prepared by the polymeric precursor method, calcinated at 700 deg C for 2 h and characterized by X-ray diffraction, particle size analysis, scanning electronic microscopy and compacts' dilatometry. The synthesis method used provided the attainment of nanopowders with perovskite structure and particles sizes below 100 nm. The thermal expansion coefficients of LSM 15 and LSM 22 were found to be 12.2 x 10 -6 deg C -1 and 11.7 x 10 -6 deg C -1 respectively, which are very close to that of the YSZ. (author)

  2. Synthesis and characterization of scandia ceria stabilized zirconia powders prepared by polymeric precursor method for integration into anode-supported solid oxide fuel cells

    Tu, Hengyong; Liu, Xin; Yu, Qingchun

    2011-03-01

    Scandia ceria stabilized zirconia (10Sc1CeSZ) powders are synthesized by polymeric precursor method for use as the electrolyte of anode-supported solid oxide fuel cell (SOFC). The synthesized powders are characterized in terms of crystalline structure, particle shape and size distribution by X-ray diffraction (XRD), transmission electron microscopy (TEM) and photon correlation spectroscopy (PCS). 10Sc1CeSZ electrolyte films are deposited on green anode substrate by screen-printing method. Effects of 10Sc1CeSZ powder characteristics on sintered films are investigated regarding the integration process for application as the electrolytes in anode-supported SOFCs. It is found that the 10Sc1CeSZ films made from nano-sized powders with average size of 655 nm are very porous with many open pores. In comparison, the 10Sc1CeSZ films made from micron-sized powders with average size of 2.5 μm, which are obtained by calcination of nano-sized powders at higher temperatures, are much denser with a few closed pinholes. The cell performances are 911 mW cm-2 at the current density of 1.25 A cm-2 and 800 °C by application of Ce0.8Gd0.2O2 (CGO) barrier layer and La0.6Sr0.4CoO3 (LSC) cathode.

  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. Methanol oxidation reaction on Ti/RuO{sub 2(x)}Pt{sub (1-x)} electrodes prepared by the polymeric precursor method

    Freitas, R.G.; Marchesi, L.F.; Mattos-Costa, F.I.; Pereira, E.C. [Laboratorio Interdisciplinar de Eletroquimica e Ceramica, Centro Multidisciplinar para o Desenvolvimento de Materiais Ceramicos, Departamento de Quimica, Universidade Federal de Sao Carlos, Caixa Postal 676, 13560-905 Sao Carlos, SP (Brazil); Oliveira, R.T.S. [Laboratorio Interdisciplinar de Eletroquimica e Ceramica, Centro Multidisciplinar para o Desenvolvimento de Materiais Ceramicos, Departamento de Quimica, Universidade Federal de Sao Carlos, Caixa Postal 676, 13560-905 Sao Carlos, SP (Brazil); Grupo de Materiais Eletroquimicos e Metodos Eletroanaliticos, Instituto de Quimica de Sao Carlos, Universidade de Sao Paulo, Caixa Postal 780, 13566-590 Sao Carlos, SP (Brazil); LEMN, Laboratorio de Eletroquimica e Materiais Nanoestruturados, CCNH-Centro de Ciencias Naturais e Humanas, UFABC-Universidade Federal do ABC, CEP 09.210-170, Rua Santa Adelia 166, Bairro Bangu, Santo Andre, SP (Brazil); Bulhoes, L.O.S. [Laboratorio Interdisciplinar de Eletroquimica e Ceramica, Centro Multidisciplinar para o Desenvolvimento de Materiais Ceramicos, Departamento de Quimica, Universidade Federal de Sao Carlos, Caixa Postal 676, 13560-905 Sao Carlos, SP (Brazil); CENIP, Centro Universitario Central Paulista, UNICEP, Rua Miguel Petroni, 5111, CEP 13563-470, Sao Carlos, SP (Brazil); Santos, M.C. [Laboratorio Interdisciplinar de Eletroquimica e Ceramica, Centro Multidisciplinar para o Desenvolvimento de Materiais Ceramicos, Departamento de Quimica, Universidade Federal de Sao Carlos, Caixa Postal 676, 13560-905 Sao Carlos, SP (Brazil); LEMN, Laboratorio de Eletroquimica e Materiais Nanoestruturados, CCNH-Centro de Ciencias Naturais e Humanas, UFABC-Universidade Federal do ABC, CEP 09.210-170, Rua Santa Adelia 166, Bairro Bangu, Santo Andre, SP (Brazil)

    2007-09-27

    In this work, ruthenium oxide films containing platinum nanoparticles were prepared using the polymeric precursor method on Ti substrates with several molar ratios. This paper aims at presenting the characterization of the Pt content effect in the methanol electrochemical oxidation reaction. The films were physically characterized using X-ray diffraction and both Pt and RuO{sub 2} (rutile) phases were observed. The mean crystallite sizes were 6 nm for Pt and 25 nm for RuO{sub 2}. The X-ray photoelectronic results indicated that on the electrodes surfaces, depending on the substrate, there was RuO{sub 2}, Ru metal and Pt metal. Besides, it was not observed the formation of PtRu alloys. The atomic force microscopy images of the films showed highly rough surfaces. A decrease in the roughness mean square values is observed as the Pt content increases. These last results are similar to electroactive surface area values calculated by redox-couple (K{sub 4}FeCN{sub 6}/K{sub 3}FeCN{sub 6}). There was an increase in the globular size observed on the electrode surface and lower particle dispersion as the Pt content is increased from 12.5 to 75 mol%. Regarding the eletrode electrocatalytical behavior for methanol oxidation, it was observed that the onset oxidation overpotential is displaced towards more negative values as Pt content is decreased. Besides, an increase has been shown in the current density for methanol oxidation of 600% using a Ti/RuO{sub 2}-Pt (87.5:12.5) electrode compared to polycrystalline Pt. (author)

  7. 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

  8. 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

  9. 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.

  10. 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...

  11. 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.

  12. 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.

  13. Living catalyzed-chain-growth polymerization and block copolymerization of isoprene by rare-earth metal allyl precursors bearing a constrained-geometry-conformation ligand.

    Jian, Zhongbao; Cui, Dongmei; Hou, Zhaomin; Li, Xiaofang

    2010-05-07

    Aminophenyl functionalized cyclopentadienyl ligated rare-earth metal allyl mediated cationic systems display high cis-1,4 selectivity for the polymerization of isoprene, and living reversible and rapid chain transfer to aluminium additives.

  14. 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.

  15. 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.

  16. 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.

  17. 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.

  18. 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.

  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. 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

  1. Synthesis,Characterization and Application of Benzyl-substituted Cyclopentadienyl lanthanide Complexes as Catalyst Precursors for the Syndiotactic Polymerization of Methyl Methacrylate

    QIAN,Yan-Long(钱延龙); BALA,Muhammad D.; XIE,Xiao-Min(谢小敏); HUANG,Ji-Ling(黄吉玲)

    2004-01-01

    Benzyl-substituted cyclopentadienyl lanthanide complexes were synthesized and characterized by elemental analysis, MS and IR spectroscopy. The analytical data point out the formation of monomeric, unsolvated complexes.In conjunction with Al(Et)3 as co-catalyst, the title complexes are efficient catalysts for the syndiotactic polymerization of methyl methacrylate. For the complex (C6H5CH2C5H4)2YCI, under the optimum polymerization conditions (60 ℃, n(MMA):n(catalyst):n(co-catalyst)= 1000:1:10), a predominantly syndiotactic (rr=66%) polymer of high molecular weight (Mη = 105000) was obtained.

  2. 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.

  3. 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.

  4. 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 ...

  5. 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.

  6. 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)

  7. 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

  8. Catalytic oxidation of n-hexane promoted by Ce{sub 1−x}Cu{sub x}O{sub 2} catalysts prepared by one-step polymeric precursor method

    Araújo, Vinícius D., E-mail: dantas@ursa.ifsc.usp.br [Instituto de Física, Universidade de São Paulo – USP, 13560-970 São Carlos, SP (Brazil); Lima, Maurício M. de [Instituto de Ciencia de los Materiales, Universidad de Valencia, E-46071 Valencia (Spain); Fundación General, Universitat de Valencia, Valencia (Spain); Cantarero, Andrés [Instituto de Ciencia de los Materiales, Universidad de Valencia, E-46071 Valencia (Spain); Bernardi, Maria I.B. [Instituto de Física, Universidade de São Paulo – USP, 13560-970 São Carlos, SP (Brazil); Bellido, Jorge D.A. [CAP-Engenharia Química, Universidade Federal de São João Del-Rei – UFSJ, São João Del-Rei, MG (Brazil); Assaf, Elisabete M. [Instituto de Química, Universidade de São Paulo – USP, 13560-970 São Carlos, SP (Brazil); Balzer, Rosana; Probst, Luiz F.D. [Departamento de Química, Universidade Federal de Santa Catarina – UFSC, 88040-900 Florianópolis, SC (Brazil); Fajardo, Humberto V. [Departamento de Química, Universidade Federal de Ouro Preto – UFOP, 35400-000 Ouro Preto, MG (Brazil)

    2013-11-01

    Ceria-supported copper catalysts (Ce{sub 1−x}Cu{sub x}O{sub 2}, with x (mol) = 0, 0.01, 0.03, 0.05 and 0.10) were prepared in one step through the polymeric precursor method. The textural properties of the catalysts were investigated by X-ray diffraction (XRD), Rietveld refinement, N{sub 2}-physisorption (BET surface area), electron paramagnetic resonance (EPR), UV–visible diffuse reflectance and photoluminescence spectroscopies and temperature-programmed reduction (TPR). In a previous study ceria-supported copper catalysts were found to be efficient in the preferential oxidation of CO. In this study, we extended the catalytic application of Ce{sub 1−x}Cu{sub x}O{sub 2} systems to n-hexane oxidation and it was verified that the catalysts were highly efficient in the proposed reaction. The best performance (up to 95% conversion) was observed for the catalysts with low copper loads (Ce{sub 0.97}Cu{sub 0.03}O{sub 2} and Ce{sub 0.99}Cu{sub 0.01}O{sub 2}, respectively). The physicochemical characterizations revealed that these behaviors could be attributed to the copper species present in the catalysts and the interaction between CuO and CeO{sub 2}, which vary according to the copper content. - Highlights: • Synthesis of CuO/CeO2 catalysts by the one-step polymeric precursor method. • 95% n-hexane conversion on Ce0.97Cu0.03O2 catalyst. • Redox properties play a key role in the catalytic performance.

  9. 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.

  10. 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

  11. 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...

  12. 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.

  13. 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.

  14. 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.

  15. Synthesis and characterization of SnO2 doped with fluorine by the technique of polymeric precursors; Sintese e caracterizacao de SnO2 dopado com fluor pela tecnica dos precursores polimericos

    Pereira, Gilberto J.; Lopes, Rafael Ialago, E-mail: gilbertop@fei.edu.br [Centro Universitario FEI, Sao Bernardo do Campo, SP (Brazil). Departamento de Engenharia de Materiais

    2016-07-01

    The present work deals with the synthesis of tin dioxide powders doped with fluorine and chlorine anions to evaluate the influence of these on the physico-chemical properties of SnO2, as well as to verify if the dopant does not make a solid solution with the material and its possible use as sintering additive. The samples were synthesized by Pechini method (polymer precursors) with tin oxalate as a source not contaminated with chlorine of this metal. Specific surface area characterization (BET method) and X-ray diffractometry (XRD) show that doping reduces the particle size of SnO2, being more effective at lower dopant levels. The dilatometry of the doped powders shows a reduction in the beginning and end temperatures of the sintering of the tin dioxide when compared with values in the literature.

  16. Dark Current And Voltage Measurements Of Metal-Organic-Semiconductor (M-Or-S) Diode

    Adianto

    1996-01-01

    . Some Metal-Organic-Semiconductor (M-Or-S) thin film diodes, constructed with an organic polymer (polymerized toluene) as an active component has been successfully fabricated. The thin film M-Or-S diodes were fabricated on an n-type silicon with resistivity of 250-500 Ocm and p type silicon with resistivity of 10-20 Ocm as a substrate with polymerized toluene used as insulator. When deposited on silicon wafers with electrode of evaporated Ni on the n-type silicon and evaporated Au as the electrode on the polymerized toluene film, the electronic devices of Metal-Organic- Semiconductor (M-Or-S) type can be produced with one of its characteristics is that their light sensitivity. A plasma ion deposition system was constructed and used to deposit organic monomeric substance (toluene) that functioned as an isolator between semiconductor and the evaporated metal electrodes. The current-voltage measurements for different configurations of M-Or-S devices were carried out to determine the current-voltage (1-V) characteristics for M-Or-S devices with different materials and thicknesses. In addition to the 1-V measurement mentioned before, 1-V measurements of the devices were also carried out by using a curve tracer oscilloscope, and the picture of the effective parameters of each of the device could be taken by using a polaroid camera. Since the devices are very sensitive to light, the devices were all tested in a black-box which was covered by a black cloth to make sure that there was no light coming through. The experimental results for p- and n-type silicon substrates showed that an M-Or-S diode with n-type gave a higher breakdown voltage than that p- type silicon. In addition, the reverse bias breakdown voltage increased as the thickness of the thin film increased in the range of 50 -2500 V/μm

  17. Polymeric precursors method for obtaining pigments based on Inorganic oxides of chromium and iron deposited on TiO{sub 2}; Metodo dos precursores polimericos para obtencao de pigmentos inorganicos a base de oxidos de cromo e de ferro, depositados sobre TiO{sub 2}

    NONE

    2011-07-01

    The case study was the use of chromium oxides and iron, as a precursor in the synthesis of inorganic pigments. The synthesis was based on the dissolution of citric acid as a complexing agent, addition of metal oxides, such as ion chromophores; polymerization with ethylene glycol and doping with titanium oxide. Going through pre-calcination, breakdown, calcination at different temperatures (700, 900 and 1100 deg C resulting in pigments: green for pigment and chromium deposited on TiO2, orange for iron on TiO2. The thermal analysis (TG and DTA), evaluated their thermal decompositions, the XRD revealed the formation of crystalline phases such as iron titanate and chrome titanate; SEM showed the formation of hexagonal particles for both oxides. Under the different analysis, one can see the potential stability of pigments and powders, can be proposed its use as pigments in polymers. (author)

  18. Structural and morphological characterization of TiO{sub 2}-ZrO{sub 2} powders obtained by the polymeric precursors method; Caracterizacao estrutural e morfologica de pos de TiO{sub 2}-ZrO{sub 2} obtidos pelo metodo dos precursores polimericos

    Ribeiro, M.A.; Gama, L.; Bispo, A.; Neiva, L.S., E-mail: m_aparecidaribeiro@yahoo.com.b [Universidade Federal de Campina Grande (DEMa/UFCG), PB (Brazil). Dept. de Engenharia de Materiais; Bernardi, M.I.B. [Universidade de Sao Paulo (IFSC/USP), Sao Carlos, SP (Brazil). Inst. de Fisica; Kiminami, R.H.G.A. [Universidade Federal de Sao Carlos (DEMa/UFSCar), SP (Brazil). Dept. de Engenharia de Materiais

    2010-07-01

    This work aims to characterize the structure and morphology of TiO{sub 2}-ZrO{sub 2} powders obtained by polymeric precursor method. For this we studied the following compositions: 0.25, 0.5 and 0.75 moles of Zr and calcined at 800 deg C for one hour. The powders obtained were characterized by XRD, SEM and nitrogen adsorption (BET). The analysis of X-ray diffraction showed that the powders had a phase of TiO{sub 2} in the anatase form and a tetragonal phase of ZrO{sub 2}. The crystallite size was between 8, 13 and 11 nm respectively. The analysis of scanning electron microscopy showed the growth of ZrO{sub 2} nanoparticles and that these comprise spherical agglomerates of less than 100 nm. Particle size determined by the BET ranging 28.1-29.5 nm, showing thereby the character of nanosized powders. (author)

  19. Properties of alumina films prepared by metal-organic chemical vapour deposition at atmospheric pressure in hte presence of small amounts of water

    Haanappel, V.A.C.; Haanappel, V.A.C.; van Corbach, H.D.; Rem, J.B.; Fransen, T.; Gellings, P.J.

    1995-01-01

    Thin alumina films were deposited on stainless steel, type AISI 304. The deposition process was carried out in nitrogen with low partial pressures of water (0–2.6 × 10−2 kPa (0−0.20 mmHg)) by metal-organic chemical vapour deposition (MOCVD) with aluminium-tri-sec-butoxide (ATSB) as the precursor.

  20. Rare earth metal bis(amide) complexes bearing amidinate ancillary ligands: synthesis, characterization, and performance as catalyst precursors for cis-1,4 selective polymerization of isoprene.

    Luo, Yunjie; Fan, Shimin; Yang, Jianping; Fang, Jianghua; Xu, Ping

    2011-03-28

    A family of rare earth metal bis(amide) complexes bearing monoanionic amidinate [RC(N-2,6-Me(2)C(6)H(3))(2)](-) (R = cyclohexyl (Cy), phenyl (Ph)) as ancillary ligands were synthesized and characterized. One-pot salt metathesis reaction of anhydrous LnCl(3) with one equivalent of amidinate lithium [RC(N-2,6-Me(2)C(6)H(3))(2)]Li, following the introduction of two equivalents of NaN(SiMe(3))(2) in THF at room temperature afforded the neutral and unsolvated mono(amidinate) rare earth metal bis(amide) complexes [RC(N-2,6-Me(2)C(6)H(3))(2)]Y[N(SiMe(3))(2)](2) (R = Cy (1); R = Ph (2)), and the "ate" mono(amidinate) rare earth metal bis(amide) complex [CyC(N-2,6-Me(2)C(6)H(3))(2)]Lu[N(SiMe(3))(2)](2)(μ-Cl)Li(THF)(3) (3) in 61-72% isolated yields. These complexes were characterized by elemental analysis, NMR spectroscopy, FT-IR spectroscopy, and X-ray single crystal diffraction. Single crystal structural determination revealed that the central metal in complexes 1 and 2 adopts a distorted tetrahedral geometry, and in complex 3 forms a distorted trigonal bipyramidal geometry. In the presence of AlMe(3), and in combination with one equimolar amount of [Ph(3)C][B(C(6)F(5))(4)], complexes 1 and 2 showed high activity towards isoprene polymerization to give high molecular weight polyisoprene (M(n) > 10(4)) with good cis-1,4 selectivity (>90%).

  1. A Simple Approach to Enhance the Water Stability of a Metal-Organic Framework.

    Shih, Yung-Han; Kuo, Yu-Ching; Lirio, Stephen; Wang, Kun-Yun; Lin, Chia-Her; Huang, Hsi-Ya

    2017-01-01

    A facile method to improve the feasibility of water-unstable metal-organic frameworks in an aqueous environment has been developed that involves imbedding in a polymer monolith. The effect of compartment type during polymerization plays a significant role in maintaining the crystalline structure and thermal stability of the MOFs, which was confirmed by powder X-ray diffraction (PXRD) and thermogravimetric analysis (TGA), respectively. The MOF-polymer composite prepared in a narrow compartment (column, ID 0.8 mm) has better thermal and chemical stability than that prepared in a broad compartment (vial, ID 7 mm). The developed MOF-polymer composite was applied as an adsorbent in solid-phase microextraction of nine non-steroidal anti-inflammatory drugs (NSAIDs) and could be used for extraction more than 30 times, demonstrating that the proposed approach has potential for industrial applications. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. 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.

  3. 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.

  4. Er{sup 3+}-doped Y{sub 2}O{sub 3} obtained by polymeric precursor: Synthesis, structure and upconversion emission properties

    Perrella, Rafael V.; Santos, Daniela P. dos [Grupo de Pesquisa em Química de Materiais – (GPQM), Departamento de Ciências Naturais, Universidade Federal de São João del-Rei, Campus Dom Bosco, Praça Dom Helvécio, 74, 36301-160 São João del-Rei, MG (Brazil); Poirier, Gael Y. [Instituto de Ciência e Tecnologia, Universidade Federal de Alfenas, Cidade Universitária, 37715400 Poços de Caldas, MG (Brazil); Góes, Márcio S. [Universidade Federal da Integração Latino-Americana (UNILA), Av. Tancredo Neves, 6731 – Bloco 4, Cx P. 2044, CEP: 85867-970 Foz do Iguaçu, PR (Brazil); Ribeiro, Sidney José L. [Instituto de Química, UNESP, P.O. Box 355, 14800-970 Araraquara, SP (Brazil); Schiavon, Marco A. [Grupo de Pesquisa em Química de Materiais – (GPQM), Departamento de Ciências Naturais, Universidade Federal de São João del-Rei, Campus Dom Bosco, Praça Dom Helvécio, 74, 36301-160 São João del-Rei, MG (Brazil); and others

    2014-05-01

    The relentless pursuit for materials containing rare earth ions with photoluminescent properties has led to several studies with applications in the development of new technologies. The main focus of this work is the preparation of Er{sup 3+}-doped polycrystalline Y{sub 2}O{sub 3} with photoluminescent properties using PEG as an organic precursor and heat-treated at different temperatures. The methodology used in this synthesis is highly attractive due to its high feasibility for improved technology and low cost for preparing materials. The behavior of the viscous resin has been evaluated and the final compounds exhibited the formation of a cubic polycrystalline phase, which is able to support variations in Er{sup 3+} doping concentrations up to 10 mol%, without significant changes in the polycrystalline parameters. The values of the nanocrystallite size calculated by Scherrer's equation showed direct dependence on the heat-treatment temperature as well as the Er{sup 3+} concentration. Intense emission in the visible region under excitation at 980 nm was attributed to an upconversion phenomenon assigned to the intraconfigurational f–f transitions of Er{sup 3+} ions. The upconversion mechanism was investigated and it was demonstrated that the higher intense emission in the red region in comparison to the emission in the green region is related to the crystallite size. The studies about the intensity showed the dependence of upconversion emission of power source, indicating that two-photon are responsible for the green and red photoluminescence. These polycrystalline materials exhibit properties that make them promising for use in solar energy systems, C-telecom band or solid-state laser devices. - Highlights: • Intense red upconversion emission. • Very easy way to prepare the material. • Potential application in solar cells. • Application for C-telecom band.

  5. Coordination Polymers and Metal Organic Frameworks Derived from 1,2,4-Triazole Amino Acid Linkers

    Yann Garcia

    2011-10-01

    Full Text Available The perceptible appearance of biomolecules as prospective building blocks in the architecture of coordination polymers (CPs and metal-organic frameworks (MOFs are redolent of their inclusion in the synthon/tecton library of reticular chemistry. In this frame, for the first time a synthetic strategy has been established for amine derivatization in amino acids into 1,2,4-triazoles. A set of novel 1,2,4-triazole derivatized amino acids were introduced as superlative precursors in the design of 1D coordination polymers, 2D chiral helicates and 3D metal-organic frameworks. Applications associated with these compounds are diverse and include gas adsorption-porosity partitioning, soft sacrificial matrix for morphology and phase selective cadmium oxide synthesis, FeII spin crossover materials, zinc-b-lactamases inhibitors, logistics for generation of chiral/non-centrosymmetric networks; and thus led to a foundation of a new family of functional CPs and MOFs that are reviewed in this invited contribution.

  6. 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...

  7. 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 ...

  8. 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

  9. Selective epitaxial growth of Ge1-xSnx on Si by using metal-organic chemical vapor deposition

    Washizu, Tomoya; Ike, Shinichi; Inuzuka, Yuki; Takeuchi, Wakana; Nakatsuka, Osamu; Zaima, Shigeaki

    2017-06-01

    Selective epitaxial growth of Ge and Ge1-xSnx layers on Si substrates was performed by using metal-organic chemical vapor deposition (MOCVD) with precursors of tertiary-butyl-germane (t-BGe) and tri-butyl-vinyl-tin (TBVSn). We investigated the effects of growth temperature and total pressure during growth on the selectivity and the crystallinity of the Ge and Ge1-xSnx epitaxial layers. Under low total pressure growth conditions, the dominant mechanism of the selective growth of Ge epitaxial layers is the desorption of the Ge precursors. At a high total pressure case, it is needed to control the surface migration of precursors to realize the selectivity because the desorption of Ge precursors was suppressed. The selectivity of Ge growth was improved by diffusion of the Ge precursors on the SiO2 surfaces when patterned substrates were used at a high total pressure. The selective epitaxial growth of Ge1-xSnx layer was also realized using MOCVD. We found that the Sn precursors less likely to desorb from the SiO2 surfaces than the Ge precursors.

  10. Co3O4 protective coatings prepared by Pulsed Injection Metal Organic Chemical Vapour Deposition

    Burriel, M.; Garcia, G.; Santiso, J.

    2005-01-01

    of deposition temperature. Pure Co3O4 spinel structure was found for deposition temperatures ranging from 360 to 540 degreesC. The optimum experimental parameters to prepare dense layers with a high growth rate were determined and used to prepare corrosion protective coatings for Fe-22Cr metallic interconnects......Cobalt oxide films were grown by Pulsed Injection Metal Organic Chemical Vapour Deposition (PI-MOCVD) using Co(acac)(3) (acac=acetylacetonate) precursor dissolved in toluene. The structure, morphology and growth rate of the layers deposited on silicon substrates were studied as a function......, to be used in Intermediate Temperature Solid Oxide Fuel Cells. (C) 2004 Elsevier B.V. All rights reserved....

  11. Nanosheets of Nonlayered Aluminum Metal-Organic Frameworks through a Surfactant-Assisted Method

    Pustovarenko, Alexey

    2018-05-18

    During the last decade, the synthesis and application of metal-organic framework (MOF) nanosheets has received growing interest, showing unique performances for different technological applications. Despite the potential of this type of nanolamellar materials, the synthetic routes developed so far are restricted to MOFs possessing layered structures, limiting further development in this field. Here, a bottom-up surfactant-assisted synthetic approach is presented for the fabrication of nanosheets of various nonlayered MOFs, broadening the scope of MOF nanosheets application. Surfactant-assisted preorganization of the metallic precursor prior to MOF synthesis enables the manufacture of nonlayered Al-containing MOF lamellae. These MOF nanosheets are shown to exhibit a superior performance over other crystal morphologies for both chemical sensing and gas separation. As revealed by electron microscopy and diffraction, this superior performance arises from the shorter diffusion pathway in the MOF nanosheets, whose 1D channels are oriented along the shortest particle dimension.

  12. 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).

  13. Method for forming polymerized microfluidic devices

    Sommer, Gregory J.; Hatch, Anson V.; Wang, Ying-Chih; Singh, Anup K.; Renzi, Ronald F.; Claudnic, Mark R.

    2013-03-12

    Methods for making a microfluidic device according to embodiments of the present invention include defining.about.cavity. Polymer precursor solution is positioned in the cavity, and exposed to light to begin the polymerization process and define a microchannel. In some embodiments, after the polymerization process is partially complete, a solvent rinse is performed, or fresh polymer precursor introduced into the microchannel. This may promote removal of unpolymerized material from the microchannel and enable smaller feature sizes. The polymer precursor solution may contain an iniferter. Polymerized features therefore may be capped with the iniferter, which is photoactive. The iniferter may aid later binding of a polyacrylamide gel to the microchannel surface.

  14. 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.

  15. 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...

  16. 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...

  17. 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.

  18. 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.

  19. 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.

  20. 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.

  1. 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.

  2. Complex Nanostructures from Materials based on Metal-Organic Frameworks for Electrochemical Energy Storage and Conversion.

    Guan, Bu Yuan; Yu, Xin Yao; Wu, Hao Bin; Lou, Xiong Wen David

    2017-12-01

    Metal-organic frameworks (MOFs) have drawn tremendous attention because of their abundant diversity in structure and composition. Recently, there has been growing research interest in deriving advanced nanomaterials with complex architectures and tailored chemical compositions from MOF-based precursors for electrochemical energy storage and conversion. Here, a comprehensive overview of the synthesis and energy-related applications of complex nanostructures derived from MOF-based precursors is provided. After a brief summary of synthetic methods of MOF-based templates and their conversion to desirable nanostructures, delicate designs and preparation of complex architectures from MOFs or their composites are described in detail, including porous structures, single-shelled hollow structures, and multishelled hollow structures, as well as other unusual complex structures. Afterward, their applications are discussed as electrode materials or catalysts for lithium-ion batteries, hybrid supercapacitors, water-splitting devices, and fuel cells. Lastly, the research challenges and possible development directions of complex nanostructures derived from MOF-based-templates for electrochemical energy storage and conversion applications are outlined. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. Efeito do vapor d'água na síntese pelo método do precursor polimérico da alumina contendo aditivos Effect of water vapor on the synthesis by the polymeric precursor method of alumina doped powders

    R. H. R. Castro

    2005-12-01

    Full Text Available A presença de H2O nos processos de síntese e transformação de fase da alumina tem usualmente função catalisadora, diminuindo as temperaturas dos processos e facilitando os possíveis rearranjos atômicos. Neste trabalho mostrou-se que o vapor de H2O durante a síntese pode não apenas acelerar os processos diminuindo as energias de ativação, mas também induzir diferentes formas de ação de aditivos. O estudo foi possível utilizando-se o método dos precursores poliméricos para a síntese dos pós, que permite um controle absoluto do teor de H2O na etapa de cristalização do material. Alumina contendo Mn ou Mg como aditivos foram sintetizadas na ausência de H2O e na presença de excesso controlado desta e fases diferentes para cada situação foram observadas. Uma explicação do fenômeno é descrita em função da dependência da cristalização da gama-Al2O3 na presença de H+ para compensação das vacâncias catiônicas.It is commonly accepted that the presence of H2O during the synthesis and phase transformation of alumina causes decreasing temperatures of these processes since it increases the atomic motilities. In addition to this general concept, in this work H2O vapor is also shown to play an important role on the influence of additives in alumina based systems. Alumina powders containing Mn or Mg were synthesized by the polymeric precursor method under H2O vapor or dry atmosphere during the crystallization stage. Each atmosphere promoted a different phase and an explanation for the phenomenon was given bases on the gamma-Al2O3 crystallization dependence on the H+ presence due to the required cationic vacancies compensations.

  4. Physical-chemical and technological aspects of the preparation of think layers of the high temperature superconductors Bi-Sr-Ca-Cu-O by method of metal organic vapour phase epitaxy

    Stejskal, J.; Nevriva, M.; Leitner, J.

    1995-01-01

    The method of metal organic vapour phase epitaxy (MO VPE) was used for preparation of think layers of the high temperature superconductors Bi-Sr-Ca-Cu-O. The suitable chemical precursors (β-diketonates) on the literature data and of the own thermodynamic calculations were selected. The optimal thermodynamic data and thermodynamic stability of the prepared samples were determined

  5. 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.

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

    Alsadun, Norah Sadun

    2017-01-01

    -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

  7. 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.

  8. 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.

  9. 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.

  10. 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

  11. 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.

  12. 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.

  13. 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.

  14. 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.

  15. 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.

  16. 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.

  17. Metal-Organic Frameworks Derived Okra-like SnO2 Encapsulated in Nitrogen-Doped Graphene for Lithium Ion Battery.

    Zhou, Xiangyang; Chen, Sanmei; Yang, Juan; Bai, Tao; Ren, Yongpeng; Tian, Hangyu

    2017-04-26

    A facile process is developed to prepare SnO 2 -based composites through using metal-organic frameworks (MOFs) as precursors. The nitrogen-doped graphene wrapped okra-like SnO 2 composites (SnO 2 @N-RGO) are successfully synthesized for the first time by using Sn-based metal-organic frameworks (Sn-MOF) as precursors. When utilized as an anode material for lithium-ion batteries, the SnO 2 @N-RGO composites possess a remarkably superior reversible capacity of 1041 mA h g -1 at a constant current of 200 mA g -1 after 180 charge-discharge processes and excellent rate capability. The excellent performance can be primarily ascribed to the unique structure of 1D okra-like SnO 2 in SnO 2 @N-RGO which are actually composed of a great number of SnO 2 primary crystallites and numerous well-defined internal voids, can effectively alleviate the huge volume change of SnO 2 , and facilitate the transport and storage of lithium ions. Besides, the structural stability acquires further improvement when the okra-like SnO 2 are wrapped by N-doped graphene. Similarly, this synthetic strategy can be employed to synthesize other high-capacity metal-oxide-based composites starting from various metal-organic frameworks, exhibiting promising application in novel electrode material field of lithium-ion batteries.

  18. A malonitrile-functionalized metal-organic framework for hydrogen sulfide detection and selective amino acid molecular recognition

    Li, Haiwei; Feng, Xiao; Guo, Yuexin; Chen, Didi; Li, Rui; Ren, Xiaoqian; Jiang, Xin; Dong, Yuping; Wang, Bo

    2014-03-01

    A novel porous polymeric fluorescence probe, MN-ZIF-90, has been designed and synthesized for quantitative hydrogen sulfide (H2S) fluorescent detection and highly selective amino acid recognition. This distinct crystalline structure, derived from rational design and malonitrile functionalization, can trigger significant enhancement of its fluorescent intensity when exposed to H2S or cysteine molecules. Indeed this new metal-organic framework (MOF) structure shows high selectivity of biothiols over other amino acids and exhibits favorable stability. Moreover, in vitro viability assays on HeLa cells show low cytotoxicity of MN-ZIF-90 and its imaging contrast efficiency is further demonstrated by fluorescence microscopy studies. This facile yet powerful strategy also offers great potential of using open-framework materials (i.e. MOFs) as the novel platform for sensing and other biological applications.

  19. Dynamical Effects in Metal-Organic Frameworks: The Microporous Materials as Shock Absorbers

    Banlusan, Kiettipong; Strachan, Alejandro

    2017-06-01

    Metal-organic frameworks (MOFs) are a class of nano-porous crystalline solids consisting of inorganic units coordinated to organic linkers. The unique molecular structures and outstanding properties with ultra-high porosity and tunable chemical functionality by various choices of metal clusters and organic ligands make this class of materials attractive for many applications. The complex and quite unique responses of these materials to mechanical loading including void collapse make them attractive for applications in energy absorption and storage. We will present using large-scale molecular dynamics simulations to investigate shock propagation in zeolitic imidazolate framework ZIF-8 and MOF-5. We find that for shock strengths above a threshold a two-wave structure develops with a leading elastic precursor followed by a second wave of structural collapse to relax the stress. Structural transition of MOFs in response to shock waves corresponds to the transition between two Hugoniot curves, and results in abrupt change in temperature. The pore-collapse wave propagates at slower velocity than the leading wave and weakens it, resulting in shock attenuation. Increasing piston speed results in faster propagation of pore-collapse wave, but the leading elastic wave remains unchanged below the overdriven regime. We discuss how the molecular structure of the MOFs and shock propagation direction affect the response of the materials and their ability to weaken shocks. Office of Naval Research, MURI 2012 02341 01.

