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Sample records for metal organic chemical

  1. Metal Organic-Chemical Vapor Deposition fabrication of semiconductor lasers

    NASA Astrophysics Data System (ADS)

    Thomas, C.

    1980-08-01

    The metal organic chemical vapor deposition (MO-CVD) process was studied and implemented in detail. Single crystal GaAs, and Ga(x)Al(1-x)As films were grown on GaAs by depositing metal organic alkyl gallium compounds in the presence of an arsine mixture. The metal organic chemical vapor deposition process allowed formation of the semiconductor compound directly on the heated substrate in only one hot temperature zone. With MO-CVD, semiconductor films can be efficiently produced by a more economical, less complicated process which will lend itself more easily than past fabrication procedures, to high quantity, high quality reproduction techniques of semiconductor lasers. Clearly MO-CVD is of interest to the communication industry where semiconductor lasers are used extensively in fiber optic communication systems, and similarly to the solar energy business where GaAs substrates are used as photoelectric cells.

  2. Metal-Organic Frameworks for CO2 Chemical Transformations.

    PubMed

    He, Hongming; Perman, Jason A; Zhu, Guangshan; Ma, Shengqian

    2016-12-01

    Carbon dioxide (CO2 ), as the primary greenhouse gas in the atmosphere, triggers a series of environmental and energy related problems in the world. Therefore, there is an urgent need to develop multiple methods to capture and convert CO2 into useful chemical products, which can significantly improve the environment and promote sustainable development. Over the past several decades, metal-organic frameworks (MOFs) have shown outstanding heterogeneous catalytic activity due in part to their high internal surface area and chemical functionalities. These properties and the ability to synthesize MOF platforms allow experiments to test structure-function relationships for transforming CO2 into useful chemicals. Herein, recent developments are highlighted for MOFs participating as catalysts for the chemical fixation and photochemical reduction of CO2 . Finally, opportunities and challenges facing MOF catalysts are discussed in this ongoing research area.

  3. Destruction of chemical warfare agents using metal-organic frameworks

    NASA Astrophysics Data System (ADS)

    Mondloch, Joseph E.; Katz, Michael J.; Isley, William C., III; Ghosh, Pritha; Liao, Peilin; Bury, Wojciech; Wagner, George W.; Hall, Morgan G.; Decoste, Jared B.; Peterson, Gregory W.; Snurr, Randall Q.; Cramer, Christopher J.; Hupp, Joseph T.; Farha, Omar K.

    2015-05-01

    Chemical warfare agents containing phosphonate ester bonds are among the most toxic chemicals known to mankind. Recent global military events, such as the conflict and disarmament in Syria, have brought into focus the need to find effective strategies for the rapid destruction of these banned chemicals. Solutions are needed for immediate personal protection (for example, the filtration and catalytic destruction of airborne versions of agents), bulk destruction of chemical weapon stockpiles, protection (via coating) of clothing, equipment and buildings, and containment of agent spills. Solid heterogeneous materials such as modified activated carbon or metal oxides exhibit many desirable characteristics for the destruction of chemical warfare agents. However, low sorptive capacities, low effective active site loadings, deactivation of the active site, slow degradation kinetics, and/or a lack of tailorability offer significant room for improvement in these materials. Here, we report a carefully chosen metal-organic framework (MOF) material featuring high porosity and exceptional chemical stability that is extraordinarily effective for the degradation of nerve agents and their simulants. Experimental and computational evidence points to Lewis-acidic ZrIV ions as the active sites and to their superb accessibility as a defining element of their efficacy.

  4. Destruction of chemical warfare agents using metal-organic frameworks.

    PubMed

    Mondloch, Joseph E; Katz, Michael J; Isley, William C; Ghosh, Pritha; Liao, Peilin; Bury, Wojciech; Wagner, George W; Hall, Morgan G; DeCoste, Jared B; Peterson, Gregory W; Snurr, Randall Q; Cramer, Christopher J; Hupp, Joseph T; Farha, Omar K

    2015-05-01

    Chemical warfare agents containing phosphonate ester bonds are among the most toxic chemicals known to mankind. Recent global military events, such as the conflict and disarmament in Syria, have brought into focus the need to find effective strategies for the rapid destruction of these banned chemicals. Solutions are needed for immediate personal protection (for example, the filtration and catalytic destruction of airborne versions of agents), bulk destruction of chemical weapon stockpiles, protection (via coating) of clothing, equipment and buildings, and containment of agent spills. Solid heterogeneous materials such as modified activated carbon or metal oxides exhibit many desirable characteristics for the destruction of chemical warfare agents. However, low sorptive capacities, low effective active site loadings, deactivation of the active site, slow degradation kinetics, and/or a lack of tailorability offer significant room for improvement in these materials. Here, we report a carefully chosen metal-organic framework (MOF) material featuring high porosity and exceptional chemical stability that is extraordinarily effective for the degradation of nerve agents and their simulants. Experimental and computational evidence points to Lewis-acidic Zr(IV) ions as the active sites and to their superb accessibility as a defining element of their efficacy.

  5. Toxic Industrial Chemical Removal by Isostructural Metal-Organic Frameworks

    DTIC Science & Technology

    2011-01-01

    ISOSTRUCTURAL METAL-ORGANIC FRAMEWORKS Gregory W. Peterson RESEARCH AND TECHNOLOGY DIRECTORATE T. Grant Glover Bryan J. Schindler SCIENCE...APPLICATIONS INTERNATIONAL CORPORATION Gunpowder, MD 21010-0068 David Britt Omar Yaghi UNIVERSITY OF CALIFORNIA Los Angeles, CA 90095-1569 January 2011...Frameworks 5a. CONTRACT NUMBER 5b. GRANT NUMBER 5c. PROGRAM ELEMENT NUMBER 6. AUTHOR(S) Peterson, Gregory W. (ECBC); Glover, T. Grant; Schindler

  6. Natural and active chemical remediation of toxic metals, organics, and radionuclides in the aquatic environment

    SciTech Connect

    McPherson, G.; Pintauro, P.; O`Connor, S.

    1996-05-02

    This project focuses on the chemical aspects of remediation, with the underlying theme that chemical remediation does occur naturally. Included are studies on the fate of heavy metal and organic contaminants discharged into aquatic environments; accurate assay metal contaminants partitioned into soils, water and tissue; development of novel polymeric membranes and microporous solids for the entrapment of heavy metals; and the development of hybrid chemo-enzymatic oxidative schemes for aromatics decontamination. 49 refs.

  7. Comparison of InGaAs(100) Grown by Chemical Beam Epitaxy and Metal Organic Chemical Vapor Deposition

    NASA Technical Reports Server (NTRS)

    Williams, M. D.; Greene, A. L.; Daniels-Race, T.; Lum, R. M.

    2000-01-01

    Secondary ion mass spectrometry is used to study the effects of substrate temperature on the composition and growth rate of InGaAs/InP(100) multilayers grown by chemical beam epitaxy, metal-organic chemical vapor deposition and solid source molecular beam epitaxy. The growth kinetics of the material grown by the different techniques are analyzed and compared.

  8. High index of refraction films for dielectric mirrors prepared by metal-organic chemical vapor deposition

    SciTech Connect

    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.

  9. Catalyst accessibility to chemical reductants in metal-organic frameworks.

    PubMed

    Roy, Souvik; Pascanu, Vlad; Pullen, Sonja; González Miera, Greco; Martín-Matute, Belén; Ott, Sascha

    2017-03-18

    A molecular H2-evolving catalyst, [Fe2(cbdt)(CO)6] ([FeFe], cbdt = 3-carboxybenzene-1,2-dithiolate), has been attached covalently to an amino-functionalized MIL-101(Cr) through an amide bond. Chemical reduction experiments reveal that the MOF channels can be clogged by ion pairs that are formed between the oxidized reductant and the reduced catalyst. This effect is lessened in MIL-101-NH-[FeFe] with lower [FeFe] loadings. On longer timescales, it is shown that large proportions of the [FeFe] catalysts within the MOF engage in photochemical hydrogen production and the amount of produced hydrogen is proportional to the catalyst loading.

  10. GaN Stress Evolution During Metal-Organic Chemical Vapor Deposition

    SciTech Connect

    Amano, H.; Chason, E.; Figiel, J.; Floro, J.A.; Han, J.; Hearne, S.; Hunter, J.; Tsong, I.

    1998-10-14

    The evolution of stress in gallium nitride films on sapphire has been measured in real- time during metal organic chemical vapor deposition. In spite of the 161%0 compressive lattice mismatch of GaN to sapphire, we find that GaN consistently grows in tension at 1050"C. Furthermore, in-situ stress monitoring indicates that there is no measurable relaxation of the tensile growth stress during annealing or thermal cycling.

  11. Metal organic chemical vapor deposition of phase change Ge1Sb2Te4 nanowires.

    PubMed

    Longo, Massimo; Fallica, Roberto; Wiemer, Claudia; Salicio, Olivier; Fanciulli, Marco; Rotunno, Enzo; Lazzarini, Laura

    2012-03-14

    The self-assembly of Ge(1)Sb(2)Te(4) nanowires (NWs) for phase change memories application was achieved by metal organic chemical vapor deposition, catalyzed by Au nanoislands in a narrow range of temperatures and deposition pressures. In the optimized conditions of 400 °C, 50 mbar, the NWs are Ge(1)Sb(2)Te(4) single hexagonal crystals. Phase change memory switching was reversibly induced by nanosecond current pulses through metal-contacted NWs with threshold voltage of about 1.35 V.

  12. Y-Ba-Cu-O film deposition by metal organic chemical vapor deposition on buffered metal substrates.

    SciTech Connect

    Selvamanickam, V.; Galinski, G.; DeFrank, J.; Trautwein, C.; Haldar, P.; Balachandran, U.; Lanagan, M.; Chudzik, M.

    1999-10-12

    YBa{sub 2}Cu{sub 3}O{sub 2} (YBCO) films have been deposited on buffered metal substrates by Metal Organic Chemical Vapor Deposition (MOCVD). Cube-textured nickel substrates were fabricated by a thermomechanical process. Epitaxial CeO{sub 2}films were deposited on these substrates by thermal evaporation. Nickel alloy substrates with biaxially-textured Yttria-Stabilized Zirconia (YSZ) buffer layers deposited by Ion Beam Assisted Deposition were also prepared. Highly biaxially-textured YBCO films were deposited by MOCVD on both types of metal substrates. A critical current density greater than 10{sup 5} A/cm{sup 2} at 77 K has been achieved in YBCO films on metal substrates.

  13. Micro- and Nanostructured Metal Oxide Chemical Sensors for Volatile Organic Compounds

    NASA Technical Reports Server (NTRS)

    Alim, M. A.; Penn, B. G.; Currie, J. R., Jr.; Batra, A. K.; Aggarwal, M. D.

    2008-01-01

    Aeronautic and space applications warrant the development of chemical sensors which operate in a variety of environments. This technical memorandum incorporates various kinds of chemical sensors and ways to improve their performance. The results of exploratory investigation of the binary composite polycrystalline thick-films such as SnO2-WO3, SnO2-In2O3, SnO2-ZnO for the detection of volatile organic compound (isopropanol) are reported. A short review of the present status of the new types of nanostructured sensors such as nanobelts, nanorods, nanotube, etc. based on metal oxides is presented.

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

    PubMed

    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.

  15. Method of making AlInSb by metal-organic chemical vapor deposition

    DOEpatents

    Biefeld, Robert M.; Allerman, Andrew A.; Baucom, Kevin C.

    2000-01-01

    A method for producing aluminum-indium-antimony materials by metal-organic chemical vapor deposition (MOCVD). This invention provides a method of producing Al.sub.X In.sub.1-x Sb crystalline materials by MOCVD wherein an Al source material, an In source material and an Sb source material are supplied as a gas to a heated substrate in a chamber, said Al source material, In source material, and Sb source material decomposing at least partially below 525.degree. C. to produce Al.sub.x In.sub.1-x Sb crystalline materials wherein x is greater than 0.002 and less than one.

  16. Peptide-Metal Organic Framework Swimmers that Direct the Motion toward Chemical Targets.

    PubMed

    Ikezoe, Yasuhiro; Fang, Justin; Wasik, Tomasz L; Shi, Menglu; Uemura, Takashi; Kitagawa, Susumu; Matsui, Hiroshi

    2015-06-10

    Highly efficient and robust chemical motors are expected for the application in microbots that can selectively swim toward targets and accomplish their tasks in sensing, labeling, and delivering. However, one of major issues for such development is that current artificial swimmers have difficulty controlling their directional motion toward targets like bacterial chemotaxis. To program synthetic motors with sensing capability for the target-directed motion, we need to develop swimmers whose motions are sensitive to chemical gradients in environments. Here we create a new intelligent biochemical swimmer by integrating metal organic frameworks (MOFs) and peptides that can sense toxic heavy metals in solution and swim toward the targets. With the aid of Pb-binding enzymes, the peptide-MOF motor can directionally swim toward PbSe quantum dots (QD) by sensing pH gradient and eventually complete the motion as the swimmer reaches the highest gradient point at the target position in solution. This type of technology could be evolved to miniaturize chemical robotic systems that sense target chemicals and swim toward target locations.

  17. Computational Investigations of Potential Energy Function Development for Metal--Organic Framework Simulations, Metal Carbenes, and Chemical Warfare Agents

    NASA Astrophysics Data System (ADS)

    Cioce, Christian R.

    Metal-Organic Frameworks (MOFs) are three-dimensional porous nanomaterials with a variety of applications, including catalysis, gas storage and separation, and sustainable energy. Their potential as air filtration systems is of interest for designer carbon capture materials. The chemical constituents (i.e. organic ligands) can be functionalized to create rationally designed CO2 sequestration platforms, for example. Hardware and software alike at the bleeding edge of supercomputing are utilized for designing first principles-based molecular models for the simulation of gas sorption in these frameworks. The classical potentials developed herein are named PHAST --- Potentials with High Accuracy, Speed, and Transferability, and thus are designed via a "bottom-up" approach. Specifically, models for N2 and CH4 are constructed and presented. Extensive verification and validation leads to insights and range of applicability. Through this experience, the PHAST models are improved upon further to be more applicable in heterogeneous environments. Given this, the models are applied to reproducing high level ab initio energies for gas sorption trajectories of helium atoms in a variety of rare-gas clusters, the geometries of which being representative of sorption-like environments commonly encountered in a porous nanomaterial. This work seeks to push forward the state of classical and first principles materials modeling. Additionally, the characterization of a new type of tunable radical metal---carbene is presented. Here, a cobalt(II)---porphyrin complex, [Co(Por)], was investigated to understand its role as an effective catalyst in stereoselective cyclopropanation of a diazoacetate reagent. Density functional theory along with natural bond order analysis and charge decomposition analysis gave insight into the electronics of the catalytic intermediate. The bonding pattern unveiled a new class of radical metal---carbene complex, with a doublet cobalt into which a triplet carbene

  18. High quality AlN epilayers grown on nitrided sapphire by metal organic chemical vapor deposition.

    PubMed

    Wang, Jiaming; Xu, Fujun; He, Chenguang; Zhang, Lisheng; Lu, Lin; Wang, Xinqiang; Qin, Zhixin; Shen, Bo

    2017-02-21

    Influence of sapphire pretreatment conditions on crystalline quality of AlN epilayers has been investigated by metal organic chemical vapor deposition (MOCVD). Compared to alumination treatment, it is found that appropriate sapphire nitridation significantly straightens the surface atomic terraces and decreases the X-ray diffraction (0002) full width at half maximum (FWHM) to a minimum of 55 arcsec, indicating a great improvement of the tilting feature of the grain structures in the AlN epilayer. More importantly, there is no inversion domains (IDs) found in the AlN epilayers, which clarifies that optimal sapphire nitridation is promising in the growth of high quality AlN. It is deduced that the different interfacial atomic structures caused by various pretreatment conditions influence the orientation of the AlN nucleation layer grains, which eventually determines the tilting features of the AlN epilayers.

  19. Controlling nucleation of monolayer WSe2 during metal-organic chemical vapor deposition growth

    NASA Astrophysics Data System (ADS)

    Eichfeld, Sarah M.; Oliveros Colon, Víctor; Nie, Yifan; Cho, Kyeongjae; Robinson, Joshua A.

    2016-06-01

    Tungsten diselenide (WSe2) is a semiconducting, two-dimensional (2D) material that has gained interest in the device community recently due to its electronic properties. The synthesis of atomically thin WSe2, however, is still in its infancy. In this work we elucidate the requirements for large selenium/tungsten precursor ratios and explain the effect of nucleation temperature on the synthesis of WSe2 via metal-organic chemical vapor deposition (MOCVD). The introduction of a nucleation-step prior to growth demonstrates that increasing nucleation temperature leads to a transition from a Volmer-Weber to Frank-van der Merwe growth mode. Additionally, the nucleation step prior to growth leads to an improvement of WSe2 layer coverage on the substrate. Finally, we note that the development of this two-step technique may allow for improved control and quality of 2D layers grown via CVD and MOCVD processes.

  20. Optical properties of InP doping superlattices grown by metal organic chemical vapor deposition

    NASA Astrophysics Data System (ADS)

    Gal, M.; Viner, J. M.; Taylor, P. C.; Yaun, J. S.; Stringfellow, G. B.

    1987-04-01

    Photoluminescence (PL), time-resolved PL, and photoreflectance spectroscopy are applied to InP doping superlattices grown by metal organic chemical vapor deposition. It is observed that the emission peak and line shape depend on the optical excitation intensity; the peak of the CW PL spectrum increases in energy with the intensity of the pumping light; the highest energy peak is at 888 nm; and the time-resolved PL exhibits long decay times. The energy separation of the quantized subbands is studied by measuring the PR spectra of two samples. The measurements reveal that PR line shapes are explained by photomodulation of the subbands in the conduction band; these line shapes account for the dependence of the spectrum on the power of the exciting light and on the layer thickness.

  1. High quality AlN epilayers grown on nitrided sapphire by metal organic chemical vapor deposition

    PubMed Central

    Wang, Jiaming; Xu, Fujun; He, Chenguang; Zhang, Lisheng; Lu, Lin; Wang, Xinqiang; Qin, Zhixin; Shen, Bo

    2017-01-01

    Influence of sapphire pretreatment conditions on crystalline quality of AlN epilayers has been investigated by metal organic chemical vapor deposition (MOCVD). Compared to alumination treatment, it is found that appropriate sapphire nitridation significantly straightens the surface atomic terraces and decreases the X-ray diffraction (0002) full width at half maximum (FWHM) to a minimum of 55 arcsec, indicating a great improvement of the tilting feature of the grain structures in the AlN epilayer. More importantly, there is no inversion domains (IDs) found in the AlN epilayers, which clarifies that optimal sapphire nitridation is promising in the growth of high quality AlN. It is deduced that the different interfacial atomic structures caused by various pretreatment conditions influence the orientation of the AlN nucleation layer grains, which eventually determines the tilting features of the AlN epilayers. PMID:28220829

  2. III-nitride quantum cascade detector grown by metal organic chemical vapor deposition

    SciTech Connect

    Song, Yu Huang, Tzu-Yung; Badami, Pranav; Gmachl, Claire; Bhat, Rajaram; Zah, Chung-En

    2014-11-03

    Quantum cascade (QC) detectors in the GaN/Al{sub x}Ga{sub 1−x}N material system grown by metal organic chemical vapor deposition are designed, fabricated, and characterized. Only two material compositions, i.e., GaN as wells and Al{sub 0.5}Ga{sub 0.5}N as barriers are used in the active layers. The QC detectors operates around 4 μm, with a peak responsivity of up to ∼100 μA/W and a detectivity of up to 10{sup 8} Jones at the background limited infrared performance temperature around 140 K.

  3. High quality AlN epilayers grown on nitrided sapphire by metal organic chemical vapor deposition

    NASA Astrophysics Data System (ADS)

    Wang, Jiaming; Xu, Fujun; He, Chenguang; Zhang, Lisheng; Lu, Lin; Wang, Xinqiang; Qin, Zhixin; Shen, Bo

    2017-02-01

    Influence of sapphire pretreatment conditions on crystalline quality of AlN epilayers has been investigated by metal organic chemical vapor deposition (MOCVD). Compared to alumination treatment, it is found that appropriate sapphire nitridation significantly straightens the surface atomic terraces and decreases the X-ray diffraction (0002) full width at half maximum (FWHM) to a minimum of 55 arcsec, indicating a great improvement of the tilting feature of the grain structures in the AlN epilayer. More importantly, there is no inversion domains (IDs) found in the AlN epilayers, which clarifies that optimal sapphire nitridation is promising in the growth of high quality AlN. It is deduced that the different interfacial atomic structures caused by various pretreatment conditions influence the orientation of the AlN nucleation layer grains, which eventually determines the tilting features of the AlN epilayers.

  4. Metallated metal-organic frameworks

    DOEpatents

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

    2017-02-07

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

  5. Adsorptive removal and separation of chemicals with metal-organic frameworks: Contribution of π-complexation.

    PubMed

    Khan, Nazmul Abedin; Jhung, Sung Hwa

    2017-03-05

    Efficient removal and separation of chemicals from the environment has become a vital issue from a biological and environmental point of view. Currently, adsorptive removal/separation is one of the most promising approaches for cleaning purposes. Selective adsorption/removal of various sulfur- and nitrogen-containing compounds, olefins, and π-electron-rich gases via π-complex formation between an adsorbent and adsorbate molecules is very competitive. Porous metal-organic framework (MOF) materials are very promising in the adsorption/separation of various liquids and gases owing to their distinct characteristics. This review summarizes the literature on the adsorptive removal/separation of various π-electron-rich compounds mainly from fuel and gases using MOF materials containing metal ions that are active for π-complexation. Details of the π-complexation, including mechanism, pros/cons, applications, and efficient ways to form the complex, are discussed systematically. For in-depth understanding, molecular orbital calculations regarding charge transfer between the π-complexing species are also explained in a separate section. From this review, readers will gain an understanding of π-complexation for adsorption and separation, especially with MOFs, to develop new insight for future research.

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

    NASA Astrophysics Data System (ADS)

    Li, Wei; Henke, Sebastian; Cheetham, Anthony K.

    2014-12-01

    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.

  7. Diagenesis of Metals Chemically Complexed to Bacteria: Laboratory Formation of Metal Phosphates, Sulfides, and Organic Condensates in Artificial Sediments

    PubMed Central

    Beveridge, T. J.; Meloche, J. D.; Fyfe, W. S.; Murray, R. G. E.

    1983-01-01

    Cells of Bacillus subtilis, when suspended in a 5mM metal solution, bind metals tenaciously to their cell walls. These metal-loaded cells, when mixed with a synthetic sediment and put under laboratory conditions to simulate low-temperature sediment diagenesis, nucleate the formation of a mixed assemblage of crystalline metal phosphates, metal sulfides, and polymeric, metal-complexed, organic residues. The sequential series of diagenetic events leading to the formation of authigenic mineral phases was followed by transmission electron microscopy and energy-dispersive X-ray analysis. The minerals quartz (SiO2) and calcite (CaCO3) were employed in the synthetic sediment. Crystalline magnetite (Fe2O3) and elemental sulfur were added as redox buffering agents to ensure anoxic conditions. Quartz and magnetite appeared unreactive throughout the experimental conditions. Elemental sulfur interacted with the metal-loaded cells, affected both the eventual chemistry and crystal habit of the metal phosphates, and formed a variety of crystalline metal sulfides. Calcite raised the pH of the fluid phase of the sediment, which influenced phosphate mineralization and inhibited metal sulfide genesis. Images PMID:16346230

  8. Opportunities and challenges in GaN metal organic chemical vapor deposition for electron devices

    NASA Astrophysics Data System (ADS)

    Matsumoto, Koh; Yamaoka, Yuya; Ubukata, Akinori; Arimura, Tadanobu; Piao, Guanxi; Yano, Yoshiki; Tokunaga, Hiroki; Tabuchi, Toshiya

    2016-05-01

    The current situation and next challenge in GaN metal organic chemical vapor deposition (MOCVD) for electron devices of both GaN on Si and GaN on GaN are presented. We have examined the possibility of increasing the growth rate of GaN on 200-mm-diameter Si by using a multiwafer production MOCVD machine, in which the vapor phase parasitic reaction is well controlled. The impact of a high-growth-rate strained-layer-superlattice (SLS) buffer layer is presented in terms of material properties. An SLS growth rate of as high as 3.46 µm/h, which was 73% higher than the current optimum, was demonstrated. As a result, comparable material properties were obtained. Next, a typical result of GaN doped with Si of 1 × 1016 cm-3 grown at the growth rate of 3.7 µm/h is shown. For high-voltage application, we need a thick high-purity GaN drift layer with a low carbon concentration, of less than 1016 cm-3. It is shown that achieving a high growth rate by precise control of the vapor phase reaction is still challenge in GaN MOCVD.