  20. Scalable synthesis and post-modification of a mesoporous metal-organic framework called NU-1000.

    Wang, Timothy C; Vermeulen, Nicolaas A; Kim, In Soo; Martinson, Alex B F; Stoddart, J Fraser; Hupp, Joseph T; Farha, Omar K

    2016-01-01

    The synthesis of NU-1000, a highly robust mesoporous (containing pores >2 nm) metal-organic framework (MOF), can be conducted efficiently on a multigram scale from inexpensive starting materials. Tetrabromopyrene and (4-(ethoxycarbonyl)phenyl)boronic acid can easily be coupled to prepare the requisite organic strut with four metal-binding sites in the form of four carboxylic acids, while zirconyl chloride octahydrate is used as a precursor for the well-defined metal oxide clusters. NU-1000 has been reported as an excellent candidate for the separation of gases, and it is a versatile scaffold for heterogeneous catalysis. In particular, it is ideal for the catalytic deactivation of nerve agents, and it shows great promise as a new generic platform for a wide range of applications. Multiple post-synthetic modification protocols have been developed using NU-1000 as the parent material, making it a potentially useful scaffold for several catalytic applications. The procedure for the preparation of NU-1000 can be scaled up reliably, and it is suitable for the production of 50 g of the tetracarboxylic acid containing organic linker and 200 mg-2.5 g of NU-1000. The entire synthesis is performed without purification by column chromatography and can be completed within 10 d.

  1. Structure-directing effects of ionic liquids in the ionothermal synthesis of metal-organic frameworks.

    Vaid, Thomas P; Kelley, Steven P; Rogers, Robin D

    2017-07-01

    Traditional synthesis of metal-organic frameworks (MOFs) involves the reaction of a metal-containing precursor with an organic linker in an organic solvent at an elevated temperature, in what is termed a 'solvothermal' reaction. More recently, many examples have been reported of MOF synthesis in ionic liquids (ILs), rather than an organic solvent, in 'ionothermal' reactions. The high concentration of both cations and anions in an ionic liquid allows for the formation of new MOF structures in which the IL cation or anion or both are incorporated into the MOF. Most commonly, the IL cation is included in the open cavities of the MOF, countering the anionic charge of the MOF framework itself and acting as a template around which the MOF structure forms. Ionic liquids can also serve other structure-directing roles, for example, when an IL containing a single enantiomer of a chiral anion leads to a homochiral MOF, even though the IL anion is not itself incorporated into the MOF. A comprehensive review of ionothermal syntheses of MOFs, and the structure-directing effects of the ILs, is given.

  2. Half-sandwich cobalt complexes in the metal-organic chemical vapor deposition process

    Georgi, Colin [Technische Universität Chemnitz, Faculty of Natural Science, Institute of Chemistry, Inorganic Chemistry, Chemnitz 09107 (Germany); Hapke, Marko; Thiel, Indre [Leibniz-Institut für Katalyse e.V. an der Universität Rostock (LIKAT), Albert-Einstein-Straße 29a, Rostock 18059 (Germany); Hildebrandt, Alexander [Technische Universität Chemnitz, Faculty of Natural Science, Institute of Chemistry, Inorganic Chemistry, Chemnitz 09107 (Germany); Waechtler, Thomas; Schulz, Stefan E. [Fraunhofer Institute of Electronic Nano Systems (ENAS), Technologie-Campus 3, Chemnitz 09126 (Germany); Technische Universität Chemnitz, Center for Microtechnologies (ZfM), Chemnitz 09107 (Germany); Lang, Heinrich, E-mail: heinrich.lang@chemie.tu-chemnitz.de [Technische Universität Chemnitz, Faculty of Natural Science, Institute of Chemistry, Inorganic Chemistry, Chemnitz 09107 (Germany)

    2015-03-02

    A series of cobalt half-sandwich complexes of type [Co(η{sup 5}-C{sub 5}H{sub 5})(L)(L′)] (1: L, L′ = 1,5-hexadiene; 2: L = P(OEt){sub 3}, L′ = H{sub 2}C=CHSiMe{sub 3}; 3: L = L′ = P(OEt){sub 3}) has been studied regarding their physical properties such as the vapor pressure, decomposition temperature and applicability within the metal-organic chemical vapor deposition (MOCVD) process, with a focus of the influence of the phosphite ligands. It could be shown that an increasing number of P(OEt){sub 3} ligands increases the vapor pressure and thermal stability of the respective organometallic compound. Complex 3 appeared to be a promising MOCVD precursor with a high vapor pressure and hence was deposited onto Si/SiO{sub 2} (100 nm) substrates. The resulting reflective layer is closed, dense and homogeneous, with a slightly granulated surface morphology. X-ray photoelectron spectroscopy (XPS) studies demonstrated the formation of metallic cobalt, cobalt phosphate, cobalt oxide and cobalt carbide. - Highlights: • Thermal studies and vapor pressure measurements of cobalt half-sandwich complexes was carried out. • Chemical vapor deposition with cobalt half-sandwich complexes is reported. • The use of Co-phosphites results in significant phosphorous-doped metallic layers.

  3. CFA-1: the first chiral metal-organic framework containing Kuratowski-type secondary building units.

    Schmieder, Phillip; Denysenko, Dmytro; Grzywa, Maciej; Baumgärtner, Benjamin; Senkovska, Irena; Kaskel, Stefan; Sastre, German; van Wüllen, Leo; Volkmer, Dirk

    2013-08-14

    The novel homochiral metal-organic framework CFA-1 (Coordination Framework Augsburg-1), [Zn5(OAc)4(bibta)3], containing the achiral linker {H2-bibta = 1H,1'H-5,5'-bibenzo[d][1,2,3]triazole}, has been synthesised. The reaction of H2-bibta and Zn(OAc)2·2H2O in N-methylformamide (NMF) (90 °C, 3 d) yields CFA-1 as trigonal prismatic single crystals. CFA-1 serves as a convenient precursor for the synthesis of isostructural frameworks with redox-active metal centres, which is demonstrated by the postsynthetic exchange of Zn(2+) by Co(2+) ions. The framework is robust to solvent removal and has been structurally characterized by synchrotron single-crystal X-ray diffraction and solid state NMR measurements ((13)C MAS- and (1)H MAS-NMR at 10 kHz). Results from MAS-NMR and IR spectroscopy studies are corroborated by cluster and periodic DFT calculations performed on CFA-1 cluster fragments.

  4. 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.

  5. 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.

  6. Mesoporous carbon-zirconium oxide nanocomposite derived from carbonized metal organic framework: A coating for solid-phase microextraction.

    Saraji, Mohammad; Mehrafza, Narges

    2016-08-19

    In this paper, a mesoporous carbon-ZrO2 nanocomposite was fabricated on a stainless steel wire for the first time and used as the solid-phase microextraction coating. The fiber was synthesized with the direct carbonization of a Zr-based metal organic framework. With the utilization of the metal organic framework as the precursor, no additional carbon source was used for the synthesis of the mesoporous carbon-ZrO2 nanocomposite coating. The fiber was applied for the determination of BTEX compounds (benzene, toluene, ethylbenzene and m, p-xylenes) in different water samples prior to gas chromatography-flame ionization detection. Such important experimental factors as synthesis time and temperature, salt concentration, equilibrium and extraction time, extraction temperature, desorption time and desorption temperature were studied and optimized. Good linearity in the concentration range of 0.2-200μgL(-1) and detection limits in the range of 0.05-0.56μgL(-1) was achieved for BTEX compounds. The intra- and inter-day relative standard deviations were in the range of 3.5-4.8% and 4.9-6.7%, respectively. The prepared fiber showed high capability for the analysis of BTEX compounds in different water and wastewater samples with good relative recoveries in the range of 93-107%. Copyright © 2016 Elsevier B.V. All rights reserved.

  7. Metal-Organic Framework Derived Iron Sulfide-Carbon Core-Shell Nanorods as a Conversion-Type Battery Material

    Huang, Wei; Li, Shuo; Cao, Xianyi

    2017-01-01

    of a redox conversion-type lithium-ion battery, this composite material has demonstrated high lithium-ion storage capacity at 1148 mA h g-1 under the current rate of 500 mA g-1 for 170 cycles and an impressive rate-retention capability at 657 mA h g-1 with a current density of 2000 mA g-1. On the basis......We report the design and nanoengineering of carbon-film-coated iron sulfide nanorods (C@Fe7S8) as an advanced conversion-type lithium-ion storage material. The structural advantages of the iron-based metal-organic framework (MIL-88-Fe) as both a sacrificed template and a precursor are explored...

  8. Nanoscale leakage current measurements in metal organic chemical vapor deposition crystalline SrTiO3 films

    Rozier, Y.; Gautier, B.; Hyvert, G.; Descamps, A.; Plossu, C.; Dubourdieu, C.; Ducroquet, F.

    2009-01-01

    The properties of SrTiO 3 thin films, grown by liquid injection metal organic chemical vapor deposition on Si/SiO 2 , using a mixture of precursors, have been investigated at the nanoscale using an Atomic Force Microscope in the so-called Conductive Atomic Force Microscopy mode. Maps of the leakage currents with a nanometric resolution have been obtained on films elaborated at different temperatures and stoichiometries in order to discriminate the role of each parameter on the onset of leakage currents in the resulting layers. It appears that the higher the deposition temperature, the higher the leakage currents of the films. The mapping with a nanometric precision allows to show a heterogeneous behaviour of the surface with leaky grains and insulating boundaries. The study of films elaborated at the same temperature with different compositions supports the assumption that the leakage currents on Ti-rich layers are far higher than on Sr-rich layers

  9. Mesoporous ZnO microcube derived from a metal-organic framework as photocatalyst for the degradation of organic dyes

    Ban, Jin-jin; Xu, Guan-cheng; Zhang, Li; Lin, He; Sun, Zhi-peng; Lv, Yan; Jia, Dian-zeng

    2017-12-01

    A cube-like porous ZnO architecture was synthesized by direct two-step thermolysis of a zinc-based metal-organic framework [(CH3)2NH2][Zn(HCOO)3]. The obtained ZnO microcube was characterized by powder X-ray diffraction, scanning electron microscopy, transmission electron microscopy and nitrogen adsorption and desorption isotherms. The mesoporous ZnO microcube was comprised by many nanoparticles, and inherited the cube shape from [(CH3)2NH2][Zn(HCOO)3] precursor. With large surface area and mesoporous structure, the ZnO microcube exhibits excellent photocatalytic activities against methyl orange (MO) and rhodamine B (RhB) under UV irradiation, and the degradation rates reached 99.7% and 98.1% within 120 min, respectively.

  10. 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.

  11. 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.

  12. 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.

  13. 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.

  14. 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.

  15. 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.

  16. 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.

  17. 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.

  18. 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.

  19. 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.

  20. Elektroaktive polymerer

    West, K.

    Traditionelt tænker vi på polymerer (plastik) som elektrisk isolerende materialer - det som er udenpå ledningerne. I dag kender vi imidlertid også polymerer med intrinsisk elektrisk ledningsevne, og plast er på vej ind i anvendelser, der tidligereudelukkende var baseret på metaller og uorganiske...... halvledere. Hertil kommer, at en del af de ledende polymerer kan stimuleres til at skifte mellem en ledende og en halvledende tilstand, hvorved de ændret både form og farve. I foredraget gives der enrække eksempler på anvendelse af polymerer som elektriske komponenter - rækkende fra polymer elektronik over...

  1. 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%.

  2. 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.

  3. 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.

  4. 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)).

  5. 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.

  6. Synthesis of Thin Film Composite Metal-Organic Frameworks Membranes on Polymer Supports

    Barankova, Eva

    2017-06-01

    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 chemical and thermal stability, recent commercial availability and attractive pore size. The aim of this work is to develop convenient methods for growing ZIF thin layers on polymer supports to obtain defect-free ZIF membranes with good gas separation properties. We present new approaches for ZIF membranes preparation on polymers. We introduce zinc oxide nanoparticles in the support as a secondary metal source for ZIF-8 growth. Initially the ZnO particles were incorporated into the polymer matrix and later on the surface of the polymer by magnetron sputtering. In both cases, the ZnO facilitated to create more nucleation opportunities and improved the ZIF-8 growth compared to the synthesis without using ZnO. By employing the secondary seeded growth method, we were able to obtain thin (900 nm) ZIF-8 layer with good gas separation performance. Next, we propose a metal-chelating polymer as a suitable support for growing ZIF layers. Defect-free ZIF-8 films with a thickness of 600 nm could be obtained by a contra-diffusion method. ZIF-8 membranes were tested for permeation of hydrogen and hydrocarbons, and one of the highest selectivities reported so far for hydrogen/propane, and propylene/propane was obtained. Another promising method to facilitate the growth of MOFs on polymeric supports is the chemical functionalization of the support surface with functional groups, which can complex metal ions and which can covalently bond the MOF crystals. We functionalized the surface of a common porous polymeric membrane with amine groups, which took part in the reaction to form ZIF-8 nanocrystals. We observed an enhancement in adhesion between the ZIF layer and the support. The effect of parameters of the contra-diffusion experiment

  7. 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.

  8. 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.

  9. 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.

  10. 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.

  11. 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.

  12. Thermoset precursor

    Yamamoto, Y.

    1983-04-01

    This invention pertains to a distinctive thermoset precursor which is prepared by mixing a resin composition (A) which can be hardened by ionizing radiation, and a resin composition (B) which can be hardened by heat but cannot be hardened by, or is resistant to, ionizing radiation, and by coating or impregnating a molding or other substrate with a sheet or film of this mixture and irradiating this with an ionizing radiation. The principal components of composition (A) and (B) can be the following: (1) an acrylate or methacrylate and an epoxy resin and an epoxy resin hardener; (2) an unsaturated polyester resin and epoxy resin and an epoxy resin hardener; (3) a diacrylate or dimethacrylate or polyethylene glycol and an epoxy resin; (4) an epoxy acrylates or epoxy methacrylate obtained by the addition reaction of epoxy resin and acrylic or methacrylic acid

  13. 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

  14. 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

  15. 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.

  16. Symbiosis of zeolite-like metal-organic frameworks (rho-ZMOF) and hydrogels: Composites for controlled drug release

    Ananthoji, Ramakanth

    2011-01-01

    The design and synthesis of new finely tunable porous materials has spurred interest in developing novel uses in a variety of systems. Zeolites, inorganic materials with high thermal and mechanical stability, in particular, have been widely examined for use in applications such as catalysis, ion exchange and separation. A relatively new class of inorganic-organic hybrid materials known as metal-organic frameworks (MOFs) have recently surfaced, and many have exhibited their efficiency in potential applications such as ion exchange and drug delivery. A more recent development is the design and synthesis of a subclass of MOFs based on zeolite topologies (i.e. ZMOFs), which often exhibit traits of both zeolites and MOFs. Bio-compatible hydrogels already play an important role in drug delivery systems, but are often limited by stability issues. Thus, the addition of ZMOFs to hydrogel formulations is expected to enhance the hydrogel mechanical properties, and the ZMOF-hydrogel composites should present improved, symbiotic drug storage and release for delivery applications. Herein we present the novel composites of a hydrogel with a zeolite-like metal-organic framework, rho-ZMOF, using 2-hydroxyethyl methacrylate (HEMA), 2,3-dihydroxypropyl methacrylate (DHPMA), N-vinyl-2-pyrolidinone (VP) and ethylene glycol dimethacrylate (EGDMA), and the corresponding drug release. An ultraviolet (UV) polymerization method is employed to synthesize the hydrogels, VP 0, VP 15, VP 30, VP 45 and the ZMOF-VP 30 composite, by varying the VP content (mol%). The rho-ZMOF, VP 30, and ZMOF-VP 30 composite are all tested for the controlled release of procainamide (protonated, PH), an anti-arrhythmic drug, in phosphate buffer solution (PBS) using UV spectroscopy. © 2011 The Royal Society of Chemistry.

  17. Bismuth-, Tin-, and Lead-Containing Metal-Organic Materials: Synthesis, Structure, Photoluminescence, Second Harmonic Generation, and Ferroelectric Properties

    Wibowo, Arief Cahyo

    Metal-Organic Materials (MOMs) contain metal moieties and organic ligands that combine to form discrete (e.g. metal-organic polyhedra, spheres or nanoballs, metal-organic polygons) or polymeric structures with one-, two-, or three-dimensional periodicities that can exhibit a variety of properties resulting from the presence of the metal moieties and/or ligand connectors in the structure. To date, MOMs with a range of functional attributes have been prepared, including record-breaking porosity, catalytic properties, molecular magnetism, chemical separations and sensing ability, luminescence and NLO properties, multiferroic, ferroelectric, and switchable molecular dielectric properties. We are interested in synthesizing non-centrosymmetric MOM single crystals possessing one of the ten polar space groups required for non-linear optical properties (such as second harmonic generation) and ferroelectric applications. This thesis is divided into two main parts: materials with optical properties, such as photoluminescence and materials for targeted applications such as second harmonic generation and ferroelectric properties. This thesis starts with an introduction describing material having centrosymmetric, non-polar space groups, single crystals structures and their photoluminescence properties. These crystals exhibit very interesting and rare structures as well as interesting photoluminescence properties. Chapters 2-5 of this thesis focus on photoluminescent properties of new MOMs, and detail the exploratory research involving the comparatively rare bismuth, lead, and tin coordination polymers. Specifically, the formation of single white-light emitting phosphors based on the combination of bismuth or lead with pyridine-2,5-dicarboxylate is discussed (Chapter 2). The observation of a new Bi2O2 layer and a new Bi4O 3 chain in bismuth terephthalate-based coordination polymers is presented in Chapter 3, while the formation of diverse structures of tin-based coordination

  18. 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.

  19. 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

  20. 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

  1. 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

  2. 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

  3. 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.

  4. 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.

  5. 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.

  6. Gas Phase Sensing of Alcohols by Metal Organic Framework–Polymer Composite Materials

    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 a Matrimid polymer matrix with different weight ratios (0–100 wt %) and drop-casted on planar capacitive transducer devices. These coated devices were electrically analyzed using impedance spectroscopy and investigated for their sensing properties toward the detection of a series of alcohols and water in the gas phase. The measurements indicated a reversible and reproducible response in all devices. Sensor devices containing 40 wt % NH2-MIL-53(Al) in Matrimid showed a maximum response for methanol and water. The sensor response time slowed down with increasing MOF concentration until 40 wt %. The half time of saturation response (τ0.5) increased by ∼1.75 times for the 40 wt % composition compared to devices coated with Matrimid only. This is attributed to polymer rigidification near the MOF/polymer interface. Higher MOF loadings (≥50 wt %) resulted in brittle coatings with a response similar to the 100 wt % MOF coating. Cross-sensitivity studies showed the ability to kinetically distinguish between the different alcohols with a faster response for methanol and water compared to ethanol and 2-propanol. The observed higher affinity of the pure Matrimid polymer toward methanol compared to water allows also for a higher uptake of methanol in the composite matrices. Also, as indicated by the sensing studies with a mixture of water and methanol, the methanol uptake is independent of the presence of water up to 6000 ppm of water. The NH2-MIL-53(Al) MOFs dispersed in the Matrimid matrix show a sensitive and reversible capacitive response, even in the presence of water. By tuning the precise compositions, the affinity kinetics and overall affinity can be tuned, showing

  7. The volatile pivalates of Y, Ba and Cu as prospective precursors for metal-organic chemical vapour deposition

    Iljina, E. (Dept. of Chemistry, Moscow State Univ. (Russian Federation)); Korjeva, A. (Dept. of Chemistry, Moscow State Univ. (Russian Federation)); Kuzmina, N. (Dept. of Chemistry, Moscow State Univ. (Russian Federation)); Troyanov, S. (Dept. of Chemistry, Moscow State Univ. (Russian Federation)); Dunaeva, K. (Dept. of Chemistry, Moscow State Univ. (Russian Federation)); Martynenko, L. (Dept. of Chemistry, Moscow State Univ. (Russian Federation))

    1993-04-15

    The volatile pivalates of Y, Ba and Cu were synthesized and characterized by chemical and thermogravimetric analysis, IR spectroscopy, X-ray diffraction and mass spectrometry. The volatilities of metal pivalates was studied; the vapour pressures, thermodynamic characteristics and rates of sublimation were investigated. The volatile pivalates of Y, Ba and Cu are new prospective accessible compounds. (orig.)

  8. In situ stabilizer formation from methacrylic acid macromonomers in emulsion polymerization

    Schreur-Piet, Ingeborg; Heuts, Johan P.A.

    2017-01-01

    Oligomers of methacrylic acid containing a propenyl ω-endgroup (i.e. MAA-macromonomers) were synthesized by cobalt-mediated catalytic chain transfer polymerization and used as precursors to stabilizers in emulsion polymerization. It was found that only in those polymerizations in which these

  9. Functional Nanoporous Polymers from Block Copolymer Precursors

    Guo, Fengxiao

    Abstract Self-assembly of block copolymers provides well-defined morphologies with characteristic length scales in the nanometer range. Nanoporous polymers prepared by selective removal of one block from self-assembled block copolymers offer great technological promise due to their many potential...... functionalities remains a great challenge due to the limitation of available polymer synthesis and the nanoscale confinement of the porous cavities. The main topic of this thesis is to develop methods for fabrication of functional nanoporous polymers from block copolymer precursors. A method has been developed......, where living anionic polymerization and atom transfer radical polymerization (ATRP) are combined to synthesize a polydimethylsiloxane-b-poly(tert-butyl acrylate)-b-polystyrene (PDMS-b-PtBA-b-PS) triblock copolymer precursor. By using either anhydrous hydrogen fluoride or trifluoroacetic acid, PtBA block...

  10. 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.

  11. Effect of the pillar ligand on preventing agglomeration of ZnO nanoparticles prepared from Zn(II metal-organic frameworks

    Maryam Moeinian

    2016-01-01

    Full Text Available Metal-Organic Frameworks (MOFs represent a new class of highly porous materials. On this regard,  two nano porous metal-organic frameworks of [Zn2(1,4-bdc2(H2O2∙(DMF2]n (1 and [Zn2(1,4-bdc2(dabco]·4DMF·1⁄2H2O (2, (1,4-bdc = benzene-1,4-dicarboxylate, dabco = 1,4-diazabicyclo[2.2.2]octane and DMF = N,N-dimethylformamide were synthesized and characterized. They were used for preparation of ZnO nanomaterials. With calcination of 1, agglomerated ZnO nanoparticles could be fabricated, but by the same process on 2, the tendency of ZnO nanoparticles to agglomeration was decreased. In addition, the ZnO nanoparticles prepared from compound 2 had smaller diameter than those obtained from compound 1. In fact, the role of organic dabco ligands in 2 is similar to the role of polymeric stabilizers in formation of nanoparticles. Finally, considering the various applications of ZnO nanomaterials such as light-emitting diodes, photodetectors, photodiodes, gas sensors and dye-sensitized solar cells (DSSCs, it seems that preparation of ZnO nanomaterials from their MOFs could be one of the simple and effective methods which may be applied for preparation of them.

  12. Aerogels of 1D Coordination Polymers: From a Non-Porous Metal-Organic Crystal Structure to a Highly Porous Material

    Adrián Angulo-Ibáñez

    2016-01-01

    Full Text Available The processing of an originally non-porous 1D coordination polymer as monolithic gel, xerogel and aerogel is reported as an alternative method to obtain novel metal-organic porous materials, conceptually different to conventional crystalline porous coordination polymer (PCPs or metal-organic frameworks (MOFs. Although the work herein reported is focused upon a particular kind of coordination polymer ([M(μ-ox(4-apy2]n, M: Co(II, Ni(II, the results are of interest in the field of porous materials and of MOFs, as the employed synthetic approach implies that any coordination polymer could be processable as a mesoporous material. The polymerization conditions were fixed to obtain stiff gels at the synthesis stage. Gels were dried at ambient pressure and at supercritical conditions to render well shaped monolithic xerogels and aerogels, respectively. The monolithic shape of the synthesis product is another remarkable result, as it does not require a post-processing or the use of additives or binders. The aerogels of the 1D coordination polymers are featured by exhibiting high pore volumes and diameters ranging in the mesoporous/macroporous regions which endow to these materials the ability to deal with large-sized molecules. The aerogel monoliths present markedly low densities (0.082–0.311 g·cm−3, an aspect of interest for applications that persecute light materials.

  13. Synthesis, characterizations and catalytic studies of a new two-dimensional metal-organic framework based on Co-carboxylate secondary building units

    Bagherzadeh, Mojtaba; Ashouri, Fatemeh; Đaković, Marijana

    2015-03-01

    A metal-organic framework [Co3(BDC)3(DMF)2(H2O)2] was synthesized and structurally characterized. X-ray single crystal analysis revealed that the framework contains a 2D polymeric chain through coordination of 1,4-benzenedicarboxylic acid linker ligand to cobalt centers. The polymer crystallize in monoclinic P21/n space group with a=13.989(3) Å, b=9.6728(17) Å, c=16.707(3) Å, and Z=2. The polymer features a framework based on the perfect octahedral Co-O6 secondary building units. The catalytic activities of [Co3(BDC)3(DMF)2(H2O)2]n for olefins oxidation was conducted. The heterogeneous catalyst could be facilely separated from the reaction mixture, and reused three times without significant degradation in catalytic activity. Furthermore, no contribution from homogeneous catalysis of active species leaching into reaction solution was detected.

  14. Chelating polymeric membranes

    Peinemann, Klaus-Viktor; Villalobos Vazquez de la Parra, Luis Francisco; Hilke, Roland

    2015-01-01

    microporous chelating polymeric membrane. Embodiments include, but are not limited to, microporous chelating polymeric membranes, device comprising the membranes, and methods of using and making the same.

  15. 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.

  16. 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.

  17. Electric and ferroelectric properties of PZT/BLT multilayer films prepared by photochemical metal-organic deposition

    Park, Hyeong-Ho; Lee, Hong-Sub; Park, Hyung-Ho; Hill, Ross H.; Hwang, Yun Taek

    2009-01-01

    The electric and ferroelectric properties of lead zirconate titanate (PZT) and lanthanum-substituted bismuth titanate (BLT) multilayer films prepared using photosensitive precursors were characterized. The electric and ferroelectric properties were investigated by studying the effect of the stacking order of four ferroelectric layers of PZT or BLT in 4-PZT, PZT/2-BLT/PZT, BLT/2-PZT/BLT, and 4-BLT multilayer films. The remnant polarization values of the 4-BLT and BLT/2-PZT/BLT multilayer films were 12 and 17 μC/cm 2, respectively. Improved ferroelectric properties of the PZT/BLT multilayer films were obtained by using a PZT intermediate layer. The films which contained a BLT layer on the Pt substrate had improved leakage currents of approximately two orders of magnitude and enhanced fatigue resistances compared to the films with a PZT layer on the Pt substrate. These improvements are due to the reduced number of defects and space charges near the Pt electrodes. The PZT/BLT multilayer films prepared by photochemical metal-organic deposition (PMOD) possessed enhanced electric and ferroelectric properties, and allow direct patterning to fabricate micro-patterned systems without dry etching.

  18. Electric and ferroelectric properties of PZT/BLT multilayer films prepared by photochemical metal-organic deposition

    Park, Hyeong-Ho; Lee, Hong-Sub; Park, Hyung-Ho; Hill, Ross H.; Hwang, Yun Taek

    2009-01-01

    The electric and ferroelectric properties of lead zirconate titanate (PZT) and lanthanum-substituted bismuth titanate (BLT) multilayer films prepared using photosensitive precursors were characterized. The electric and ferroelectric properties were investigated by studying the effect of the stacking order of four ferroelectric layers of PZT or BLT in 4-PZT, PZT/2-BLT/PZT, BLT/2-PZT/BLT, and 4-BLT multilayer films. The remnant polarization values of the 4-BLT and BLT/2-PZT/BLT multilayer films were 12 and 17 μC/cm 2 , respectively. Improved ferroelectric properties of the PZT/BLT multilayer films were obtained by using a PZT intermediate layer. The films which contained a BLT layer on the Pt substrate had improved leakage currents of approximately two orders of magnitude and enhanced fatigue resistances compared to the films with a PZT layer on the Pt substrate. These improvements are due to the reduced number of defects and space charges near the Pt electrodes. The PZT/BLT multilayer films prepared by photochemical metal-organic deposition (PMOD) possessed enhanced electric and ferroelectric properties, and allow direct patterning to fabricate micro-patterned systems without dry etching.

  19. Stacking effect on the ferroelectric properties of PZT/PLZT multilayer thin films formed by photochemical metal-organic deposition

    Park, Hyeong-Ho; Park, Hyung-Ho; Hill, Ross H.

    2004-01-01

    The ferroelectric properties of lead zirconate titanate (PZT) and lanthanum-doped lead zirconate titanate (PLZT) multilayer films formed by photochemical metal-organic deposition (PMOD) using photosensitive precursors have been characterized. The substitution of La for Pb was reported to induce improved ferroelectric properties, especially fatigue resistance, through the reduction of oxygen vacancies. The relation between La-substitution and the ferroelectric properties was investigated by characterization of the effect of the order of stacking four ferroelectric layers of PZT or PLZT in the multilayer films 4-PZT, PZT/2-PLZT/PZT, PLZT/2-PZT/PLZT, and 4-PLZT. The films with the PLZT layer at the top and bottom showed an improvement in the fatigue resistance. It was revealed that defect dipole such as O vacancy was reduced at the ferroelectric/Pt interface by doping with La. Also, the bottom layer, just on Pt substrate had a significant influence on the surface microstructure and growth orientation of ferroelectric film

  20. Supramolecular metal-organic frameworks that display high homogeneous and heterogeneous photocatalytic activity for H2 production

    Tian, Jia; Xu, Zi-Yue; Zhang, Dan-Wei; Wang, Hui; Xie, Song-Hai; Xu, Da-Wen; Ren, Yuan-Hang; Wang, Hao; Liu, Yi; Li, Zhan-Ting

    2016-05-01

    Self-assembly has a unique presence when it comes to creating complicated, ordered supramolecular architectures from simple components under mild conditions. Here, we describe a self-assembly strategy for the generation of the first homogeneous supramolecular metal-organic framework (SMOF-1) in water at room temperature from a hexaarmed [Ru(bpy)3]2+-based precursor and cucurbit[8]uril (CB[8]). The solution-phase periodicity of this cubic transition metal-cored supramolecular organic framework (MSOF) is confirmed by small-angle X-ray scattering and diffraction experiments, which, as supported by TEM imaging, is commensurate with the periodicity in the solid state. We further demonstrate that SMOF-1 adsorbs anionic Wells-Dawson-type polyoxometalates (WD-POMs) in a one-cage-one-guest manner to give WD-POM@SMOF-1 hybrid assemblies. Upon visible-light (500 nm) irradiation, such hybrids enable fast multi-electron injection from photosensitive [Ru(bpy)3]2+ units to redox-active WD-POM units, leading to efficient hydrogen production in aqueous media and in organic media. The demonstrated strategy opens the door for the development of new classes of liquid-phase and solid-phase ordered porous materials.

  1. Porous ZnCo 2 O 4 nanoparticles derived from a new mixed-metal organic framework for supercapacitors

    Chen, Siru

    2015-01-01

    Cobalt-based oxides have been shown to be promising materials for application in high-energy-density Li-ion batteries and supercapacitors. In this paper, we report a new and simple strategy for the synthesis of a mixed-metal spinel phase (ZnCo2O4) from a zinc and cobalt mixed-metal organic framework (JUC-155). It is important to rationally design a MOF with a precise ratio (Co/Zn) and a synthetic process that is simple and time saving. After solid-state annealing of the mixed-metal MOF precursor at 400 °C for two hours, a pure ZnCo2O4 phase with a high surface area (55 cm2 g−1) was obtained. When used as electrode materials for supercapacitors, an exceptionally high specific capacitance of 451 F g−1 was obtained at the scan rate of 5 mV s−1. The capacitance loss after 1500 cycles was only 2.1% at a current density of 2 A g−1, indicating that this phase has an excellent cycling stability. These remarkable electrochemical performances suggest that this phase is potentially promising for application as an efficient electrode in electrochemical capacitors.

  2. 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.

  3. MOCVD and ALD of rare earth containing multifunctional materials. From precursor chemistry to thin film deposition and applications

    Milanov, Andrian Petrov

    2010-01-01

    The present thesis deals with the development of metal-organic complexes of rare elements. They should be used as novel precursors for the production of rare earth thin films by metal-organic chemical vapor deposition (MOCVD) and Atomic Layer Deposition (ALD). Within the work two precursor classes were examined, the tris-Malonato-complexes as well as the tris-Guanidinato-complexes of a series of rare earth metals. The latter showed excellent properties regarding to their volatility, their thermal stability, the defined decomposition and high reactivity towards water. They have been successfully used as precursors for the MOCVD of rare earth oxide layers. By using of a gadolinium guanidinate it could also be shown that the rare earth guanidinates are promising precursors for ALD of rare earth oxide and MOCVD of rare earth nitride layers. [de

  4. 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.

  5. 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...

  6. 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

  7. 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

  8. 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

  9. 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.

  10. 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.

  11. 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.

  12. 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

  13. 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

  14. 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

  15. 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

  16. 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...

  17. 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.

  18. 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.

  19. 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

  20. 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.

  1. 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.

  2. 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

  3. 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

  4. 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

  5. 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

  6. 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

  7. 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...

  8. Synthesis and characterization of nanoporous strontium-doped lanthanum cobaltite thin film using metal organic chemical solution deposition

    Park, Jun-Sik [Department of Mechanical Convergence Engineering, Hanyang University, Seoul 133-791 (Korea, Republic of); Kim, Young-Beom, E-mail: ybkim@hanyang.ac.kr [Department of Mechanical Convergence Engineering, Hanyang University, Seoul 133-791 (Korea, Republic of); Institute of Nano Science and Technology, Hanyang University, Seoul 133-791 (Korea, Republic of)

    2016-01-29

    By employing strontium as a dopant of lanthanum cobaltite (LaCoO{sub 3}), strontium-doped lanthanum cobaltite (La{sub 1−x}Sr{sub x}CoO{sub 3−δ}, LSC) thin film was fabricated using a metal organic chemical solution deposition (MOCSD) method. Lanthanum nitrate hexahydrate [La(NO{sub 3}){sub 3}6H{sub 2}O], strontium acetate [Sr(CH{sub 3}COO){sub 2}], and cobalt acetate tetrahydrate [Co(CH{sub 3}COO){sub 2}4H{sub 2}O] were used as precursors. The coating process was performed through a spin coating method on a substrate, which were then heat treated under various temperature conditions. Electrical properties, microstructures, and crystalline structures with respect to sintering temperature were analyzed. According to these analyses, the change in surface morphology, phase shift, and conductive properties were closely related, which could explain their respective behaviors. Furthermore, sintered strontium-doped lanthanum perovskite oxides showed various conductivities according to the amount of dopant. With the molar ratio of strontium that is stoichiometrically equivalent to lanthanum (La{sub 0.5}Sr{sub 0.5}CoO{sub 3−δ}) thin film showed the best conductivity in the sintering temperature range of 650–700 °C, with perovskite phases formed at this temperature condition. As the electrically conductive properties of the thin film are a function of thickness, the films were coated several times to a thickness of approximately 300 nm, with the lowest resistivity (approximately 9.06 × 10{sup −4} Ω cm) observed at the optimized sintering temperature and solution composition. - Highlights: • LSC thin film was fabricated by metal organic chemical solution deposition (MOCSD). • The film shows good agreement on the electrical conductivity of LSC by conventional methods. • The properties of LSC film are influenced by the surface morphology and crystalline phase. • Optimal molar ratio of strontium for the highest conductivity was investigated.

  9. Ionospheric earthquake precursors

    Bulachenko, A.L.; Oraevskij, V.N.; Pokhotelov, O.A.; Sorokin, V.N.; Strakhov, V.N.; Chmyrev, V.M.