  9. Highly scalable, atomically thin WSe2 grown via metal-organic chemical vapor deposition.

    PubMed

    Eichfeld, Sarah M; Hossain, Lorraine; Lin, Yu-Chuan; Piasecki, Aleksander F; Kupp, Benjamin; Birdwell, A Glen; Burke, Robert A; Lu, Ning; Peng, Xin; Li, Jie; Azcatl, Angelica; McDonnell, Stephen; Wallace, Robert M; Kim, Moon J; Mayer, Theresa S; Redwing, Joan M; Robinson, Joshua A

    2015-02-24

    Tungsten diselenide (WSe2) is a two-dimensional material that is of interest for next-generation electronic and optoelectronic devices due to its direct bandgap of 1.65 eV in the monolayer form and excellent transport properties. However, technologies based on this 2D material cannot be realized without a scalable synthesis process. Here, we demonstrate the first scalable synthesis of large-area, mono and few-layer WSe2 via metal-organic chemical vapor deposition using tungsten hexacarbonyl (W(CO)6) and dimethylselenium ((CH3)2Se). In addition to being intrinsically scalable, this technique allows for the precise control of the vapor-phase chemistry, which is unobtainable using more traditional oxide vaporization routes. We show that temperature, pressure, Se:W ratio, and substrate choice have a strong impact on the ensuing atomic layer structure, with optimized conditions yielding >8 μm size domains. Raman spectroscopy, atomic force microscopy (AFM), and cross-sectional transmission electron microscopy (TEM) confirm crystalline monoto-multilayer WSe2 is achievable. Finally, TEM and vertical current/voltage transport provide evidence that a pristine van der Waals gap exists in WSe2/graphene heterostructures.

  10. Improving source efficiency for aluminum nitride grown by metal organic chemical vapor deposition

    NASA Astrophysics Data System (ADS)

    Foronda, Humberto M.; Laurent, Matthew A.; Yonkee, Benjanim; Keller, Stacia; DenBaars, Steven P.; Speck, James S.

    2016-08-01

    Parasitic pre-reactions are known to play a role in the growth of aluminum nitride (AlN) via metal organic chemical vapor deposition, where they can deplete precursor molecules before reaching the substrate, leading to poor growth efficiency. Studies have shown that reducing the growth pressure and growth temperature results in improved growth efficiency of AlN; however, superior crystal quality and reduced impurity incorporation are generally best obtained when growing at high temperatures. This study shows that, with proper alkyl source dilution, parasitic pre-reactions can be suppressed while maintaining high growth temperatures. The results show an 18× increase in growth rate and efficiency of AlN films: from 0.04 μm h-1 to 0.73 μm h-1, and 26 μm mol-1 to 502 μm mol-1, respectively; under constant TMAl flow and a small change in total gas flow. This results in 6.8% of Al atoms from the injected TMAl being utilized for AlN layer growth for this reactor configuration. This is better than the standard GaN growth, where 6.0% of the Ga atoms injected from TMGa are utilized for GaN growth.

  11. Metal-Organic Frameworks as Potential Platforms for Carbon Dioxide Capture and Chemical Transformation

    NASA Astrophysics Data System (ADS)

    Gao, Wenyang

    The anthropogenic carbon dioxide (CO2) emission into the atmosphere, mainly through the combustion of fossil fuels, has resulted in a balance disturbance of the carbon cycle. Overwhelming scientific evidence proves that the escalating level of atmospheric CO2 is deemed as the main culprit for global warming and climate change. It is thus imperative to develop viable CO2 capture and sequestration (CCS) technologies to reduce CO2 emissions, which is also essential to avoid the potential devastating effects in future. The drawbacks of energy-cost, corrosion and inefficiency for amine-based wet-scrubbing systems which are currently used in industry, have prompted the exploration of alternative approaches for CCS. Extensive efforts have been dedicated to the development of functional porous materials, such as activated carbons, zeolites, porous organic polymers, and metal-organic frameworks (MOFs) to capture CO2. However, these adsorbents are limited by either poor selectivity for CO2 separation from gas mixtures or low CO2 adsorption capacity. Therefore, it is still highly demanding to design next-generation adsorbent materials fulfilling the requirements of high CO2 selectivity and enough CO2 capacity, as well as high water/moisture stability under practical conditions. Metal-organic frameworks (MOFs) have been positioned at the forefront of this area as a promising type of candidate amongst various porous materials. This is triggered by the modularity and functionality of pore size, pore walls and inner surface of MOFs by use of crystal engineering approaches. In this work, several effective strategies, such as incorporating 1,2,3-triazole groups as moderate Lewis base centers into MOFs and employing flexible azamacrocycle-based ligands to build MOFs, demonstrate to be promising ways to enhance CO 2 uptake capacity and CO2 separation ability of porous MOFs. It is revealed through in-depth studies on counter-intuitive experimental observations that the local electric

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

    SciTech Connect

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

    2009-09-01

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

  13. Soluble organic carbon and pH of organic amendments affect metal mobility and chemical speciation in mine soils.

    PubMed

    Pérez-Esteban, Javier; Escolástico, Consuelo; Masaguer, Alberto; Vargas, Carmen; Moliner, Ana

    2014-05-01

    We evaluated the effects of pH and soluble organic carbon affected by organic amendments on metal mobility to find out the optimal conditions for their application in the stabilization of metals in mine soils. Soil samples (pH 5.5-6.2) were mixed with 0, 30 and 60 th a(-1) of sheep-horse manure (pH 9.4) and pine bark compost (pH 5.7). A single-step extraction procedure was performed using 0.005 M CaCl2 adjusted to pH 4.0-7.0 and metal speciation in soil solution was simulated using NICA-Donnan model. Sheep-horse manure reduced exchangeable metal concentrations (up to 71% Cu, 75% Zn) due to its high pH and degree of maturity, whereas pine bark increased them (32% Cu, 33% Zn). However, at increasing dose and hence pH, sheep-horse manure increased soluble Cu because of higher soluble organic carbon, whereas soluble Cu and organic carbon increased at increasing dose and correspondingly decreasing pH in pine bark and non-amended treatments. Near the native pH of these soils (at pH 5.8-6.3), with small doses of amendments, there was minimum soluble Cu and organic carbon. Pine bark also increased Zn solubility, whereas sheep-horse manure reduced it as soluble Zn always decreased with increasing pH. Sheep-horse manure also reduced the proportion of free metals in soil solution (from 41% to 4% Cu, from 97% to 94% Zn), which are considered to be more bioavailable than organic species. Sheep-horse manure amendment could be efficiently used for the stabilization of metals with low risk of leaching to groundwater at low doses and at relatively low pH, such as the native pH of mine soils.

  14. Heteroepitaxial growth of 3-5 semiconductor compounds by metal-organic chemical vapor deposition for device applications

    NASA Technical Reports Server (NTRS)

    Collis, Ward J.; Abul-Fadl, Ali

    1988-01-01

    The purpose of this research is to design, install and operate a metal-organic chemical vapor deposition system which is to be used for the epitaxial growth of 3-5 semiconductor binary compounds, and ternary and quaternary alloys. The long-term goal is to utilize this vapor phase deposition in conjunction with existing current controlled liquid phase epitaxy facilities to perform hybrid growth sequences for fabricating integrated optoelectronic devices.

  15. A Metal Organic Framework with Spherical Protein Nodes: Rational Chemical Design of 3D Protein Crystals.

    PubMed

    Sontz, Pamela A; Bailey, Jake B; Ahn, Sunhyung; Tezcan, F Akif

    2015-09-16

    We describe here the construction of a three-dimensional, porous, crystalline framework formed by spherical protein nodes that assemble into a prescribed lattice arrangement through metal-organic linker-directed interactions. The octahedral iron storage enzyme, ferritin, was engineered in its C3 symmetric pores with tripodal Zn coordination sites. Dynamic light scattering and crystallographic studies established that this Zn-ferritin construct could robustly self-assemble into the desired bcc-type crystals upon coordination of a ditopic linker bearing hydroxamic acid functional groups. This system represents the first example of a ternary protein-metal-organic crystalline framework whose formation is fully dependent on each of its three components.

  16. Metal-organic chemical vapor deposition in silicon/zinc sulfide quantum confined structures

    NASA Astrophysics Data System (ADS)

    Bretschneider, Eric Colin

    A comprehensive study of low pressure metal-organic chemical vapor deposition growth of zinc sulfide and silicon has been performed. The parameter space for successful deposition of both materials has been investigated and found to overlap, allowing successful deposition of both zinc sulfide and silicon under similar conditions. Undoped and aluminum doped zinc sulfide and silicon films were grown on both (100) and (111) 4sp° off orientation silicon substrates. Diethyl zinc, hydrogen sulfide, triethyl aluminum and disilane where used as precursor materials. It was found that high quality epitaxial zinc sulfide films could be deposited over the temperature range of 300 to 650sp°C. Growth rate was found to be nearly independent of temperature over this temperature range indicating a mass transfer limited growth mechanism. Aluminum doping yielded low resistivity, n-type material. Key parameters affecting the surface roughness of zinc sulfide films were determined using a fractional factorial design. This method increases the efficiency of data collection and allows easy determination of the magnitude of multi-parameter interactions. The parameters studied included substrate orientation, deposition temperature, precursor concentrations, total hydrogen flow and the push flow ratio of the alkyl and hydride injectors. Silicon growth rates varied from 120 to 9000 A/hour at 450 and 600sp° C respectively. A strong temperature dependence of the growth rate was found indicating a reaction limited step with an activation energy of 153.6 ± 18.0 kJ/mol. This agrees well with the energy barrier of 144.3 ± 19.2 kJ/mol for surface diffusion of hydrogen. Quantum mechanical calculations that take into account the differences in effective masses for electrons and holes in silicon and zinc sulfide indicate that the band gap energy of a silicon quantum well shifts into the visible portion of the spectrum for well widths below 20A. Samples containing single and multiple quantum wells

  17. Chemical reactions of metal powders with organic and inorganic liquids during ball milling

    NASA Technical Reports Server (NTRS)

    Arias, A.

    1975-01-01

    Chromium and/or nickel powders were milled in metal chlorides and in organic liquids representative of various functional groups. The powders always reacted with the liquid and became contaminated with elements from them. The milled powders had specific surface areas ranging from 0.14 to 37 sq m/g, and the total contamination with elements from the milling liquid ranged from 0.01 to 56 weight percent. Compounds resulting from substitution, addition, or elimination reactions formed in or from the milling liquid.

  18. A Sr2+-metal-organic framework with high chemical stability: synthesis, crystal structure and photoluminescence property.

    PubMed

    Jia, Yan-Yuan; Liu, Xiao-Ting; Wang, Wen-He; Zhang, Li-Zhu; Zhang, Ying-Hui; Bu, Xian-He

    2017-01-13

    Metal-organic frameworks (MOFs) are typically built by assembly of metal centres and organic linkers, and have emerged as promising crystalline materials in a variety of fields. However, the stability of MOFs is a key limitation for their practical applications. Herein, we report a novel Sr 2+: -MOF [Sr4(Tdada)2(H2O)3(DMF)2] (denoted as NKU- 105: , NKU = Nankai University; H4Tdada = 5,5'-((thiophene-2,5-dicar bonyl)bis(azanediyl))diisophthalic acid; DMF = N,N-dimethylformamide) featuring an open square channel of about 6 Å along the c-axis. Notably, NKU- 105: exhibits much outstanding chemical stability against common organic solvents, boiling water, acids and bases, relative to most MOF materials. Furthermore, NKU- 105: is an environment-friendly luminescent material with a bright cyan emission.This article is part of the themed issue 'Coordination polymers and metal-organic frameworks: materials by design'.

  19. Groundwater and organic chemicals

    SciTech Connect

    Dawson, H.E.

    1995-12-01

    Groundwater is a major source of drinking water for many communities. Unfortunately, organic chemicals such as dry cleaning fluids, solvent, fuels, and pesticides have contaminated groundwater in many areas, rendering the groundwater useless as a drinking water resource. In many cases, the groundwater cannot be cleaned up with current technologies, particularly if the groundwater has been contaminated with immiscible (low solubility) organic liquids. In this talk, I will describe the path I have followed from geologist to geochemist and finally to environmental engineer. As a geologist, I studied the chemistry of rock metamorphosis. As a geochemist, I explored for gold and other metals. Now as an environmental engineer, I investigate the behavior of organic liquids in the subsurface. While these fields all appear very different, in reality I have always focused on the interaction of rocks or sediments with the fluids with which they come in contact.

  20. Crystal engineering of an nbo topology metal-organic framework for chemical fixation of CO2 under ambient conditions.

    PubMed

    Gao, Wen-Yang; Chen, Yao; Niu, Youhong; Williams, Kia; Cash, Lindsay; Perez, Pastor J; Wojtas, Lukasz; Cai, Jianfeng; Chen, Yu-Sheng; Ma, Shengqian

    2014-03-03

    Crystal engineering of the nbo metal-organic framework (MOF) platform MOF-505 with a custom-designed azamacrocycle ligand (1,4,7,10-tetrazazcyclododecane-N,N',N'',N'''-tetra-p-methylbenzoic acid) leads to a high density of well-oriented Lewis active sites within the cuboctahedral cage in MMCF-2, [Cu2(Cu-tactmb)(H2O)3(NO3)2]. This MOF demonstrates high catalytic activity for the chemical fixation of CO2 into cyclic carbonates at room temperature under 1 atm pressure.

  1. Production of strontium sulfide coatings by metal organic chemical vapor deposition

    SciTech Connect

    Moss, T.S.; Dye, R.C.; Tuenge, R.T.

    1998-11-01

    This work was focused on the MOCVD of the cerium-doped strontium sulfide (SrS:Ce) phosphor for use in thin film electroluminescent displays (TFELs). Following previous research on a small scale reactor, a feasibility scale-up using a commercially available reactor enlarged the size of the deposition area to a 4`` diameter wafer or a 2`` by 2`` glass slide. Films were deposited from the reaction of Sr(thd){sub 2}, Ce(thd){sub 4}, and H{sub 2}S at 450{degrees}C and 5 torr. This system employed a liquid delivery system for the accurate and repeatable delivery of the metal organic reagents. The deposition from this reactor was shown to be crystalline-as-deposited SrS with a (200) orientation, possibly a result of the thin nature of the coating and the involvement of (200) grains in the initial nucleation process. The wafers showed good uniformity, but had some thickness variation near the outer radius of the wafer resulting from the addition of H{sub 2}S from the outer edge. There were eighteen total deposition experiments, of which nine were characterized for EL performance. The highest brightness observed was 5 fL.. The samples were exceedingly thin as a result of the fifteen fold increase in the surface area between the deposition reactors. Increasing the sample thickness to 7,000{angstrom} or higher will dramatically increase the brightness of the emission.

  2. Organic polymer-metal nano-composites for opto-electronic sensing of chemicals in agriculture

    NASA Astrophysics Data System (ADS)

    Sarkisov, Sergey S.; Czarick, Michael; Fairchild, Brian D.; Liang, Yi; Kukhtareva, Tatiana; Curley, Michael J.

    2013-03-01

    Recent research findings led the team to conclude that a long lasting and inexpensive colorimetric sensor for monitoring ammonia emission from manure in confined animal feeding operations could eventually become feasible. The sensor uses robust method of opto-electronic spectroscopic measurement of the reversible change of the color of a sensitive nano-composite reagent film in response to ammonia. The film is made of a metal (gold, platinum, or palladium) nano-colloid in a polymer matrix with an ammonia-sensitive indicator dye additive. The response of the indicator dye (increase of the optical absorption in the region 550 to 650 nm) is enhanced by the nano-particles (~10 nm in size) in two ways: (a) concentration of the optical field near the nano-particle due to the plasmon resonance; and (b) catalytic acceleration of the chemical reaction of deprotonization of the indicator dye in the presence of ammonia and water vapor. This enhancement helps to make a miniature and rugged sensing element without compromising its sensitivity of less than 1 ppm for the range 0 to 100 ppm. The sensor underwent field tests in commercial broiler farms in Georgia, Alabama, and Arkansas and was compared against a commercial photoacoustic gas analyzer. The sensor output correlated well with the data from the photoacoustic analyzer (correlation coefficient not less than 0.9 and the linear regression slope after calibration close to 1.0) for several weeks of continuous operation. The sources of errors were analyzed and the conclusions on the necessary improvements and the potential use of the proposed device were made.

  3. Encapsulation of redox polysulphides via chemical interaction with nitrogen atoms in the organic linkers of metal-organic framework nanocrystals

    PubMed Central

    Park, Jung Hyo; Choi, Kyung Min; Lee, Dong Ki; Moon, Byeong Cheul; Shin, Sang Rim; Song, Min-Kyu; Kang, Jeung Ku

    2016-01-01

    Lithium polysulphides generated during discharge in the cathode of a lithium-sulphur redox cell are important, but their dissolution into the electrolyte from the cathode during each redox cycle leads to a shortened cycle life. Herein, we use in situ spectroelectrochemical measurements to demonstrate that sp2 nitrogen atoms in the organic linkers of nanocrystalline metal-organic framework-867 (nMOF-867) are able to encapsulate lithium polysulphides inside the microcages of nMOF-867, thus helping to prevent their dissolution into the electrolyte during discharge/charge cycles. This encapsulation mechanism of lithiated/delithiated polysulphides was further confirmed by observations of shifted FTIR spectra for the C = N and C-N bonds, the XPS spectra for the Li-N bonds from nMOF-867, and a visualization method, demonstrating that nMOF-867 prevents lithium polysulphides from being dissolved in the electrolyte. Indeed, a cathode fabricated using nMOF-867 exhibited excellent capacity retention over a long cycle life of 500 discharge/charge cycles, with a capacity loss of approximately 0.027% per cycle from a discharge capacity of 788 mAh/g at a high current rate of 835 mA/g. PMID:27149405

  4. Encapsulation of redox polysulphides via chemical interaction with nitrogen atoms in the organic linkers of metal-organic framework nanocrystals

    NASA Astrophysics Data System (ADS)

    Park, Jung Hyo; Choi, Kyung Min; Lee, Dong Ki; Moon, Byeong Cheul; Shin, Sang Rim; Song, Min-Kyu; Kang, Jeung Ku

    2016-05-01

    Lithium polysulphides generated during discharge in the cathode of a lithium-sulphur redox cell are important, but their dissolution into the electrolyte from the cathode during each redox cycle leads to a shortened cycle life. Herein, we use in situ spectroelectrochemical measurements to demonstrate that sp2 nitrogen atoms in the organic linkers of nanocrystalline metal-organic framework-867 (nMOF-867) are able to encapsulate lithium polysulphides inside the microcages of nMOF-867, thus helping to prevent their dissolution into the electrolyte during discharge/charge cycles. This encapsulation mechanism of lithiated/delithiated polysulphides was further confirmed by observations of shifted FTIR spectra for the C = N and C-N bonds, the XPS spectra for the Li-N bonds from nMOF-867, and a visualization method, demonstrating that nMOF-867 prevents lithium polysulphides from being dissolved in the electrolyte. Indeed, a cathode fabricated using nMOF-867 exhibited excellent capacity retention over a long cycle life of 500 discharge/charge cycles, with a capacity loss of approximately 0.027% per cycle from a discharge capacity of 788 mAh/g at a high current rate of 835 mA/g.

  5. Natural radioactivity levels and heavy metals in chemical and organic fertilizers used in Kingdom of Saudi Arabia.

    PubMed

    El-Taher, A; Althoyaib, S S

    2012-01-01

    The present work deals with identifying and determining the activity levels of natural occuring radionuclides, (226)Ra and (232)Th series, their decay products and (40)K, in chemical and organic fertilizers used in Kingdom of Saudi Arabia. A total of 30 samples: 20 phosphatic fertilizers (single super-phosphate SSP and triple super-phosphate,TSP) and 10 organic fertilizers (cow, sheep and chicken) collected from markets and farms. The gamma-ray spectrometer consists of NaI(Tl) detector and its electronic circuit was used for measuring γ-ray spectra. The ranges of radioactivity levels of (226)Ra, (232)Th and (40)K in chemical fertilizers are 51.5±5.2-106.3±7.5, 5.1±1.6-9.9±3.2. and 462.6±21-607.3±14Bqkg(-1), respectively. The activities of (226)Ra, (232)Th and (40)K in natural fertilizers (cow, sheep and chicken) are lower than the activities in chemical fertilizers. The obtained data are compared with available reported data from other countries in literature. The Ra(eq) in chemical fertilizer ranges from 100.37 to 161.43Bqkg(-1) and in organic fertilizer ranges from 34.07 to 102.19Bqkg(-1), which are lower than the limit of 370Bqkg(-1) adopted from NEA-OECD (1979). The average heavy metal (Pb, Cd, Ni, Co and Cr) contents of the fertilizers marketed in the Kingdom of Saudi Arabia are also determined and within the limits of those used worldwide.

  6. High mobility single-crystalline-like GaAs thin films on inexpensive flexible metal substrates by metal-organic chemical vapor deposition

    SciTech Connect

    Dutta, P. Rathi, M.; Gao, Y.; Yao, Y.; Selvamanickam, V.; Zheng, N.; Ahrenkiel, P.; Martinez, J.

    2014-09-01

    We demonstrate heteroepitaxial growth of single-crystalline-like n and p-type doped GaAs thin films on inexpensive, flexible, and light-weight metal foils by metal-organic chemical vapor deposition. Single-crystalline-like Ge thin film on biaxially textured templates made by ion beam assisted deposition on metal foil served as the epitaxy enabling substrate for GaAs growth. The GaAs films exhibited strong (004) preferred orientation, sharp in-plane texture, low grain misorientation, strong photoluminescence, and a defect density of ∼10{sup 7 }cm{sup −2}. Furthermore, the GaAs films exhibited hole and electron mobilities as high as 66 and 300 cm{sup 2}/V-s, respectively. High mobility single-crystalline-like GaAs thin films on inexpensive metal substrates can pave the path for roll-to-roll manufacturing of flexible III-V solar cells for the mainstream photovoltaics market.

  7. Effect of Hydrogen in Zinc Oxide Thin-Film Transistor Grown by Metal Organic Chemical Vapor Deposition

    NASA Astrophysics Data System (ADS)

    Jo, Jungyol; Seo, Ogweon; Jeong, Euihyuk; Seo, Hyunseok; Lee, Byeongon; Choi, Yearn-Ik

    2007-04-01

    We studied the transport characteristics of ZnO grown by metal organic chemical vapor deposition (MOCVD) at temperatures between 200 and 500 °C. The crystal quality, measured by X-ray diffraction, improved as the growth temperature increased. However, the mobility measured in the thin-film transistor (TFT) decreased in films grown at higher temperatures. In our experiments, a ZnO TFT grown at 250 °C showed good electrical characteristics, with a 13 cm2 V-1 s-1 mobility and a 103 on/off ratio. We conclude that hydrogen incorporated during MOCVD growth plays an important role in determining the transistor characteristics. This was supported by results of secondary ion mass spectroscopy (SIMS), where a higher hydrogen concentration was observed in films grown at lower temperatures.

  8. Structural and electrical characterization of Bi₂Se₃ nanostructures grown by metal-organic chemical vapor deposition.

    PubMed

    Alegria, L D; Schroer, M D; Chatterjee, A; Poirier, G R; Pretko, M; Patel, S K; Petta, J R

    2012-09-12

    We characterize nanostructures of Bi(2)Se(3) that are grown via metal-organic chemical vapor deposition using the precursors diethyl selenium and trimethyl bismuth. By adjusting growth parameters, we obtain either single-crystalline ribbons up to 10 μm long or thin micrometer-sized platelets. Four-terminal resistance measurements yield a sample resistivity of 4 mΩ·cm. We observe weak antilocalization and extract a phase coherence length l(ϕ) = 178 nm and spin-orbit length l(so) = 93 nm at T = 0.29 K. Our results are consistent with previous measurements on exfoliated samples and samples grown via physical vapor deposition.

  9. Dual-Function Metal-Organic Framework as a Versatile Catalyst for Detoxifying Chemical Warfare Agent Simulants.

    PubMed

    Liu, Yangyang; Moon, Su-Young; Hupp, Joseph T; Farha, Omar K

    2015-12-22

    The nanocrystals of a porphyrin-based zirconium(IV) metal-organic framework (MOF) are used as a dual-function catalyst for the simultaneous detoxification of two chemical warfare agent simulants at room temperature. Simulants of nerve agent (such as GD, VX) and mustard gas, dimethyl 4-nitrophenyl phosphate and 2-chloroethyl ethyl sulfide, have been hydrolyzed and oxidized, respectively, to nontoxic products via a pair of pathways catalyzed by the same MOF. Phosphotriesterase-like activity of the Zr6-containing node combined with photoactivity of the porphyrin linker gives rise to a versatile MOF catalyst. In addition, bringing the MOF crystals down to the nanoregime leads to acceleration of the catalysis.

  10. Dislocation analysis of InGaN/GaN quantum dots grown by metal organic chemical vapor deposition

    NASA Astrophysics Data System (ADS)

    Yang, Di; Wang, Lai; Hao, Zhi-Biao; Luo, Yi; Sun, Changzheng; Han, Yanjun; Xiong, Bing; Wang, Jian; Li, Hongtao

    2016-11-01

    The dislocations in InGaN/GaN quantum dots grown by metal organic chemical vapor deposition were studied by high-resolution transmission electron microscopy combining the Fourier filtering process. The misfit dislocations were observed in uncapped InGaN/GaN quantum dots. However, for the capped InGaN/GaN quantum dots, the GaN capping layer was found to suppress the generation of misfit dislocations and hence hindered the strain relaxation. Therefore, an overgrowth InGaN layer was used to relieve the strain in InGaN quantum dots and misfit dislocations were correspondingly found in these samples. In addition, defects were observed in low temperature GaN layers which suggested the existence of stacking faults.