    1996-01-01

    Results of experimental study on ionospheric earthquake precursors, program development on processes in the earthquake focus and physical mechanisms of formation of various type precursors are considered. Composition of experimental cosmic system for earthquake precursors monitoring is determined. 36 refs., 5 figs

  10. Plasma-assisted MOCVD growth of superconducting NbN thin films using Nb dialkylamide and Nb alkylimide precursors

    Liu Xiang; Ott, A.W.; Chang, R.P.H.; Babcok, J.R.; Belot, J.A.; Metz, M.V.; Marks, T.J.; Lane, M.A.; Kannewurf, C.R.

    2001-01-01

    The first example of the use of metal-organic precursors for depositing NbN superconducting thin films is described. The study, which employed niobium(IV) and niobium(V) pulsed source precursors and hydrazine plasma as the nitrogen source, indicates that T c is highly dependent on the lattice parameters and level of oxygen impurities, which are in turn governed by growth and post-deposition annealing temperatures. (orig.)

  11. Selective growth of Ge1- x Sn x epitaxial layer on patterned SiO2/Si substrate by metal-organic chemical vapor deposition

    Takeuchi, Wakana; Washizu, Tomoya; Ike, Shinichi; Nakatsuka, Osamu; Zaima, Shigeaki

    2018-01-01

    We have investigated the selective growth of a Ge1- x Sn x epitaxial layer on a line/space-patterned SiO2/Si substrate by metal-organic chemical vapor deposition. We examined the behavior of a Sn precursor of tributyl(vinyl)tin (TBVSn) during the growth on Si and SiO2 substrates and investigated the effect of the Sn precursor on the selective growth. The selective growth of the Ge1- x Sn x epitaxial layer was performed under various total pressures and growth temperatures of 300 and 350 °C. The selective growth of the Ge1- x Sn x epitaxial layer on the patterned Si region is achieved at a low total pressure without Ge1- x Sn x growth on the SiO2 region. In addition, we found that the Sn content in the Ge1- x Sn x epitaxial layer increases with width of the SiO2 region for a fixed Si width even with low total pressure. To control the Sn content in the selective growth of the Ge1- x Sn x epitaxial layer, it is important to suppress the decomposition and migration of Sn and Ge precursors.

  12. A rapid process of Yba2Cu3O7-δ thin film fabrication using trifluoroacetate metal-organic deposition with polyethylene glycol additive

    Wu, Wei; Feng, Feng; Shi, Kai

    2013-01-01

    Trifluoroacetate metal-organic deposition (TFA-MOD) is a promising technique to fabricate YBa2Cu3O7-δ (YBCO) superconducting films. However, its slow pyrolysis process, which usually takes more than 10 h, constitutes a barrier for industrial production. In this study, polyethylene glycol (PEG......) was utilized to reduce the stress generation inside the coated films when the strong pyrolysis reactions happen. With the addition of 30 wt% PEG2000 to the precursor solution, a smooth film surface could be obtained through a rapid pyrolysis process of 15 min. After the optimizations of the crystallization...... and oxygenation processes, mass percentage and molecular weight of PEG additive, YBCO thin films with Jc of about 4.5 MA cm-2 (77 K, self-field) could be routinely fabricated using (20-30) wt% PEG(1000-2000) additive with a total treatment time of about 2 h including the 15 min pyrolysis process time. The effects...

  13. Characterization of Pb(Zr, Ti)O sub 3 thin films prepared by metal-organic chemical-vapor deposition using a solid delivery system

    Shin, J C; Hwang, C S; Kim, H J; Lee, J M

    1999-01-01

    Pb(Zr, Ti)O sub 3 (PZT) thin films were deposited on Pt/SiO sub 2 /Si substrates by metal-organic chemical-vapor deposition technique using a solid delivery system to improve the reproducibility of the deposition. The self-regulation mechanism, controlling the Pb-content of the film, was observed to work above a substrate temperature of 620 .deg. C. Even with the self-regulation mechanism, PZT films having low leakage current were obtained only when the molar mixing ratio of the input precursors was 1

  14. Development of Y-BA-CU-O Coated Conductor Using Metal Organic Chemical Vapor Deposition

    Selvamanickam, V

    2003-01-01

    .... The program includes a study of the a) influence of MOCVD processing conditions such as the flow rate of precursor vapors, precursor vaporization temperatures, oxygen partial pressure, reactor pressure, and the deposition temperature...

  15. 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.

  16. Organometallic Polymeric Conductors

    Youngs, Wiley J.

    1997-01-01

    For aerospace applications, the use of polymers can result in tremendous weight savings over metals. Suitable polymeric materials for some applications like EMI shielding, spacecraft grounding, and charge dissipation must combine high electrical conductivity with long-term environmental stability, good processability, and good mechanical properties. Recently, other investigators have reported hybrid films made from an electrically conductive polymer combined with insulating polymers. In all of these instances, the films were prepared by infiltrating an insulating polymer with a precursor for a conductive polymer (either polypyrrole or polythiophene), and oxidatively polymerizing the precursor in situ. The resulting composite films have good electrical conductivity, while overcoming the brittleness inherent in most conductive polymers. Many aerospace applications require a combination of properties. Thus, hybrid films made from polyimides or other engineering resins are of primary interest, but only if conductivities on the same order as those obtained with a polystyrene base could be obtained. Hence, a series of experiments was performed to optimize the conductivity of polyimide-based composite films. The polyimide base chosen for this study was Kapton. 3-MethylThiophene (3MT) was used for the conductive phase. Three processing variables were identified for producing these composite films, namely time, temperature, and oxidant concentration for the in situ oxidation. Statistically designed experiments were used to examine the effects of these variables and synergistic/interactive effects among variables on the electrical conductivity and mechanical strength of the films. Multiple linear regression analysis of the tensile data revealed that temperature and time have the greatest effect on maximum stress. The response surface of maximum stress vs. temperature and time (for oxidant concentration at 1.2 M) is shown. Conductivity of the composite films was measured for

  17. Carbon molecular sieve membranes prepared from porous fiber precursor

    Barsema, J.N.; van der Vegt, N.F.A.; Koops, G.H.; Wessling, Matthias

    2002-01-01

    Carbon molecular sieve (CMS) membranes are usually prepared from dense polymeric precursors that already show intrinsic gas separation properties. The rationale behind this approach is that the occurrence of any kind of initial porosity will deteriorate the final CMS performance. We will show that

  18. 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

  19. Giant negative linear compression positively coupled to massive thermal expansion in a metal-organic framework.

    Cai, Weizhao; Katrusiak, Andrzej

    2014-07-04

    Materials with negative linear compressibility are sought for various technological applications. Such effects were reported mainly in framework materials. When heated, they typically contract in the same direction of negative linear compression. Here we show that this common inverse relationship rule does not apply to a three-dimensional metal-organic framework crystal, [Ag(ethylenediamine)]NO3. In this material, the direction of the largest intrinsic negative linear compression yet observed in metal-organic frameworks coincides with the strongest positive thermal expansion. In the perpendicular direction, the large linear negative thermal expansion and the strongest crystal compressibility are collinear. This seemingly irrational positive relationship of temperature and pressure effects is explained and the mechanism of coupling of compressibility with expansivity is presented. The positive coupling between compression and thermal expansion in this material enhances its piezo-mechanical response in adiabatic process, which may be used for designing new artificial composites and ultrasensitive measuring devices.

  20. Computational studies of adsorption in metal organic frameworks and interaction of nanoparticles in condensed phases

    Annapureddy, HVR; Motkuri, RK; Nguyen, PTM; Truong, TB; Thallapally, PK; McGrail, BP; Dang, LX

    2014-02-05

    In this review, we describe recent efforts to systematically study nano-structured metal organic frameworks (MOFs), also known as metal organic heat carriers, with particular emphasis on their application in heating and cooling processes. We used both molecular dynamics and grand canonical Monte Carlo simulation techniques to gain a molecular-level understanding of the adsorption mechanism of gases in these porous materials. We investigated the uptake of various gases such as refrigerants R12 and R143a. We also evaluated the effects of temperature and pressure on the uptake mechanism. Our computed results compared reasonably well with available measurements from experiments, thus validating our potential models and approaches. In addition, we investigated the structural, diffusive and adsorption properties of different hydrocarbons in Ni-2(dhtp). Finally, to elucidate the mechanism of nanoparticle dispersion in condensed phases, we studied the interactions among nanoparticles in various liquids, such as n-hexane, water and methanol.

  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. 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.

  3. 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.

  4. 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.

  5. Peptide assembly-driven metal-organic framework (MOF) motors for micro electric generators.

    Ikezoe, Yasuhiro; Fang, Justin; Wasik, Tomasz L; Uemura, Takashi; Zheng, Yongtai; Kitagawa, Susumu; Matsui, Hiroshi

    2015-01-14

    Peptide-metal-organic framework (Pep-MOF) motors, whose motions are driven by anisotropic surface tension gradients created via peptide self-assembly around frameworks, can rotate microscopic rotors and magnets fast enough to generate an electric power of 0.1 μW. A new rigid Pep-MOF motor can be recycled by refilling the peptide fuel into the nanopores of the MOF. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. Spectroscopic micro-tomography of metallic-organic composites by means of photon-counting detectors

    Pichotka, Martin; Jakůbek, Jan; Vavřík, Daniel

    2015-01-01

    Roč. 10, č. 12 (2015), C12033 ISSN 1748-0221 R&D Projects: GA MŠk(CZ) LO1219 Keywords : micro-tomography * photon-counting detectors * metallic-organic composites Subject RIV: BH - Optics, Masers, Lasers Impact factor: 1.310, year: 2015 http://iopscience.iop.org/article/10.1088/1748-0221/10/12/C12033/pdf

  7. Preparation Methods of Metal Organic Frameworks and Their Capture of CO2

    Zhang, Linjian; Liand, Fangqin; Luo, Liangfei

    2018-01-01

    The increasingly serious greenhouse effect makes people pay more attention to the capture and storage technology of CO2. Metal organic frameworks (MOFs) have the advantages of high specific surface area, porous structure and controllable structure, and become the research focus of CO2 emission reduction technology in recent years. In this paper, the characteristics, preparation methods and application of MOFs in the field of CO2 adsorption and separation are discussed, especially the application of flue gas environment in power plants.

  8. A high rotational barrier for physisorbed hydrogen in an fcu-metal-organic framework

    Pham, Tony T.; Forrest, Katherine A.; Georgiev, Peter A L; Lohstroh, Wiebke; Xue, Dongxu; Hogan, Adam; Eddaoudi, Mohamed; Space, Brian; Eckert, Juergen

    2014-01-01

    A combined inelastic neutron scattering (INS) and theoretical study of H2 sorption in Y-FTZB, a recently reported metal-organic framework (MOF) with fcu topology, reveals that the strongest binding site in the MOF causes a high barrier to rotation on the sorbed H2. This rotational barrier for H2 is the highest yet of reported MOF materials based on physisorption. This journal is

  9. 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.

  10. 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

  11. Metal-organic framework tethering PNIPAM for ON-OFF controlled release in solution.

    Nagata, Shunjiro; Kokado, Kenta; Sada, Kazuki

    2015-05-21

    A smart metal-organic framework (MOF) exhibiting controlled release was achieved by modification with a thermoresponsive polymer (PNIPAM) via a surface-selective post-synthetic modification technique. Simple temperature variation readily switches "open" (lower temperature) and "closed" (higher temperature) states of the polymer-modified MOF through conformational change of PNIPAM grafted onto the MOF, resulting in controlled release of the included guest molecules such as resorufin, caffeine, and procainamide.

  12. Nano- and microsized cubic gel particles from cyclodextrin metal-organic frameworks.

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

    2012-10-15

    Sweet cube o' mine: Bottom-up control of gel particles has been regarded as a great challenge. By employing internal cross-linking of cyclodextrin metal-organic frameworks, cubic sugar gels were formed with sharp edges that reflect the shape of the crystals. This enabled the fabrication of shape- and size-controlled polymer gels from porous crystals (see picture). Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  13. 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.

  14. 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...

  15. Surfactant media to grow new crystalline cobalt 1,3,5-benzenetricarboxylate metal-organic frameworks

    Lu, Haisheng; Bai, Linlu; Xiong, Weiwei; Li, Peizhou; Ding, Junfeng; Zhang, Guodong; Wu, Tao; Zhao, Yanli; Lee, Jongmin; Yang, Yanhui; Geng, Baoyou; Zhang, Qichun

    2014-01-01

    In this report, three new metal-organic frameworks (MOFs), [Co 3(μ3-OH)(HBTC)(BTC)2Co(HBTC)]·(HTEA) 3·H2O (NTU-Z30), [Co(BTC)] ·HTEA·H2O (NTU-Z31), [Co3(BTC) 4]·(HTEA)4 (NTU-Z32), where H3BTC = 1,3,5-benzenetricarboxylic acid, TEA = triethylamine

  16. Metal-Organic Framework-Stabilized CO2/Water Interfacial Route for Photocatalytic CO2 Conversion.

    Luo, Tian; Zhang, Jianling; Li, Wei; He, Zhenhong; Sun, Xiaofu; Shi, Jinbiao; Shao, Dan; Zhang, Bingxing; Tan, Xiuniang; Han, Buxing

    2017-11-29

    Here, we propose a CO 2 /water interfacial route for photocatalytic CO 2 conversion by utilizing a metal-organic framework (MOF) as both an emulsifier and a catalyst. The CO 2 reduction occurring at the CO 2 /water interface produces formate with remarkably enhanced efficiency as compared with that in conventional solvent. The route is efficient, facile, adjustable, and environmentally benign, which is applicable for the CO 2 transformation photocatalyzed by different kinds of MOFs.

  17. Fabrication of single-phase ε-GaSe films on Si(100) substrate by metal organic chemical vapor deposition

    Chang, Chia-Chen; Zeng, Jia-Xian; Lan, Shan-Ming [Department of Electronic Engineering, College of Electrical Engineering and Computer Science, Chung Yuan Christian University, Chung-Li 32023, Taiwan (China); Uen, Wu-Yih, E-mail: uenwuyih@ms37.hinet.net [Department of Electronic Engineering, College of Electrical Engineering and Computer Science, Chung Yuan Christian University, Chung-Li 32023, Taiwan (China); Liao, Sen-Mao [Department of Electronic Engineering, College of Electrical Engineering and Computer Science, Chung Yuan Christian University, Chung-Li 32023, Taiwan (China); Yang, Tsun-Neng; Ma, Wei-Yang [Institute of Nuclear Energy Research, P.O. Box 3-11, Lungtan 32500, Taiwan (China); Chang, Kuo-Jen [Chung-Shan Institute of Science and Technology, No.15, Shi Qi Zi, Gaoping Village, Longtan Township, Taoyuan County, Taiwan (China)

    2013-09-02

    Single-phase ε-gallium selenide (GaSe) films were fabricated on Si(100) substrate by metal organic chemical vapor deposition using dual-source precursors: triethylgallium (TEG) and hydrogen selenide (H{sub 2}Se) with the flow ratio of [H{sub 2}Se]/[TEG] being maintained at 1.2. In particular, an arsine (AsH{sub 3}) flow was introduced to the Si substrate before the film deposition to induce an arsenic (As)-passivation effect on the substrate. The crystalline structure of GaSe films prepared was analyzed using X-ray diffraction and the surface morphology of them was characterized by scanning electron microscopy. It was found that the film quality could be improved by the As-passivation effect. The optical properties of the films were studied by temperature dependent photoluminescence (PL) measurements. PL spectra obtained with different distributions and intensities favored for resolving the superior material quality of the films produced on the substrate with As-passivation compared to those produced on the substrate without As-passivation. The former was dominated by the excitonic emissions for the whole temperature range of 20–300 K examined, while the latter was initially dominated by the defect-related emission at 1.907 eV for a low-temperature range ≦ 80 K and then became dominated by the weak excitonic emission band instead. The ε modification of GaSe films prepared was further recognized by the Raman scattering measurements conducted at room temperature. - Highlights: • Gallium selenide (GaSe) layered structures are fabricated on Si(100) substrate. • Metal–organic chemical vapor deposition is used for film fabrication. • Arsenic-passivation effects of Si substrate on the GaSe film quality are analyzed. • Photoluminescence measurements of GaSe polycrystals are reported.

  18. Surfactant-thermal method to prepare two new cobalt metal-organic frameworks

    Yu, Xianglin [School of Materials Science and Engineering and School of Chemical and Biomedical Engineering, Nanyang Technological University, Singapore 639798 (Singapore); Key Laboratory for Green Chemical Process of Ministry of Education, School of Chemical Engineering and Pharmacy, Wuhan Institute of Technology, Wuhan 430074 (China); Toh, Yong Siang [School of Materials Science and Engineering and School of Chemical and Biomedical Engineering, Nanyang Technological University, Singapore 639798 (Singapore); Zhao, Jun [College of Materials and Chemical Engineering, Hubei Provincial Collaborative Innovation Center for New Energy Microgrid, China Three Gorges University, Yichang 443002 (China); Nie, Lina [School of Materials Science and Engineering and School of Chemical and Biomedical Engineering, Nanyang Technological University, Singapore 639798 (Singapore); Ye, Kaiqi; Wang, Yue [State Key Laboratory of Supramolecular Structure and Materials, College of Chemistry, Jilin University, Changchun 130012 (China); Li, Dongsheng [College of Materials and Chemical Engineering, Hubei Provincial Collaborative Innovation Center for New Energy Microgrid, China Three Gorges University, Yichang 443002 (China); Zhang, Qichun, E-mail: qczhang@ntu.edu.sg [School of Materials Science and Engineering and School of Chemical and Biomedical Engineering, Nanyang Technological University, Singapore 639798 (Singapore); Division of Chemistry and Biological Chemistry, School of Physical and Mathematical Sciences, Nanyang Technological University, Singapore 637371 (Singapore)

    2015-12-15

    Employing surfactants as reaction media, two new metal-organic frameworks (MOFs):(HTEA){sub 3}[Co{sub 3}(BTC){sub 3}] (NTU-Z33) and (HTEA)[Co{sub 3}(HBTC){sub 2}(BTC)] (NTU-Z34) (H{sub 3}BTC=1,3,5-benzenetricarboxylic acid, TEA=trimethylamine, and NTU=Nanyang Technological University), have been successfully synthesized and fully characterized. Note that NTU-Z33 has an unusual trimeric [Co{sub 3}(COO){sub 9}] secondary building unit (SBU). Magnetic characterization suggests that both compounds have weak antiferromagnetic behaviors. Our success in preparing new crystalline Co-BTC based MOFs under different surfactant media could provide a new road to prepare new diverse MOFs through various combinations of surfactants. - Graphical abstract: Employing surfactants as reaction media, two new metal-organic frame-works (MOFs) have been successfully synthesized and magnetic study suggests that both compounds have weak antiferromagnetic behaviors. - Highlights: • Two novel metal-organic frame-works (MOFs). • Synthesis through surfactant-thermal condition. • weak antiferromagnetic behaviors for both compounds.

  19. 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.

  20. Metal-organic aerogel as a coating for solid-phase microextraction

    Saraji, Mohammad, E-mail: saraji@cc.iut.ac.ir; Shahvar, Ali

    2017-06-22

    An iron-based metal-organic aerogel was synthesized using metal-organic framework nanoparticles and applied as a fiber coating for solid-phase microextraction (SPME). Chemical, thermal and morphological characteristics of the material were investigated. Headspace SPME followed by gas chromatography-electron capture detection was used for the determination of chlorobenzenes in the environmental samples. The key experimental factors affecting the extraction efficiency of the analytes, such as ionic strength, extraction and desorption temperature, and extraction time were investigated and optimized. The applicability of the coating for the extraction of chlorobenzenes from the environmental samples including river and tap water, sludge, and coastal soil was evaluated. The detection limits were in the range of 0.1–60 ng L{sup −1}. The relative standard deviations were between 2.0 and 5.0%. The extraction recovery of the analytes was in the range of 88–100%. Compared to the commercial PDMS fiber, the present fiber showed better extraction efficiency. - Highlights: • Metal-organic aerogel was synthesized and used as a novel fiber coating for SPME. • The new coating material showed high surface area and good thermal stability. • GC-ECD was used for determination of chlorobenzenes in environmental samples. • The method showed fast extraction and better efficiency than PDMS commercial fiber.

  1. 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.

  2. Surfactant-thermal method to prepare two new cobalt metal-organic frameworks

    Yu, Xianglin; Toh, Yong Siang; Zhao, Jun; Nie, Lina; Ye, Kaiqi; Wang, Yue; Li, Dongsheng; Zhang, Qichun

    2015-01-01

    Employing surfactants as reaction media, two new metal-organic frameworks (MOFs):(HTEA)_3[Co_3(BTC)_3] (NTU-Z33) and (HTEA)[Co_3(HBTC)_2(BTC)] (NTU-Z34) (H_3BTC=1,3,5-benzenetricarboxylic acid, TEA=trimethylamine, and NTU=Nanyang Technological University), have been successfully synthesized and fully characterized. Note that NTU-Z33 has an unusual trimeric [Co_3(COO)_9] secondary building unit (SBU). Magnetic characterization suggests that both compounds have weak antiferromagnetic behaviors. Our success in preparing new crystalline Co-BTC based MOFs under different surfactant media could provide a new road to prepare new diverse MOFs through various combinations of surfactants. - Graphical abstract: Employing surfactants as reaction media, two new metal-organic frame-works (MOFs) have been successfully synthesized and magnetic study suggests that both compounds have weak antiferromagnetic behaviors. - Highlights: • Two novel metal-organic frame-works (MOFs). • Synthesis through surfactant-thermal condition. • weak antiferromagnetic behaviors for both compounds.

  3. 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.

  4. 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.

  5. "Click" i polymerer 2

    Hvilsted, Søren

    2012-01-01

    "Click"-reaktioner til fremstilling af ledende polymerer med funktionelle håndtag og bipolymermaterialer......"Click"-reaktioner til fremstilling af ledende polymerer med funktionelle håndtag og bipolymermaterialer...

  6. Conducting Polymeric Materials

    Hvilsted, Søren

    2016-01-01

    The overall objective of this collection is to provide the most recent developments within the various areas of conducting polymeric materials. The conductivity of polymeric materials is caused by electrically charged particles, ions, protons and electrons. Materials in which electrons...

  7. Thin metal organic frameworks coatings by cathodic electrodeposition for solid-phase microextraction and analysis of trace exogenous estrogens in milk.

    Lan, Hangzhen; Pan, Daodong; Sun, Yangying; Guo, Yuxing; Wu, Zhen

    2016-09-21

    Cathodic electrodeposition (CED) has received great attention in metal-organic frameworks (MOFs) synthesis due to its distinguished properties including simplicity, controllability, mild synthesis conditions, and product continuously. Here, we report the fabrication of thin (Et3NH)2Zn3(BDC)4 (E-MOF-5) film coated solid phase microextraction (SPME) fiber by a one-step in situ cathodic electrodeposition strategy. Several etched stainless steel fibers were placed in parallel in order to achieve simultaneously electrochemical polymerization. The influence of different polymerization parameters Et3NHCl concentration and polymerization time were evaluated. The proposed method requires only 20 min for the preparation of E-MOF-5 coating. The optimum coating showed excellent thermal stability and mechanical durability with a long lifetime of more than 120 repetitions SPME operations, and also exhibited higher extraction selectivity and capacity to four estrogens than commonly-used commercial PDMS coating. The limits of detection for the estrogens were 0.17-0.56 ng mL(-1). Fiber-to-fiber reproducibility (n = 8) was in the respective ranges of 3.5%-6.1% relative standard deviation (RSD) for four estrogens for triplicate measurements at 200 ng mL(-1). Finally, the (E-MOF-5) coated fiber was evaluated for ethinylestradiol (EE2), bisphenol A (BPA), diethylstilbestrol (DES), and hexestrol (HEX) extraction in the spiked milk samples. The extraction performance of this new coating was satisfied enough for repeatable use without obvious decline. Copyright © 2016 Elsevier B.V. All rights reserved.

  8. 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

  9. New group III precursors for the MOVPE of GaAs and InP based material

    Hostaler, M.; Pohl, L.; Brauers, A.; Balk, P.; Frese, V.; Hovel, R.; Regel, G.K.; Hardtdegen, H.

    1989-01-01

    This paper presents proposals for the synthesis of several group III metal organics (In, Ga, Al compounds) and preliminary results on their use in the MOVPE (metal organic vapor phase epitaxy) of III-V semiconductors. The common feature of all these precursors is that they are saturated by inter- or intramolecular coordination. They are even non-pyrophoric and air resistant which is an interesting aspect with respect to safe handling. In addition, the compounds are liquid at room temperature with a low but sufficient vapor pressure for MOVPE without additional heating of the source

  10. 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

  11. Cu-Al alloy formation by thermal annealing of Cu/Al multilayer films deposited by cyclic metal organic chemical vapor deposition

    Moon, Hock Key; Yoon, Jaehong; Kim, Hyungjun; Lee, Nae-Eung

    2013-05-01

    One of the most important issues in future Cu-based interconnects is to suppress the resistivity increase in the Cu interconnect line while decreasing the line width below 30 nm. For the purpose of mitigating the resistivity increase in the nanoscale Cu line, alloying Cu with traces of other elements is investigated. The formation of a Cu alloy layer using chemical vapor deposition or electroplating has been rarely studied because of the difficulty in forming Cu alloys with elements such as Al. In this work, Cu-Al alloy films were successfully formed after thermal annealing of Cu/Al multilayers deposited by cyclic metal-organic chemical vapor deposition (C-MOCVD). After the C-MOCVD of Cu/Al multilayers without gas phase reaction between the Cu and Al precursors in the reactor, thermal annealing was used to form Cu-Al alloy films with a small Al content fraction. The resistivity of the alloy films was dependent on the Al precursor delivery time and was lower than that of the aluminum-free Cu film. No presence of intermetallic compounds were detected in the alloy films by X-ray diffraction measurements and transmission electron spectroscopy.

  12. Epitaxial Pb(Mg1/3Nb2/3)O3 thin films synthesized by metal-organic chemical vapor deposition

    Bai, G. R.; Streiffer, S. K.; Baumann, P. K.; Auciello, O.; Ghosh, K.; Stemmer, S.; Munkholm, A.; Thompson, Carol; Rao, R. A.; Eom, C. B.

    2000-01-01

    Metal-organic chemical vapor deposition was used to prepare Pb(Mg 1/3 Nb 2/3 )O 3 (PMN) thin films on (001) SrTiO 3 and SrRuO 3 /SrTiO 3 substrates, using solid Mg β-diketonate as the Mg precursor. Parameters including the precursor ratio in the vapor phase, growth temperature, growth rate, and reaction pressure in the reactor chamber were varied in order to determine suitable growth conditions for producing phase-pure, epitaxial PMN films. A cube-on-cube orientation relationship between the thin film and the SrTiO 3 substrate was found, with a (001) rocking curve width of 0.1 degree sign , and in-plane rocking-curve width of 0.8 degree sign . The root-mean-square surface roughness of a 200-nm-thick film on SrTiO 3 was 2 to 3 nm as measured by scanning probe microscopy. The zero-bias dielectric constant and loss measured at room temperature and 10 kHz for a 200-nm-thick film on SrRuO 3 /SrTiO 3 were approximately 1100 and 2%, respectively. The remnant polarization for this film was 16 μC/cm 2 . (c) 2000 American Institute of Physics

  13. 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.

  14. Reticular Chemistry and Metal-Organic Frameworks: Design and Synthesis of Functional Materials for Clean Energy Applications

    Alezi, Dalal

    2017-01-01

    Gaining control over the assembly of crystalline solid-state materials has been significantly advanced through the field of reticular chemistry and metal organic frameworks (MOFs). MOFs have emerged as a unique modular class of porous materials

  15. Zirconium-Based metal organic framework (Zr-MOF) material with high hydrostability for hydrogen storage applications

    Ren, Jianwei

    2013-09-01

    Full Text Available Material-based solutions, such as metal organic frameworks (MOFs), continue to attract increasing attention as viable options for hydrogen storage applications. MOFs are widely regarded as promising materials for hydrogen storage due to their high...

  16. Precursor directed synthesis - ``molecular'' mechanisms in the Soft Chemistry approaches and their use for template-free synthesis of metal, metal oxide and metal chalcogenide nanoparticles and nanostructures

    Seisenbaeva, Gulaim A.; Kessler, Vadim G.

    2014-05-01

    This review provides an insight into the common reaction mechanisms in Soft Chemistry processes involved in nucleation, growth and aggregation of metal, metal oxide and chalcogenide nanoparticles starting from metal-organic precursors such as metal alkoxides, beta-diketonates, carboxylates and their chalcogene analogues and demonstrates how mastering the precursor chemistry permits us to control the chemical and phase composition, crystallinity, morphology, porosity and surface characteristics of produced nanomaterials.This review provides an insight into the common reaction mechanisms in Soft Chemistry processes involved in nucleation, growth and aggregation of metal, metal oxide and chalcogenide nanoparticles starting from metal-organic precursors such as metal alkoxides, beta-diketonates, carboxylates and their chalcogene analogues and demonstrates how mastering the precursor chemistry permits us to control the chemical and phase composition, crystallinity, morphology, porosity and surface characteristics of produced nanomaterials. To Professor David Avnir on his 65th birthday.

  17. Structure-Property of Metal Organic Frameworks Calcium Terephthalates Anodes for Lithium-ion Batteries

    Wang, Liping; Mou, Chengxu; Sun, Yang; Liu, Wei; Deng, Qijiu; Li, Jingze

    2015-01-01

    Graphical Abstract: Effects of hydration water in calcium terephthalates anodes on the structure, operational voltage and electrochemical performance are systematically studied. Display Omitted -- Highlights: •Metal organic frameworks CaC 8 H 4 O 4 ·3H 2 O and CaC 8 H 4 O 4 are applied as anodes for lithium ion batteries. •Appearance of hydration water leads different crystallography structures and electrochemical performance. •Anhydrous CaC 8 H 4 O 4 has a spacious ordered layer structure, a higher Ca-O chemical bonding interaction and a higher transparent lithium ion diffusion coefficient, delivering a higher capacity, better cycling performance and rate performance than CaC 8 H 4 O 4 ·3H 2 O. -- Abstract: Metal organic frameworks have attracted considerable interest as electrode materials for lithium ion batteries. In this paper, the metal organic frameworks hydrated calcium terephthalate (CaC 8 H 4 O 4 ·3H 2 O) and anhydrous calcium terephthalate (CaC 8 H 4 O 4 ) as anodes for lithium ion batteries are comparatively studied. Crystallography and local chemical bond analysis are combined to interpret the structure-property of calcium terephthalates. Results show that the anhydrous CaC 8 H 4 O 4 has a spacious ordered layer structure and a higher Ca-O chemical bonding interaction, delivering a higher capacity, better cycling performance and rate performance than CaC 8 H 4 O 4 ·3H 2 O

  18. 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.

  19. 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.

  20. 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.

  1. 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.

  2. The direct heat measurement of mechanical energy storage metal-organic frameworks.

    Rodriguez, Julien; Beurroies, Isabelle; Loiseau, Thierry; Denoyel, Renaud; Llewellyn, Philip L

    2015-04-07

    In any process, the heat exchanged is an essential property required in its development. Whilst the work related to structural transitions of some flexible metal-organic frameworks (MOFs) has been quantified and linked with potential applications such as molecular springs or shock absorbers, the heat related to such transitions has never been directly measured. This has now been carried out with MIL-53(Al) using specifically devised calorimetry experiments. We project the importance of these heats in devices such as molecular springs or dampers. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. Metal-Organic-Framework-Mediated Nitrogen-Doped Carbon for CO2 Electrochemical Reduction

    Wang, Riming; Sun, Xiaohui; Ould-Chikh, Samy; Osadchii, Dmitrii; Bai, Fan; Kapteijn, Freek; Gascon, Jorge

    2018-01-01

    A nitrogen-doped carbon was synthesized through the pyrolysis of the well-known metal-organic framework ZIF-8, followed by a subsequent acid treatment, and has been applied as a catalyst in the electrochemical reduction of carbon dioxide. The resulting electrode shows Faradaic efficiencies to carbon monoxide as high as ∼78%, with hydrogen being the only byproduct. The pyrolysis temperature determines the amount and the accessibility of N species in the carbon electrode, in which pyridinic-N and quaternary-N species play key roles in the selective formation of carbon monoxide.

  4. A highly stable zeotype mesoporous zirconium metal-organic framework with ultralarge pores.

    Feng, Dawei; Wang, Kecheng; Su, Jie; Liu, Tian-Fu; Park, Jihye; Wei, Zhangwen; Bosch, Mathieu; Yakovenko, Andrey; Zou, Xiaodong; Zhou, Hong-Cai

    2015-01-02

    Through topological rationalization, a zeotype mesoporous Zr-containing metal-organic framework (MOF), namely PCN-777, has been designed and synthesized. PCN-777 exhibits the largest cage size of 3.8nm and the highest pore volume of 2.8cm(3)g(-1) among reported Zr-MOFs. Moreover, PCN-777 shows excellent stability in aqueous environments, which makes it an ideal candidate as a support to incorporate different functional moieties. Through facile internal surface modification, the interaction between PCN-777 and different guests can be varied to realize efficient immobilization

  5. Versatile, High Quality and Scalable Continuous Flow Production of Metal-Organic Frameworks

    Rubio-Martinez, Marta; Batten, Michael P.; Polyzos, Anastasios; Carey, Keri-Constanti; Mardel, James I.; Lim, Kok-Seng; Hill, Matthew R.

    2014-01-01

    Further deployment of Metal-Organic Frameworks in applied settings requires their ready preparation at scale. Expansion of typical batch processes can lead to unsuccessful or low quality synthesis for some systems. Here we report how continuous flow chemistry can be adapted as a versatile route to a range of MOFs, by emulating conditions of lab-scale batch synthesis. This delivers ready synthesis of three different MOFs, with surface areas that closely match theoretical maxima, with production rates of 60 g/h at extremely high space-time yields. PMID:24962145

  6. Metal-Organic-Framework-Mediated Nitrogen-Doped Carbon for CO2 Electrochemical Reduction

    Wang, Riming

    2018-04-11

    A nitrogen-doped carbon was synthesized through the pyrolysis of the well-known metal-organic framework ZIF-8, followed by a subsequent acid treatment, and has been applied as a catalyst in the electrochemical reduction of carbon dioxide. The resulting electrode shows Faradaic efficiencies to carbon monoxide as high as ∼78%, with hydrogen being the only byproduct. The pyrolysis temperature determines the amount and the accessibility of N species in the carbon electrode, in which pyridinic-N and quaternary-N species play key roles in the selective formation of carbon monoxide.

  7. A Redox-Active Bistable Molecular Switch Mounted inside a Metal-Organic Framework.

    Chen, Qishui; Sun, Junling; Li, Peng; Hod, Idan; Moghadam, Peyman Z; Kean, Zachary S; Snurr, Randall Q; Hupp, Joseph T; Farha, Omar K; Stoddart, J Fraser

    2016-11-02

    We describe the incorporation of a bistable mechanically interlocked molecule (MIM) into a robust Zr-based metal-organic framework (MOF), NU-1000, by employing a post-synthetic functionalization protocol. On average, close to two bistable [2]catenanes can be incorporated per repeating unit of the hexagonal channels of NU-1000. The reversible redox-switching of the bistable [2]catenanes is retained inside the MOF, as evidenced by solid-state UV-vis-NIR reflectance spectroscopy and cyclic voltammetry. This research demonstrates that bistable MIMs are capable of exhibiting robust dynamics inside the nanopores of a MOF.