  11. Electric, dielectric and optical properties of Ga2O3 grown by metal organic chemical vapour deposition

    NASA Astrophysics Data System (ADS)

    Paskaleva, A.; Spassov, D.; Terziyska, P.

    2017-01-01

    Thin film (15-130 nm) of gallium oxide were grown by the industry relevant metal organic chemical vapour deposition (MOCVD) technique on p-type Si to check the possibility for integration of newly rediscovered wide bandgap material with the Si technology. Electric, dielectric and optical properties were studied and analyzed. To perform electrical characterization, Ga2O3 films were integrated into Al/Ga2O3/p-Si metal–oxide–semiconductor (MOS) capacitors. Relative dielectric permittivity, flat-band voltage shift and effective oxide charge density were obtained from C-V measurements. Spectroscopic ellipsometry measurements reveal that Ga2O3 deposited by MOCVD is a direct bandgap material with a large optical bandgap of about 5.1 eV. Both ellipsometrical and electrical results show formation of a thick interfacial SiO2.

  12. A computational study of the effect of the metal organic framework environment on the release of chemically stored nitric oxide.

    PubMed

    Li, Tanping; Taylor-Edinbyrd, Kiara; Kumar, Revati

    2015-09-28

    The use of copper based metal organic frameworks as a vehicle for the storage and delivery of chemically stored nitric oxide has been proposed based on recent experiments [J. Am. Chem. Soc., 2012, 134, 3330-3333]. In these experiments copper based metal organic frameworks (MOFs) suspended in ethanol catalytically convert chemically stored nitric oxide (in the S-nitrosothiol or RSNO form) to free nitric oxide at a slow and sustained rate, as compared to a quick release in a solution of ethanol containing free copper ions. In order to gain insight on the effect of the MOF environment on the catalytic activity, a combination of electronic structure calculations on representative clusters and classical simulations using a force-field (partly parameterized on the above calculations) is used to study a simple RSNO species, S-nitrosomethane (CH3SNO) as well as the biologically compatible S-nitrosocysteine, both in the MOF and free copper solution. The free energy profiles of bringing the RSNO species to the catalytic centers have been compared and related to the different solvation environments of the copper catalyst in the complex solvated MOF and in free copper solution. Surprisingly, in the case of the simple CH3SNO moiety as well as the S-nitrosocysteine case, the free energy profile of bringing the first RSNO from the center of one of the pores to the catalytic site in the pore is very similar to the free solution case. On the other hand, bringing a second RSNO molecule to the same catalytic site or to the adjacent catalytic copper site show relatively higher barriers. These studies help shed light on the sustained nitric oxide release in the MOF environment.

  13. A novel three-jet microreactor for localized metal-organic chemical vapour deposition of gallium arsenide: design and simulation

    NASA Astrophysics Data System (ADS)

    Konakov, S. A.; Krzhizhanovskaya, V. V.

    2016-08-01

    We present a novel three-jet microreactor design for localized deposition of gallium arsenide (GaAs) by low-pressure Metal-Organic Chemical Vapour Deposition (MOCVD) for semiconductor devices, microelectronics and solar cells. Our approach is advantageous compared to the standard lithography and etching technology, since it preserves the nanostructure of the deposited material, it is less time-consuming and less expensive. We designed two versions of reactor geometry with a 10-micron central microchannel for precursor supply and with two side jets of a dilutant to control the deposition area. To aid future experiments, we performed computational modeling of a simplified-geometry (twodimensional axisymmetric) microreactor, based on Navier-Stokes equations for a laminar flow of chemically reacting gas mixture of Ga(CH3)3-AsH3-H2. Simulation results show that we can achieve a high-rate deposition (over 0.3 μm/min) on a small area (less than 30 μm diameter). This technology can be used in material production for microelectronics, optoelectronics, photovoltaics, solar cells, etc.

  14. Metal organic chemical vapor deposition of 111-v compounds on silicon

    DOEpatents

    Vernon, Stanley M.

    1986-01-01

    Expitaxial composite comprising thin films of a Group III-V compound semiconductor such as gallium arsenide (GaAs) or gallium aluminum arsenide (GaAlAs) on single crystal silicon substrates are disclosed. Also disclosed is a process for manufacturing, by chemical deposition from the vapor phase, epitaxial composites as above described, and to semiconductor devices based on such epitaxial composites. The composites have particular utility for use in making light sensitive solid state solar cells.

  15. Impregnated Metal-Organic Frameworks for the Removal of Toxic Industrial Chemicals

    DTIC Science & Technology

    2008-11-01

    with various chemicals for enhanced reactivity. Specifically, MOF-5 (IRMOF- l ) was impregnated with citric acid, copper acetate, copper oxide, and...177, MOF-199, and ZIF-8 and provided recommendations for future material syntheses . The present report describes an initial effort aimed at...PROCESS 2.1 Materials MOF-5 (IRMOF-1) was synthesized at UCLA and subsequently sent to Guild Associates, Inc. (Dublin, Ohio) for impregnation. The

  16. Modified dislocation filter method: toward growth of GaAs on Si by metal organic chemical vapor deposition

    NASA Astrophysics Data System (ADS)

    Hu, Haiyang; Wang, Jun; He, Yunrui; Liu, Kai; Liu, Yuanyuan; Wang, Qi; Duan, Xiaofeng; Huang, Yongqing; Ren, Xiaomin

    2016-06-01

    In this paper, metamorphic growth of GaAs on (001) oriented Si substrate, with a combination method of applying dislocation filter layer (DFL) and three-step growth process, was conducted by metal organic chemical vapor deposition. The effectiveness of the multiple InAs/GaAs self-organized quantum dot (QD) layers acting as a dislocation filter was researched in detail. And the growth conditions of the InAs QDs were optimized by theoretical calculations and experiments. A 2-μm-thick buffer layer was grown on the Si substrate with the three-step growth method according to the optimized growth conditions. Then, a 114-nm-thick DFL and a 1-μm-thick GaAs epilayer were grown. The results we obtained demonstrated that the DFL can effectively bend dislocation direction via the strain field around the QDs. The optimal structure of the DFL is composed of three-layer InAs QDs with a growth time of 55 s. The method could reduce the etch pit density from about 3 × 106 cm-2 to 9 × 105 cm-2 and improve the crystalline quality of the GaAs epilayers on Si.

  17. Chemically functionalized magnetic exchange interactions of hybrid organic-ferromagnetic metal interfaces

    NASA Astrophysics Data System (ADS)

    Friedrich, Rico; Caciuc, Vasile; Kiselev, Nikolai S.; Atodiresei, Nicolae; Blügel, Stefan

    2015-03-01

    We theoretically explore through systematic multiscale ab initio and Monte Carlo calculations how the surface magnetism of a ferromagnetic surface can be fine-tuned by nonmagnetic organic molecules containing a single π bond. We demonstrate that a magnetic hardening or softening can be induced depending on the electronegativity of the heteroatom or when the π -bond "bridges" the magnetic surface atoms. Finally, the Monte Carlo simulations revealed taylored macroscopic hysteresis loops corresponding to soft and hard molecule-surface magnets.

  18. Growth mechanism of single-crystalline NiO thin films grown by metal organic chemical vapor deposition

    NASA Astrophysics Data System (ADS)

    Roffi, Teuku Muhammad; Nozaki, Shinji; Uchida, Kazuo

    2016-10-01

    Nickel oxide (NiO) thin films were grown by atmospheric-pressure metal organic chemical vapor deposition (APMOCVD). Growth was carried out using various growth parameters, including the growth temperature, the input precursor (O2/Ni) ratio, and the type of substrate material. Effects of the growth parameters on the structural and electrical properties of the films were investigated. X-ray diffraction analysis revealed that the crystal structure and quality were strongly affected by the growth temperature and the type of substrate material. At an optimized growth temperature, single-crystalline NiO films were grown on MgO(100) and MgO(111) substrates in a cube-on-cube orientation relationship, while on an Al2O3(001) substrate, the film was grown in the NiO[111] direction. The use of MgO substrates successfully suppressed the formation of twin defects, which have been frequently reported in the growth of NiO. The difference in the formation of the twin defects on MgO and Al2O3 substrates was discussed. It was observed that the resistivity dependence on crystal quality was affected by the choice of substrate material. The effects of the precursor ratio on the transmittance and resistivity of the films were also investigated. Improved transparency in the visible wavelength region and higher conductivity were found in films grown with higher O2/Ni ratios.

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

    PubMed Central

    DeCoste, Jared B.; Peterson, Gregory W.

    2013-01-01

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

  20. Effective, Facile, and Selective Hydrolysis of the Chemical Warfare Agent VX Using Zr6-Based Metal-Organic Frameworks.

    PubMed

    Moon, Su-Young; Wagner, George W; Mondloch, Joseph E; Peterson, Gregory W; DeCoste, Jared B; Hupp, Joseph T; Farha, Omar K

    2015-11-16

    The nerve agent VX is among the most toxic chemicals known to mankind, and robust solutions are needed to rapidly and selectively deactivate it. Herein, we demonstrate that three Zr6-based metal-organic frameworks (MOFs), namely, UiO-67, UiO-67-NH2, and UiO-67-N(Me)2, are selective and highly active catalysts for the hydrolysis of VX. Utilizing UiO-67, UiO-67-NH2, and UiO-67-N(Me)2 in a pH 10 buffered solution of N-ethylmorpholine, selective hydrolysis of the P-S bond in VX was observed. In addition, UiO-67-N(Me)2 was found to catalyze VX hydrolysis with an initial half-life of 1.8 min. This half-life is nearly 3 orders of magnitude shorter than that of the only other MOF tested to date for hydrolysis of VX and rivals the activity of the best nonenzymatic materials. Hydrolysis utilizing Zr-based MOFs is also selective and facile in the absence of pH 10 buffer (just water) and for the destruction of the toxic byproduct EA-2192.

  1. Catalyst-free growth of ZnO nanowires by metal-organic chemical vapour deposition (MOCVD) and thermal evaporation

    SciTech Connect

    Lee, Woong; Jeong, Min-Chang; Myoung, Jae-Min

    2004-08-02

    ZnO nanowires were grown on GaAs(0 0 2) substrates using metal-organic chemical vapour deposition (MOCVD) and on Si(0 0 1) substrates using thermal evaporation of source powders, respectively. It was demonstrated that well-aligned single crystalline nanowires could be grown with controlled sizes using a typical thin film deposition technique without catalysts. Arsenic doping of the ZnO nanowires grown on GaAs substrate was possible using post-growth heat-treatment, proposing a possible way of producing p-type ZnO nanowires. It was also shown that simplified process of carrier-free thermal evaporation without catalyst could be employed to grow nanowires with high yield while maintaining good crystalline and optical properties. Application potential of the nanowires as probes of atomic force microscopes (AFMs) was discussed by predicting their structural compatibility with AFM cantilevers based on continuum elasticity. It was predicted that the nanowires fabricated herein are structurally compatible with typical AFM cantilevers suggesting that they are promising candidates for high aspect ratio probes.

  2. In Situ Probes of Capture and Decomposition of Chemical Warfare Agent Simulants by Zr-Based Metal Organic Frameworks.

    PubMed

    Plonka, Anna M; Wang, Qi; Gordon, Wesley O; Balboa, Alex; Troya, Diego; Guo, Weiwei; Sharp, Conor H; Senanayake, Sanjaya D; Morris, John R; Hill, Craig L; Frenkel, Anatoly I

    2017-01-18

    Zr-based metal organic frameworks (MOFs) have been recently shown to be among the fastest catalysts of nerve-agent hydrolysis in solution. We report a detailed study of the adsorption and decomposition of a nerve-agent simulant, dimethyl methylphosphonate (DMMP), on UiO-66, UiO-67, MOF-808, and NU-1000 using synchrotron-based X-ray powder diffraction, X-ray absorption, and infrared spectroscopy, which reveals key aspects of the reaction mechanism. The diffraction measurements indicate that all four MOFs adsorb DMMP (introduced at atmospheric pressures through a flow of helium or air) within the pore space. In addition, the combination of X-ray absorption and infrared spectra suggests direct coordination of DMMP to the Zr6 cores of all MOFs, which ultimately leads to decomposition to phosphonate products. These experimental probes into the mechanism of adsorption and decomposition of chemical warfare agent simulants on Zr-based MOFs open new opportunities in rational design of new and superior decontamination materials.

  3. Thermoelectric properties of lattice-matched AlInN alloy grown by metal organic chemical vapor deposition

    NASA Astrophysics Data System (ADS)

    Tong, Hua; Zhang, Jing; Liu, Guangyu; Herbsommer, Juan A.; Huang, G. S.; Tansu, Nelson

    2010-09-01

    Thermoelectric properties of lattice-matched AlInN grown by metal organic chemical vapor deposition were measured and analyzed. The n-type Al0.83In0.17N alloy exhibited thermal conductivity of 4.87 W/(m K) measured by 3ω differential method. The Seebeck coefficient of n-Al0.83In0.17N was measured as -6.012×10-4 V/K by thermal gradient method. The sheet resistivity of n-Al0.83In0.17N was measured by using Van der Pauw method, and the electrical conductivity was measured as 2.38×104/(Ω m). The thermoelectric figure of merit (Z∗T) of n-type Al0.83In0.17N was measured as 0.532 at room temperature (T =300 K). The finding indicates lattice-matched AlInN alloy on GaN as excellent material candidate for thermoelectric application.

  4. Direct Growth of a-Plane GaN on r-Plane Sapphire by Metal Organic Chemical Vapor Deposition

    NASA Astrophysics Data System (ADS)

    Hsu, Hsiao-Chiu; Su, Yan-Kuin; Huang, Shyh-Jer; Wang, Yu-Jen; Wu, Chun-Ying; Chou, Ming-Chieh

    2010-04-01

    In this study, we had demonstrated the direct growth of nonpolar a-plane GaN on an r-plane sapphire by metal organic chemical vapor deposition (MOCVD) without any buffer layer. First, in this experiment, we had determined the optimum temperature for two-step growth, including obtaining three-dimensional (3D) GaN islands in the nucleation layer and coalescing with a further two-dimensional (2D) growth mode. The result shows that the nucleation layer grown under high temperature (1150 °C) leads to large islands with few grain boundaries. Under the same temperature, the effect of the V/III ratio on the growth of the overlaying GaN layer to obtain a flat and void free a-plane GaN layer is also studied. The result indicates one can directly grow a smooth epitaxial layer on an r-plane sapphire by changing the V/III ratio. The rms roughness decreases from 13.61 to 2.02 nm. The GaN crystal quality is verified using a mixed acid to etch the film surface. The etch pit density (EPD) is 3.16 ×107 cm-2.

  5. In Situ Probes of Capture and Decomposition of Chemical Warfare Agent Simulants by Zr-Based Metal Organic Frameworks

    DOE PAGES

    Plonka, Anna M.; Wang, Qi; Gordon, Wesley O.; ...

    2016-12-30

    Recently, Zr-based metal organic frameworks (MOFs) were shown to be among the fastest catalysts of nerve-agent hydrolysis in solution. Here, we report a detailed study of the adsorption and decomposition of a nerve-agent simulant, dimethyl methylphosphonate (DMMP), on UiO-66, UiO-67, MOF-808, and NU-1000 using synchrotron-based X-ray powder diffraction, X-ray absorption, and infrared spectroscopy, which reveals key aspects of the reaction mechanism. The diffraction measurements indicate that all four MOFs adsorb DMMP (introduced at atmospheric pressures through a flow of helium or air) within the pore space. In addition, the combination of X-ray absorption and infrared spectra suggests direct coordination ofmore » DMMP to the Zr6 cores of all MOFs, which ultimately leads to decomposition to phosphonate products. Our experimental probes into the mechanism of adsorption and decomposition of chemical warfare agent simulants on Zr-based MOFs open new opportunities in rational design of new and superior decontamination materials.« less

  6. In Situ Probes of Capture and Decomposition of Chemical Warfare Agent Simulants by Zr-Based Metal Organic Frameworks

    SciTech Connect

    Plonka, Anna M.; Wang, Qi; Gordon, Wesley O.; Balboa, Alex; Troya, Diego; Guo, Weiwei; Sharp, Conor H.; Senanayake, Sanjaya D.; Morris, John R.; Hill, Craig L.; Frenkel, Anatoly I.

    2016-12-30

    Recently, Zr-based metal organic frameworks (MOFs) were shown to be among the fastest catalysts of nerve-agent hydrolysis in solution. Here, we report a detailed study of the adsorption and decomposition of a nerve-agent simulant, dimethyl methylphosphonate (DMMP), on UiO-66, UiO-67, MOF-808, and NU-1000 using synchrotron-based X-ray powder diffraction, X-ray absorption, and infrared spectroscopy, which reveals key aspects of the reaction mechanism. The diffraction measurements indicate that all four MOFs adsorb DMMP (introduced at atmospheric pressures through a flow of helium or air) within the pore space. In addition, the combination of X-ray absorption and infrared spectra suggests direct coordination of DMMP to the Zr6 cores of all MOFs, which ultimately leads to decomposition to phosphonate products. Our experimental probes into the mechanism of adsorption and decomposition of chemical warfare agent simulants on Zr-based MOFs open new opportunities in rational design of new and superior decontamination materials.

  7. Organic chemical evolution

    NASA Technical Reports Server (NTRS)

    Chang, S.

    1981-01-01

    The course of organic chemical evolution preceding the emergence of life on earth is discussed based on evidence of processes occurring in interstellar space, the solar system and the primitive earth. Following a brief review of the equilibrium condensation model for the origin and evolution of the solar system, consideration is given to the nature and organic chemistry of interstellar clouds, comets, Jupiter, meteorites, Venus and Mars, and the prebiotic earth. Major issues to be resolved in the study of organic chemical evolution on earth are identified regarding condensation and accretion in the solar nebula, early geological evolution, the origin and evolution of the atmosphere, organic production rates, organic-inorganic interactions, environmental fluctuations, phase separation and molecular selectivity.

  8. Growth of high Mg content wurtzite MgZnO epitaxial films via pulsed metal organic chemical vapor deposition

    NASA Astrophysics Data System (ADS)

    Alema, Fikadu; Ledyaev, Oleg; Miller, Ross; Beletsky, Valeria; Osinsky, Andrei; Schoenfeld, Winston V.

    2016-02-01

    We report on the growth of high Mg content, high quality, wurtzite MgxZn1-xO (MgZnO) epitaxial films using a pulsed metal organic chemical vapor deposition (PMOCVD) method. Series of MgZnO films with variable Mg concentration were deposited on bare and AlN coated sapphire substrates. The band gap of the films estimated using UV-visible transmission spectra ranges from 3.24 eV to 4.49 eV, corresponding to fraction of Mg between x=0.0 and x=0.51, as determined by Rutherford backscattering spectroscopy. The cathodoluminescence (CL) measurement has shown a blue-shift in the peak position of MgZnO with an increasing Mg content. No multi-absorption edges and CL band splitting were observed, suggesting the absence of phase segregation in the as grown films. The crystal structure and phase purity of the films were also confirmed by XRD analysis. Hall effect measurement in van der Pauw configuration was employed to evaluate the electrical properties of the films. With a rise in Mg incorporation into the ZnO lattice, the films became very resistive, consistent with the widening of the band gap. The AFM measurement on the films has shown a decreasing surface roughness with an Mg content. To the best of our knowledge, the current result shows the highest Mg content (x=0.51), high quality, wurtzite MgZnO epitaxial film ever grown by MOCVD. The high Mg incorporation without phase separation is believed to be due to the non-equilibrium behavior of the PMOCVD in which the kinetic processes dominate the thermodynamic one.

  9. Growth of superconducting NdFe0.88Co0.12AsO films by metal-organic chemical vapor deposition and post arsenic diffusion

    NASA Astrophysics Data System (ADS)

    Corrales-Mendoza, I.; Bartolo-Pèrez, P.; Sánchez-Reséndiz, V. M.; Gallardo-Hernández, S.; Conde-Gallardo, A.

    2015-01-01

    Metal-organic chemical vapor deposition (MOCVD) and post-deposition arsenic diffusion processes were successfully employed to grow superconducting NdFe0.88Co0.12AsO thin films. First, by employing iron, cobalt and neodymium metal-organic precursors, a precursor film is grown by MOCVD on (001)-oriented LaAlO3 substrates. Subsequently, the arsenic is incorporated during an annealing of these precursor films in the presence of a NdFe0.9Co0.1AsO pellet. The chemical composition and crystallographic results indicate the formation of the cobalt-doped NdFeAsO polycrystalline phase. The secondary ion mass spectroscopy indicates a homogeneous arsenic diffusion process. The resistance and magnetization measurements as a function of temperature indicate a superconducting transition ˜15 \\text{K} .

  10. Real-time in-situ chemical sensing in aluminum gallium nitride/gallium nitride metal-organic chemical vapor deposition processes for advanced process control

    NASA Astrophysics Data System (ADS)

    Cho, Soon

    Gallium nitride and its alloys promise to be key materials for future semiconductor devices aimed at high frequency, high power electronic applications. However, manufacturing for such high performance products is challenged by reproducibility and material quality constraints that are notably more stringent than those required for optoelectronic applications. To meet this challenge, in-situ mass spectrometry was implemented as a real-time process- and wafer-state metrology tool in AlGaN/GaN/AlN metal-organic chemical vapor deposition processes on semi-insulating SiC substrate wafers. Dynamic chemical sensing through the process cycle, carried out downstream from the wafer, revealed generation of methane and ethane reaction byproducts, as well as other residual gas species. Real-time metrics were derived based on the chemical signals to predict/control material quality and thickness of critical layers within the heterostructure in real time during growth, and corresponding metrologies were used for real-time advanced process control. Using the methane/ethane ratio, GaN epilayer crystal quality was predicted in real time to 2--5% precision, which was verified by post-process x-ray diffraction. Moreover, the same real-time metric predicted material quality as indicated by post-process photoluminescence band-edge intensities to ˜5% precision. The methane/ethane ratio has a fundamental significance in terms of the intrinsic chemistry in that the two byproducts are believed to reflect two parallel reaction pathways leading to GaN-based material growth, namely the gas phase adduct formation route and the surface route for direct precursor decomposition, respectively. The fact that lower methane/ethane ratios consistently yield better material quality suggests that the surface pathway is preferred for high quality GaN growth. In addition, a metric based on methane and ethane signals integrated through the AlGaN growth period (˜1 min or less) enabled prediction of the cap

  11. The nature of catalyst particles and growth mechanisms of GaN nanowires grown by Ni-assisted metal-organic chemical vapor deposition.

    PubMed

    Weng, Xiaojun; Burke, Robert A; Redwing, Joan M

    2009-02-25

    The structure and chemistry of the catalyst particles that terminate GaN nanowires grown by Ni-assisted metal-organic chemical vapor deposition were investigated using a combination of electron diffraction, high-resolution transmission electron microscopy, and x-ray energy dispersive spectrometry. The crystal symmetry, lattice parameter, and chemical composition obtained reveal that the catalyst particles are Ni(3)Ga with an ordered L 1(2) structure. The results suggest that the catalyst is a solid particle during growth and therefore favor a vapor-solid-solid mechanism for the growth of GaN nanowires under these conditions.

  12. Crystal Engineering of an nbo Topology Metal-Organic Framework for Chemical Fixation of CO₂ under Ambient Conditions

    SciTech Connect

    Gao, Wen-Yang; Chen, Yao; Niu, Youhong; Williams, Kia; Cash, Lindsay; Perez, Pastor J.; Wojtas, Lukasz; Cai, Jianfeng; Chen, Yu-Sheng; Ma, Shengqian

    2015-02-20

    Crystal engineering of the nbo metal–organic framework (MOF) platform MOF-505 with a custom-designed azamacrocycle ligand (1,4,7,10-tetrazazcyclododecane-N,N',N'',N'''-tetra-p-methylbenzoic acid) leads to a high density of well-oriented Lewis active sites within the cuboctahedral cage in MMCF-2, [Cu₂(Cu-tactmb)(H₂O)₃(NO₃)₂]. This MOF demonstrates high catalytic activity for the chemical fixation of CO₂ into cyclic carbonates at room temperature under 1 atm pressure.

  13. Chemical characteristics of dissolved organic matter (DOM) in relation to heavy metal concentrations in soil water from boreal peatlands after clear-cut harvesting

    NASA Astrophysics Data System (ADS)

    Kiikkilä, O.; Nieminen, T.; Starr, M.; Ukonmaanaho, L.