  8. Exciplex formation and energy transfer in a self-assembled metal-organic hybrid system.

    Haldar, Ritesh; Rao, K Venkata; George, Subi J; Maji, Tapas Kumar

    2012-05-07

    Exciting assemblies: A metal-organic self-assembly of pyrenebutyric acid (PBA), 1,10-phenanthroline (o-phen), and Mg(II) shows solid-state fluorescence originating from a 1:1 PBA-o-phen exciplex. This exciplex fluorescence is sensitized by another residual PBA chromophore through an excited-state energy-transfer process. The solvent polarity modulates the self-assembly and the corresponding exciplex as well as the energy transfer, resulting in tunable emission of the hybrid (see figure). Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. Pulsed injection metal organic chemical vapour deposition and characterisation of thin CaO films

    Borges, R.P.; Ferreira, P.; Saraiva, A.; Goncalves, R.; Rosa, M.A.; Goncalves, A.P.; Silva, R.C. da; Magalhaes, S.; Lourenco, M.J.V.; Santos, F.J.V.; Godinho, M.

    2009-01-01

    Thin films of CaO were grown on silicon (Si) and lanthanum aluminate (LaAlO 3 ) substrates by pulsed injection metal-organic chemical vapour deposition in a vertical injection MOCVD system. Growth parameters were systematically varied to study their effect on film growth and quality and to determine the optimal growth conditions for this material. Film quality and growth rate were evaluated by atomic force microscopy, X-ray diffraction and Rutherford Backscattering Spectroscopy measurements. Optimised conditions allowed growing transparent, single phase films textured along the (0 0 l) direction.

  10. 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.

  11. 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.

  12. 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.

  13. 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.

  14. Chiral metal-organic frameworks bearing free carboxylic acids for organocatalyst encapsulation.

    Liu, Yan; Xi, Xiaobing; Ye, Chengcheng; Gong, Tengfei; Yang, Zhiwei; Cui, Yong

    2014-12-08

    Two chiral carboxylic acid functionalized micro- and mesoporous metal-organic frameworks (MOFs) are constructed by the stepwise assembly of triple-stranded heptametallic helicates with six carboxylic acid groups. The mesoporous MOF with permanent porosity functions as a host for encapsulation of an enantiopure organic amine catalyst by combining carboxylic acids and chiral amines in situ through acid-base interactions. The organocatalyst-loaded framework is shown to be an efficient and recyclable heterogeneous catalyst for the asymmetric direct aldol reactions with significantly enhanced stereoselectivity in relative to the homogeneous organocatalyst. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. 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.

  16. The Functionalization, Size Control and Properties of Metal-Organic Frameworks

    Xu, Hui; Iversen, Bo Brummerstedt

    Recent years, Metal-Organic Framework (MOF) materials have drawn great attentions due to their potential applications in gas sorption/separation and luminescent sensing. In this dissertation, the recent progress of MOF materials is reviewed, with specific focus on the functionalization, size....... A nanoscale MOF material with controllable size was realized whose morphology has been simulated base on the BFDH method, and the sensing of bacteria endospores was research in detail. We also report the synthesis and sensing of nitroaromatic explosives of a nanoscale MOF material....

  17. Earthquakes: hydrogeochemical precursors

    Ingebritsen, Steven E.; Manga, Michael

    2014-01-01

    Earthquake prediction is a long-sought goal. Changes in groundwater chemistry before earthquakes in Iceland highlight a potential hydrogeochemical precursor, but such signals must be evaluated in the context of long-term, multiparametric data sets.

  18. 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.

  19. Sensing and capture of toxic and hazardous gases and vapors by metal-organic frameworks.

    Wang, Hao; Lustig, William P; Li, Jing

    2018-03-13

    Toxic and hazardous chemical species are ubiquitous, predominantly emitted by anthropogenic activities, and pose serious risks to human health and the environment. Thus, the sensing and subsequent capture of these chemicals, especially in the gas or vapor phase, are of extreme importance. To this end, metal-organic frameworks have attracted significant interest, as their high porosity and wide tunability make them ideal for both applications. These tailorable framework materials are particularly promising for the specific sensing and capture of targeted chemicals, as they can be designed to fit a diverse range of required conditions. This review will discuss the advantages of metal-organic frameworks in the sensing and capture of harmful gases and vapors, as well as principles and strategies guiding the design of these materials. Recent progress in the luminescent detection of aromatic and aliphatic volatile organic compounds, toxic gases, and chemical warfare agents will be summarized, and the adsorptive removal of fluorocarbons/chlorofluorocarbons, volatile radioactive species, toxic industrial gases and chemical warfare agents will be discussed.

  20. A spin transition mechanism for cooperative adsorption in metal-organic frameworks

    Reed, Douglas A.; Keitz, Benjamin K.; Oktawiec, Julia; Mason, Jarad A.; Runčevski, Tomče; Xiao, Dianne J.; Darago, Lucy E.; Crocellà, Valentina; Bordiga, Silvia; Long, Jeffrey R.

    2017-10-01

    Cooperative binding, whereby an initial binding event facilitates the uptake of additional substrate molecules, is common in biological systems such as haemoglobin. It was recently shown that porous solids that exhibit cooperative binding have substantial energetic benefits over traditional adsorbents, but few guidelines currently exist for the design of such materials. In principle, metal-organic frameworks that contain coordinatively unsaturated metal centres could act as both selective and cooperative adsorbents if guest binding at one site were to trigger an electronic transformation that subsequently altered the binding properties at neighbouring metal sites. Here we illustrate this concept through the selective adsorption of carbon monoxide (CO) in a series of metal-organic frameworks featuring coordinatively unsaturated iron(II) sites. Functioning via a mechanism by which neighbouring iron(II) sites undergo a spin-state transition above a threshold CO pressure, these materials exhibit large CO separation capacities with only small changes in temperature. The very low regeneration energies that result may enable more efficient Fischer-Tropsch conversions and extraction of CO from industrial waste feeds, which currently underutilize this versatile carbon synthon. The electronic basis for the cooperative adsorption demonstrated here could provide a general strategy for designing efficient and selective adsorbents suitable for various separations.

  1. 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.

  2. Missing Linker Defects in a Homochiral Metal-Organic Framework: Tuning the Chiral Separation Capacity.

    Slater, Benjamin; Wang, Zeru; Jiang, Shanxue; Hill, Matthew R; Ladewig, Bradley P

    2017-12-20

    Efficient chiral separation remains a very challenging task due to the identical physical and chemical properties of the enantiomers of a molecule. Enantiomers only behave differently from each other in the presence of other chiral species. Homochiral metal-organic frameworks (MOFs) have received much attention for their promising enantioseparation properties. However, there are still challenges to overcome in this field such as high enantiomeric separation. Structural defects play an important role in the properties of MOFs and can significantly change the pore architecture. In this work, we introduced missing linker defects into a homochiral metal-organic framework [Zn 2 (bdc)(l-lac)(dmf)] (ZnBLD; bdc = 1,4-benzenedicarboxylic acid, l-lac = l-lactic acid, dmf = N,N'-dimethylformamide) and observed an increase in enantiomeric excess for 1-phenylethanol of 35% with the defective frameworks. We adjusted the concentration of monocarboxylic acid ligand l-lactic acid by varying the ratio of Zn 2+ to ligand from 0.5 to 0.85 mmol. Additionally, a defective framework was synthesized with propanoic acid as modulator. In order to elucidate the correlation between defects and enantiomeric excess, five characterization techniques (FTIR, TGA, 1 H NMR, ICP, and PXRD) were employed. Full width at half-maximum analysis (fwhm) was performed on the powder X-ray diffraction traces and showed that the higher concentration of monocarboxylic acid MOFs were isostructural but suffered from increased fwhm values.

  3. Ab initio study of hydrogen adsorption on benzenoid linkers in metal-organic framework materials

    Gao Yi; Zeng, X C

    2007-01-01

    We have computed the energies of adsorption of molecular hydrogen on a number of molecular linkers in metal-organic framework solid materials using density functional theory (DFT) and ab initio molecular orbital methods. We find that the hybrid B3LYP (Becke three-parameter Lee-Yang-Parr) DFT method gives a qualitatively incorrect prediction of the hydrogen binding with benzenoid molecular linkers. Both local-density approximation (LDA) and generalized gradient approximation (GGA) DFT methods are inaccurate in predicting the values of hydrogen binding energies, but can give a qualitatively correct prediction of the hydrogen binding. When compared to the more accurate binding-energy results based on the ab initio Moeller-Plesset second-order perturbation (MP2) method, the LDA results may be viewed as an upper limit while the GGA results may be viewed as a lower limit. Since the MP2 calculation is impractical for realistic metal-organic framework systems, the combined LDA and GGA calculations provide a cost-effective way to assess the hydrogen binding capability of these systems

  4. Creating Hierarchical Pores by Controlled Linker Thermolysis in Multivariate Metal-Organic Frameworks.

    Feng, Liang; Yuan, Shuai; Zhang, Liang-Liang; Tan, Kui; Li, Jia-Luo; Kirchon, Angelo; Liu, Ling-Mei; Zhang, Peng; Han, Yu; Chabal, Yves J; Zhou, Hong-Cai

    2018-02-14

    Sufficient pore size, appropriate stability, and hierarchical porosity are three prerequisites for open frameworks designed for drug delivery, enzyme immobilization, and catalysis involving large molecules. Herein, we report a powerful and general strategy, linker thermolysis, to construct ultrastable hierarchically porous metal-organic frameworks (HP-MOFs) with tunable pore size distribution. Linker instability, usually an undesirable trait of MOFs, was exploited to create mesopores by generating crystal defects throughout a microporous MOF crystal via thermolysis. The crystallinity and stability of HP-MOFs remain after thermolabile linkers are selectively removed from multivariate metal-organic frameworks (MTV-MOFs) through a decarboxylation process. A domain-based linker spatial distribution was found to be critical for creating hierarchical pores inside MTV-MOFs. Furthermore, linker thermolysis promotes the formation of ultrasmall metal oxide nanoparticles immobilized in an open framework that exhibits high catalytic activity for Lewis acid-catalyzed reactions. Most importantly, this work provides fresh insights into the connection between linker apportionment and vacancy distribution, which may shed light on probing the disordered linker apportionment in multivariate systems, a long-standing challenge in the study of MTV-MOFs.

  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. 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. Energy level alignment and electron transport through metal/organic contacts. From interfaces to molecular electronics

    Abad, Enrique

    2013-07-01

    A new calculational approach to describing metal/organic interfaces. A valuable step towards a better understanding of molecular electronics. Nominated as an outstanding contribution by the Autonomous University of Madrid. In recent years, ever more electronic devices have started to exploit the advantages of organic semiconductors. The work reported in this thesis focuses on analyzing theoretically the energy level alignment of different metal/organic interfaces, necessary to tailor devices with good performance. Traditional methods based on density functional theory (DFT), are not appropriate for analyzing them because they underestimate the organic energy gap and fail to correctly describe the van der Waals forces. Since the size of these systems prohibits the use of more accurate methods, corrections to those DFT drawbacks are desirable. In this work a combination of a standard DFT calculation with the inclusion of the charging energy (U) of the molecule, calculated from first principles, is presented. Regarding the dispersion forces, incorrect long range interaction is substituted by a van der Waals potential. With these corrections, the C60, benzene, pentacene, TTF and TCNQ/Au(111) interfaces are analyzed, both for single molecules and for a monolayer. The results validate the induced density of interface states model.

  8. Hydrogen adsorption on metal-organic frameworks (MOFs) and single-walled carbon nanotubes (SWNTs)

    Poirier, E.; Chahine, R.; Benard, P.; Lafi, L.; Dorval-Douville, G.; Chandonia, P.-A. [Univ. du Quebec a Trois-Rivieres, Inst. de recherche sur l' hydrogene, Trois-Rivieres, Quebec (Canada)]. E-mail: Lyubov.Lafi@uqtr.ca

    2006-07-01

    'Full text:' In recent years, several novel carbon-based microporous materials such as single-walled carbon nanotubes (SWNTs) and metal-organic frameworks (MOFs) have been proposed as promising adsorbents for hydrogen. Hydrogen adsorption measurements on Al-, Cr- and Zn-based metal-organic frameworks (MOFs) and single-walled carbon nanotubes (SWNTs) are presented. The measurements were performed at temperatures ranging from 77 to 300K and pressures up to 50 atm using a volumetric approach. The maximum excess adsorption at 77K ranges from 2,8 to 3,9 wt % for the MOFs and from 1,5 to 2,5 wt % for the SWNTs. These values are reached at pressures below 40 atm. At room temperature and 40 atm, modest amounts of hydrogen are adsorbed (< 0,4 wt %). A Dubinin-Astakhov (DA) approach is used to investigate the measured adsorption isotherms and retrieve energetic and structural parameters. The adsorption enthalpy averaged over filling is found to be about 2,9 kJ/mol for the MOF-5 and about 3,6 - 4,2 kJ/mol for SWNTs. The uptake of hydrogen on SWNTs and MOF-5 appears to be due to physisorption and can be described, through the DA-model, by a traditional theory of micropore filling. (author)

  9. Made-to-order metal-organic frameworks for trace carbon dioxide removal and air capture

    Shekhah, Osama

    2014-06-25

    Direct air capture is regarded as a plausible alternate approach that, if economically practical, can mitigate the increasing carbon dioxide emissions associated with two of the main carbon polluting sources, namely stationary power plants and transportation. Here we show that metal-organic framework crystal chemistry permits the construction of an isostructural metal-organic framework (SIFSIX-3-Cu) based on pyrazine/copper(II) two-dimensional periodic 4 4 square grids pillared by silicon hexafluoride anions and thus allows further contraction of the pore system to 3.5 versus 3.84 for the parent zinc(II) derivative. This enhances the adsorption energetics and subsequently displays carbon dioxide uptake and selectivity at very low partial pressures relevant to air capture and trace carbon dioxide removal. The resultant SIFSIX-3-Cu exhibits uniformly distributed adsorption energetics and offers enhanced carbon dioxide physical adsorption properties, uptake and selectivity in highly diluted gas streams, a performance, to the best of our knowledge, unachievable with other classes of porous materials. 2014 Macmillan Publishers Limited.

  10. 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.

  11. Polymerization Using Phosphazene Bases

    Zhao, Junpeng

    2015-09-01

    In the recent rise of metal-free polymerization techniques, organic phosphazene superbases have shown their remarkable strength as promoter/catalyst for the anionic polymerization of various types of monomers. Generally, the complexation of phosphazene base with the counterion (proton or lithium cation) significantly improves the nucleophilicity of the initiator/chain end resulting in highly enhanced polymerization rates, as compared with conventional metalbased initiating systems. In this chapter, the general features of phosphazenepromoted/catalyzed polymerizations and the applications in macromolecular engineering (synthesis of functionalized polymers, block copolymers, and macromolecular architectures) are discussed with challenges and perspectives being pointed out.

  12. Precursors for use in vapour and solution phase thermolysis routes to II-VI thin films and nanodispersed oxide materials

    Chunggaze, M.

    1999-12-01

    Monothiocarbamates M(OSCNEt 2 ) 2 M = Cd (1) Zn (2) analogous to the dithiocarbamates (Et 2 NCS 2 ) 2 M which have been extensively studied for metal-organic chemical vapour deposition (MOCVD), have been prepared as alternative single-source precursors for depositing II-VI semiconducting materials. Structural analysis of (1) revealed a new, O-binucleating, bonding mode for the monothiocarbamato ligand resulting in polymeric chains which are co-aligned to give a distorted close-packed hexagonal array. The mixed alkyl zinc derivative [Et 4 Zn 4 (OSCNEt 2 ) 2 (NEt 2 ) 2 ] is formed as the only isolable product from the reaction of EtZnNEt 2 with carbonyl sulfide and also exhibits a second new bonding mode for the monothiocarbamato ligand in which both the oxygen and sulfur atoms are binucleating. Uniform adherent films of CdS films with various morphologies were grown on GaAs(100) and glass at substrate temperatures between 350-450 deg C. No oxygen incorporation within the films was observed. Mechanistic studies into the decompositional behaviour of the monothiocarbamate precursors in comparison to the dithiocarbamate precursors were investigated by using pyrolysis GC-MS and EI-MS; with GC-MS conditions comparable to those usually used in MOCVD reactors. GC-MS analysis showed that the major decomposition product during the deposition of CdS is Et 2 NC(O)SC(O)NEt 2 . Similar mechanistic studies into the deposition of MSe by MOCVD from the diselenocarbamates M(Se 2 CNEt 2 ) 2 M = Zn (3), Cd (4); M(Se 2 CNMe n Hex) 2 M = Zn (5), Cd (6); and EtZnSe 2 CNEt 2 (7) were carried out in an effort to determine why the symmetric selenocarbamates (3) and (4) deposit films heavily contaminated with selenium in comparison to the asymmetric analogues (5) and (6). The EI-MS of all five selenium compounds revealed similar decomposition pathways, which start with the loss of an alkyl group. However, studies of compounds (1)-(5) by pyrolysis GC-MS show that selenium clusters Se n n = 1

  13. Applied bioactive polymeric materials

    Carraher, Charles; Foster, Van

    1988-01-01

    The biological and biomedical applications of polymeric materials have increased greatly in the past few years. This book will detail some, but not all, of these recent developments. There would not be enough space in this book to cover, even lightly, all of the major advances that have occurred. Some earlier books and summaries are available by two of this book's Editors (Gebelein & Carraher) and these should be consul ted for additional information. The books are: "Bioactive Polymeric Systems" (Plenum, 1985); "Polymeric Materials In Medication" (Plenum, 1985); "Biological Acti vi ties of Polymers" (American Chemical Society, 1982). Of these three, "Bioacti ve Polymeric Systems" should be the most useful to a person who is new to this field because it only contains review articles written at an introductory level. The present book primarily consists of recent research results and applications, with only a few review or summary articles. Bioactive polymeric materials have existed from the creation of life...

  14. Hyperbranched polymers from polymerization in solid state

    Tomaz, Vivian A.; Silva, Rafael; Muniz, Edvani C.; Rubira, Adley F.

    2009-01-01

    The macroscopic properties of polymers are directly related to the chemical characteristics of the monomeric units and also with the geometric arrangement of polymer chains. Thus, polymers were synthesized from two well-known chelators EDTA and EDA. We evaluated the conditions for the polymerization of the precursors in the solid state. The polymerization was carried out varying the proportions of reagents, aiming the polymers with different degrees of chain branching and the materials were characterized by FTIR. The materials obtained from the best condition for synthesis were purified by size-exclusion chromatography of and were subjected to characterization by FTIR and NMR of 1 H and 13 C. The content of end groups in these samples was determined by back titration. (author)

  15. Antifungal activity of water-stable copper-containing metal-organic frameworks

    Bouson, Supaporn; Krittayavathananon, Atiweena; Phattharasupakun, Nutthaphon; Siwayaprahm, Patcharaporn; Sawangphruk, Montree

    2017-10-01

    Although metal-organic frameworks (MOFs) or porous coordination polymers have been widely studied, their antimicrobial activities have not yet been fully investigated. In this work, antifungal activity of copper-based benzene-tricarboxylate MOF (Cu-BTC MOF), which is water stable and industrially interesting, is investigated against Candida albicans, Aspergillus niger, Aspergillus oryzae and Fusarium oxysporum. The Cu-BTC MOF can effectively inhibit the growth rate of C. albicans and remarkably inhibit the spore growth of A. niger, A. oryzae and F. oxysporum. This finding shows the potential of using Cu-BTC MOF as a strong biocidal material against representative yeasts and moulds that are commonly found in the food and agricultural industries.

  16. Gas storage in porous metal-organic frameworks for clean energy applications.

    Ma, Shengqian; Zhou, Hong-Cai

    2010-01-07

    Depletion of fossil oil deposits and the escalating threat of global warming have put clean energy research, which includes the search for clean energy carriers such as hydrogen and methane as well as the reduction of carbon dioxide emissions, on the urgent agenda. A significant technical challenge has been recognized as the development of a viable method to efficiently trap hydrogen, methane and carbon dioxide gas molecules in a confined space for various applications. This issue can be addressed by employing highly porous materials as storage media, and porous metal-organic frameworks (MOFs) which have exceptionally high surface areas as well as chemically-tunable structures are playing an unusual role in this respect. In this feature article we provide an overview of the current status of clean energy applications of porous MOFs, including hydrogen storage, methane storage and carbon dioxide capture.

  17. Centimetre-scale micropore alignment in oriented polycrystalline metal-organic framework films via heteroepitaxial growth.

    Falcaro, Paolo; Okada, Kenji; Hara, Takaaki; Ikigaki, Ken; Tokudome, Yasuaki; Thornton, Aaron W; Hill, Anita J; Williams, Timothy; Doonan, Christian; Takahashi, Masahide

    2017-03-01

    The fabrication of oriented, crystalline films of metal-organic frameworks (MOFs) is a critical step toward their application to advanced technologies such as optics, microelectronics, microfluidics and sensing. However, the direct synthesis of MOF films with controlled crystalline orientation remains a significant challenge. Here we report a one-step approach, carried out under mild conditions, that exploits heteroepitaxial growth for the rapid fabrication of oriented polycrystalline MOF films on the centimetre scale. Our methodology employs crystalline copper hydroxide as a substrate and yields MOF films with oriented pore channels on scales that primarily depend on the dimensions of the substrate. To demonstrate that an anisotropic crystalline morphology can translate to a functional property, we assembled a centimetre-scale MOF film in the presence of a dye and showed that the optical response could be switched 'ON' or 'OFF' by simply rotating the film.

  18. 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.

  19. Mechanized azobenzene-functionalized zirconium metal-organic framework for on-command cargo release.

    Meng, Xiangshi; Gui, Bo; Yuan, Daqiang; Zeller, Matthias; Wang, Cheng

    2016-08-01

    Stimuli-responsive metal-organic frameworks (MOFs) have gained increasing attention recently for their potential applications in many areas. We report the design and synthesis of a water-stable zirconium MOF (Zr-MOF) that bears photoresponsive azobenzene groups. This particular MOF can be used as a reservoir for storage of cargo in water, and the cargo-loaded MOF can be further capped to construct a mechanized MOF through the binding of β-cyclodextrin with the azobenzene stalks on the MOF surface. The resulting mechanized MOF has shown on-command cargo release triggered by ultraviolet irradiation or addition of competitive agents without premature release. This study represents a simple approach to the construction of stimuli-responsive mechanized MOFs, and considering mechanized UiO-68-azo made from biocompatible components, this smart system may provide a unique MOF platform for on-command drug delivery in the future.

  20. Efficient photocatalytic degradation of rhodamine 6G with a quantum dot-metal organic framework nanocomposite.

    Kaur, Rajnish; Vellingiri, Kowsalya; Kim, Ki-Hyun; Paul, A K; Deep, Akash

    2016-07-01

    The hybrid structures of metal organic frameworks (MOFs) and nanoparticles may offer the realization of effective photocatalytic materials due to combined benefits of the porous and molecular sieving properties of MOF matrix and the functional characteristics of encapsulated nanoparticles. In this study, cadmium telluride (CdTe) quantum dots (QD) are conjugated with a europium-MOF for the synthesis of a novel nanocomposite material with photocatalytic properties. Successful synthesis of a QD/Eu-MOF nanocomposite was characterized with various spectroscopic and microscopic techniques. This QD/Eu-MOF is found to be an effective catalyst to complete the degradation of Rhodamine 6G dye within 50 min. Copyright © 2016 Elsevier Ltd. All rights reserved.

  1. 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.

  2. Characterization of Adsorption Enthalpy of Novel Water-Stable Zeolites and Metal-Organic Frameworks

    Kim, Hyunho; Cho, H. Jeremy; Narayanan, Shankar; Yang, Sungwoo; Furukawa, Hiroyasu; Schiffres, Scott; Li, Xiansen; Zhang, Yue-Biao; Jiang, Juncong; Yaghi, Omar M.; Wang, Evelyn N.

    2016-01-01

    Water adsorption is becoming increasingly important for many applications including thermal energy storage, desalination, and water harvesting. To develop such applications, it is essential to understand both adsorbent-adsorbate and adsorbate-adsorbate interactions, and also the energy required for adsorption/desorption processes of porous material-adsorbate systems, such as zeolites and metal-organic frameworks (MOFs). In this study, we present a technique to characterize the enthalpy of adsorption/desorption of zeolites and MOF-801 with water as an adsorbate by conducting desorption experiments with conventional differential scanning calorimetry (DSC) and thermogravimetric analyzer (TGA). With this method, the enthalpies of adsorption of previously uncharacterized adsorbents were estimated as a function of both uptake and temperature. Our characterizations indicate that the adsorption enthalpies of type I zeolites can increase to greater than twice the latent heat whereas adsorption enthalpies of MOF-801 are nearly constant for a wide range of vapor uptakes.

  3. 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.

  4. A metal-organic framework-based splitter for separating propylene from propane

    Cadiau, Amandine

    2016-07-07

    The chemical industry is dependent on the olefin/paraffin separation, which is mainly accomplished by using energy-intensive processes. We report the use of reticular chemistry for the fabrication of a chemically stable fluorinated metal-organic framework (MOF) material (NbOFFIVE-1-Ni, also referred to as KAUST-7). The bridging of Ni(II)-pyrazine square-grid layers with (NbOF5)2- pillars afforded the construction of a three-dimensional MOF, enclosing a periodic array of fluoride anions in contracted square-shaped channels. The judiciously selected bulkier (NbOF5)2- caused the looked-for hindrance of the previously free-rotating pyrazine moieties, delimiting the pore system and dictating the pore aperture size and its maximum opening. The restricted MOF window resulted in the selective molecular exclusion of propane from propylene at atmospheric pressure, as evidenced through multiple cyclic mixed-gas adsorption and calorimetric studies.

  5. Improved synthesis and hydrogen storage of a microporous metal-organic framework material

    Cheng Shaojuan; Liu Shaobing; Zhao Qiang; Li Jinping

    2009-01-01

    A microporous metal-organic framework MOF-5 [Zn 4 O(BDC) 3 , BDC = 1,4-benzenedicarboxylic] was synthesized with and without H 2 O 2 by improved methods based on the previous studies. The obtained materials were characterized by X-ray diffraction, scanning electron microscopy and nitrogen adsorption, and their hydrogen storage capacities were measured. The synthesis experiments showed that H 2 O 2 favored the growth of high quality sample, large pore volume and high specific surface area. The measurements of hydrogen storage indicated that the sample with higher specific surface area and large pore volume showed better hydrogen storage behavior than other samples. It was suggested that specific surface area and pore volume influenced the capacity of hydrogen storage for MOF-5 material.

  6. Recent Progress in Metal-Organic Frameworks and Their Derived Nanostructures for Energy and Environmental Applications.

    Xie, Zhiqiang; Xu, Wangwang; Cui, Xiaodan; Wang, Ying

    2017-04-22

    Metal-organic frameworks (MOFs), as a very promising category of porous materials, have attracted increasing interest from research communities due to their extremely high surface areas, diverse nanostructures, and unique properties. In recent years, there is a growing body of evidence to indicate that MOFs can function as ideal templates to prepare various nanostructured materials for energy and environmental cleaning applications. Recent progress in the design and synthesis of MOFs and MOF-derived nanomaterials for particular applications in lithium-ion batteries, sodium-ion batteries, supercapacitors, dye-sensitized solar cells, and heavy-metal-ion detection and removal is reviewed herein. In addition, the remaining major challenges in the above fields are discussed and some perspectives for future research efforts in the development of MOFs are also provided. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. Remote stabilization of copper paddlewheel based molecular building blocks in metal-organic frameworks

    Gao, Wenyang

    2015-03-24

    Copper paddlewheel based molecular building blocks (MBBs) are ubiquitous and have been widely employed for the construction of highly porous metal-organic frameworks (MOFs). However, most copper paddlewheel based MOFs fail to retain their structural integrity in the presence of water. This instability is directly correlated to the plausible displacement of coordinating carboxylates in the copper paddlewheel MBB, [Cu2(O2C-)4], by the strongly coordinating water molecules. In this comprehensive study, we illustrate the chemical stability control in the rht-MOF platform via strengthening the coordinating bonds within the triangular inorganic MBB, [Cu3O(N4-x(CH)xC-)3] (x = 0, 1, or 2). Remotely, the chemical stabilization propagated into the paddlewheel MBB to afford isoreticular rht-MOFs with remarkably enhanced water/chemical stabilities compared to the prototypal rht-MOF-1. © 2015 American Chemical Society.

  8. Construction of hierarchically porous metal-organic frameworks through linker labilization

    Yuan, Shuai; Zou, Lanfang; Qin, Jun-Sheng; Li, Jialuo; Huang, Lan; Feng, Liang; Wang, Xuan; Bosch, Mathieu; Alsalme, Ali; Cagin, Tahir; Zhou, Hong-Cai

    2017-05-01

    A major goal of metal-organic framework (MOF) research is the expansion of pore size and volume. Although many approaches have been attempted to increase the pore size of MOF materials, it is still a challenge to construct MOFs with precisely customized pore apertures for specific applications. Herein, we present a new method, namely linker labilization, to increase the MOF porosity and pore size, giving rise to hierarchical-pore architectures. Microporous MOFs with robust metal nodes and pro-labile linkers were initially synthesized. The mesopores were subsequently created as crystal defects through the splitting of a pro-labile-linker and the removal of the linker fragments by acid treatment. We demonstrate that linker labilization method can create controllable hierarchical porous structures in stable MOFs, which facilitates the diffusion and adsorption process of guest molecules to improve the performances of MOFs in adsorption and catalysis.

  9. Experimental comparison of chiral metal-organic framework used as stationary phase in chromatography.

    Xie, Sheng-Ming; Zhang, Mei; Fei, Zhi-Xin; Yuan, Li-Ming

    2014-10-10

    Chiral metal-organic frameworks (MOFs) are a new class of multifunctional material, which possess diverse structures and unusual properties such as high surface area, uniform and permanent cavities, as well as good chemical and thermal stability. Their chiral functionality makes them attractive as novel enantioselective adsorbents and stationary phases in separation science. In this paper, the experimental comparison of a chiral MOF [In₃O(obb)₃(HCO₂)(H₂O)] solvent used as a stationary phase was investigated in gas chromatography (GC), high-performance liquid chromatography (HPLC) and capillary electrochromatography (CEC). The potential relationship between the structure and components of chiral MOFs with their chiral recognition ability and selectivity are presented. Copyright © 2014 Elsevier B.V. All rights reserved.

  10. 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....

  11. 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).

  12. Computational design of metal-organic frameworks with paddlewheel-type secondary building units

    Schwingenschlogl, Udo; Peskov, Maxim V.; Masghouni, Nejib

    We employ the TOPOS package to study 697 coordination polymers containing paddlewheel-type secondary building units. The underlying nets are analyzed and 3 novel nets are chosen as potential topologies for paddlewheel-type metal organic frameworks (MOFs). Dicarboxylate linkers are used to build basic structures for novel isoreticular MOF series, aiming at relatively compact structures with a low number of atoms per unit cell. The structures are optimized using density functional theory. Afterwards the Grand Canonical Monte Carlo approach is employed to generate adsorption isotherms for CO2, CO, and CH4 molecules. We utilize the universal forcefield for simulating the interaction between the molecules and hosting MOF. The diffusion behavior of the molecules inside the MOFs is analyzed by molecular dynamics simulations.

  13. Chiral Recognition and Separation by Chirality-Enriched Metal-Organic Frameworks.

    Das, Saikat; Xu, Shixian; Ben, Teng; Qiu, Shilun

    2018-05-16

    Endowed with chiral channels and pores, chiral metal-organic frameworks (MOFs) are highly useful; however, their synthesis remains a challenge given that most chiral building blocks are expensive. Although MOFs with induced chirality have been reported to avoid this shortcoming, no study providing evidence for the ee value of such MOFs has yet been reported. We herein describe the first study on the efficiency of chiral induction in MOFs using inexpensive achiral building blocks and fully recoverable chiral dopants to control the handedness of racemic MOFs. This method yielded chirality-enriched MOFs with accessible pores. The ability of the materials to form host-guest complexes was probed with enantiomers of varying size and coordination and in solvents with varying polarity. Furthermore, mixed-matrix membranes (MMMs) composed of chirality-enriched MOF particles dispersed in a polymer matrix demonstrated a new route for chiral separation. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. A multifunctional chemical sensor based on a three-dimensional lanthanide metal-organic framework

    Du, Pei-Yao [College of Chemistry and Key Laboratory of Advanced Energy Materials Chemistry (MOE), Collaborative Innovation Center of Chemical Science and Engineering, Nankai University, Tianjin 300071 (China); Liao, Sheng-Yun [Department of Applied Chemistry, Tianjin University of Technology, Tianjin 300384 (China); Gu, Wen, E-mail: guwen68@nankai.edu.cn [College of Chemistry and Key Laboratory of Advanced Energy Materials Chemistry (MOE), Collaborative Innovation Center of Chemical Science and Engineering, Nankai University, Tianjin 300071 (China); Liu, Xin, E-mail: liuxin64@nankai.edu.cn [College of Chemistry and Key Laboratory of Advanced Energy Materials Chemistry (MOE), Collaborative Innovation Center of Chemical Science and Engineering, Nankai University, Tianjin 300071 (China)

    2016-12-15

    A 3D lanthanide MOF with formula [Sm{sub 2}(abtc){sub 1.5}(H{sub 2}O){sub 3}(DMA)]·H{sub 2}O·DMA (1) has been successfully synthesized via solvothermal method. Luminescence studies reveal that 1 exhibits dual functional detection benzyl alcohol and benzaldehyde among different aromatic molecules. In addition, 1 displays a turn-on luminescence sensing with respect to ethanol among different alcohol molecules, which suggests that 1 is also a promising luminescent probe for high selective sensing of ethanol. - Highlights: • A three-dimensional lanthanide metal-organic framework has been synthesized. • Complex 1 exhibits dual functional detection benzyl alcohol and benzaldehyde among different aromatic molecules. • Complex 1 displays a turn-on luminescence sensing with respect to ethanol among different alcohol molecules.

  15. Rapid and Accurate Machine Learning Recognition of High Performing Metal Organic Frameworks for CO2 Capture.

    Fernandez, Michael; Boyd, Peter G; Daff, Thomas D; Aghaji, Mohammad Zein; Woo, Tom K

    2014-09-04

    In this work, we have developed quantitative structure-property relationship (QSPR) models using advanced machine learning algorithms that can rapidly and accurately recognize high-performing metal organic framework (MOF) materials for CO2 capture. More specifically, QSPR classifiers have been developed that can, in a fraction of a section, identify candidate MOFs with enhanced CO2 adsorption capacity (>1 mmol/g at 0.15 bar and >4 mmol/g at 1 bar). The models were tested on a large set of 292 050 MOFs that were not part of the training set. The QSPR classifier could recover 945 of the top 1000 MOFs in the test set while flagging only 10% of the whole library for compute intensive screening. Thus, using the machine learning classifiers as part of a high-throughput screening protocol would result in an order of magnitude reduction in compute time and allow intractably large structure libraries and search spaces to be screened.