    2012-04-01

    Boreal peatlands form an important terrestrial carbon reserve and are a major source of dissolved organic matter (DOM) to surface waters, particularly when disturbed through forestry practices such as draining or timber harvesting. Heavy metals show a strong affinity to organic matter and so, along with DOM, heavy metals can be mobilized and transported from the soil to surface waters and sediments where they may become toxic to aquatic organisms and pass up the food chain. The complexation of heavy metals with DOM can be expected to be related and determined by the chemical characteristics of DOM and oxidation/reducing conditions in the peat. We extracted interstitial water from peat samples and determined the concentrations of dissolved organic carbon (DOC), dissolved organic nitrogen (DON) and Al, Cu, Zn and Fe in various fractions of DOM isolated by adsorption properties (XAD-8 fractionation) and molecular-weight (ultrafiltration). The peat samples were taken from 0-30 and 30-50 cm depth in drained peatland catchments two years after whole-tree or stem-only clear-cut harvesting (Scots pine or Norway spruce) had been carried out. The samples from the upper layer had been subject to alternating saturation/aeration conditions while the deeper layer had been continuously under the water table. The fractionation of DOC and DON according to both adsorption properties and molecular-weight fractions clearly differed between the upper and lower peat layers. While the hydrophobic acid fraction contained proportionally more DOC and DON than the hydrophilic acid fraction in the upper peat layer the results were vice versa in the lower peat layer. High-molecular-weight compounds (> 100 kDa) were proportionally more abundant in the upper and low-molecular-weight compounds (< 1 kDa) in the lower peat layer. These differences are assumed to reflect differences in the aerobic/ anaerobic conditions and degree of decomposition between the two layers. The concentrations of Zn, Al

  14. Influence of vicinal sapphire substrate on the properties of N-polar GaN films grown by metal-organic chemical vapor deposition

    SciTech Connect

    Lin, Zhiyu; Zhang, Jincheng Xu, Shengrui; Chen, Zhibin; Yang, Shuangyong; Tian, Kun; Hao, Yue; Su, Xujun; Shi, Xuefang

    2014-08-25

    The influence of vicinal sapphire substrates on the growth of N-polar GaN films by metal-organic chemical vapor deposition is investigated. Smooth GaN films without hexagonal surface feature are obtained on vicinal substrate. Transmission electron microscope results reveal that basal-plane stacking faults are formed in GaN on vicinal substrate, leading to a reduction in threading dislocation density. Furthermore, it has been found that there is a weaker yellow luminescence in GaN on vicinal substrate than that on (0001) substrate, which might be explained by the different trends of the carbon impurity incorporation.

  15. Elemental diffusion during the droplet epitaxy growth of In(Ga)As/GaAs(001) quantum dots by metal-organic chemical vapor deposition

    NASA Astrophysics Data System (ADS)

    Chen, Z. B.; Lei, W.; Chen, B.; Wang, Y. B.; Liao, X. Z.; Tan, H. H.; Zou, J.; Ringer, S. P.; Jagadish, C.

    2014-01-01

    Droplet epitaxy is an important method to produce epitaxial semiconductor quantum dots (QDs). Droplet epitaxy of III-V QDs comprises group III elemental droplet deposition and the droplet crystallization through the introduction of group V elements. Here, we report that, in the droplet epitaxy of InAs/GaAs(001) QDs using metal-organic chemical vapor deposition, significant elemental diffusion from the substrate to In droplets occurs, resulting in the formation of In(Ga)As crystals, before As flux is provided. The supply of As flux suppresses the further elemental diffusion from the substrate and promotes surface migration, leading to large island formation with a low island density.

  16. Elemental diffusion during the droplet epitaxy growth of In(Ga)As/GaAs(001) quantum dots by metal-organic chemical vapor deposition

    SciTech Connect

    Chen, Z. B.; Chen, B.; Wang, Y. B.; Liao, X. Z.; Lei, W.; Tan, H. H.; Jagadish, C.; Zou, J.; Ringer, S. P.

    2014-01-13

    Droplet epitaxy is an important method to produce epitaxial semiconductor quantum dots (QDs). Droplet epitaxy of III-V QDs comprises group III elemental droplet deposition and the droplet crystallization through the introduction of group V elements. Here, we report that, in the droplet epitaxy of InAs/GaAs(001) QDs using metal-organic chemical vapor deposition, significant elemental diffusion from the substrate to In droplets occurs, resulting in the formation of In(Ga)As crystals, before As flux is provided. The supply of As flux suppresses the further elemental diffusion from the substrate and promotes surface migration, leading to large island formation with a low island density.

  17. The optimization of interfaces in InAsSb/InGaAs strained-layer superlattices grown by metal-organic chemical vapor deposition

    SciTech Connect

    Biefeld, R.M.; Baucom, K.C.; Kurtz, S.R.

    1993-12-31

    We have prepared InAsSb/InGaAs strained-layer superlattice (SLS) semiconductors by metal-organic chemical vapor deposition (MOCVD) under a variety of conditions. Presence of an InGaAsSb interface layer is indicated by x-ray diffraction patterns. Optimized growth conditions involved the use of low pressure, short purge times, and no reactant flow during the purges. MOCVD was used to prepare an optically pumped, single heterostructure InAsSb/InGaAs SLS/InPSb laser which emitted at 3.9 {mu}m with a maximum operating temperature of approximately 100 K.

  18. High hole concentration Li-doped NiZnO thin films grown by photo-assisted metal-organic chemical vapor deposition

    NASA Astrophysics Data System (ADS)

    Zhao, Y. D.; Dong, X.; Ma, Z. Z.; Zhang, Y. T.; Wu, B.; Zhuang, S. W.; Zhang, B. L.; Li, W. C.; Du, G. T.

    2016-11-01

    High hole concentration Li-doped NiZnO thin films were grown by metal-organic chemical vapor deposition (MOCVD). The crystalline, optical, electrical, and morphological characteristics of the NiZnO films were studied as a function of lithium content. The resistance of the films decreased and the hole concentration greatly increased with increasing lithium content. However, the crystalline and optical properties were observed to degrade as the lithium content was increased. To relieve the degradation, a photo-assisted MOCVD method was used in order to restrict this degradation and this represents a new way to obtain stable high hole concentration NiZnO films.

  19. Recycling of metal-organic chemical vapor deposition waste of GaN based power device and LED industry by acidic leaching: Process optimization and kinetics study

    NASA Astrophysics Data System (ADS)

    Swain, Basudev; Mishra, Chinmayee; Kang, Leeseung; Park, Kyung-Soo; Lee, Chan Gi; Hong, Hyun Seon; Park, Jeung-Jin

    2015-05-01

    Recovery of metal values from GaN, a metal-organic chemical vapor deposition (MOCVD) waste of GaN based power device and LED industry is investigated by acidic leaching. Leaching kinetics of gallium rich MOCVD waste is studied and the process is optimized. The gallium rich waste MOCVD dust is characterized by XRD and ICP-AES analysis followed by aqua regia digestion. Different mineral acids are used to find out the best lixiviant for selective leaching of the gallium and indium. Concentrated HCl is relatively better lixiviant having reasonably faster kinetic and better leaching efficiency. Various leaching process parameters like effect of acidity, pulp density, temperature and concentration of catalyst on the leaching efficiency of gallium and indium are investigated. Reasonably, 4 M HCl, a pulp density of 50 g/L, 100 °C and stirring rate of 400 rpm are the effective optimum condition for quantitative leaching of gallium and indium.

  20. Growth of TiO2 anti-reflection layer on textured Si (100) wafer substrate by metal-organic chemical vapor deposition method.

    PubMed

    Nam, Sang-Hun; Choi, Jin-Woo; Cho, Sang-Jin; Kimt, Keun Soo; Boo, Jin-Hyo

    2011-08-01

    Recently anti-reflective films (AR) have been intensely studied. Particularly for textured silicon solar cells, the AR films can further reduce the reflection of the incident light through trapping the incident light into the cells. In this work, TiO2 anti-reflection films have been grown on the textured Si (100) substrate which is processed in two steps, and the films are deposited using metal-organic chemical vapor deposition (MOCVD) with a precursor of titanium tetra-isopropoxide (TTIP). The effect of the substrate texture and the growth conditions of TiO2 films on the reflectance has been investigated. Pyramid size of textured silicon had approximately 2-9 microm. A well-textured silicon surface can lower the reflectance to 10%. For more reduced reflection, TiO2 anti-reflection films on the textured silicon were deposited at 600 degrees C using titanium tetra-isopropoxide (TTIP) as a precursor by metal-organic chemical vapor deposition (MOCVD), and the deposited TiO2 layers were then treated by annealing for 2 h in air at 600 and 1000 degrees C, respectively. In this process, the treated samples by annealing showed anatase and rutile phases, respectively. The thickness of TiO2 films was about 75 +/- 5 nm. The reflectance at specific wavelength can be reduced to 3% in optimum layer.

  1. Organic Superconductor, Made without Metals.

    ERIC Educational Resources Information Center

    Science News, 1980

    1980-01-01

    The discovery of a superconducting organic compound is reported. The compound, (TMTSF)-2, has no metal in its composition, and the author believes that it is the precursor of a family of superconducting organics. (Author/SA)

  2. A study on the synthesis of Ni50Co50 alloy nanostructures with tuned morphology through metal-organic chemical routes.

    PubMed

    Mourdikoudis, Stefanos; Collière, Vincent; Fau, Pierre; Kahn, Myrtil L

    2014-06-14

    NiCo bimetallic nanostructures with various morphologies have been synthesized using a broad range of solvents, surfactants and precursors that are available in the metal-organic chemical toolbox. Polygonal particles, nanowires and isotropic nanospheres have been obtained, among others. We describe the chemical pathways to achieve anisotropic growth either by an 'in situ' seed-mediated approach or by simply selecting suitable reaction media and growth modifiers. We describe the role of a variety of synthetic factors that influence the final shape of such an alloy material at the nanoscale. The alloying between cobalt and nickel is evidenced by XRD and HRTEM techniques. Room-temperature ferromagnetic behavior is observed for NiCo nanoparticles and high values for saturation magnetization and coercivity are recorded by SQuID magnetometry. The saturation magnetization value for the NiCo nanostructures is typically set between the corresponding "bulk" ones of cobalt and nickel metals. It is always comparable to the suggested value of the Ni50Co50 bulk alloy. The synthetic protocols derived from our extensive study are quantitative and versatile, allowing high reaction yields. Although macroscopic characterization techniques evidence the presence of a stoichiometric NiCo alloy, we show that in certain cases nanoscale characterization analyses are also needed for a more accurate evaluation of the alloy composition at the atomic level.

  3. Growth and characterization of a multi-dimensional ZnO hybrid structure on a glass substrate by using metal organic chemical vapor deposition

    NASA Astrophysics Data System (ADS)

    Kim, Dae-Sik; Lee, Dohan; Lee, Je-Haeng; Byun, Dongjin

    2014-05-01

    A multi-dimensional zinc oxide (ZnO) hybrid structure was successfully grown on a glass substrate by using metal organic chemical vapor deposition (MOCVD). The ZnO hybrid structure was composed of nanorods grown continuously on the ZnO film without any catalysts. The growth mode could be changed from a two-dimensional (2D) film to one-dimensional (1D) nanorods by simply controlling the substrate's temperature. The ZnO with a hybrid structure showed improved electrical and optical properties. The ZnO hybrid structure grown by using MOCVD has excellent potential for applications in opto-electronic devices and solar cells as anti-reflection coatings (ARCs), transparent conductive oxides (TCOs) and transparent thin-film transistors (TTFTs).

  4. Growth of ultrathin GaSb layer on GaAs using metal-organic chemical vapor deposition with Sb interfacial treatment

    NASA Astrophysics Data System (ADS)

    Hsiao, Chih-Jen; Ha, Minh-Thien-Huu; Hsu, Ching-Yi; Lin, Yueh-Chin; Chang, Sheng-Po; Chang, Shoou-Jinn; Chang, Edward Yi

    2016-09-01

    GaSb epitaxial layers were directly grown on GaAs substrates by metal-organic chemical vapor deposition involving Sb interfacial treatment with optimized growth temperature and V/III ratio. The interfacial treatment effectively reduces the surface energy and strain energy difference, resulting in a quasi-2D growth mode. When the GaSb layer was grown at 520 °C, the strain induced by lattice mismatch was accommodated by 90° dislocations with a period of 5.67 nm. By optimizing the V/III ratio, the surface roughness of the ultrathin GaSb/GaAs heterostructure was reduced, resulting in a reduced carrier scattering and improved electronic properties.

  5. In situ and real-time characterization of metal-organic chemical vapor deposition growth by high resolution x-ray diffraction

    SciTech Connect

    Kharchenko, A.; Lischka, K.; Schmidegg, K.; Sitter, H.; Bethke, J.; Woitok, J.

    2005-03-01

    We present an x-ray diffractometer for the analysis of epitaxial layers during (in situ) metal-organic chemical vapor deposition (MOCVD). Our diffractometer has a conventional x-ray source, does not need a goniometer stage, and is not sensitive to precise adjustment of the samples before measurement. It allows us to perform measurements within a few seconds even from rotating and wobbling samples. The first results of laboratory tests performed with our x-ray diffraction system show that it is well suited for in situ and real-time monitoring of the MOCVD growth process. We were able to measure the growth rate of a cubic GaN layer and the intensity and peak position of Bragg reflections of the growing layer in less than 20 s only.