  16. Lithium inclusion in indium metal-organic frameworks showing increased surface area and hydrogen adsorption

    Mathieu Bosch

    2014-12-01

    Full Text Available Investigation of counterion exchange in two anionic In-Metal-Organic Frameworks (In-MOFs showed that partial replacement of disordered ammonium cations was achieved through the pre-synthetic addition of LiOH to the reaction mixture. This resulted in a surface area increase of over 1600% in {Li [In(1,3 − BDC2]}n and enhancement of the H2 uptake of approximately 275% at 80 000 Pa at 77 K. This method resulted in frameworks with permanent lithium content after repeated solvent exchange as confirmed by inductively coupled plasma mass spectrometry. Lithium counterion replacement appears to increase porosity after activation through replacement of bulkier, softer counterions and demonstrates tuning of pore size and properties in MOFs.

  17. Characterization of Adsorption Enthalpy of Novel Water-Stable Zeolites and Metal-Organic Frameworks

    Kim, Hyunho; Cho, H. Jeremy; Narayanan, Shankar; Yang, Sungwoo; Furukawa, Hiroyasu; Schiffres, Scott; Li, Xiansen; Zhang, Yue-Biao; Jiang, Juncong; Yaghi, Omar M.; Wang, Evelyn N.

    2016-01-01

    Water adsorption is becoming increasingly important for many applications including thermal energy storage, desalination, and water harvesting. To develop such applications, it is essential to understand both adsorbent-adsorbate and adsorbate-adsorbate interactions, and also the energy required for adsorption/desorption processes of porous material-adsorbate systems, such as zeolites and metal-organic frameworks (MOFs). In this study, we present a technique to characterize the enthalpy of adsorption/desorption of zeolites and MOF-801 with water as an adsorbate by conducting desorption experiments with conventional differential scanning calorimetry (DSC) and thermogravimetric analyzer (TGA). With this method, the enthalpies of adsorption of previously uncharacterized adsorbents were estimated as a function of both uptake and temperature. Our characterizations indicate that the adsorption enthalpies of type I zeolites can increase to greater than twice the latent heat whereas adsorption enthalpies of MOF-801 are nearly constant for a wide range of vapor uptakes. PMID:26796523

  18. Sensitive resonant gas sensor operating in air with metal organic frameworks coating

    Jaber, Nizar; Ilyas, Saad; Shekhah, Osama; Eddaoudi, Mohamed; Younis, Mohammad I.

    2017-01-01

    We report a practical resonant gas sensor that is uniformly coated with metal organic frameworks (MOFs) and excited near the higher order modes for a higher attained sensitivity. The resonator is based on an electrostatically excited clamped-clamped microbeam. The microbeam is fabricated from a polyimide layer coated from the top with Cr/Au and from the bottom with Cr/Au/Cr layer. The geometry of the resonator is optimized to reduce the effect of the squeeze film damping, thereby allowing operation under atmospheric pressure. The electrostatic force electrode is designed to enhance the excitation of the second mode of vibration with the minimum power required. Significant frequency shift (kHz) is demonstrated for the first time upon water vapor, acetone, and ethanol exposure due to the MOFs functionalization and the higher order modes excitation. Also, the adsorption dynamics and MOF selectivity is investigated by studying the decaying time constants of the response upon gas exposure.

  19. Hydrolytically stable fluorinated metal-organic frameworks for energy-efficient dehydration

    Cadiau, Amandine

    2017-05-18

    Natural gas must be dehydrated before it can be transported and used, but conventional drying agents such as activated alumina or inorganic molecular sieves require an energy-intensive desiccant-regeneration step. We report a hydrolytically stable 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 streams containing CO2, N2, CH4, and higher hydrocarbons typical of natural gas, as well as selectively removed both H2O and CO2 in N2-containing streams. The complete desorption of the adsorbed water molecules contained by the AlFFIVE-1-Ni sorbent requires relatively moderate temperature (~105°C) and about half the energy input for commonly used desiccants.

  20. Adsorptive removal of naproxen and clofibric acid from water using metal-organic frameworks.

    Hasan, Zubair; Jeon, Jaewoo; Jhung, Sung Hwa

    2012-03-30

    Adsorptive removal of naproxen and clofibric acid, two typical PPCPs (pharmaceuticals and personal care products), has been studied using metal-organic frameworks (MOFs) for the first time. The removal efficiency decreases in the order of MIL-101>MIL-100-Fe>activated carbon both in adsorption rate and adsorption capacity. The adsorption kinetics and capacity of PPCPs generally depend on the average pore size and surface area (or pore volume), respectively, of the adsorbents. The adsorption mechanism may be explained with a simple electrostatic interaction between PPCPs and the adsorbent. Finally, it can be suggested that MOFs having high porosity and large pore size can be potential adsorbents to remove harmful PPCPs in contaminated water. Copyright © 2012 Elsevier B.V. All rights reserved.

  1. Light Hydrocarbons Adsorption Mechanisms in Two Calcium-based Microporous Metal Organic Frameworks

    Plonka, Anna M.

    2016-01-25

    The adsorption mechanism of ethane, ethylene and acetylene (C2Hn; n=2, 4, 6) on two microporous metal organic frameworks (MOFs) is described here that is consistent with observations from single crystal and powder X-ray diffraction, calorimetric measurments and gas adsorption isotherm measurements. Two calcium-based MOFs, designated as SBMOF-1 and SBMOF-2 (SB: Stony Brook), form three-dimensional frameworks with one-dimensional open channels. As determined form single crystal diffraction experiments channel geometries of both SBMOF-1 and SBMOF-2 provide multiple adsorption sites for hydrocarbon molecules trough C-H…π and C-H…O interactions, similarly to interactions in the molecular and protein crystals. Both materials selectively adsorb C2 hydrocarbon gases over methane as determined with IAST and breakthrough calculations, with C2H6/CH4 selectivity as high as 74 in SBMOF-1.

  2. Design and construction of porous metal-organic frameworks based on flexible BPH pillars

    Hao, Xiang-Rong; Yang, Guang-sheng; Shao, Kui-Zhan; Su, Zhong-Min; Yuan, Gang; Wang, Xin-Long

    2013-02-01

    Three metal-organic frameworks (MOFs), [Co2(BPDC)2(4-BPH)·3DMF]n (1), [Cd2(BPDC)2(4-BPH)2·2DMF]n (2) and [Ni2(BDC)2(3-BPH)2 (H2O)·4DMF]n (3) (H2BPDC=biphenyl-4,4'-dicarboxylic acid, H2BDC=terephthalic acid, BPH=bis(pyridinylethylidene)hydrazine and DMF=N,N'-dimethylformamide), have been solvothermally synthesized based on the insertion of heterogeneous BPH pillars. Framework 1 has "single-pillared" MOF-5-like motif with inner cage diameters of up to 18.6 Å. Framework 2 has "double pillared" MOF-5-like motif with cage diameters of 19.2 Å while 3 has "double pillared" 8-connected framework with channel diameters of 11.0 Å. Powder X-ray diffraction (PXRD) shows that 3 is a dynamic porous framework.

  3. Single Pt Atoms Confined into a Metal-Organic Framework for Efficient Photocatalysis.

    Fang, Xinzuo; Shang, Qichao; Wang, Yu; Jiao, Long; Yao, Tao; Li, Yafei; Zhang, Qun; Luo, Yi; Jiang, Hai-Long

    2018-02-01

    It is highly desirable yet remains challenging to improve the dispersion and usage of noble metal cocatalysts, beneficial to charge transfer in photocatalysis. Herein, for the first time, single Pt atoms are successfully confined into a metal-organic framework (MOF), in which electrons transfer from the MOF photosensitizer to the Pt acceptor for hydrogen production by water splitting under visible-light irradiation. Remarkably, the single Pt atoms exhibit a superb activity, giving a turnover frequency of 35 h -1 , ≈30 times that of Pt nanoparticles stabilized by the same MOF. Ultrafast transient absorption spectroscopy further unveils that the single Pt atoms confined into the MOF provide highly efficient electron transfer channels and density functional theory calculations indicate that the introduction of single Pt atoms into the MOF improves the hydrogen binding energy, thus greatly boosting the photocatalytic H 2 production activity. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  4. Application of Two Cobalt-Based Metal-Organic Frameworks as Oxidative Desulfurization Catalysts.

    Masoomi, Mohammad Yaser; Bagheri, Minoo; Morsali, Ali

    2015-12-07

    Two new porous cobalt-based metal-organic frameworks, [Co6(oba)5(OH)2(H2O)2(DMF)4]n · 5DMF (TMU-10) and [Co3(oba)3(O) (Py)0.5] n · 4DMF · Py (TMU-12) have been synthesized by solvothermal method using a nonlinear dicarboxylate ligand. Under mild reaction conditions, these compounds exhibited good catalytic activity and reusability in oxidative desulfurization (ODS) reaction of model oil which was prepared by dissolving dibenzothiophene (DBT) in n-hexane. FT-IR and Mass analysis showed that the main product of DBT oxidation is its corresponding sulfone, which was adsorbed on the surfaces of catalysts. The activation energy was obtained as 13.4 kJ/mol.

  5. InAs film grown on Si(111) by metal organic vapor phase epitaxy

    Caroff, P; Jeppsson, M; Mandl, B; Wernersson, L-E; Wheeler, D; Seabaugh, A; Keplinger, M; Stangl, J; Bauer, G

    2008-01-01

    We report the successful growth of high quality InAs films directly on Si(111) by Metal Organic Vapor Phase Epitaxy. A nearly mirror-like and uniform InAs film is obtained at 580 0 C for a thickness of 2 μm. We measured a high value of the electron mobility of 5100 cm 2 /Vs at room temperature. The growth is performed using a standard two-step procedure. The influence of the nucleation layer, group V flow rate, and layer thickness on the electrical and morphological properties of the InAs film have been investigated. We present results of our studies by Atomic Force Microscopy, Scanning Electron Microscopy, electrical Hall/van der Pauw and structural X-Ray Diffraction characterization

  6. 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.

  7. Condensation of Methane in the Metal-Organic Framework IRMOF-1: Evidence for Two Critical Points.

    Höft, Nicolas; Horbach, Jürgen

    2015-08-19

    Extensive grand canonical Monte Carlo simulations in combination with successive umbrella sampling are used to investigate the condensation of methane in the nanoporous crystalline material IRMOF-1. Two different types of novel condensation transitions are found, each of them ending in a critical point: (i) a fluid-fluid transition at higher densities (the analog of the liquid-gas transition in the bulk) and (ii) a phase transition at low densities on the surface of the IRMOF-1 structure. The nature of these transitions is different from the usual capillary condensation in thin films and cylindrical pores where the coexisting phases are confined in one or two of the three spatial dimensions. In contrast to that, in IRMOF-1 the different phases can be described as bulk phases that are inhomogeneous due to the presence of the metal-organic framework. As a consequence, the condensation transitions in IRMOF-1 belong to the three-dimensional (3D) Ising universality class.

  8. Thermodynamic analysis of trimethylgallium decomposition during GaN metal organic vapor phase epitaxy

    Sekiguchi, Kazuki; Shirakawa, Hiroki; Chokawa, Kenta; Araidai, Masaaki; Kangawa, Yoshihiro; Kakimoto, Koichi; Shiraishi, Kenji

    2018-04-01

    We analyzed the decomposition of Ga(CH3)3 (TMG) during the metal organic vapor phase epitaxy (MOVPE) of GaN on the basis of first-principles calculations and thermodynamic analysis. We performed activation energy calculations of TMG decomposition and determined the main reaction processes of TMG during GaN MOVPE. We found that TMG reacts with the H2 carrier gas and that (CH3)2GaH is generated after the desorption of the methyl group. Next, (CH3)2GaH decomposes into (CH3)GaH2 and this decomposes into GaH3. Finally, GaH3 becomes GaH. In the MOVPE growth of GaN, TMG decomposes into GaH by the successive desorption of its methyl groups. The results presented here concur with recent high-resolution mass spectroscopy results.

  9. Remote stabilization of copper paddlewheel based molecular building blocks in metal-organic frameworks

    Gao, Wenyang; Cai, Rong; Pham, Tony T.; Forrest, Katherine A.; Hogan, Adam; Nugent, Patrick S.; Williams, Kia R.; Wojtas, Łukasz; Luebke, Ryan; Weselinski, Lukasz Jan; Zaworotko, Michael J.; Space, Brian; Chen, Yusheng; Eddaoudi, Mohamed; Shi, Xiaodong; Ma, Shengqian

    2015-01-01

    Copper paddlewheel based molecular building blocks (MBBs) are ubiquitous and have been widely employed for the construction of highly porous metal-organic frameworks (MOFs). However, most copper paddlewheel based MOFs fail to retain their structural integrity in the presence of water. This instability is directly correlated to the plausible displacement of coordinating carboxylates in the copper paddlewheel MBB, [Cu2(O2C-)4], by the strongly coordinating water molecules. In this comprehensive study, we illustrate the chemical stability control in the rht-MOF platform via strengthening the coordinating bonds within the triangular inorganic MBB, [Cu3O(N4-x(CH)xC-)3] (x = 0, 1, or 2). Remotely, the chemical stabilization propagated into the paddlewheel MBB to afford isoreticular rht-MOFs with remarkably enhanced water/chemical stabilities compared to the prototypal rht-MOF-1. © 2015 American Chemical Society.

  10. Direct Synthesis of 7 nm Thick Zinc(II)-Benzimidazole-Acetate Metal-Organic Framework Nanosheets

    Xue, Feng; Kumar, Prashant; Xu, Wenqian; Mkhoyan, K. Andre; Tsapatsis, Michael

    2018-01-09

    Two-dimensional metal-organic frameworks (MOFs) are promising candidates for high performance gas sepa-ration membranes. Currently, MOF nanosheets are mostly fabricated through delamination of layered MOFs, which often re-sults in a low yield of intact free-standing nanosheets. In this work, we present a direct synthesis method for zinc(II)-benzimidazole-acetate (Zn(Bim)OAc) MOF nanosheets. The obtained nanosheets have a lateral dimension of 600 nm when synthesized at room temperature. By adjusting the synthesis temperature, the morphology of obtained nanosheets can be readily tuned from nanosheets to nanobelts. A thickness of 7 nm is determined for Zn(Bim)OAc using high-angle annular dark-field scanning transmission electron microscopy, which makes these nanosheets promising building blocks of gas sepa-ration membranes.

  11. Titanium-Phosphonate-Based Metal-Organic Frameworks with Hierarchical Porosity for Enhanced Photocatalytic Hydrogen Evolution

    Li, Hui

    2018-02-01

    Photocatalytic hydrogen production is crucial for solar-to-chemical conversion process, wherein high-efficiency photocatalysts lie in the heart of this area. Herein a new photocatalyst of hierarchically mesoporous titanium-phosphonate-based metal-organic frameworks, featuring well-structured spheres, periodic mesostructure and large secondary mesoporosity, are rationally designed with the complex of polyelectrolyte and cathodic surfactant serving as the template. The well-structured hierarchical porosity and homogeneously incorporated phosphonate groups can favor the mass transfer and strong optical absorption during the photocatalytic reactions. Correspondingly, the titanium phosphonates exhibit significantly improved photocatalytic hydrogen evolution rate along with impressive stability. This work can provide more insights into designing advanced photocatalysts for energy conversion and render a tunable platform in photoelectrochemical field.

  12. A novel series of isoreticular metal organic frameworks: Realizing metastable structures by liquid phase epitaxy

    Liu, Jinxuan

    2012-12-04

    A novel class of metal organic frameworks (MOFs) has been synthesized from Cu-acetate and dicarboxylic acids using liquid phase epitaxy. The SURMOF-2 isoreticular series exhibits P4 symmetry, for the longest linker a channel-size of 3 3 nm2 is obtained, one of the largest values reported for any MOF so far. High quality, ab-initio electronic structure calculations confirm the stability of a regular packing of (Cu++) 2-carboxylate paddle-wheel planes with P4 symmetry and reveal, that the SURMOF-2 structures are in fact metastable, with a fairly large activation barrier for the transition to the bulk MOF-2 structures exhibiting a lower, twofold (P2 or C2) symmetry. The theoretical calculations also allow identifying the mechanism for the low-temperature epitaxial growth process and to explain, why a synthesis of this highly interesting, new class of high-symmetry, metastable MOFs is not possible using the conventional solvothermal process.

  13. A novel series of isoreticular metal organic frameworks: Realizing metastable structures by liquid phase epitaxy

    Liu, Jinxuan; Lukose, Binit; Shekhah, Osama; Arslan, Hasan Kemal; Weidler, Peter; Gliemann, Hartmut; Brä se, Stefan; Grosjean, Sylvain; Godt, Adelheid; Feng, Xinliang; Mü llen, Klaus; Magdau, Ioan-Bogdan; Heine, Thomas; Wö ll, Christof

    2012-01-01

    A novel class of metal organic frameworks (MOFs) has been synthesized from Cu-acetate and dicarboxylic acids using liquid phase epitaxy. The SURMOF-2 isoreticular series exhibits P4 symmetry, for the longest linker a channel-size of 3 3 nm2 is obtained, one of the largest values reported for any MOF so far. High quality, ab-initio electronic structure calculations confirm the stability of a regular packing of (Cu++) 2-carboxylate paddle-wheel planes with P4 symmetry and reveal, that the SURMOF-2 structures are in fact metastable, with a fairly large activation barrier for the transition to the bulk MOF-2 structures exhibiting a lower, twofold (P2 or C2) symmetry. The theoretical calculations also allow identifying the mechanism for the low-temperature epitaxial growth process and to explain, why a synthesis of this highly interesting, new class of high-symmetry, metastable MOFs is not possible using the conventional solvothermal process.

  14. Metal-organic framework based highly selective fluorescence turn-on probe for hydrogen sulphide

    Nagarkar, Sanjog S.; Saha, Tanmoy; Desai, Aamod V.; Talukdar, Pinaki; Ghosh, Sujit K.

    2014-11-01

    Hydrogen sulphide (H2S) is known to play a vital role in human physiology and pathology which stimulated interest in understanding complex behaviour of H2S. Discerning the pathways of H2S production and its mode of action is still a challenge owing to its volatile and reactive nature. Herein we report azide functionalized metal-organic framework (MOF) as a selective turn-on fluorescent probe for H2S detection. The MOF shows highly selective and fast response towards H2S even in presence of other relevant biomolecules. Low cytotoxicity and H2S detection in live cells, demonstrate the potential of MOF towards monitoring H2S chemistry in biological system. To the best of our knowledge this is the first example of MOF that exhibit fast and highly selective fluorescence turn-on response towards H2S under physiological conditions.

  15. 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...

  16. Adsorption of methane on Zn(bdc)(ted)0.5 microporous metal-organic framework

    Krungleviciute, Vaiva; Pramanik, Sanhita; Migone, Aldo; Li, Jing

    2011-03-01

    Zn(bdc)(ted)0.5 is metal-organic framework crystallized in a tetragonal space group with a 3D porous structure containing intersecting channels of two different sizes. The larger channels are parallel to the c axis and have a cross section 7.5 × 7.5 AA. The smaller channels are along both the a- and b-axes and have a cross section of 4.8 × 3.2 AA. We measured methane adsorption isotherms at several different temperatures between 82 and 102 K. We calculated the effective specific surface area, isosteric heat and binding energy values. Two distinct substeps were observed in the isotherms corresponding to two different adsorption sites. The origin of the substeps will be discussed.

  17. A multifunctional chemical sensor based on a three-dimensional lanthanide metal-organic framework

    Du, Pei-Yao; Liao, Sheng-Yun; Gu, Wen; Liu, Xin

    2016-01-01

    A 3D lanthanide MOF with formula [Sm 2 (abtc) 1.5 (H 2 O) 3 (DMA)]·H 2 O·DMA (1) has been successfully synthesized via solvothermal method. Luminescence studies reveal that 1 exhibits dual functional detection benzyl alcohol and benzaldehyde among different aromatic molecules. In addition, 1 displays a turn-on luminescence sensing with respect to ethanol among different alcohol molecules, which suggests that 1 is also a promising luminescent probe for high selective sensing of ethanol. - Highlights: • A three-dimensional lanthanide metal-organic framework has been synthesized. • Complex 1 exhibits dual functional detection benzyl alcohol and benzaldehyde among different aromatic molecules. • Complex 1 displays a turn-on luminescence sensing with respect to ethanol among different alcohol molecules.

  18. Synthesis, functionalization, and applications of metal-organic frameworks in biomedicine.

    Chen, Wei; Wu, Chunsheng

    2018-02-13

    Metal-organic frameworks (MOFs), also known as coordination polymers, have attracted extensive research interest in the past few decades due to their unique physical structures and potentially vast applications. In this review, we outline the recent progress in the synthesis, functionalization and applications of MOFs in biomedicine, mainly focusing on two promising, yet challenging areas, i.e., drug delivery and biosensing applications. A major challenge is the proper functionalization of MOFs with demanding properties suitable for biomedical applications. Extensive studies on MOFs in biomedicine have led to substantial progress in the control of key properties of MOFs such as toxicity, size and shape, and biological stability. Due to their flexible composition, pore size and easy functionalization properties, MOFs can be utilized as key components for the development of various functional systems, and their applications in drug delivery and biosensing are reviewed. Future trends and perspectives in these research areas are also outlined.

  19. Mechanical tunability via hydrogen bonding in metal-organic frameworks with the perovskite architecture.

    Li, Wei; Thirumurugan, A; Barton, Phillip T; Lin, Zheshuai; Henke, Sebastian; Yeung, Hamish H-M; Wharmby, Michael T; Bithell, Erica G; Howard, Christopher J; Cheetham, Anthony K

    2014-06-04

    Two analogous metal-organic frameworks (MOFs) with the perovskite architecture, [C(NH2)3][Mn(HCOO)3] (1) and [(CH2)3NH2][Mn(HCOO)3] (2), exhibit significantly different mechanical properties. The marked difference is attributed to their distinct modes of hydrogen bonding between the A-site amine cation and the anionic framework. The stronger cross-linking hydrogen bonding in 1 gives rise to Young's moduli and hardnesses that are up to twice those in 2, while the thermal expansion is substantially smaller. This study presents clear evidence that the mechanical properties of MOF materials can be substantially tuned via hydrogen-bonding interactions.

  20. 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.

  1. A Stable Metal-Organic Framework Featuring a Local Buffer Environment for Carbon Dioxide Fixation.

    He, Hongming; Sun, Qi; Gao, Wenyang; Perman, Jason A; Sun, Fuxing; Zhu, Guangshan; Aguila, Briana; Forrest, Katherine; Space, Brian; Ma, Shengqian

    2018-04-16

    A majority of metal-organic frameworks (MOFs) fail to preserve their physical and chemical properties after exposure to acidic, neutral, or alkaline aqueous solutions, therefore limiting their practical applications in many areas. The strategy demonstrated herein is the design and synthesis of an organic ligand that behaves as a buffer to drastically boost the aqueous stability of a porous MOF (JUC-1000), which maintains its structural integrity at low and high pH values. The local buffer environment resulting from the weak acid-base pairs of the custom-designed organic ligand also greatly facilitates the performance of JUC-1000 in the chemical fixation of carbon dioxide under ambient conditions, outperforming a series of benchmark catalysts. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. Sensitive resonant gas sensor operating in air with metal organic frameworks coating

    Jaber, Nizar

    2017-08-09

    We report a practical resonant gas sensor that is uniformly coated with metal organic frameworks (MOFs) and excited near the higher order modes for a higher attained sensitivity. The resonator is based on an electrostatically excited clamped-clamped microbeam. The microbeam is fabricated from a polyimide layer coated from the top with Cr/Au and from the bottom with Cr/Au/Cr layer. The geometry of the resonator is optimized to reduce the effect of the squeeze film damping, thereby allowing operation under atmospheric pressure. The electrostatic force electrode is designed to enhance the excitation of the second mode of vibration with the minimum power required. Significant frequency shift (kHz) is demonstrated for the first time upon water vapor, acetone, and ethanol exposure due to the MOFs functionalization and the higher order modes excitation. Also, the adsorption dynamics and MOF selectivity is investigated by studying the decaying time constants of the response upon gas exposure.

  3. 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

  4. 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.

  5. 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.

  6. 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.

  7. 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.

  8. 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.

  9. 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.

  10. 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.

  11. 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...

  12. 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.

  13. MOFwich: Sandwiched Metal-Organic Framework-Containing Mixed Matrix Composites for Chemical Warfare Agent Removal.

    Peterson, Gregory W; Lu, Annie X; Hall, Morgan G; Browe, Matthew A; Tovar, Trenton; Epps, Thomas H

    2018-02-28

    This work describes a new strategy for fabricating mixed matrix composites containing layered metal-organic framework (MOF)/polymer films as functional barriers for chemical warfare agent protection. Through the use of mechanically robust polymers as the top and bottom encasing layers, a high-MOF-loading, high-performance-core layer can be sandwiched within. We term this multifunctional composite "MOFwich". We found that the use of elastomeric encasing layers enabled core layer reformation after breakage, an important feature for composites and membranes alike. The incorporation of MOFs into the core layer led to enhanced removal of chemical warfare agents while simultaneously promoting moisture vapor transport through the composite, showcasing the promise of these composites for protection applications.

  14. Textile/metal-organic-framework composites as self-detoxifying filters for chemical-warfare agents.

    López-Maya, Elena; Montoro, Carmen; Rodríguez-Albelo, L Marleny; Aznar Cervantes, Salvador D; Lozano-Pérez, A Abel; Cenís, José Luis; Barea, Elisa; Navarro, Jorge A R

    2015-06-01

    The current technology of air-filtration materials for protection against highly toxic chemicals, that is, chemical-warfare agents, is mainly based on the broad and effective adsorptive properties of hydrophobic activated carbons. However, adsorption does not prevent these materials from behaving as secondary emitters once they are contaminated. Thus, the development of efficient self-cleaning filters is of high interest. Herein, we report how we can take advantage of the improved phosphotriesterase catalytic activity of lithium alkoxide doped zirconium(IV) metal-organic framework (MOF) materials to develop advanced self-detoxifying adsorbents of chemical-warfare agents containing hydrolysable P-F, P-O, and C-Cl bonds. Moreover, we also show that it is possible to integrate these materials onto textiles, thereby combining air-permeation properties of the textiles with the self-detoxifying properties of the MOF material. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. 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.

  16. Sinter-Resistant Platinum Catalyst Supported by Metal-Organic Framework

    Kim, In Soo [Materials Science Division, Argonne National Lab, 9700 S Cass Ave. Argonne IL 60439 USA; Nanophotonics Center, Korea Institute of Science and Technology, Seoul 02792 South Korea; Li, Zhanyong [Department of Chemistry, Northwestern University, 2145 Sheridan Rd. Evanston IL 60208 USA; Zheng, Jian [Institute for Integrated Catalysis, Pacific Northwest National Lab, P.O. Box 999 Richland WA 99352 USA; Platero-Prats, Ana E. [X-ray Science Division, Argonne National Lab, 9700 S Cass Ave. Argonne IL 60439 USA; Mavrandonakis, Andreas [Department of Chemistry, University of Minnesota, 207 Pleasant St. SE Minneapolis MN 55455 USA; Pellizzeri, Steven [Chemical and Biomolecular Engineering, Clemson University, 205 Earle Hall Clemson SC 29634 USA; Ferrandon, Magali [Chemical Sciences and Engineering Division, Argonne National Lab, 9700 S. Cass Ave. Argonne IL 60439 USA; Vjunov, Aleksei [Institute for Integrated Catalysis, Pacific Northwest National Lab, P.O. Box 999 Richland WA 99352 USA; Gallington, Leighanne C. [X-ray Science Division, Argonne National Lab, 9700 S Cass Ave. Argonne IL 60439 USA; Webber, Thomas E. [Department of Chemistry, University of Minnesota, 207 Pleasant St. SE Minneapolis MN 55455 USA; Vermeulen, Nicolaas A. [Department of Chemistry, Northwestern University, 2145 Sheridan Rd. Evanston IL 60208 USA; Penn, R. Lee [Department of Chemistry, University of Minnesota, 207 Pleasant St. SE Minneapolis MN 55455 USA; Getman, Rachel B. [Chemical and Biomolecular Engineering, Clemson University, 205 Earle Hall Clemson SC 29634 USA; Cramer, Christopher J. [Department of Chemistry, University of Minnesota, 207 Pleasant St. SE Minneapolis MN 55455 USA; Chapman, Karena W. [X-ray Science Division, Argonne National Lab, 9700 S Cass Ave. Argonne IL 60439 USA; Camaioni, Donald M. [Institute for Integrated Catalysis, Pacific Northwest National Lab, P.O. Box 999 Richland WA 99352 USA; Fulton, John L. [Institute for Integrated Catalysis, Pacific Northwest National Lab, P.O. Box 999 Richland WA 99352 USA; Lercher, Johannes A. [Institute for Integrated Catalysis, Pacific Northwest National Lab, P.O. Box 999 Richland WA 99352 USA; Department of Chemistry and Catalysis Research Institute, Technische Universität München, Lichtenbergstrasse 4 85748 Garching Germany; Farha, Omar K. [Department of Chemistry, Northwestern University, 2145 Sheridan Rd. Evanston IL 60208 USA; Hupp, Joseph T. [Materials Science Division, Argonne National Lab, 9700 S Cass Ave. Argonne IL 60439 USA; Department of Chemistry, Northwestern University, 2145 Sheridan Rd. Evanston IL 60208 USA; Martinson, Alex B. F. [Materials Science Division, Argonne National Lab, 9700 S Cass Ave. Argonne IL 60439 USA

    2018-01-02

    Installed on the zirconia nodes of a metal-organic framework (MOF) NU-1000 via targeted vapor-phase synthesis. The catalytic Pt clusters, site-isolated by organic linkers, are shown to exhibit high catalytic activity for ethylene hydrogenation while exhibiting resistance to sintering up to 200 degrees C. In situ IR spectroscopy reveals the presence of both single atoms and few-atom clusters that depend upon synthesis conditions. Operando X-ray absorption spectroscopy and Xray pair distribution analyses reveal unique changes in chemical bonding environment and cluster size stability while on stream. Density functional theory calculations elucidate a favorable reaction pathway for ethylene hydrogenation with the novel catalyst. These results provide evidence that atomic layer deposition (ALD) in MOFs is a versatile approach to the rational synthesis of size-selected clusters, including noble metals, on a high surface area support.

  17. Diffusion of Vitamin B12 Across a Mesoporous Metal Organic Framework

    Veronica Valencia

    2013-01-01

    Full Text Available We measure the rate of uptake and the rate of release of a Vitamin B12 solution (dissolved in water at 2 different temperatures (room temperature and 37°C by the mesoporous metal organic framework TbMOF-100 at 1-hour intervals using a spectrophotometer. Using the Beer-Lambert law, we calculate the concentration of the stock solution based on the absorbance values obtained with the spectrophotometer. These values allow for the quantification of the initial rate of uptake and the rate of uptake at a random incubation time of the Vitamin B12 by the TbMOF-100. We also calculate the value of the coefficient of diffusion for this 2-phase system using Fick’s laws of diffusion.

  18. Catalyst-free growth of InN nanorods by metal-organic chemical vapor deposition

    Kim, Min Hwa; Moon, Dae Young; Park, Jinsub; Nanishi, Yasushi; Yi, Gyu-Chul; Yoon, Euijoon

    2012-01-01

    We demonstrated the growth of catalyst-free InN nanostructures including nanorods on (0001) Al 2 O 3 substrates using metal-organic chemical vapor deposition. As the growth time increased, growth rate along c-direction increased superlinearly with decreasing c-plane area fractions and increasing side wall areas. It was also found that desorption from the sidewalls of InN nanostructures during the InN nanorods formation was one of essential key parameters of the growth mechanism. We propose a growth model to explain the InN nanostructure evolution by considering the side wall desorption and re-deposition of indium at top c-plane surfaces. (Copyright copyright 2012 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  19. Titanium-Phosphonate-Based Metal-Organic Frameworks with Hierarchical Porosity for Enhanced Photocatalytic Hydrogen Evolution

    Li, Hui; Sun, Ying; Yuan, Zhong-Yong; Zhu, Yun-Pei; Ma, Tianyi

    2018-01-01

    Photocatalytic hydrogen production is crucial for solar-to-chemical conversion process, wherein high-efficiency photocatalysts lie in the heart of this area. Herein a new photocatalyst of hierarchically mesoporous titanium-phosphonate-based metal-organic frameworks, featuring well-structured spheres, periodic mesostructure and large secondary mesoporosity, are rationally designed with the complex of polyelectrolyte and cathodic surfactant serving as the template. The well-structured hierarchical porosity and homogeneously incorporated phosphonate groups can favor the mass transfer and strong optical absorption during the photocatalytic reactions. Correspondingly, the titanium phosphonates exhibit significantly improved photocatalytic hydrogen evolution rate along with impressive stability. This work can provide more insights into designing advanced photocatalysts for energy conversion and render a tunable platform in photoelectrochemical field.

  20. Applications of Immobilized Bio-Catalyst in Metal-Organic Frameworks

    Qi Wang

    2018-04-01

    Full Text Available Immobilization of bio-catalysts in solid porous materials has attracted much attention in the last few decades due to its vast application potential in ex vivo catalysis. Despite the high efficiency and selectivity of enzymatic catalytic processes, enzymes may suffer from denaturation under industrial production conditions, which, in turn, diminish their catalytic performances and long-term recyclability. Metal-organic frameworks (MOFs, as a growing type of hybrid materials, have been identified as promising platforms for enzyme immobilization owing to their enormous structural and functional tunability, and extraordinary porosity. This review mainly focuses on the applications of enzyme@MOFs hybrid materials in catalysis, sensing, and detection. The improvements of catalytic activity and robustness of encapsulated enzymes over the free counterpart are discussed in detail.

  1. Metal-Organic Framework of Lanthanoid Dinuclear Clusters Undergoes Slow Magnetic Relaxation

    Hikaru Iwami

    2017-01-01

    Full Text Available Lanthanoid metal-organic frameworks (Ln-MOFs can adopt a variety of new structures due to the large coordination numbers of Ln metal ions, and Ln-MOFs are expected to show new luminescence and magnetic properties due to the localized f electrons. In particular, some Ln metal ions, such as Dy(III and Tb(III ions, work as isolated quantum magnets when they have magnetic anisotropy. In this work, using 4,4′,4″-s-triazine-2,4,6-triyl-tribenzoic acid (H3TATB as a ligand, two new Ln-MOFs, [Dy(TATB(DMF2] (1 and [Tb(TATB(DMF2] (2, were obtained. The Ln-MOFs contain Ln dinuclear clusters as secondary building units, and 1 underwent slow magnetic relaxation similar to single-molecule magnets.

  2. Sonochemical Synthesis of Photoluminescent Nanoscale Eu(III-Containing Metal-Organic Frameworks

    Cheng-an TAO

    2015-11-01

    Full Text Available Nanoscale lanthanide-containing metal-organic frameworks (MOFs have more and more interest due to their great properties and potential applications, but how to construct them easily is still challenging. Here, we present a facile and rapid synthesis of Eu(III-containing Nanoscale MOF (denoted as NMOF under ultrasonic irradiation. The effect of the ratio and the addition order of metal ions and linkers on the morphology and size of MOFs was investigated. It is found that both of the ratio and the addition order can affect the morphology and size of 1.4-benzenedicarboxylic acid(H2BDC -based MOFs, but they show no evident influence on that of H2aBDC-based MOFs. The former exhibit typical emission bands of Eu(III ions, while the latter only show the photoluminescent properties of ligands.DOI: http://dx.doi.org/10.5755/j01.ms.21.4.9695

  3. 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.

  4. Design and construction of porous metal-organic frameworks based on flexible BPH pillars

    Hao, Xiang-Rong; Yang, Guang-sheng; Shao, Kui-Zhan [Institute of Functional Material Chemistry, Faculty of Chemistry, Northeast Normal University, Changchun 130024, Jilin (China); Su, Zhong-Min, E-mail: zmsu@nenu.edu.cn [Institute of Functional Material Chemistry, Faculty of Chemistry, Northeast Normal University, Changchun 130024, Jilin (China); Yuan, Gang; Wang, Xin-Long [Institute of Functional Material Chemistry, Faculty of Chemistry, Northeast Normal University, Changchun 130024, Jilin (China)

    2013-02-15

    Three metal-organic frameworks (MOFs), [Co{sub 2}(BPDC){sub 2}(4-BPH){center_dot}3DMF]{sub n} (1), [Cd{sub 2}(BPDC){sub 2}(4-BPH){sub 2}{center_dot}2DMF]{sub n} (2) and [Ni{sub 2}(BDC){sub 2}(3-BPH){sub 2} (H{sub 2}O){center_dot}4DMF]{sub n} (3) (H{sub 2}BPDC=biphenyl-4,4 Prime -dicarboxylic acid, H{sub 2}BDC=terephthalic acid, BPH=bis(pyridinylethylidene)hydrazine and DMF=N,N Prime -dimethylformamide), have been solvothermally synthesized based on the insertion of heterogeneous BPH pillars. Framework 1 has 'single-pillared' MOF-5-like motif with inner cage diameters of up to 18.6 A. Framework 2 has 'double pillared' MOF-5-like motif with cage diameters of 19.2 A while 3 has 'double pillared' 8-connected framework with channel diameters of 11.0 A. Powder X-ray diffraction (PXRD) shows that 3 is a dynamic porous framework. - Graphical abstract: By insertion of flexible BPH pillars based on 'pillaring' strategy, three metal-organic frameworks are obtained showing that the porous frameworks can be constructed in a much greater variety. Highlights: Black-Right-Pointing-Pointer Frameworks 1 and 2 have MOF-5 like motif. Black-Right-Pointing-Pointer The cube-like cages in 1 and 2 are quite large, comparable to the IRMOF-10. Black-Right-Pointing-Pointer Framework 1 is 'single-pillared' mode while 2 is 'double-pillared' mode. Black-Right-Pointing-Pointer PXRD and gas adsorption analysis show that 3 is a dynamic porous framework.

  5. Characterization of crystallinity of Ge{sub 1−x}Sn{sub x} epitaxial layers grown using metal-organic chemical vapor deposition

    Inuzuka, Yuki [Department of Crystalline Materials Science, Graduate School of Engineering, Nagoya University, Furo-cho, Chikusa-ku, Nagoya 464-8603 (Japan); Ike, Shinichi; Asano, Takanori [Department of Crystalline Materials Science, Graduate School of Engineering, Nagoya University, Furo-cho, Chikusa-ku, Nagoya 464-8603 (Japan); Japan Society for the Promotion of Science, Chiyoda-ku, Tokyo 102-8472 (Japan); Takeuchi, Wakana [Department of Crystalline Materials Science, Graduate School of Engineering, Nagoya University, Furo-cho, Chikusa-ku, Nagoya 464-8603 (Japan); Nakatsuka, Osamu, E-mail: nakatuka@alice.xtal.nagoya-u.ac.jp [Department of Crystalline Materials Science, Graduate School of Engineering, Nagoya University, Furo-cho, Chikusa-ku, Nagoya 464-8603 (Japan); Zaima, Shigeaki [Department of Crystalline Materials Science, Graduate School of Engineering, Nagoya University, Furo-cho, Chikusa-ku, Nagoya 464-8603 (Japan); EcoTopia Science Institute, Nagoya University, Furo-cho, Chikusa-ku, Nagoya 464-8603 (Japan)

    2016-03-01

    The epitaxial growth of a Ge{sub 1−x}Sn{sub x} layer was examined using metal-organic chemical vapor deposition (MOCVD) with two types of Ge precursors; tetra-ethyl-germane (TEGe) and tertiary-butyl-germane (TBGe); and the Sn precursor tri-butyl-vinyl-tin (TBVSn). Though the growth of a Ge{sub 1−x}Sn{sub x} layer on a Ge(001) substrate by MOCVD has been reported, a high-Sn-content Ge{sub 1−x}Sn{sub x} layer and the exploration of MO material combinations for Ge{sub 1−x}Sn{sub x} growth have not been reported. Therefore, the epitaxial growth of a Ge{sub 1−x}Sn{sub x} layer on Ge(001) and Si(001) substrates was examined using these precursors. The Ge{sub 1−x}Sn{sub x} layers were pseudomorphically grown on a Ge(001) substrate, while the Ge{sub 1−x}Sn{sub x} layer with a high degree of strain relaxation was obtained on a Si(001) substrate. Additionally, it was found that the two Ge precursors have different growth temperature ranges, where the TBGe could realize a higher growth rate at a lower growth temperature than the TEGe. The Ge{sub 1−x}Sn{sub x} layers grown using a combination of TBGe and TBVSn exhibited a higher crystalline quality and a smoother surface compared with the Ge{sub 1−x}Sn{sub x} layer prepared by low-temperature molecular beam epitaxy. In this study, a Ge{sub 1−x}Sn{sub x} epitaxial layer with a Sn content as high as 5.1% on a Ge(001) substrate was achieved by MOCVD at 300 °C. - Highlights: • Tertiary-butyl-germane and tri-butyl-vinyl-tin are suitable for Ge{sub 1−x}Sn{sub x} MOCVD growth. • We achieved a Sn content of 5.1% in Ge{sub 1−x}Sn{sub x} epitaxial layer on Ge(001). • The Ge{sub 1−x}Sn{sub x} layers grown on Ge and Si by MOCVD have high crystalline quality.

  6. Polymer-metal organic frameworks (MOFs) mixed matrix membranes for gas separation applications

    Shahid, S.

    2015-01-01

    The performance of polymeric membranes is often limited by a trade-off between membrane permeability and selectivity, the so-called Robeson upper bound. Additionally, in high pressure CO2 capture applications, excessive swelling of the polymer membrane often leads to plasticization resulting in

  7. Preparation of value-added metal-organic frameworks (MOFs) using waste PET bottles as source of acid linker

    Dyosiba, Xoliswa

    2016-12-01

    Full Text Available of Value-added Metal-organic Frameworks (MOFs) Using Waste PET Bottles as Source of Acid Linker Xoliswa Dyosiba, Jianwei Ren, Nicholas M. Musyoka, Henrietta W. Langmi, Mkhulu Mathe, Maurice S. Onyango PII: S2214-9937(16)30053-7 DOI: doi:10.1016/j..., Hen- rietta W. Langmi, Mkhulu Mathe, Maurice S. Onyango, Preparation of Value-added Metal-organic Frameworks (MOFs) Using Waste PET Bottles as Source of Acid Linker, Sustainable Materials and Technologies (2016), doi:10.1016/j.susmat.2016...

  8. The Structural Evolution of (Gd, Y)Ba2Cu3Ox Tapes With Zr Addition Made by Metal Organic Chemical Vapor Deposition

    Lei, CH; Galstyan, E; Chen, YM; Shi, T; Liu, YH; Khatri, N; Liu, JF; Xiong, XM; Majkic, G; Selvamanickam, V

    2013-06-01

    Structural analysis of (Gd, Y) Ba2Cu3Ox tapes with Zr addition made by metal organic chemical vapor deposition has been conducted with transmission electron microscopy and X-ray diffraction. Zr content in the films was varied from 0 to 25% in the precursor. In all Zr-doped films, self-assembled nanocolumnar structures of BaZrO3 (BZO) were observed along the c-axis. The amount of BaZrO3 was found to increase steadily with Zr content. Additionally, planar BZO plates were found on the (001) plane of (Gd, Y) Ba2Cu3Ox film. The size and thickness of BZO plates were seen to increase with Zr doping level. Rare-earth copper oxide phases were observed to begin to emerge in the 20% Zr-doped film. Cross-sectional study of the interface between (Gd, Y)Ba2Cu3Ox and LaMnO3 cap layer revealed a thin discrete BZO layer on the LaMnO3 in the 20% Zr doped film.

  9. Self-Catalyzed Growth and Characterization of In(As)P Nanowires on InP(111)B Using Metal-Organic Chemical Vapor Deposition.

    Park, Jeung Hun; Pozuelo, Marta; Setiawan, Bunga P D; Chung, Choong-Heui

    2016-12-01

    We report the growth of vertical -oriented InAs x P1-x (0.11 ≤ x ≤ 0.27) nanowires via metal-organic chemical vapor deposition in the presence of indium droplets as catalysts on InP(111)B substrates at 375 °C. Trimethylindium, tertiarybutylphosphine, and tertiarybutylarsine are used as the precursors, corresponding to P/In and As/In molar ratios of 29 and 0.01, respectively. The as-grown nanowire growth morphologies, crystallinity, composition, and optical characteristics are determined using a combination of scanning and transmission electron microscopies, electron diffraction, and X-ray photoelectron, energy dispersive X-ray, and Raman spectroscopies. We find that the InAs x P1-x nanowires are tapered with narrow tops, wider bases, and In-rich In-As alloy tips, characteristic of vapor-liquid-solid process. The wires exhibit a mixture of zinc blende and wurtzite crystal structures and a high density of structural defects such as stacking faults and twins. Our results suggest that the incorporation of As into InP wires decreases with increasing substrate temperature. The Raman spectra obtained from the In(As)P nanowires reveal a red-shift and lower intensity of longitudinal optical mode relative to both InP nanowires and InP(111)B bulk, due to the incorporation of As into the InP matrix.

  10. Fabrication of γ-Fe2O3 Nanoparticles by Solid-State Thermolysis of a Metal-Organic Framework, MIL-100(Fe, for Heavy Metal Ions Removal

    Shengtao Hei

    2014-01-01

    Full Text Available Porous γ-Fe2O3 nanoparticles were prepared via a solid-state conversion process of a mesoporous iron(III carboxylate crystal, MIL-100(Fe. First, the MIL-100(Fe crystal that served as the template of the metal oxide was synthesized by a low-temperature (<100°C synthesis route. Subsequently, the porous γ-Fe2O3 nanoparticles were fabricated by facile thermolysis of the MIL-100(Fe powders via a two-step calcination treatment. The obtained γ-Fe2O3 was characterized by X-ray diffraction (XRD, N2 adsorption, X-ray photoelectron spectroscopy (XPS, and scanning electron microscopy (SEM techniques, and then used as an adsorbent for heavy metal ions removal in water treatment. This study illustrates that the metal-organic frameworks may be suitable precursors for the fabrication of metal oxides nanomaterials with large specific surface area, and the prepared porous γ-Fe2O3 exhibits a superior adsorption performance for As(V and As(III ions removal in water treatment.

  11. Improvement in crystallization and electrical properties of barium strontium titanate thin films by gold doping using metal-organic deposition method

    Wang, H.-W.; Nien, S.-W.; Lee, K.-C.; Wu, M.-C.

    2005-01-01

    The effect of gold (Au) on the crystallization, dielectric constant and leakage current density of barium strontium titanate (BST) thin films was investigated. BST thin films with various gold concentrations were prepared via a metal-organic deposition process. The X-ray diffraction shows enhanced crystallization as well as expanded lattice constants for the gold-doped BST films. Thermal analysis reveals that the gold dopant induces more complete decomposition of precursor for the doped films than those of undoped ones. The leakage current density of BST films is greatly reduced by the gold dopant over a range of biases (1-5 V). The distribution of gold was confirmed by electron energy loss spectroscopy and found to be inside the BST grains, not in the grain-boundaries. Gold acted as a catalyst, inducing the nucleation of crystallites and improving the crystallinity of the structure. Its addition is shown to be associated to the improvement of the electrical properties of BST films

  12. Thermogravimetric evaluation of the suitability of precursors for MOCVD

    Kunte, G V; Shivashankar, S A; Umarji, A M

    2008-01-01

    A method based on the Langmuir equation for the estimation of vapour pressure and enthalpy of sublimation of subliming compounds is described. The variable temperature thermogravimetric/differential thermogravimetric (TG/DTG) curve of benzoic acid is used to arrive at the instrument parameters. Employing these parameters, the vapour pressure–temperature curves are derived for salicylic acid and camphor from their TG/DTG curves. The values match well with vapour pressure data in the literature, obtained by effusion methods. By employing the Clausius–Clapeyron equation, the enthalpy of sublimation could be calculated. Extending the method further, two precursors for metal-organic chemical vapour deposition (MOCVD) of titanium oxide bis-isopropyl bis tert-butyl 2-oxobutanoato titanium, Ti(O i Pr) 2 (tbob) 2 , and bis-oxo-bis-tertbutyl 2-oxobutanoato titanium, [TiO(tbob) 2 ] 2 , have been evaluated. The complex Ti(O i Pr) 2 (tbob) 2 is found to be a more suitable precursor. This approach can be helpful in quickly screening for the suitability of a compound as a CVD precursor

  13. Polymeric bicontinuous microemulsions

    Bates, F.S.; Maurer, W.W.; Lipic, P.M.

    1997-01-01

    High molecular weight block copolymers can be viewed as macromolecular surfactants when blended with thermodynamically incompatible homopolymers. This Letter describes the formation of polymeric bicontinuous microemulsions in nurtures containing a model diblock copolymer and two homopolymers. Alt...

  14. Polymerization Using Phosphazene Bases

    Zhao, Junpeng; Hadjichristidis, Nikolaos; Schlaad, Helmut

    2015-01-01

    . In this chapter, the general features of phosphazenepromoted/catalyzed polymerizations and the applications in macromolecular engineering (synthesis of functionalized polymers, block copolymers, and macromolecular architectures) are discussed with challenges

  15. Radical-Mediated Enzymatic Polymerizations

    Zavada, Scott R.; Battsengel, Tsatsral; Scott, Timothy F.

    2016-01-01

    Polymerization reactions are commonly effected by exposing monomer formulations to some initiation stimulus such as elevated temperature, light, or a chemical reactant. Increasingly, these polymerization reactions are mediated by enzymes―catalytic proteins―owing to their reaction efficiency under mild conditions as well as their environmental friendliness. The utilization of enzymes, particularly oxidases and peroxidases, for generating radicals via reduction-oxidation mechanisms is especially common for initiating radical-mediated polymerization reactions, including vinyl chain-growth polymerization, atom transfer radical polymerization, thiol–ene step-growth polymerization, and polymerization via oxidative coupling. While enzyme-mediated polymerization is useful for the production of materials intended for subsequent use, it is especially well-suited for in situ polymerizations, where the polymer is formed in the place where it will be utilized. Such polymerizations are especially useful for biomedical adhesives and for sensing applications. PMID:26848652

  16. Chelating polymeric membranes

    Peinemann, Klaus-Viktor

    2015-01-22

    The present application offers a solution to the current problems associated with recovery and recycling of precious metals from scrap material, discard articles, and other items comprising one or more precious metals. The solution is premised on a microporous chelating polymeric membrane. Embodiments include, but are not limited to, microporous chelating polymeric membranes, device comprising the membranes, and methods of using and making the same.

  17. 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.

  18. 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.

  19. Screening metal-organic frameworks by analysis of transient breakthrough of gas mixtures in a fixed bed adsorber

    Krishna, R.; Long, J.R.

    2011-01-01

    Metal-organic frameworks (MOFs) offer considerable potential for separating a variety of mixtures that are important in applications such as CO2 capture and H2 purification. In view of the vast number of MOFs that have been synthesized, there is a need for a reliable procedure for comparing

  20. 2-periodic metal-organic frameworks (MOFs) as supermolecular building layers (SBLs) for making targeted 3-periodic MOFs

    Eddaoudi, Mohamed; Eubank, Jarrod F.

    2015-01-01

    Embodiments of the present disclosure provide for chemical assemblies, multidimensional metal-organic frameworks (MOFs), supermolecular building layers (SBLs), inorganic molecular building blocks (MBBs), organic MBBs (designed ligands), methods of making each, and methods of using each, and the like. In an embodiment, the composition can be used in catalysis, separations, gas storage, and drug delivery.

  1. A systematic study on the use of ultrasound energy for the synthesis of nickel-metal organic framework compounds

    Sargazi, G.; Afzali, D.; Daldosso, N.; Kazemian, H.; Chauhan, N.P.S.; Sadeghian, Z.; Tajerian, T.; Ghafarinazari, A.; Mozafari, M.

    2015-01-01

    A nickel metal-organic framework (Ni-MOF) was successfully synthesized using ultrasound irradiation. Further to this, X-ray Diffraction (XRD), Scanning Electron Microscopy (SEM), Fourier Transform Infrared Spectroscopy (FT-IR), Thermo-Gravimetric Analysis (TGA), Differential Scanning Calorimetry

  2. A charge-polarized porous metal-organic framework for gas chromatographic separation of alcohols from water.

    Sun, Jian-Ke; Ji, Min; Chen, Cheng; Wang, Wu-Gen; Wang, Peng; Chen, Rui-Ping; Zhang, Jie

    2013-02-25

    A bipyridinium ligand with a charge separated skeleton has been introduced into a metal-organic framework to yield a porous material with charge-polarized pore space, which exhibits selective adsorption for polar guest molecules and can be further used in gas chromatography for the separation of alcohol-water mixtures.

  3. 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.

  4. Gas transport in metal organic framework–polyetherimide mixed matrix membranes: The role of the polyetherimide backbone structure

    Hegde, Maruti; Shahid, S.; Norder, Ben; Dingemans, Theo J.; Nijmeijer, Dorothea C.

    2015-01-01

    We report on how the morphology of the polymer matrix, i.e. amorphous vs. semi-crystalline, affects the gas transport properties in a series of mixed matrix membranes (MMMs) using Cu3(BTC)2 as the metal organic framework (MOF) filler. The aim of our work is to demonstrate how incorporation of

  5. Gas transport in metal organic framework-polyetherimide mixed matrix membranes: The role of the polyetherimide backbone structure

    Hegde, Maruti; Shahid, Salman; Norder, Ben; Dingemans, T.J.; Nijmeijer, Kitty

    2015-01-01

    We report on how the morphology of the polymer matrix, i.e. amorphous vs. semi-crystalline, affects the gas transport properties in a series of mixed matrix membranes (MMMs) using Cu3(BTC)2 as the metal organic framework (MOF) filler. The aim of our work is to demonstrate how incorporation of

  6. CO 2 adsorption in mono-, di- and trivalent cation-exchanged metal-organic frameworks: A molecular simulation study

    Chen, Yifei; Nalaparaju, Anjaiah; Eddaoudi, Mohamed; JIANG, Jianwen

    2012-01-01

    A molecular simulation study is reported for CO 2 adsorption in rho zeolite-like metal-organic framework (rho-ZMOF) exchanged with a series of cations (Na +, K +, Rb +, Cs +, Mg 2+, Ca 2+, and Al 3+). The isosteric heat and Henry's constant

  7. Cerium-based metal organic frameworks with UiO-66 architecture: synthesis, properties and redox catalytic activity.

    Lammert, Martin; Wharmby, Michael T; Smolders, Simon; Bueken, Bart; Lieb, Alexandra; Lomachenko, Kirill A; Vos, Dirk De; Stock, Norbert

    2015-08-14

    A series of nine Ce(iv)-based metal organic frameworks with the UiO-66 structure containing linker molecules of different sizes and functionalities were obtained under mild synthesis conditions and short reaction times. Thermal and chemical stabilities were determined and a Ce-UiO-66-BDC/TEMPO system was successfully employed for the aerobic oxidation of benzyl alcohol.

  8. A tetrapyridine ligand with a rigid tetrahedral core forms metal-organic frameworks with PtS type architecture.

    Caputo, Christopher B; Vukotic, V Nicholas; Sirizzotti, Natalie M; Loeb, Stephen J

    2011-08-14

    A new tetradentate, pyridine ligand with a rigid tetrahedral core can be prepared in good yield by a cross-coupling methodology. Two metal organic framework structures of Cu(II) with PtS-type topology having a carbon atom as the tetrahedral node have been characterized utilising this ligand. This journal is © The Royal Society of Chemistry 2011

  9. Mechanistic Insights into Growth of Surface-Mounted Metal-Organic Framework Films Resolved by Infrared (Nano-) Spectroscopy

    Delen, Guusje; Ristanovic, Zoran; Mandemaker, Laurens D. B.; Weckhuysen, Bert M.

    2018-01-01

    Control over assembly, orientation, and defect-free growth of metal-organic framework (MOF) films is crucial for their future applications. A layer-by-layer approach is considered a suitable method to synthesize highly oriented films of numerous MOF topologies, but the initial stages of the film

  10. 2-periodic metal-organic frameworks (MOFs) as supermolecular building layers (SBLs) for making targeted 3-periodic MOFs

    Eddaoudi, Mohamed

    2015-09-22

    Embodiments of the present disclosure provide for chemical assemblies, multidimensional metal-organic frameworks (MOFs), supermolecular building layers (SBLs), inorganic molecular building blocks (MBBs), organic MBBs (designed ligands), methods of making each, and methods of using each, and the like. In an embodiment, the composition can be used in catalysis, separations, gas storage, and drug delivery.

  11. Direct Observation of Xe and Kr Adsorption in a Xe-Selective Microporous Metal-Organic Framework

    Chen, X.; Plonka, A.M.; Banerjee, D.; Krishna, R.; Schaef, H.T.; Ghose, S.; Thallapally, P.K.; Parise, J.B.

    2015-01-01

    The cryogenic separation of noble gases is energy-intensive and expensive, especially when low concentrations are involved. Metal organic frameworks (MOFs) containing polarizing groups within their pore spaces are predicted to be efficient Xe/Kr solid,state adsorbents, but no experimental insights

  12. CO2 Capture Using the SIFSIX-2-Cu-i Metal-Organic Framework: A Computational Approach

    Skarmoutsos, Ioannis; Belmabkhout, Youssef; Adil, Karim; Eddaoudi, Mohamed; Maurin, Guillaume

    2017-01-01

    The adsorption of carbon dioxide and its separation from mixtures with methane using the recently synthetized SIFSIX-2-Cu-i metal-organic framework (Nature, 2014, 495, 80-84) has been systematically studied by employing a variety of molecular

  13. Ab initio investigation on hydrogen adsorption capability in Zn and Cu-based metal organic frameworks

    Tanuwijaya, V. V., E-mail: viny.veronika@gmail.com [Engineering Physics, Faculty of Industrial Technology, Institut Teknologi Bandung Jalan Ganeca 10 Gd. T.P. Rachmat, Bandung 40132 (Indonesia); Hidayat, N. N., E-mail: avantgarde.vee@gmail.com; Agusta, M. K., E-mail: kemal@fti.itb.ac.id; Dipojono, H. K., E-mail: dipojono@tf.itb.ac.id

    2015-09-30

    One of the biggest challenge in material technology for hydrogen storage application is to increase hydrogen uptake in room temperature and pressure. As a class of highly porous material, Metal-Organic Frameworks (MOF) holds great potential with its tunable structure. However, little is known about the effect of metal cluster to its hydrogen storage capability. Investigation on this matter has been carried out carefully on small cluster of Zn and Cu-based MOF using first principles method. The calculation of two distinct building units of MOFs, namely octahedral and paddle-wheel models, have been done with B3LYP density functional method using 6-31G(d,p) and LANL2DZ basis sets. From geometry optimization of Zn-based MOF linked by benzene-dicarboxylate (MOF-5), it is found that hydrogen tends to keep distance from metal cluster group and stays above benzene ring. In the other hand, hydrogen molecule prefers to stay atop of the exposed Cu atom in Cu-based MOF system linked by the same linker group (Cu-bdc). Calculated hydrogen binding enthalpies for Zn and Cu octahedral cages at ZnO{sub 3} sites are 1.64kJ/mol and 2.73kJ/mol respectively, while hydrogen binding enthalpies for Zn and Cu paddle-wheel cages calculated on top of metal atoms are found to be at 6.05kJ/mol and 6.10kJ/mol respectively. Major difference between Zn-MOF-5 and Cu-bdc hydrogen uptake performance might be caused by unsaturated metal sites present in Cu-bdc system and the influence of their geometric structures, although a small difference on binding energy in the type of transition metal used is also observed. The comparison between Zn and Cu-based MOF may contribute to a comprehensive understanding of metal clusters and the importance of selecting best transition metal for design and synthesis of metal-organic frameworks.

  14. Epitaxial Oxide Thin Films Grown by Solid Source Metal-Organic Chemical Vapor Deposition.

    Lu, Zihong

    1995-01-01

    The conventional liquid source metal-organic chemical vapor deposition (MOCVD) technique is capable of producing large area, high quality, single crystal semiconductor films. However, the growth of complex oxide films by this method has been hampered by a lack of suitable source materials. While chemists have been actively searching for new source materials, the research work reported here has demonstrated the successful application of solid metal-organic sources (based on tetramethylheptanedionate) to the growth of high quality thin films of binary compound cerium dioxide (CeO_2), and two more complex materials, the ternary compound lithium niobate (LiNbO_3), with two cations, and the quaternary compound strontium barium niobate (SBN), with three cations. The growth of CeO_2 thin films on (1012)Al_2O_3 substrates has been used as a model to study the general growth behavior of oxides. Factors affecting deposition rate, surface morphology, out-of-plane mosaic structure, and film orientation have been carefully investigated. A kinetic model based on gas phase prereaction is proposed to account for the substrate temperature dependence of film orientation found in this system. Atomically smooth, single crystal quality cerium dioxide thin films have been obtained. Superconducting YBCO films sputtered on top of solid source MOCVD grown thin cerium dioxide buffer layers on sapphire have been shown to have physical properties as good as those of YBCO films grown on single crystal MgO substrates. The thin film growth of LiNbO_3 and Sr_{1-x}Ba _{x}Nb_2 O_6 (SBN) was more complex and challenging. Phase purity, transparency, in-plane orientation, and the ferroelectric polarity of LiNbO _3 films grown on sapphire substrates was investigated. The first optical quality, MOCVD grown LiNbO _3 films, having waveguiding losses of less than 2 dB/cm, were prepared. An important aspect of the SBN film growth studies involved finding a suitable single crystal substrate material. Mg

  15. Electronic properties and chemistry of metal / organic semiconductor/ S-GaAs(100) heterosructures

    Gavrila, G.N.

    2005-10-21

    in the framework of this thesis three perylene derivates are applied as interlayers in metal/organic layer/S-GaAs(100) heterostructures. The aim of this thesis is to prove the influence of different chemical end-groups on the electronic and chemical properties of the interfaces, as well as the molecular orientation in the organic layers. The molecules 3,4,9,10-perylene tetracarbonic acid dianhydride (PTCDA), 3,4,9,10-perylene tetracarbonic acid diimide (PTCDI), and dimethyl-3,4,9,10-perylene tetracarbonic acid diimide (DiMe-PTCDI) were evaporated by organic molecular beam deposition (OMBD) in the ultrahigh vacuum on sulfur-passivated GaAs(001):2 x 1 substrates. Surface-sensitive characterization procedures as photoemission spectroscopy (PES), inverse photoemission spectroscopy (IPES), and near-edge X-ray fine-structure measurements (NEXAFS) were applied for the characterization. Theoretical calculations by means of the density-functional methods were performed, in order to allow an assignment of different components in core-level spectra. The NEXAFS spectra allow a precise determination of the molecule orientation in relation to the substrate. So it can be proved that a small change of chemical end-groups for instance in DiMe-PTCDI compared with PTCDI causes a dramatic change of the molecule orientation. The valence-band spectra of DiMe-PTCDI show an energetic dispersion of 0.2 eV, which can be assigned to a {pi}-orbital overlap and covers the formation of valence bands. The energy-level fitting to the organic-layer/S-GaAs interface as well as the transport band gap of PTCDI, DiMe-PTCDI, and PTCDA were deteminde by means of PES and IPES. The electronic, chemical, and structural properties of metal/organic-layer interfaces were studied by means of core-level spectroscopy and NEXAFS. Mg reacts strongly with the end-groups of PTCDA AND ptcdi, while the In atoms contribute to a charge-transfer process with the perylene cores of all three molecules, whereby the

  16. Flexible metal-organic framework compounds: In situ studies for selective CO{sub 2} capture

    Allen, A.J., E-mail: andrew.allen@nist.gov [Material Measurement Laboratory, National Institute of Standards and Technology (NIST), Gaithersburg, MD 20899-8520 (United States); Espinal, L.; Wong-Ng, W. [Material Measurement Laboratory, National Institute of Standards and Technology (NIST), Gaithersburg, MD 20899-8520 (United States); Queen, W.L. [NIST Center for Neutron Research, Gaithersburg, MD 20899-6102 (United States); The Molecular Foundry, Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA 94720 (United States); Brown, C.M. [NIST Center for Neutron Research, Gaithersburg, MD 20899-6102 (United States); Department of Chemical and Biomolecular Engineering, University of Delaware, Newark, DE 19716 (United States); Kline, S.R. [NIST Center for Neutron Research, Gaithersburg, MD 20899-6102 (United States); Kauffman, K.L. [National Energy Technology Laboratory (NETL), US Department of Energy, Pittsburgh, PA 15236 (United States); Culp, J.T. [National Energy Technology Laboratory (NETL), US Department of Energy, Pittsburgh, PA 15236 (United States); URS Corporation, South Park, PA 15219 (United States); Matranga, C. [National Energy Technology Laboratory (NETL), US Department of Energy, Pittsburgh, PA 15236 (United States)

    2015-10-25

    Results are presented that explore the dynamic structural changes occurring in two highly flexible nanocrystalline metal-organic framework (MOF) compounds during the adsorption and desorption of pure gases and binary mixtures. The Ni(1,2-bis(4-pyridyl)ethylene)[Ni(CN){sub 4}] and catena-bis(dibenzoylmethanato)-(4,4′-bipyridyl)nickel(II) chosen for this study are 3-D and 1-D porous coordination polymers (PCP) with a similar gate opening pressure response for CO{sub 2} isotherms at 303 K, but with differing degrees of flexibility for structural change to accommodate guest molecules. As such, they serve as a potential model system for evaluating the complex kinetics associated with dynamic structure changes occurring in response to gas adsorption in flexible MOF systems. Insights into the crystallographic changes occurring as the MOF pore structure expands and contracts in response to interactions with CO{sub 2}, N{sub 2}, and CO{sub 2}/N{sub 2} mixtures have been obtained from in situ small-angle neutron scattering and neutron diffraction, combined with ex situ X-ray diffraction structure measurements. The role of structure in carbon capture functionality is discussed with reference to the ongoing characterization challenges and a possible materials-by-design approach. - Graphical abstract: We present in situ small-angle neutron scattering results for two flexible metal-organic frameworks (MOFs). The figure shows that for one (NiBpene, high CO{sub 2} adsorption) the intensity of the Bragg peak for the expandable d-spacing most associated with CO{sub 2} adsorption varies approximately with the isotherm, while for the other (NiDBM-Bpy, high CO{sub 2} selectivity) the d-spacing, itself, varies with the isotherm. The cartoons show the proposed modes of structural change. - Highlights: • Dynamic structures of two flexible MOF CO{sub 2} sorbent compounds are compared in situ. • These porous solid sorbents serve as models for pure & dual gas adsorption. • Different

  17. The EM Earthquake Precursor

    Jones, K. B., II; Saxton, P. T.

    2013-12-01

    Many attempts have been made to determine a sound forecasting method regarding earthquakes and warn the public in turn. Presently, the animal kingdom leads the precursor list alluding to a transmission related source. By applying the animal-based model to an electromagnetic (EM) wave model, various hypotheses were formed, but the most interesting one required the use of a magnetometer with a differing design and geometry. To date, numerous, high-end magnetometers have been in use in close proximity to fault zones for potential earthquake forecasting; however, something is still amiss. The problem still resides with what exactly is forecastable and the investigating direction of EM. After the 1989 Loma Prieta Earthquake, American earthquake investigators predetermined magnetometer use and a minimum earthquake magnitude necessary for EM detection. This action was set in motion, due to the extensive damage incurred and public outrage concerning earthquake forecasting; however, the magnetometers employed, grounded or buried, are completely subject to static and electric fields and have yet to correlate to an identifiable precursor. Secondly, there is neither a networked array for finding any epicentral locations, nor have there been any attempts to find even one. This methodology needs dismissal, because it is overly complicated, subject to continuous change, and provides no response time. As for the minimum magnitude threshold, which was set at M5, this is simply higher than what modern technological advances have gained. Detection can now be achieved at approximately M1, which greatly improves forecasting chances. A propagating precursor has now been detected in both the field and laboratory. Field antenna testing conducted outside the NE Texas town of Timpson in February, 2013, detected three strong EM sources along with numerous weaker signals. The antenna had mobility, and observations were noted for recurrence, duration, and frequency response. Next, two

  18. 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

  19. 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.

  20. Asymmetric supercapacitors utilizing highly porous metal-organic framework derived Co3O4 nanosheets grown on Ni foam and polyaniline hydrogel derived N-doped nanocarbon electrode materials

    Fan, Xin; Chen, Weiliang; Pang, Shuhua; Lu, Wei; Zhao, Yu; Liu, Zheng; Fang, Dong

    2017-12-01

    In the present work, asymmetric supercapacitors (ASCs) are assembled using a highly conductive N-doped nanocarbon (NDC) material derived from a polyaniline hydrogel as a cathode, and Ni foam covered with flower-like Co3O4 nanosheets (Co3O4-Ni) prepared from a zeolitic imidazolate metal-organic framework as a single precursor serves as a high gravimetric capacitance anode. At a current of 0.2 A g-1, the Co3O4-Ni electrode provides a gravimetric capacitance of 637.7 F g-1, and the NDC electrode provides a gravimetric capacitance of 359.6 F g-1. The ASC assembled with an optimal active material loading operates within a wide potential window of 0-1.1 V, and provides a high areal capacitance of 25.7 mF cm-2. The proposed ASC represents a promising strategy for designing high-performance supercapacitors.

  1. Precursor directed synthesis--"molecular" mechanisms in the Soft Chemistry approaches and their use for template-free synthesis of metal, metal oxide and metal chalcogenide nanoparticles and nanostructures.

    Seisenbaeva, Gulaim A; Kessler, Vadim G

    2014-06-21

    This review provides an insight into the common reaction mechanisms in Soft Chemistry processes involved in nucleation, growth and aggregation of metal, metal oxide and chalcogenide nanoparticles starting from metal-organic precursors such as metal alkoxides, beta-diketonates, carboxylates and their chalcogene analogues and demonstrates how mastering the precursor chemistry permits us to control the chemical and phase composition, crystallinity, morphology, porosity and surface characteristics of produced nanomaterials.

  2. 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.

  3. Nanoscale Metal-Organic Frameworks Decorated with Graphene Oxide for Magnetic Resonance Imaging Guided Photothermal Therapy.

    Meng, Jing; Chen, Xiujin; Tian, Yang; Li, Zhongfeng; Zheng, Qingfeng

    2017-12-11

    Imaging-guided photothermal therapy (PTT) provides an attractive way to treat cancer. A composite material of a nanoscale metal-organic framework (NMOF) and graphene oxide (GO) has been prepared for potential use in tumor-guided PTT with magnetic resonance imaging (MRI). The NMOFs containing Fe 3+ were prefabricated with an octahedral morphology through a solvothermal reaction to offer a strong T 2 -weighted contrast in MRI. Then the NMOFs were decorated with GO nanosheets, which had good photothermal properties. After decoration, zeta-potential characterization shows that the aqueous stability of the composite material is enhanced, UV/Vis and near-infrared (NIR) spectra confirm that NIR absorption is also increased, and photothermal experiments reveal that the composite materials express higher photothermal conversion effects and conversion stability. The fabricated NMOF/GO shows low cytotoxicity, effective T 2 -weighted contrast of MRI, and positive PTT behavior for a tumor model in vitro. The performance of the composite NMOF/GO for MRI and PTT was also tested upon injection into A549 tumor-bearing mice. The studies in vivo revealed that the fabricated NMOF/GO was efficient in T 2 -weighted imaging and ablation of the A549 tumor with low cytotoxicity, which implied that the prepared composite contrast agent was a potential multifunctional nanotheranostic agent. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  4. Density functional theory for adsorption of gas mixtures in metal-organic frameworks.

    Liu, Yu; Liu, Honglai; Hu, Ying; Jiang, Jianwen

    2010-03-04

    In this work, a recently developed density functional theory in three-dimensional space was extended to the adsorption of gas mixtures. Weighted density approximations to the excess free energy with different weighting functions were adopted for both repulsive and attractive contributions. An equation of state for hard-sphere mixtures and a modified Benedict-Webb-Rubin equation for Lennard-Jones mixtures were used to estimate the excess free energy of a uniform fluid. The theory was applied to the adsorption of CO(2)/CH(4) and CO(2)/N(2) mixtures in two metal-organic frameworks: ZIF-8 and Zn(2)(BDC)(2)(ted). To validate the theoretical predictions, grand canonical Monte Carlo simulations were also conducted. The predicted adsorption and selectivity from DFT were found to agree well with the simulation results. CO(2) has stronger adsorption than CH(4) and N(2), particularly in Zn(2)(BDC)(2)(ted). The selectivity of CO(2) over CH(4) or N(2) increases with increasing pressure as attributed to the cooperative interactions of adsorbed CO(2) molecules. The composition of the gas mixture exhibits a significant effect on adsorption but not on selectivity.

  5. Microstructural Engineering and Architectural Design of Metal-Organic Framework Membranes.

    Liu, Yi; Ban, Yujie; Yang, Weishen

    2017-08-01

    In the past decade, a huge development in rational design, synthesis, and application of molecular sieve membranes, which typically included zeolites, metal-organic frameworks (MOFs), and graphene oxides, has been witnessed. Owing to high flexibility in both pore apertures and functionality, MOFs in the form of membranes have offered unprecedented opportunities for energy-efficient gas separations. Reports on the fabrication of well-intergrown MOF membranes first appeared in 2009. Since then there has been tremendous growth in this area along with an exponential increase of MOF-membrane-related publications. In order to compete with other separation and purification technologies, like cryogenic distillation, pressure swing adsorption, and chemical absorption, separation performance (including permeability, selectivity, and long-term stability) of molecular sieve membranes must be further improved in an attempt to reach an economically attractive region. Therefore, microstructural engineering and architectural design of MOF membranes at mesoscopic and microscopic levels become indispensable. This review summarizes some intriguing research that may potentially contribute to large-scale applications of MOF membranes in the future. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. Electronic charge rearrangement at metal/organic interfaces induced by weak van der Waals interactions

    Ferri, Nicola; Ambrosetti, Alberto; Tkatchenko, Alexandre

    2017-07-01

    Electronic charge rearrangements at interfaces between organic molecules and solid surfaces play a key role in a wide range of applications in catalysis, light-emitting diodes, single-molecule junctions, molecular sensors and switches, and photovoltaics. It is common to utilize electrostatics and Pauli pushback to control the interface electronic properties, while the ubiquitous van der Waals (vdW) interactions are often considered to have a negligible direct contribution (beyond the obvious structural relaxation). Here, we apply a fully self-consistent Tkatchenko-Scheffler vdW density functional to demonstrate that the weak vdW interactions can induce sizable charge rearrangements at hybrid metal/organic systems (HMOS). The complex vdW correlation potential smears out the interfacial electronic density, thereby reducing the charge transfer in HMOS, changes the interface work functions by up to 0.2 eV, and increases the interface dipole moment by up to 0.3 Debye. Our results suggest that vdW interactions should be considered as an additional control parameter in the design of hybrid interfaces with the desired electronic properties.

  7. Effective Recovery of Vanadium from Oil Refinery Waste into Vanadium-Based Metal-Organic Frameworks.

    Zhan, Guowu; Ng, Wei Cheng; Lin, Wenlin Yvonne; Koh, Shin Nuo; Wang, Chi-Hwa

    2018-03-06

    Carbon black waste, an oil refinery waste, contains a high concentration of vanadium(V) leftover from the processing of crude oil. For the sake of environmental sustainability, it is therefore of interest to recover the vanadium as useful products instead of disposing of it. In this work, V was recovered in the form of vanadium-based metal-organic frameworks (V-MOFs) via a novel pathway by using the leaching solution of carbon black waste instead of commercially available vanadium chemicals. Two different types of V-MOFs with high levels of crystallinity and phase purity were fabricated in very high yields (>98%) based on a coordination modulation method. The V-MOFs exhibited well-defined and controlled shapes such as nanofibers (length: > 10 μm) and nanorods (length: ∼270 nm). Furthermore, the V-MOFs showed high catalytic activities for the oxidation of benzyl alcohol to benzaldehyde, indicating the strong potential of the waste-derived V-MOFs in catalysis applications. Overall, our work offers a green synthesis pathway for the preparation of V-MOFs by using heavy metals of industrial waste as the metal source.

  8. Deposition of highly (111)-oriented PZT thin films by using metal organic chemical deposition

    Bu, K H; Choi, D K; Seong, W K; Kim, J D

    1999-01-01

    Lead zirconate titanate (PZT) thin films have been grown on Pt/Ta/SiNx/Si substrates by using metal organic chemical vapor deposition with Pb(C sub 2 H sub 5) sub 4 , Zr(O-t-C sub 4 H sub 9) sub 4 , and Ti(O-i-C sub 3 H sub 7) sub 4 as source materials and O sub 2 as an oxidizing gas. The Zr fraction in the thin films was controlled by varying the flow rate of the Zr source material. The crystal structure and the electrical properties were investigated as functions of the composition. X-ray diffraction analysis showed that at a certain range of Zr fraction, highly (111)-oriented PZT thin films with no pyrochlore phases were deposited. On the other hand, at low Zr fractions, there were peaks from Pb-oxide phases. At high Zr fractions, peaks from pyrochlore phase were seen. The films also showed good electrical properties, such as a high dielectric constant of more than 1200 and a low coercive voltage of 1.35 V.

  9. Superior removal of arsenic from water with zirconium metal-organic framework UiO-66

    Wang, Chenghong; Liu, Xinlei; Chen, J. Paul; Li, Kang

    2015-01-01

    In this study, water stable zirconium metal-organic framework (UiO-66) has been synthesized and for the first time applied as an adsorbent to remove aquatic arsenic contamination. The as-synthesized UiO-66 adsorbent functions excellently across a broad pH range of 1 to 10, and achieves a remarkable arsenate uptake capacity of 303 mg/g at the optimal pH, i.e., pH = 2. To the best of our knowledge, this is the highest arsenate As(V) adsorption capacity ever reported, much higher than that of currently available adsorbents (5–280 mg/g, generally less than 100 mg/g). The superior arsenic uptake performance of UiO-66 adsorbent could be attributed to the highly porous crystalline structure containing zirconium oxide clusters, which provides a large contact area and plenty of active sites in unit space. Two binding sites within the adsorbent framework are proposed for arsenic species, i.e., hydroxyl group and benzenedicarboxylate ligand. At equilibrium, seven equivalent arsenic species can be captured by one Zr6 cluster through the formation of Zr-O-As coordination bonds. PMID:26559001

  10. 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.

  11. Materials and Techniques for Implantable Nutrient Sensing Using Flexible Sensors Integrated with Metal-Organic Frameworks.

    Ling, Wei; Liew, Guoguang; Li, Ya; Hao, Yafeng; Pan, Huizhuo; Wang, Hanjie; Ning, Baoan; Xu, Hang; Huang, Xian

    2018-06-01

    The combination of novel materials with flexible electronic technology may yield new concepts of flexible electronic devices that effectively detect various biological chemicals to facilitate understanding of biological processes and conduct health monitoring. This paper demonstrates single- or multichannel implantable flexible sensors that are surface modified with conductive metal-organic frameworks (MOFs) such as copper-MOF and cobalt-MOF with large surface area, high porosity, and tunable catalysis capability. The sensors can monitor important nutriments such as ascorbicacid, glycine, l-tryptophan (l-Trp), and glucose with detection resolutions of 14.97, 0.71, 4.14, and 54.60 × 10 -6 m, respectively. In addition, they offer sensing capability even under extreme deformation and complex surrounding environment with continuous monitoring capability for 20 d due to minimized use of biological active chemicals. Experiments using live cells and animals indicate that the MOF-modified sensors are biologically safe to cells, and can detect l-Trp in blood and interstitial fluid. This work represents the first effort in integrating MOFs with flexible sensors to achieve highly specific and sensitive implantable electrochemical detection and may inspire appearance of more flexible electronic devices with enhanced capability in sensing, energy storage, and catalysis using various properties of MOFs. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. 2D Metal-Organic Frameworks Derived Nanocarbon Arrays for Substrate Enhancement in Flexible Supercapacitors.

    Liu, Ximeng; Guan, Cao; Hu, Yating; Zhang, Lei; Elshahawy, Abdelnaby M; Wang, John

    2017-10-27

    Direct assembling of active materials on carbon cloth (CC) is a promising way to achieve flexible electrodes for energy storage. However, the overall surface area and electrical conductivity of such electrodes are usually limited. Herein, 2D metal-organic framework derived nanocarbon nanowall (MOFC) arrays are successfully developed on carbon cloth by a facile solution + carbonization process. Upon growth of the MOFC arrays, the sites for growth of the active materials are greatly increased, and the equivalent series resistance is decreased, which contribute to the enhancement of the bare CC substrate. After decorating ultrathin flakes of MnO 2 and Bi 2 O 3 on the flexible CC/MOFC substrate, the hierarchical electrode materials show an abrupt improvement of areal capacitances by around 50% and 100%, respectively, compared to those of the active materials on pristine carbon cloth. A flexible supercapacitor can be further assembled using two hierarchical electrodes, which demonstrates an energy density of 124.8 µWh cm -2 at the power density of 2.55 mW cm -2 . © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  13. Three-Dimensional Networked Metal-Organic Frameworks with Conductive Polypyrrole Tubes for Flexible Supercapacitors.

    Xu, Xingtao; Tang, Jing; Qian, Huayu; Hou, Shujin; Bando, Yoshio; Hossain, Md Shahriar A; Pan, Likun; Yamauchi, Yusuke

    2017-11-08

    Metal-organic frameworks (MOFs) with high porosity and a regular porous structure have emerged as a promising electrode material for supercapacitors, but their poor electrical conductivity limits their utilization efficiency and capacitive performance. To increase the overall electrical conductivity as well as the efficiency of MOF particles, three-dimensional networked MOFs are developed via using preprepared conductive polypyrrole (PPy) tubes as the support for in situ growth of MOF particles. As a result, the highly conductive PPy tubes that run through the MOF particles not only increase the electron transfer between MOF particles and maintain the high effective porosity of the MOFs but also endow the MOFs with flexibility. Promoted by such elaborately designed MOF-PPy networks, the specific capacitance of MOF particles has been increased from 99.2 F g -1 for pristine zeolitic imidazolate framework (ZIF)-67 to 597.6 F g -1 for ZIF-PPy networks, indicating the importance of the design of the ZIF-PPy continuous microstructure. Furthermore, a flexible supercapacitor device based on ZIF-PPy networks shows an outstanding areal capacitance of 225.8 mF cm -2 , which is far above other MOFs-based supercapacitors reported up to date, confirming the significance of in situ synthetic chemistry as well as the importance of hybrid materials on the nanoscale.

  14. Statistical mechanics of binary mixture adsorption in metal-organic frameworks in the osmotic ensemble

    Dunne, Lawrence J.; Manos, George

    2018-03-01

    Although crucial for designing separation processes little is known experimentally about multi-component adsorption isotherms in comparison with pure single components. Very few binary mixture adsorption isotherms are to be found in the literature and information about isotherms over a wide range of gas-phase composition and mechanical pressures and temperature is lacking. Here, we present a quasi-one-dimensional statistical mechanical model of binary mixture adsorption in metal-organic frameworks (MOFs) treated exactly by a transfer matrix method in the osmotic ensemble. The experimental parameter space may be very complex and investigations into multi-component mixture adsorption may be guided by theoretical insights. The approach successfully models breathing structural transitions induced by adsorption giving a good account of the shape of adsorption isotherms of CO2 and CH4 adsorption in MIL-53(Al). Binary mixture isotherms and co-adsorption-phase diagrams are also calculated and found to give a good description of the experimental trends in these properties and because of the wide model parameter range which reproduces this behaviour suggests that this is generic to MOFs. Finally, a study is made of the influence of mechanical pressure on the shape of CO2 and CH4 adsorption isotherms in MIL-53(Al). Quite modest mechanical pressures can induce significant changes to isotherm shapes in MOFs with implications for binary mixture separation processes. This article is part of the theme issue `Modern theoretical chemistry'.

  15. Kinetic Analysis of the Uptake and Release of Fluorescein by Metal-Organic Framework Nanoparticles

    Tobias Preiß

    2017-02-01

    Full Text Available Metal-organic framework nanoparticles (MOF NPs are promising guest-host materials with applications in separation, storage, catalysis, and drug delivery. However, on- and off-loading of guest molecules by porous MOF nanostructures are still poorly understood. Here we study uptake and release of fluorescein by two representative MOF NPs, MIL-100(Fe and MIL-101(Cr. Suspensions of these MOF NPs exhibit well-defined size distributions and crystallinity, as verified by electron microscopy, dynamic light scattering, and X-ray diffraction. Using absorbance spectroscopy the equilibrium dissociation constants and maximum numbers of adsorbed fluorescein molecules per NP were determined. Time-resolved fluorescence studies reveal that rates of release and loading are pH dependent. The kinetics observed are compared to theoretical estimates that account for bulk diffusion into NPs, and retarded internal diffusion and adsorption rates. Our study shows that, rather than being simple volumetric carriers, MOF-NPs are dominated by internal surface properties. The findings will help to optimize payload levels and develop release strategies that exploit varying pH for drug delivery.

  16. 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.

  17. Two-Dimensional Metal-Organic Framework Nanosheets for Membrane-Based Gas Separation.

    Peng, Yuan; Li, Yanshuo; Ban, Yujie; Yang, Weishen

    2017-08-07

    Metal-organic framework (MOF) nanosheets could serve as ideal building blocks of molecular sieve membranes owing to their structural diversity and minimized mass-transfer barrier. To date, discovery of appropriate MOF nanosheets and facile fabrication of high performance MOF nanosheet-based membranes remain as great challenges. A modified soft-physical exfoliation method was used to disintegrate a lamellar amphiprotic MOF into nanosheets with a high aspect ratio. Consequently sub-10 nm-thick ultrathin membranes were successfully prepared, and these demonstrated a remarkable H 2 /CO 2 separation performance, with a separation factor of up to 166 and H 2 permeance of up to 8×10 -7  mol m -2  s -1  Pa -1 at elevated testing temperatures owing to a well-defined size-exclusion effect. This nanosheet-based membrane holds great promise as the next generation of ultrapermeable gas separation membrane. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. A 3D Ag(I) metal-organic framework for sensing luminescence and photocatalytic activities

    Chang, Hai-Ning; Liu, Li-Wei; Hao, Zeng Chuan; Cui, Guang-Hua

    2018-03-01

    A fluorescent metal-organic framework (MOF), [Ag(btx)0.5(DCTP)0.5]n (1) (H2DCTP = 2,5-dichloroterephthalic acid and btx = 1,4-bis(1,2,4-triazol-1-ylmethyl)benzene) has been hydrothermally synthesized and characterized by IR spectroscopy, elemental analysis, powder X-ray diffractions and thermogravimetry. The framework of 1 can be classified as a binodal (4,4)-connected PtS topological network. The fluorescence explorations demonstrated that 1 shows selective and sensitive detection towards Cr2O72- with high quenching efficiency of 1.92 × 104 M-1. The rapid and efficient response of 1 to Cr2O72- ion suggests that this material could be used as a luminescent sensor for Cr2O72- ion. Meanwhile the photocatalytic properties of 1 for the degradation of RhB have also been investigated under UV radiation. The possible photocatalytic mechanisms were also speculated. Hence, 1 can become multi-functional material in sensitive detection and effective removal of some environment pollutants in industrial waste water solutions.

  19. Ionic Liquid/Metal-Organic Framework Composites: From Synthesis to Applications.

    Kinik, Fatma Pelin; Uzun, Alper; Keskin, Seda

    2017-07-21

    Metal-organic frameworks (MOFs) have been widely studied for different applications owing to their fascinating properties such as large surface areas, high porosities, tunable pore sizes, and acceptable thermal and chemical stabilities. Ionic liquids (ILs) have been recently incorporated into the pores of MOFs as cavity occupants to change the physicochemical properties and gas affinities of MOFs. Several recent studies have shown that IL/MOF composites show superior performances compared with pristine MOFs in various fields, such as gas storage, adsorption and membrane-based gas separation, catalysis, and ionic conductivity. In this review, we address the recent advances in syntheses of IL/MOF composites and provide a comprehensive overview of their applications. Opportunities and challenges of using IL/MOF composites in many applications are reviewed and the requirements for the utilization of these composite materials in real industrial processes are discussed to define the future directions in this field. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  20. Direct Electrical Detection of Iodine Gas by a Novel Metal-Organic-Framework-Based Sensor.

    Small, Leo J; Nenoff, Tina M

    2017-12-27

    High-fidelity detection of iodine species is of utmost importance to the safety of the population in cases of nuclear accidents or advanced nuclear fuel reprocessing. Herein, we describe the success at using impedance spectroscopy to directly detect the real-time adsorption of I 2 by a metal-organic framework zeolitic imidazolate framework (ZIF)-8-based sensor. Methanolic suspensions of ZIF-8 were dropcast onto platinum interdigitated electrodes, dried, and exposed to gaseous I 2 at 25, 40, or 70 °C. Using an unoptimized sensor geometry, I 2 was readily detected at 25 °C in air within 720 s of exposure. The specific response is attributed to the chemical selectivity of the ZIF-8 toward I 2 . Furthermore, equivalent circuit modeling of the impedance data indicates a >10 5 × decrease in ZIF-8 resistance when 116 wt % I 2 is adsorbed by ZIF-8 at 70 °C in air. This irreversible decrease in resistance is accompanied by an irreversible loss in the long-range crystallinity, as evidenced by X-ray diffraction and infrared spectroscopy. Air, argon, methanol, and water were found to produce minimal changes in ZIF-8 impedance. This report demonstrates how selective I 2 adsorption by ZIF-8 can be leveraged to create a highly selective sensor using >10 5 × changes in impedance response to enable the direct electrical detection of environmentally relevant gaseous toxins.

  1. Stepwise transformation of the molecular building blocks in a porphyrin-encapsulating metal-organic material

    Zhang, ZhenJie

    2013-04-24

    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 (MBBs) into novel tetranuclear [Cu4X2(COO)6(S) 2] MBBs to form P11-Cu. The transformation occurs in single-crystal to single-crystal fashion, and its stepwise mechanism was studied by varying the Cd2+/Cu2+ ratio of the solution in which crystals of P11 were immersed. P11-16/1 (Cd in framework retained, Cd in encapsulated porphyrins exchanged) and other intermediate phases were thereby isolated and structurally characterized. P11-16/1 and P11-Cu retain the microporosity of P11, and the relatively larger MBBs in P11-Cu permit a 20% unit cell expansion and afford a higher surface area and a larger pore size. © 2013 American Chemical Society.

  2. Beryllium doped p-type GaN grown by metal-organic chemical vapor depostion

    Al-Tahtamouni, T.M.; Sedhain, A.; Lin, J.Y.; Jiang, H.X.

    2010-01-01

    The authors report on the growth of Be-doped p-type GaN epilayers by metal-organic chmical vapor deposition (MOCVD). The electrical and optical properties of the Be-doped GaN epilayers were studied by Hall-effect measurements and photoluminescence (PL) spectroscopy. The PL spectra of Be-doped GaN epilayers ethibited two emission lines at 3.36 and 2.71 eV, which were obsent in undoped epilayers. The transition at 3.36 eV was at 3.36 and 2.71eV, which were absent in undoped epilayers. The transition at 3.36 eV was assigned to the transition of free electrons to the neutral Be acceptor Be d eg.. The transition at 2.71 eV was assigned to the transition of electrons bound to deep level donors to the Be d eg. acceptors. Three independent measurements: (a) resistivity vs. temperature, (b) PL peak positions between Be doped and undoped GaN and (c) activation energy of 2.71 eV transition all indicate that the Be energy level is between 120 and 140 meV above the valence band. This is about 20-40 meV shallower than the Mg energy level (160 meV) in GaN. It is thus concluded that Be could be an excellent acceptor dopant in nitride materials. (authors).

  3. Elucidating the mechanism responsible for anomalous thermal expansion in a metal-organic framework.

    van Heerden, Dewald P; Esterhuysen, Catharine; Barbour, Leonard J

    2016-03-14

    The previously reported anisotropic thermal expansion of a three-dimensional metal-organic framework (MOF) is examined by means of theoretical calculations. Inspection of the 100, 190, 280 and 370 K single crystal X-ray diffraction (SCD) structures indicated a concerted change in the coordination sphere of the zinc centre leading to elongation of the coordination helix in the crystallographic c direction (the Zn-O(H)-Zn angle expands), while the largely unaltered ligands (the ZnLZn distance remains constant) are pulled closer together in the ab plane. This study develops and evaluates a mechanistic model at the DFT level of theory that reproduces the convergent expansion of the coordination helix of the material. The linear increase in energy calculated for extension of a model consisting of six zinc centres and truncated ligands compares favourably with results obtained from a periodic DFT evaluation of the SCD structures. It was also found that the anisotropic thermal expansion trend could be reproduced qualitatively by Molecular Dynamics (MD) simulations in the NPT ensemble.

  4. Sulfation of metal-organic framework: Opportunities for acid catalysis and proton conductivity

    Goesten, M.G.; Stavitski, E.; Juan-Alcaniz, J.; Ramos-Fernandez, E.V.; Sai Sankar Gupta, K.B.; van Bekkum, H.; Gascon, J. and Kapteijn, F.

    2011-05-24

    A new post-functionalization method for metal-organic frameworks (MOFs) has been developed to introduce acidity for catalysis. Upon treatment with a mixture of triflic anhydride and sulfuric acid, chemically stable MOF structures MIL-101(Cr) and MIL-53(Al) can be sulfated, resulting in a Broensted sulfoxy acid group attached to up to 50% of the aromatic terephthalate linkers of the structure. The sulfated samples have been extensively characterized by solid-state NMR, XANES, and FTIR spectroscopy. The functionalized acidic frameworks show catalytic activity similar to that of acidic polymers like Nafion{reg_sign} display in the esterification of n-butanol with acetic acid (TOF {approx} 1 min{sup -1} {at} 343 K). Water adsorbs strongly up to 4 molecules per sulfoxy acid group, and an additional 2 molecules are taken up at lower temperatures in the 1-D pore channels of S-MIL-53(Al). The high water content and Broensted acidity provide the structure S-MIL-53(Al) a high proton conductivity up to moderate temperatures.

  5. Synthesis of nanoporous carbohydrate metal-organic framework and encapsulation of acetaldehyde

    Al-Ghamdi, Saleh; Kathuria, Ajay; Abiad, Mohamad; Auras, Rafael

    2016-10-01

    Gamma cyclodextrin (γ-CD) metal organic frameworks (CDMOFs) were synthesized by coordinating γ-CDs with potassium hydroxide (KOH), referred hereafter as CDMOF-a, and potassium benzoate (C7H5KO2), denoted as CDMOF-b. The obtained CDMOF structures were characterized using nitrogen sorption isotherm, thermo-gravimetric analysis (TGA), X-ray diffraction (XRD), and scanning electron microscopy (SEM). High surface areas were achieved by the γ-CD based MOF structures where the Langmuir specific surface areas (SSA) of CDMOF-a and CDMOF-b were determined as 1376 m2 g-1 and 607 m2 g-1; respectively. The dehydrated CDMOF structures demonstrated good thermal stability up to 250 °C as observed by the TGA studies. XRD results for CDMOF-a and CDMOF-b reveal a body centered-cubic (BCC) and trigonal crystal system; respectively. Due to its accessible porous structure and high surface area, acetaldehyde was successfully encapsulated in CDMOF-b. During the release kinetic studies, we observed peak release of 53 μg of acetaldehyde per g of CDMOF-b, which was 100 times greater than previously reported encapsulation in β-CD. However, aldol condensation reaction occurred during encapsulation of acetaldehyde into CDMOF-a. This research work demonstrates the potential to encapsulate volatile organic compounds in CDMOF-b, and their associated release for applications including food, pharmaceuticals and packaging.

  6. Formation of a new archetypal Metal-Organic Framework from a simple monatomic liquid

    Metere, Alfredo; Oleynikov, Peter; Dzugutov, Mikhail; O’Keeffe, Michael

    2014-01-01

    We report a molecular-dynamics simulation of a single-component system of particles interacting via a spherically symmetric potential that is found to form, upon cooling from a liquid state, a low-density porous crystalline phase. Its structure analysis demonstrates that the crystal can be described by a net with a topology that belongs to the class of topologies characteristic of the Metal-Organic Frameworks (MOFs). The observed net is new, and it is now included in the Reticular Chemistry Structure Resource database. The observation that a net topology characteristic of MOF crystals, which are known to be formed by a coordination-driven self-assembly process, can be reproduced by a thermodynamically stable configuration of a simple single-component system of particles opens a possibility of using these models in studies of MOF nets. It also indicates that structures with MOF topology, as well as other low-density porous crystalline structures can possibly be produced in colloidal systems of spherical particles, with an appropriate tuning of interparticle interaction

  7. First-principles Hubbard U approach for small molecule binding in metal-organic frameworks

    Mann, Gregory W., E-mail: gmann@berkeley.edu [Department of Chemistry, University of California, Berkeley, California 94720 (United States); Mesosphere, Inc., San Francisco, California 94105 (United States); Lee, Kyuho, E-mail: kyuholee@lbl.gov [Department of Chemical and Biomolecular Engineering, University of California, Berkeley, California 94720 (United States); Molecular Foundry, Lawrence Berkeley National Laboratory, Berkeley, California 94720 (United States); Synopsys, Inc., Mountain View, California 94043 (United States); Cococcioni, Matteo, E-mail: matteo.cococcioni@epfl.ch [Theory and Simulation of Materials (THEOS), École Polytechnique Fédérale de Lausanne, Lausanne (Switzerland); Smit, Berend, E-mail: Berend-Smit@berkeley.edu [Department of Chemistry, University of California, Berkeley, California 94720 (United States); Department of Chemical and Biomolecular Engineering, University of California, Berkeley, California 94720 (United States); Laboratory of Molecular Simulation, Institut des Sciences et Ingénierie Chimiques, Valais Ecole Polytechnique Fédérale de Lausanne (EPFL), Rue de l’Industrie 17, CH-1951 Sion (Switzerland); Neaton, Jeffrey B., E-mail: jbneaton@lbl.gov [Molecular Foundry, Lawrence Berkeley National Laboratory, Berkeley, California 94720 (United States); Department of Physics, University of California, Berkeley, California 94720 (United States); Kavli Energy NanoSciences Institute at Berkeley, Berkeley, California 94720 (United States)

    2016-05-07

    We apply first-principles approaches with Hubbard U corrections for calculation of small molecule binding energetics to open-shell transition metal atoms in metal-organic frameworks (MOFs). Using density functional theory with van der Waals dispersion-corrected functionals, we determine Hubbard U values ab initio through an established linear response procedure for M-MOF-74, for a number of different metal centers (M = Ti, V, Cr, Mn, Fe, Co, Ni, and Cu). While our ab initio U values differ from those used in previous work, we show that they result in lattice parameters and electronic contributions to CO{sub 2}-MOF binding energies that lead to excellent agreement with experiments and previous results, yielding lattice parameters within 3%. In addition, U-dependent calculations for an example system, Co-MOF-74, suggest that the CO{sub 2} binding energy grows monotonically with the value of Hubbard U, with the binding energy shifting 4 kJ/mol (or 0.041 eV) over the range of U = 0-5.4 eV. These results provide insight into an approximate but computationally efficient means for calculation of small molecule binding energies to open-shell transition metal atoms in MOFs and suggest that the approach can be predictive with good accuracy, independent of the cations used and the availability of experimental data.

  8. High performance hydrogen storage from Be-BTB metal-organic framework at room temperature.

    Lim, Wei-Xian; Thornton, Aaron W; Hill, Anita J; Cox, Barry J; Hill, James M; Hill, Matthew R

    2013-07-09

    The metal-organic framework beryllium benzene tribenzoate (Be-BTB) has recently been reported to have one of the highest gravimetric hydrogen uptakes at room temperature. Storage at room temperature is one of the key requirements for the practical viability of hydrogen-powered vehicles. Be-BTB has an exceptional 298 K storage capacity of 2.3 wt % hydrogen. This result is surprising given that the low adsorption enthalpy of 5.5 kJ mol(-1). In this work, a combination of atomistic simulation and continuum modeling reveals that the beryllium rings contribute strongly to the hydrogen interaction with the framework. These simulations are extended with a thermodynamic energy optimization (TEO) model to compare the performance of Be-BTB to a compressed H2 tank and benchmark materials MOF-5 and MOF-177 in a MOF-based fuel cell. Our investigation shows that none of the MOF-filled tanks satisfy the United States Department of Energy (DOE) storage targets within the required operating temperatures and pressures. However, the Be-BTB tank delivers the most energy per volume and mass compared to the other material-based storage tanks. The pore size and the framework mass are shown to be contributing factors responsible for the superior room temperature hydrogen adsorption of Be-BTB.

  9. Nano sized bismuth oxy chloride by metal organic chemical vapour deposition

    Jagdale, Pravin, E-mail: pravin.jagdale@polito.it [Department of Applied Science and Technology (DISAT), Politecnico di Torino, 10129 (Italy); Castellino, Micaela [Center for Space Human Robotics, Istituto Italiano di Tecnologia, Corso Trento 21, 10129 Torino (Italy); Marrec, Françoise [Laboratory of Condensed Matter Physics, University of Picardie Jules Verne (UPJV), Amiens 80039 (France); Rodil, Sandra E. [Instituto de Investigaciones en Materiales, Universidad Nacional Autonoma de Mexicom (UNAM), Mexico D.F. 04510 (Mexico); Tagliaferro, Alberto [Department of Applied Science and Technology (DISAT), Politecnico di Torino, 10129 (Italy)

    2014-06-01

    Metal organic chemical vapour deposition (MOCVD) method was used to prepare thin films of bismuth based nano particles starting from bismuth salts. Nano sized bismuth oxy chloride (BiOCl) crystals were synthesized from solution containing bismuth chloride (BiCl{sub 3}) in acetone (CH{sub 3}-CO-CH{sub 3}). Self-assembly of nano sized BiOCl crystals were observed on the surface of silicon, fused silica, copper, carbon nanotubes and aluminium substrates. Various synthesis parameters and their significant impact onto the formation of self-assembled nano-crystalline BiOCl were investigated. BiOCl nano particles were characterized by X-ray diffraction, X-ray photoelectron spectroscopy, field emission scanning electron microscopy, energy-dispersive X-ray spectroscopy and Micro-Raman spectroscopy. These analyses confirm that bismuth nanometer-sized crystal structures showing a single tetragonal phase were indeed bismuth oxy chloride (BiOCl) square platelets 18–250 nm thick and a few micrometres wide.

  10. High-Throughput Molecular Simulations of Metal Organic Frameworks for CO2 Separation: Opportunities and Challenges

    Ilknur Erucar

    2018-02-01

    Full Text Available Metal organic frameworks (MOFs have emerged as great alternatives to traditional nanoporous materials for CO2 separation applications. MOFs are porous materials that are formed by self-assembly of transition metals and organic ligands. The most important advantage of MOFs over well-known porous materials is the possibility to generate multiple materials with varying structural properties and chemical functionalities by changing the combination of metal centers and organic linkers during the synthesis. This leads to a large diversity of materials with various pore sizes and shapes that can be efficiently used for CO2 separations. Since the number of synthesized MOFs has already reached to several thousand, experimental investigation of each MOF at the lab-scale is not practical. High-throughput computational screening of MOFs is a great opportunity to identify the best materials for CO2 separation and to gain molecular-level insights into the structure–performance relationships. This type of knowledge can be used to design new materials with the desired structural features that can lead to extraordinarily high CO2 selectivities. In this mini-review, we focused on developments in high-throughput molecular simulations of MOFs for CO2 separations. After reviewing the current studies on this topic, we discussed the opportunities and challenges in the field and addressed the potential future developments.

  11. Smart Resonant Gas Sensor and Switch Operating in Air With Metal-Organic Frameworks Coating

    Jaber, Nizar; Ilyas, Saad; Shekhah, Osama; Eddaoudi, Mohamed; Younis, Mohammad I.

    2017-01-01

    We report a resonant gas sensor, uniformly coated with a metal-organic framework (MOF), and excited it near the higher order modes for a higher attained sensitivity. Also, switching upon exceeding a threshold value is demonstrated by operating the resonator near the bifurcation point and the dynamic pull-in instabilities. The resonator is based on an electrostatically excited clamped-clamped microbeam. The microbeam is fabricated from a polyimide layer coated from the top with Cr/Au and from the bottom with Cr/Au/Cr layer. The geometry of the resonator is optimized to reduce the effect of squeeze film damping, thereby allowing operation under atmospheric pressure. The electrostatic electrode is designed to enhance the excitation of the second mode of vibration with the minimum power required. Significant frequency shift (kHz) is demonstrated for the first time upon water vapor, acetone, and ethanol exposure due to the MOF functionalization and the higher order modes excitation. Also, the adsorption dynamics and MOF selectivity is investigated by studying the decaying time constants of the response upon gas exposure.

  12. 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.

  13. A fine-tuned Metal-Organic Framework for Autonomous Indoor Moisture Control .

    Abdul Halim, Racha Ghassan

    2017-06-29

    Conventional adsorbents, namely zeolites and silica gel, are often used to control humidity by adsorbing water; however, adsorbents capable of dual functionality of humidification and dehumidification, offering the desired control of the moisture level at room temperature, has yet to be explored. Here we report Y-shp-MOF-5, a hybrid microporous highly-connected Rare-Earth based metal-organic framework (MOF), with dual functionality for moisture control within the recommended range of relative humidity (45% to 65% RH) set by the American Society of Heating, Refrigerating, and Air-Conditioning Engineers (ASHRAE). Y-shp-MOF-5 exhibits exceptional structural integrity, robustness and unique humidity-control performance as confirmed by the large number (thousand) of conducted water vapor adsorption-desorption cycles. The retained structural integrity and the mechanism of water sorption were corroborated using in situ single crystal X-ray diffraction (SCXRD) studies. The resultant working water uptake of 0.45 g.g-1 is solely regulated by a simple adjustment of the relative humidity, positioning this hydrolytically stable MOF as a prospective adsorbent for humidity control in confined spaces such as space shuttles, aircraft cabins and air-conditioned buildings.

  14. Ultrafast water sensing and thermal imaging by a metal-organic framework with switchable luminescence

    Chen, Ling; Ye, Jia-Wen; Wang, Hai-Ping; Pan, Mei; Yin, Shao-Yun; Wei, Zhang-Wen; Zhang, Lu-Yin; Wu, Kai; Fan, Ya-Nan; Su, Cheng-Yong

    2017-06-01

    A convenient, fast and selective water analysis method is highly desirable in industrial and detection processes. Here a robust microporous Zn-MOF (metal-organic framework, Zn(hpi2cf)(DMF)(H2O)) is assembled from a dual-emissive H2hpi2cf (5-(2-(5-fluoro-2-hydroxyphenyl)-4,5-bis(4-fluorophenyl)-1H-imidazol-1-yl)isophthalic acid) ligand that exhibits characteristic excited state intramolecular proton transfer (ESIPT). This Zn-MOF contains amphipathic micropores (behaviour. The interconversion between the hydrated and dehydrated phases can turn the ligand ESIPT process on or off, resulting in sensitive two-colour photoluminescence switching over cycles. Therefore, this Zn-MOF represents an excellent PL water-sensing material, showing a fast (on the order of seconds) and highly selective response to water on a molecular level. Furthermore, paper or in situ grown ZnO-based sensing films have been fabricated and applied in humidity sensing (RH<1%), detection of traces of water (<0.05% v/v) in various organic solvents, thermal imaging and as a thermometer.

  15. Superior removal of arsenic from water with zirconium metal-organic framework UiO-66.

    Wang, Chenghong; Liu, Xinlei; Chen, J Paul; Li, Kang

    2015-11-12

    In this study, water stable zirconium metal-organic framework (UiO-66) has been synthesized and for the first time applied as an adsorbent to remove aquatic arsenic contamination. The as-synthesized UiO-66 adsorbent functions excellently across a broad pH range of 1 to 10, and achieves a remarkable arsenate uptake capacity of 303 mg/g at the optimal pH, i.e., pH = 2. To the best of our knowledge, this is the highest arsenate As(V) adsorption capacity ever reported, much higher than that of currently available adsorbents (5-280 mg/g, generally less than 100 mg/g). The superior arsenic uptake performance of UiO-66 adsorbent could be attributed to the highly porous crystalline structure containing zirconium oxide clusters, which provides a large contact area and plenty of active sites in unit space. Two binding sites within the adsorbent framework are proposed for arsenic species, i.e., hydroxyl group and benzenedicarboxylate ligand. At equilibrium, seven equivalent arsenic species can be captured by one Zr6 cluster through the formation of Zr-O-As coordination bonds.

  16. CFA-4 - a fluorinated metal-organic framework with exchangeable interchannel cations.

    Fritzsche, J; Grzywa, M; Denysenko, D; Bon, V; Senkovska, I; Kaskel, S; Volkmer, D

    2017-05-23

    The syntheses and crystal structures of the fluorinated linker 1,4-bis(3,5-bis(trifluoromethyl)-1H-pyrazole-4-yl)benzene (H 2 -tfpb; 1) and the novel metal-organic framework family M[CFA-4] (Coordination Framework Augsburg University-4), M[Cu 5 (tfpb) 3 ] (M = Cu(i), K, Cs, Ca(0.5)), are described. The ligand 1 is fully characterized by single crystal X-ray diffraction, photoluminescence-, NMR-, IR spectroscopy, and mass spectrometry. The copper(i)-containing MOF crystallizes in the hexagonal crystal system within the chiral space group P6 3 22 (no. 182) and the unit cell parameters are as follows: a = 23.630(5) Å, c = 41.390(5) Å, V = 20 015(6) Å 3 . M[CFA-4] features a porous 3-D structure constructed from pentanuclear copper(i) secondary building units {Cu(pz) 6 } - (pz = pyrazolate). Cu(I)[CFA-4] is fully characterized by synchrotron single crystal X-ray diffraction, thermogravimetric analysis, variable temperature powder X-ray diffraction, IR spectroscopy, photoluminescence and gas sorption measurements. Moreover, thermal stability and gas sorption properties of K[CFA-4] and Cu(I)[CFA-4] are compared.

  17. Insulator-to-Proton-Conductor Transition in a Dense Metal-Organic Framework.

    Tominaka, Satoshi; Coudert, François-Xavier; Dao, Thang D; Nagao, Tadaaki; Cheetham, Anthony K

    2015-05-27

    Metal-organic frameworks (MOFs) are prone to exhibit phase transitions under stimuli such as changes in pressure, temperature, or gas sorption because of their flexible and responsive structures. Here we report that a dense MOF, ((CH3)2NH2)2[Li2Zr(C2O4)4], exhibits an abrupt increase in proton conductivity from topotactic hydration (H2O/Zr = 0.5), wherein one-fourth of the Li ions are irreversibly rearranged and coordinated by water molecules. This structure further transforms into a third crystalline structure by water uptake (H2O/Zr = 4.0). The abrupt increase in conductivity is reversible and is associated with the latter reversible structure transformation. The H2O molecules coordinated to Li ions, which are formed in the first step of the transformation, are considered to be the proton source, and the absorbed water molecules, which are formed in the second step, are considered to be proton carriers.

  18. A polyoxometalate-encapsulating cationic metal-organic framework as a heterogeneous catalyst for desulfurization.

    Hao, Xiu-Li; Ma, Yuan-Yuan; Zang, Hong-Ying; Wang, Yong-Hui; Li, Yang-Guang; Wang, En-Bo

    2015-02-23

    A new cationic triazole-based metal-organic framework encapsulating Keggin-type polyoxometalates, with the molecular formula [Co(BBPTZ)3][HPMo12O40]⋅24 H2O [compound 1; BBPTZ = 4,4'-bis(1,2,4-triazol-1-ylmethyl)biphenyl] is hydrothermally synthesized and characterized by elemental analysis, IR spectroscopy, thermogravimetric analysis, powder X-ray diffraction, and single-crystal X-ray diffraction. The structure of compound 1 contains a non-interpenetrated 3D CdSO4 (cds)-type framework with two types of channels that are interconnected with each other; straight channels that are occupied by the Keggin-type POM anions, and wavelike channels that contain lattice water molecules. The catalytic activity of compound 1 in the oxidative desulfurization reaction indicates that it is not only an effective and size-selective heterogeneous catalyst, but it also exhibits distinct structural stability in the catalytic reaction system. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. Metal organic framework Cu9Cl2(cpa)6 as tunable molecular magnet

    Hamilton, Heather S. C.; Farmer, William M.; Skinner, Samuel F.; ter Haar, Leonard W.

    2018-05-01

    Chemical modifications of the magnetic metal organic framework (MOF) Cu9X2(cpa)6.42H2O (X = F, Cl, Br; cpa = anion of 2-carboxypentonicacid) have been investigated as a means of modifying, in a tunable manner, the magnetism of this 2-D material best described as a triangles-in-triangles (TIT) or triangulated-Kagomé-latttice (TKL). Since numerous theoretical studies have already attempted to describe the enigmatic ground state of this Heisenberg lattice, tunable chemical modifications should provide an excellent opportunity to expand this class of materials for studies concerning fundamental physics of frustrated spins, and applications such as adiabatic demagnetization refrigeration (ADR) that depend on the magnetocaloric effect (MCE). The chemical modification investigated is the intercalation of d- and f-orbital ions into the voids of the framework (channels of nearly 20 Å diameter). Magnetic measurements in the temperature range 1.8 - 300 K confirm signature features of TKL magnetism in intercalated samples persist, specifically: i) large negative Weiss constant (θCW); ii) absence of a phase transition down to 1.8 K; iii) minimum in χMT; iv) low temperature χMT values increasingly divergent at low fields indicating net ferromagnetic correlations; and, v) increasing field dependence of magnetization at low temperatures suggestive of intermediate plateaus, or ferrimagnetism, not saturation.

  20. Unravelling surface and interfacial structures of a metal-organic framework by transmission electron microscopy.

    Zhu, Yihan; Ciston, Jim; Zheng, Bin; Miao, Xiaohe; Czarnik, Cory; Pan, Yichang; Sougrat, Rachid; Lai, Zhiping; Hsiung, Chia-En; Yao, Kexin; Pinnau, Ingo; Pan, Ming; Han, Yu

    2017-05-01

    Metal-organic frameworks (MOFs) are crystalline porous materials with designable topology, porosity and functionality, having promising applications in gas storage and separation, ion conduction and catalysis. It is challenging to observe MOFs with transmission electron microscopy (TEM) due to the extreme instability of MOFs upon electron beam irradiation. Here, we use a direct-detection electron-counting camera to acquire TEM images of the MOF ZIF-8 with an ultralow dose of 4.1 electrons per square ångström to retain the structural integrity. The obtained image involves structural information transferred up to 2.1 Å, allowing the resolution of individual atomic columns of Zn and organic linkers in the framework. Furthermore, TEM reveals important local structural features of ZIF-8 crystals that cannot be identified by diffraction techniques, including armchair-type surface terminations and coherent interfaces between assembled crystals. These observations allow us to understand how ZIF-8 crystals self-assemble and the subsequent influence of interfacial cavities on mass transport of guest molecules.

  1. Design and Synthesis of Novel Porous Metal-Organic Frameworks (MOFs) Toward High Hydrogen Storage Capacity

    Mohamed, Eddaoudi [USF; Zaworotko, Michael [USF; Space, Brian [USF; Eckert, Juergen [USF

    2013-05-08

    Statement of Objectives: 1. Synthesize viable porous MOFs for high H2 storage at ambient conditions to be assessed by measuring H2 uptake. 2. Develop a better understanding of the operative interactions of the sorbed H2 with the organic and inorganic constituents of the sorbent MOF by means of inelastic neutron scattering (INS, to characterize the H2-MOF interactions) and computational studies (to interpret the data and predict novel materials suitable for high H2 uptake at moderate temperatures and relatively low pressures). 3. Synergistically combine the outcomes of objectives 1 and 2 to construct a made-to-order inexpensive MOF that is suitable for super H2 storage and meets the DOE targets - 6% H2 per weight (2kWh/kg) by 2010 and 9% H2 per weight (3kWh/kg) by 2015. The ongoing research is a collaborative experimental and computational effort focused on assessing H2 storage and interactions with pre-selected metal-organic frameworks (MOFs) and zeolite-like MOFs (ZMOFs), with the eventual goal of synthesizing made-to-order high H2 storage materials to achieve the DOE targets for mobile applications. We proposed in this funded research to increase the amount of H2 uptake, as well as tune the interactions (i.e. isosteric heats of adsorption), by targeting readily tunable MOFs:

  2. A flexible ligand-based wavy layered metal-organic framework for lithium-ion storage.

    An, Tiance; Wang, Yuhang; Tang, Jing; Wang, Yang; Zhang, Lijuan; Zheng, Gengfeng

    2015-05-01

    A substantial challenge for direct utilization of metal-organic frameworks (MOFs) as lithium-ion battery anodes is to maintain the rigid MOF structure during lithiation/delithiation cycles. In this work, we developed a flexible, wavy layered nickel-based MOF (C20H24Cl2N8Ni, designated as Ni-Me4bpz) by a solvothermal approach of 3,3',5,5'-tetramethyl-4,4'-bipyrazole (H2Me4bpz) with nickel(II) chloride hexahydrate. The obtained MOF materials (Ni-Me4bpz) with metal azolate coordination mode provide 2-dimensional layered structure for Li(+) intercalation/extraction, and the H2Me4bpz ligands allow for flexible rotation feature and structural stability. Lithium-ion battery anodes made of the Ni-Me4bpz material demonstrate excellent specific capacity and cycling performance, and the crystal structure is well preserved after the electrochemical tests, suggesting the potential of developing flexible layered MOFs for efficient and stable electrochemical storage. Copyright © 2015 Elsevier Inc. All rights reserved.

  3. Characterization of compositional modifications in metal-organic frameworks using carbon and alpha particle microbeams

    Paneta, V.; Fluch, U.; Petersson, P.; Ott, S.; Primetzhofer, D.

    2017-08-01

    Zirconium-oxide based metal-organic frameworks (MOFs) were grown on p-type Si wafers. A modified linker molecule containing iodine was introduced by post synthetic exchange (PSE). Samples have been studied using Rutherford Backscattering Spectrometry (RBS) and Particle Induced X-ray Emission (PIXE) techniques, employing the 5 MV 15SDH-2 Pelletron Tandem accelerator at the Ångström laboratory. The degree of post synthetic uptake of the iodine-containing linker has been investigated with both a broad beam and a focused beam of carbon and alpha particles targeting different kind of MOF crystals which were of ∼1-10 μm in size, depending on the linker used. Iodine concentrations in MOF crystallites were also measured by Nuclear Magnetic Resonance Spectroscopy (NMR) and are compared to the RBS results. In parallel to the ion beam studies, samples were investigated by Scanning Electron Microscopy (SEM) to quantify possible crystallite clustering, develop optimum sample preparation routines and to characterize the potential ion beam induced sample damage and its dependence on different parameters. Based on these results the reliability and accuracy of ion beam data is assessed.

  4. Metal-organic gel enhanced fluorescence anisotropy for sensitive detection of prostate specific antigen

    Zhao, Ting Ting; Peng, Zhe Wei; Yuan, Dan; Zhen, Shu Jun; Huang, Cheng Zhi; Li, Yuan Fang

    2018-03-01

    In this contribution, we demonstrated that Cu-based metal-organic gel (Cu-MOG) was able to serve as a novel amplification platform for fluorescence anisotropy (FA) assay for the first time, which was confirmed by the sensitive detection of a common cancer biomarker, prostate specific antigen (PSA). The dye-labeled probe aptamer (PA) product was adsorbed onto the benzimidazole derivative-containing Cu-MOG via electrostatic incorporation and strong π-π stacking interactions, which significantly increased the FA value due to the enlargement of the molecular volume of the PA/Cu-MOG complex. With the introduction of target PSA, the FA value was obviously decreased on account of the specific recognition between PSA and PA which resulted in the detachment of PA from the surface of MOG. The linear range was from 0.5-8 ng/mL, with a detection limit of 0.33 ng/mL. Our work has thus helped to demonstrate promising application of MOG material in the fields of biomolecules analysis and disease diagnosis.

  5. 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.

  6. Nanoscale zinc-based metal-organic framework with high capacity for lithium-ion batteries

    Shi, Changdong [Changzhou University, School of Petrochemical Engineering, Jiangsu Key Laboratory of Advanced Catalytic Materials and Technology, and Advanced Catalysis and Green Manufacturing Collaborative Innovation Center (China); Gao, Yuanrui; Liu, Lili [Shanghai University, Department of Chemistry, College of Science (China); Song, Yidan; Wang, Xianmei [Changzhou University, School of Petrochemical Engineering, Jiangsu Key Laboratory of Advanced Catalytic Materials and Technology, and Advanced Catalysis and Green Manufacturing Collaborative Innovation Center (China); Liu, Hong-Jiang, E-mail: liuhj@shu.edu.cn [Shanghai University, Department of Chemistry, College of Science (China); Liu, Qi, E-mail: liuqi62@163.com [Changzhou University, School of Petrochemical Engineering, Jiangsu Key Laboratory of Advanced Catalytic Materials and Technology, and Advanced Catalysis and Green Manufacturing Collaborative Innovation Center (China)

    2016-12-15

    Layered zinc-based metal-organic framework ([Zn(4,4′-bpy)(tfbdc)(H{sub 2}O){sub 2}], Zn-LMOF) nanosheets were synthesized by a facile hydrothermal method (4,4′-bpy = 4,4′-bipyridine, H{sub 2}tfbdc = tetrafluoroterephthalic acid). The materials were characterized by IR spectrum, elemental analysis, thermogravimetric analysis, powder X-ray diffraction, transmission electron microscope (TEM), scanning electron microscope (SEM), and the Brunauer–Emmett–Teller (BET) surface. When the Zn-LMOF nanosheets with the thickness of about 24 ± 8 nm were used as an anode material of lithium-ion batteries, not only the Zn-LMOF electrode shows a high reversible capacity, retaining 623 mAh g{sup −1} after 100 cycles at a current density of 50 mA g{sup −1} but also exhibits an excellent cyclic stability and a higher rate performance.

  7. Hybrid glasses from strong and fragile metal-organic framework liquids.

    Bennett, Thomas D; Tan, Jin-Chong; Yue, Yuanzheng; Baxter, Emma; Ducati, Caterina; Terrill, Nick J; Yeung, Hamish H-M; Zhou, Zhongfu; Chen, Wenlin; Henke, Sebastian; Cheetham, Anthony K; Greaves, G Neville

    2015-08-28

    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 between amorphization and melting has so far not been investigated. Here we show how heating MOFs of zeolitic topology first results in a low density 'perfect' glass, similar to those formed in ice, silicon and disaccharides. This order-order transition leads to a super-strong liquid of low fragility that dynamically controls collapse, before a subsequent order-disorder transition, which creates a more fragile high-density liquid. After crystallization to a dense phase, which can be remelted, subsequent quenching results in a bulk glass, virtually identical to the high-density phase. We provide evidence that the wide-ranging melting temperatures of zeolitic MOFs are related to their network topologies and opens up the possibility of 'melt-casting' MOF glasses.

  8. Valuing Metal-Organic Frameworks for Postcombustion Carbon Capture: A Benchmark Study for Evaluating Physical Adsorbents

    Adil, Karim

    2017-08-22

    The development of practical solutions for the energy-efficient capture of carbon dioxide is of prime importance and continues to attract intensive research interest. Conceivably, the implementation of adsorption-based processes using different cycling modes, e.g., pressure-swing adsorption or temperature-swing adsorption, offers great prospects to address this challenge. Practically, the successful deployment of practical adsorption-based technologies depends on the development of made-to-order adsorbents expressing mutually two compulsory requisites: i) high selectivity/affinity for CO2 and ii) excellent chemical stability in the presence of impurities. This study presents a new comprehensive experimental protocol apposite for assessing the prospects of a given physical adsorbent for carbon capture under flue gas stream conditions. The protocol permits: i) the baseline performance of commercial adsorbents such as zeolite 13X, activated carbon versus liquid amine scrubbing to be ascertained, and ii) a standardized evaluation of the best reported metal-organic framework (MOF) materials for carbon dioxide capture from flue gas to be undertaken. This extensive study corroborates the exceptional CO2 capture performance of the recently isolated second-generation fluorinated MOF material, NbOFFIVE-1-Ni, concomitant with an impressive chemical stability and a low energy for regeneration. Essentially, the NbOFFIVE-1-Ni adsorbent presents the best compromise by satisfying all the required metrics for efficient CO2 scrubbing.

  9. Metal-Organic Frameworks for Sensing Applications in the Gas Phase

    Sabine Achmann

    2009-03-01

    Full Text Available Several metal-organic framework (MOF materials were under investigated to test their applicability as sensor materials for impedimetric gas sensors. The materials were tested in a temperature range of 120 °C - 240 °C with varying concentrations of O2, CO2, C3H8, NO, H2, ethanol and methanol in the gas atmosphere and under different test gas humidity conditions. Different sensor configurations were studied in a frequency range of 1 Hz -1 MHz and time-continuous measurements were performed at 1 Hz. The materials did not show any impedance response to O2, CO2, C3H8, NO, or H2 in the gas atmospheres, although for some materials a significant impedance decrease was induced by a change of the ethanol or methanol concentration in the gas phase. Moreover, pronounced promising and reversible changes in the electric properties of a special MOF material were monitored under varying humidity, with a linear response curve at 120 °C. Further investigations were carried out with differently doped MOF materials of this class, to evaluate the influence of special dopants on the sensor effect.

  10. Sinter-Resistant Platinum Catalyst Supported by Metal-Organic Framework.

    Kim, In Soo; Li, Zhanyong; Zheng, Jian; Platero-Prats, Ana E; Mavrandonakis, Andreas; Pellizzeri, Steven; Ferrandon, Magali; Vjunov, Aleksei; Gallington, Leighanne C; Webber, Thomas E; Vermeulen, Nicolaas A; Penn, R Lee; Getman, Rachel B; Cramer, Christopher J; Chapman, Karena W; Camaioni, Donald M; Fulton, John L; Lercher, Johannes A; Farha, Omar K; Hupp, Joseph T; Martinson, Alex B F

    2018-01-22

    Single atoms and few-atom clusters of platinum are uniformly installed on the zirconia nodes of a metal-organic framework (MOF) NU-1000 via targeted vapor-phase synthesis. The catalytic Pt clusters, site-isolated by organic linkers, are shown to exhibit high catalytic activity for ethylene hydrogenation while exhibiting resistance to sintering up to 200 °C. In situ IR spectroscopy reveals the presence of both single atoms and few-atom clusters that depend upon synthesis conditions. Operando X-ray absorption spectroscopy and X-ray pair distribution analyses reveal unique changes in chemical bonding environment and cluster size stability while on stream. Density functional theory calculations elucidate a favorable reaction pathway for ethylene hydrogenation with the novel catalyst. These results provide evidence that atomic layer deposition (ALD) in MOFs is a versatile approach to the rational synthesis of size-selected clusters, including noble metals, on a high surface area support. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. A study on metal organic framework (MOF-177) synthesis, characterization and hydrogen adsorption -desorption cycles

    Viditha, V.; Venkateswer Rao, M.; Srilatha, K.; Himabindu, V. [Centre for Environment, Institute of Science and Technology, Jawaharlal Nehru Technological University Hyderabad, Kukatpally, Hyderabad-500 085, A.P. (India); Yerramilli, Anjaneyulu [Director, TLGVRC, JSU Box 18739, JSU, Jackson, MS 32917-0939 (United States)

    2013-07-01

    Hydrogen has long been considered to be an ideal alternative to fossil-fuel systems and much work has now been done on its storage. There are four main methods of hydrogen storage: as a liquid; as compressed hydrogen; in the form of metal hydrides; and by physisorption. Among all the materials metal organic frameworks (MOFs) are considered to have desirable properties like high porosity, pore volume and high thermal stability. MOF-177 is considered to be an ideal storage material. In this paper we study about its synthesis and hydrogen storage capacities of MOF-177 at different pressures ranging from 25, 50, 75 and 100 bar respectively. The obtained samples are characterized by XRD, BET and SEM. The recorded results show that the obtained hydrogen capacity is 1.1, 2.20, 2.4 and 2.80 wt%. The desorption capacity is 0.9, 2.1, 2.37 and 2.7 wt% at certain temperatures like 373 K.

  12. Isolated Fe sites in Metal Organic Framework catalyze the direct conversion of methane to methanol

    Osadchii, Dmitrii

    2018-05-10

    Hybrid materials bearing organic and inorganic motives have been extensively discussed as playgrounds for the implementation of atomically resolved inorganic sites within a confined environment, with an exciting similarity to enzymes. Here, we present the successful design of a site-isolated mixed-metal Metal Organic Framework that mimics the reactivity of soluble methane monooxygenase enzyme reactivity and demonstrates the potential of this strategy to overcome current challenges in selective methane oxidation. We describe the synthesis and characterisation of an Fe-containing MOF that comprises the desired antiferromagnetically cou-pled high spin species in a coordination environment closely resembling that of the enzyme. An electrochemi-cal synthesis method is used to build the microporous MOF matrix while integrating, with an exquisite con-trol, the atomically dispersed Fe active sites in the crystalline scaffold. The model mimics the catalytic C-H activation behaviour of the enzyme to produce methanol, and shows that the key to this reactivity is the for-mation of isolated oxo-bridged Fe units.

  13. Biomolecule-embedded metal-organic frameworks as an innovative sensing platform.

    Kempahanumakkagari, Sureshkumar; Kumar, Vanish; Samaddar, Pallabi; Kumar, Pawan; Ramakrishnappa, Thippeswamy; Kim, Ki-Hyun

    Technological advancements combined with materials research have led to the generation of enormous types of novel substrates and materials for use in various biological/medical, energy, and environmental applications. Lately, the embedding of biomolecules in novel and/or advanced materials (e.g., metal-organic frameworks (MOFs), nanoparticles, hydrogels, graphene, and their hybrid composites) has become a vital research area in the construction of an innovative platform for various applications including sensors (or biosensors), biofuel cells, and bioelectronic devices. Due to the intriguing properties of MOFs (e.g., framework architecture, topology, and optical properties), they have contributed considerably to recent progresses in enzymatic catalysis, antibody-antigen interactions, or many other related approaches. Here, we aim to describe the different strategies for the design and synthesis of diverse biomolecule-embedded MOFs for various sensing (e.g., optical, electrochemical, biological, and miscellaneous) techniques. Additionally, the benefits and future prospective of MOFs-based biomolecular immobilization as an innovative sensing platform are discussed along with the evaluation on their performance to seek for further development in this emerging research area. Copyright © 2018. Published by Elsevier Inc.

  14. Isolated Fe sites in Metal Organic Framework catalyze the direct conversion of methane to methanol

    Osadchii, Dmitrii; Olivos Suarez, Alma Itzel; Szé csé nyi, Á gnes; Li, Guanna; Nasalevich, Maxim A.; Dugulan, A Iulian; Serra-Crespo, Pablo; Hensen, Emiel J. M.; Veber, Sergey L.; Fedin, Matvey V.; Sankar, Gopinathan; Pidko, Evgeny A; Gascon, Jorge

    2018-01-01

    Hybrid materials bearing organic and inorganic motives have been extensively discussed as playgrounds for the implementation of atomically resolved inorganic sites within a confined environment, with an exciting similarity to enzymes. Here, we present the successful design of a site-isolated mixed-metal Metal Organic Framework that mimics the reactivity of soluble methane monooxygenase enzyme reactivity and demonstrates the potential of this strategy to overcome current challenges in selective methane oxidation. We describe the synthesis and characterisation of an Fe-containing MOF that comprises the desired antiferromagnetically cou-pled high spin species in a coordination environment closely resembling that of the enzyme. An electrochemi-cal synthesis method is used to build the microporous MOF matrix while integrating, with an exquisite con-trol, the atomically dispersed Fe active sites in the crystalline scaffold. The model mimics the catalytic C-H activation behaviour of the enzyme to produce methanol, and shows that the key to this reactivity is the for-mation of isolated oxo-bridged Fe units.

  15. Connecting small ligands to generate large tubular metal-organic architectures

    Goforth, Andrea M.; Su, Cheng-Yong; Hipp, Rachael; Macquart, Rene B.; Smith, Mark D.; Loye, Hans-Conrad zur

    2005-01-01

    The new metal-organic framework materials, ZnF(Am 2 TAZ).solvents and ZnF(TAZ).solvents (Am 2 TAZ=3,5-diamino-1,2,4-triazole, TAZ=1,2,4-triazole), have been synthesized solvothermally and structurally characterized by either Rietveld refinement from powder XRD data or by single crystal X-ray diffraction. The three-dimensional structures of the compounds display open-ended, tubular channels, which are constituted of covalently bonded hexanuclear metallamacrocycles (Zn 6 F 6 (ligand) 6 ). The tubular channels are subsequently covalently joined into a honeycomb-like hexagonal array to generate the three-dimensional porous framework. In the case of ZnF(Am 2 TAZ).solvents, hydrophilic -NH 2 groups point into the channels, effectively reducing their inner diameter relative to ZnF(TAZ).solvents. The present compounds are isostructural to one another and to the previously reported ZnF(AmTAZ).solvents (AmTAZ=3-amino-1,2,4-triazole), illustrative of the fact that the internal size and chemical properties of the framework may be altered by modification of the small, heterocyclic ligand. In addition to demonstrating the ability to modify the basic framework, ZnF(TAZ).solvents and ZnF(Am 2 TAZ).solvents are two of the most thermally stable coordination frameworks known to date. - Graphical abstract: Top view of the open-ended, honeycomb tubular architecture of ZnF(Am 2 TAZ)

  16. Research Update: Mechanical properties of metal-organic frameworks – Influence of structure and chemical bonding

    Wei Li

    2014-12-01

    Full Text Available Metal-organic frameworks (MOFs, a young family of functional materials, have been attracting considerable attention from the chemistry, materials science, and physics communities. In the light of their potential applications in industry and technology, the fundamental mechanical properties of MOFs, which are of critical importance for manufacturing, processing, and performance, need to be addressed and understood. It has been widely accepted that the framework topology, which describes the overall connectivity pattern of the MOF building units, is of vital importance for the mechanical properties. However, recent advances in the area of MOF mechanics reveal that chemistry plays a major role as well. From the viewpoint of materials science, a deep understanding of the influence of chemical effects on MOF mechanics is not only highly desirable for the development of novel functional materials with targeted mechanical response, but also for a better understanding of important properties such as structural flexibility and framework breathing. The present work discusses the intrinsic connection between chemical effects and the mechanical behavior of MOFs through a number of prototypical examples.

  17. Mesoporous stilbene-based lanthanide metal organic frameworks: synthesis, photoluminescence and radioluminescence characteristics.

    Mathis Ii, Stephan R; Golafale, Saki T; Bacsa, John; Steiner, Alexander; Ingram, Conrad W; Doty, F Patrick; Auden, Elizabeth; Hattar, Khalid

    2017-01-03

    Ultra large pore isostructural metal organic frameworks (MOFs) which exhibit both photoluminescence and scintillation properties, were synthesized from trans-4,4'-stilbenedicarboxylic acid (H 2 L) and trivalent lanthanide (Ln) metal salts under solvothermal conditions (Ln = Er 3+ (1) and Tm 3+ (2)). This new class of mesoporous materials is a non-interpenetrating network that features ultra-large diamond shaped pores of dimensions with approximate cross-sectional dimensions of 28 Å × 12 Å. The fully deprotonated ligand, L, is isolated and rigidified as it serves as the organic linker component of the MOF structure. Its low density unit cells possess asymmetric units with two crystallographically independent Ln 3+ ions in seven coordinate arrangements. A distinct feature of the structure is the bis-bidentate carboxylate groups. They serve as a ligand that coordinates two Ln(iii) ions while each L connects four Ln(iii) ions yielding an exceptionally large diamond-shaped rectangular network. The structure exhibits ligand-based photoluminescence with increased lifetime compared to free stilbene molecules on exposure to UV radiation, and also exhibits strong scintillation characteristics, comprising of both prompt and delayed radioluminescence features, on exposure to ionizing radiation.

  18. Adsorption and Detection of Hazardous Trace Gases by Metal-Organic Frameworks.

    Woellner, Michelle; Hausdorf, Steffen; Klein, Nicole; Mueller, Philipp; Smith, Martin W; Kaskel, Stefan

    2018-06-19

    The quest for advanced designer adsorbents for air filtration and monitoring hazardous trace gases has recently been more and more driven by the need to ensure clean air in indoor, outdoor, and industrial environments. How to increase safety with regard to personal protection in the event of hazardous gas exposure is a critical question for an ever-growing population spending most of their lifetime indoors, but is also crucial for the chemical industry in order to protect future generations of employees from potential hazards. Metal-organic frameworks (MOFs) are already quite advanced and promising in terms of capacity and specific affinity to overcome limitations of current adsorbent materials for trace and toxic gas adsorption. Due to their advantageous features (e.g., high specific surface area, catalytic activity, tailorable pore sizes, structural diversity, and range of chemical and physical properties), MOFs offer a high potential as adsorbents for air filtration and monitoring of hazardous trace gases. Three advanced topics are considered here, in applying MOFs for selective adsorption: (i) toxic gas adsorption toward filtration for respiratory protection as well as indoor and cabin air, (ii) enrichment of hazardous gases using MOFs, and (iii) MOFs as sensors for toxic trace gases and explosives. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. Magnetic properties of a metal-organic porous network [Ni2(BODC)2(TED)

    Yuen, Tan; Danilovic, D.; Li, Kunhao; Li, Jing

    2008-04-01

    A new material [Ni2(BODC)2(TED)], (BODC =4,4'-bicyclo[2.2.2]octane dicarboxylate and TED =triethylene-4,4'-diamine), which is a guest-free, porous metal-organic coordination network, has been successfully synthesized. The crystal structure of this compound is tetragonal with the space group P4/mmm. It is a three-dimensional network that can be deconstructed into rectangular gridlike layers along ab planes. These planes are formed by BODC and Zn2O4 paddle-wheel-like clusters, and the TED ligands from the axial directions of the paddle-wheels connect the layers into a three-dimesional structure. There are no guest molecules found in the pores. The shortest Ni-Ni distance within the paddle wheel is found to be 2.613Å. Magnetic susceptibility χ(T )=M(T)/H and isothermal magnetization M(H ) measurements have been measured on powder samples of this compound. The results of χ(T ) show that there is a rapid increase in the susceptibility below 20K due to a spontaneous ordering of the Ni2+ moments. The effective moment μeff of Ni2+ is about 2.20μB at room temperature. The M(H ) result at 1.8K shows a clear hysteresis with a coercivity of Hcoe≈1700G. The behavior of this compound is discussed in terms of Ni-Ni coupling within the Ni dimers and dimer chains.

  20. Graphene-Templated Synthesis of Magnetic Metal Organic Framework Nanocomposites for Selective Enrichment of Biomolecules.

    Cheng, Gong; Wang, Zhi-Gang; Denagamage, Sachira; Zheng, Si-Yang

    2016-04-27

    Successful control of homogeneous and complete coating of graphene or graphene-based composites with well-defined metal organic framework (MOF) layers is a great challenge. Herein, novel magnetic graphene MOF composites were constructed via a simple strategy for self-assembly of well-distributed, dense, and highly porous MOFs on both sides of graphene nanosheets. Graphene functionalized with magnetic nanoparticles and carboxylic groups on both sides was explored as the backbone and template to direct the controllable self-assembly of MOFs. The prepared composite materials have a relatively high specific surface area (345.4 m(2) g(-1)), and their average pore size is measured to be 3.2 nm. Their relatively high saturation magnetization (23.8 emu g(-1)) indicates their strong magnetism at room temperature. Moreover, the multifunctional composite was demonstrated to be a highly effective affinity material in selective extraction and separation of low-concentration biomolecules from biological samples, in virtue of the size-selection property of the unique porous structure and the excellent affinity of the composite materials. Besides providing a solution for the construction of well-defined functional graphene-based MOFs, this work could also contribute to selective extraction of biomolecules, in virtue of the universal affinity between immobilized metal ions and biomolecules.