  6. Optical study of a-plane InGaN/GaN multiple quantum wells with different well widths grown by metal-organic chemical vapor deposition

    NASA Astrophysics Data System (ADS)

    Ko, T. S.; Lu, T. C.; Wang, T. C.; Chen, J. R.; Gao, R. C.; Lo, M. H.; Kuo, H. C.; Wang, S. C.; Shen, J. L.

    2008-11-01

    a-plane InGaN/GaN multiple quantum wells of different widths ranging from 3 to 12 nm grown on r-plane sapphire by metal-organic chemical vapor deposition were investigated. The peak emission intensity of the photoluminescence (PL) reveals a decreasing trend as the well width increases from 3 to 12 nm. Low temperature (9 K) time-resolved PL (TRPL) study shows that the sample with 3-nm-thick wells has the best optical property with a fastest exciton decay time of 0.57 ns. The results of cathodoluminescence and micro-PL scanning images for samples of different well widths further verify that the more uniform and stronger luminescence intensity distribution are observed for the samples of thinner quantum wells. In addition, more effective capturing of excitons due to larger localization energy Eloc and shorter radiative lifetime of localized excitons are observed in thinner well width samples in the temperature dependent TRPL.

  7. Optimization of InAsSb/InGaAs strained-layer superlattice growth by metal-organic chemical vapor deposition for use in infrared emitters

    SciTech Connect

    Biefeld, R.M.; Baucom, K.C.; Follstaedt, D.M.; Kurtz, S.R.

    1994-08-01

    We have prepared InAsSb/InGaAs strained-layer superlattices (SLSs) by metal-organic chemical vapor deposition using a variety of growth conditions. Presence of an InGaAsSb interface layer was indicated by x-ray diffraction. This interface effect was minimized by optimizing the purge times, reactant flows, and growth conditions. The optimized growth conditions involved the use of low pressure, short purge times between the growth of the layers, and no reactant flow during the purges. Electron diffraction indicates that CuPt-type compositional ordering occurs in InAs{sub 1{minus}x}Sb{sub x} alloys and SLSs which explains an observed bandgap reduction from previously accepted alloy values.

  8. Defects reduction in a-plane AlGaN epi-layers grown on r-plane sapphire substrates by metal organic chemical vapor deposition

    NASA Astrophysics Data System (ADS)

    Zhao, Jianguo; Zhang, Xiong; Dai, Qian; Wang, Nan; Wu, Zili; Wang, Shuchang; Cui, Yiping

    2017-01-01

    Nonpolar a-plane AlGaN epi-layers were grown on a semi-polar r-plane sapphire substrate with an innovative two-way pulsed-flows metal organic chemical vapor deposition growth technology. A root-mean-square value of 1.79 nm was achieved, and the relative light transmittance of the a-plane AlGaN epi-layer was enhanced by 36.9%. These results reveal that the innovative growth method is able to improve the surface morphology and reduce the defect density in nonpolar a-plane Al x Ga1- x N epi-layers, particularly those with an Al composition greater than 0.5, which are key materials for the fabrication of nonpolar AlGaN-based high light emission efficiency deep-ultraviolet light-emitting diodes.

  9. Multifunctional Metal-Organic Frameworks for Photocatalysis.

    PubMed

    Wang, Sibo; Wang, Xinchen

    2015-07-01

    Metal-organic frameworks (MOFs) have attracted significant research attention in diverse areas due to their unique physical and chemical characteristics that allow their innovative application in various research fields. Recently, the application of MOFs in heterogeneous photocatalysis for water splitting, CO2 reduction, and organic transformation have emerged, aiming at providing alternative solutions to address the world-wide energy and environmental problems by taking advantage of the unique porous structure together with ample physicochemical properties of the metal centers and organic ligands in MOFs. In this review, the latest progress in MOF-involved solar-to-chemical energy conversion reactions are summarized according to their different roles in the photoredox chemical systems, e.g., photocatalysts, co-catalysts, and hosts. The achieved progress and existing problems are evaluated and proposed, and the opportunities and challenges of MOFs and their related materials for their advanced development in photocatalysis are discussed and anticipated.

  10. Ultraviolet photoconductive devices with an n-GaN nanorod-graphene hybrid structure synthesized by metal-organic chemical vapor deposition

    PubMed Central

    Kang, San; Mandal, Arjun; Chu, Jae Hwan; Park, Ji-Hyeon; Kwon, Soon-Yong; Lee, Cheul-Ro

    2015-01-01

    The superior photoconductive behavior of a simple, cost-effective n-GaN nanorod (NR)-graphene hybrid device structure is demonstrated for the first time. The proposed hybrid structure was synthesized on a Si (111) substrate using the high-quality graphene transfer method and the relatively low-temperature metal-organic chemical vapor deposition (MOCVD) process with a high V/III ratio to protect the graphene layer from thermal damage during the growth of n-GaN nanorods. Defect-free n-GaN NRs were grown on a highly ordered graphene monolayer on Si without forming any metal-catalyst or droplet seeds. The prominent existence of the undamaged monolayer graphene even after the growth of highly dense n-GaN NRs, as determined using Raman spectroscopy and high-resolution transmission electron microscopy (HR-TEM), facilitated the excellent transport of the generated charge carriers through the photoconductive channel. The highly matched n-GaN NR-graphene hybrid structure exhibited enhancement in the photocurrent along with increased sensitivity and photoresponsivity, which were attributed to the extremely low carrier trap density in the photoconductive channel. PMID:26028318

  11. Low defect InGaAs quantum well selectively grown by metal organic chemical vapor deposition on Si(100) 300 mm wafers for next generation non planar devices

    NASA Astrophysics Data System (ADS)

    Cipro, R.; Baron, T.; Martin, M.; Moeyaert, J.; David, S.; Gorbenko, V.; Bassani, F.; Bogumilowicz, Y.; Barnes, J. P.; Rochat, N.; Loup, V.; Vizioz, C.; Allouti, N.; Chauvin, N.; Bao, X. Y.; Ye, Z.; Pin, J. B.; Sanchez, E.

    2014-06-01

    Metal organic chemical vapor deposition of GaAs, InGaAs, and AlGaAs on nominal 300 mm Si(100) at temperatures below 550 °C was studied using the selective aspect ratio trapping method. We clearly show that growing directly GaAs on a flat Si surface in a SiO2 cavity with an aspect ratio as low as 1.3 is efficient to completely annihilate the anti-phase boundary domains. InGaAs quantum wells were grown on a GaAs buffer and exhibit room temperature micro-photoluminescence. Cathodoluminescence reveals the presence of dark spots which could be associated with the presence of emerging dislocation in a direction parallel to the cavity. The InGaAs layers obtained with no antiphase boundaries are perfect candidates for being integrated as channels in n-type metal oxide semiconductor field effect transistor (MOSFET), while the low temperatures used allow the co-integration of p-type MOSFET.

  12. CHEMICAL STABILIZATION OF MIXED ORGANIC AND METAL COMPOUNDS - EPA SITE PROGRAM DEMONSTRATION OF THE SILICATE TECHNOLOGY CORPORATION PROCESS

    EPA Science Inventory

    In November 1990, the Silicate Technology Corporation`s (STC) proprietary process for treating soil contaminated with toxic semivolatile organic and inorganic contaminants was evaluated in a Superfund Innovative Technology Evaluation (SITE) field demonstration at the Selma Pressu...

  13. New Metal-Organic Chemistry of Barium, AN Aqueous Synthesis for Volatile Alkaline Earth Complexes, and Synthesis and Characterization of Thallium-Barium - Thin Films by Metal-Organic Chemical Vapor Deposition

    NASA Astrophysics Data System (ADS)

    Schulz, Douglas Lloyd

    The synthesis and characterization of six fluorine -free barium MOCVD (metal-organic chemical vapor deposition) precursors based upon encapsulating beta -ketoiminate-polyether ligation and having the general formula Ba(RCOCHC(NR^')R ^{''})_2 (R^' = ^{rm t}butyl, R^ ' = polyether, and R^{ ''} = methyl or ^{rm t}butyl) is reported. The complexes were prepared by a nonaqueous approach which employs BaH_2 and the corresponding beta-ketoimine. These complexes have been characterized by ^1H and ^{13}C NMR spectroscopy, elemental analysis, mass spectroscopy, cryoscopic molecular weight determination, thermogravimetric analysis, and single crystal X-ray structural analysis. These complexes serve as volatile barium MOCVD precursors. Thus, BaPbO _3 films have been grown using the aforementioned barium beta-ketoiminate complexes and Pb(dipivaloylmethanate)_2 as the respective barium and lead sources, and have been characterized by X-ray diffraction, scanning electron microscopy energy dispersive X-ray spectroscopy, and variable-temperature resistivity measurements. Investigation of thermolytic decomposition of the barium beta -ketoiminate complexes led to identification of 2-methyl -4-^{rm t}butylpyridine (17), pinacolone, and 2,2-dimethyl-5-imino-3-hexanone as the major organic thermolysis products of 11, 12, and 13. The MOCVD synthesis of Tl-Ba-Ca-Cu-O thin films on novel substrates, a growth method and film configuration which is potentially applicable toward device technologies, has been investigated. These films were prepared in three steps: first, deposition of Ba-Ca-Cu-O-(F) thin films by MOCVD; next, defluorination via water/oxygen anneal; and finally, thallination using volatile thallium oxides. Films were characterized by X-ray diffraction (theta/2 theta, omega, and phi scans), variable temperature magnetization, variable temperature conductivity, and scanning and transmission electron microscopy. Attempts at preparing Tl-Ba-Ca-Cu -O thin films on Pt resulted in the

  14. Organic Chemicals: Angels or Goblins?

    ERIC Educational Resources Information Center

    Ferguson, Lloyd N.

    1978-01-01

    Discusses some of the controversial organic chemical substances such as DDT, Red Dye No. 2, DES, Tris, Laetrile, cyclamate, and saccharin. Concludes that the use of some has to be considered on a benefit/risk ratio. (GA)

  15. Effectiveness of metal-metal and metal-organic compound combinations against Plutella xylostella: implications for plant elemental defense.

    PubMed

    Jhee, Edward M; Boyd, Robert S; Eubanks, Micky D

    2006-02-01

    Plants that contain elevated foliar metal concentrations can be categorized as accumulators or, if the accumulation is extreme, hyperaccumulators. The defense hypothesis suggests that these plants may be defended against folivore attack, and recent research has indicated that metal concentrations at or below the accumulator range may be defensively effective. This experiment explored the toxicity of four metals hyper-accumulated by plants (Cd, Ni, Pb, and Zn) and asked if combinations of metals, or metals and organic chemicals, might broaden the defensive effectiveness of metals. Metals were used alone and in certain metal + metal (Zn plus Ni, Pb, or Cd) and metal + organic defensive chemical (Ni plus tannic acid, atropine, or nicotine) combinations. Artificial diet amended with these treatments was fed to larvae of the crucifer specialist herbivore Plutella xylostella. Combinations of metals and metals + organic chemicals significantly decreased survival and pupation rates, compared to single treatments, for at least some concentrations in every experiment. Effects of combinations were additive rather than synergistic or antagonistic. Because Zn enhanced the toxicity of other metals and Ni enhanced the toxicity of organic defensive chemicals, our findings suggest that the defensive effects of metals are more widespread among plants than previously believed. They also support the hypothesis that herbivore defense may have led to the evolution of metal hyper-accumulation by increasing the preexisting defensive effects of metals at accumulator levels in plants.

  16. Emerging Multifunctional Metal-Organic Framework Materials.

    PubMed

    Li, Bin; Wen, Hui-Min; Cui, Yuanjing; Zhou, Wei; Qian, Guodong; Chen, Banglin

    2016-10-01

    Metal-organic frameworks (MOFs), also known as coordination polymers, represent an interesting type of solid crystalline materials that can be straightforwardly self-assembled through the coordination of metal ions/clusters with organic linkers. Owing to the modular nature and mild conditions of MOF synthesis, the porosities of MOF materials can be systematically tuned by judicious selection of molecular building blocks, and a variety of functional sites/groups can be introduced into metal ions/clusters, organic linkers, or pore spaces through pre-designing or post-synthetic approaches. These unique advantages enable MOFs to be used as a highly versatile and tunable platform for exploring multifunctional MOF materials. Here, the bright potential of MOF materials as emerging multifunctional materials is highlighted in some of the most important applications for gas storage and separation, optical, electric and magnetic materials, chemical sensing, catalysis, and biomedicine.

  17. Transmission electron microscopy, photoluminescence, and capacitance spectroscopy on GaAs/Si grown by metal organic chemical vapor deposition

    NASA Astrophysics Data System (ADS)

    Bremond, Georges E.; Said, Hicham; Guillot, Gerard; Meddeb, Jaafar; Pitaval, M.; Draidia, Nasser; Azoulay, Rozette

    1991-03-01

    We present a complete characterization study of GaAs/Si heteroepitaxial layers grown by metalorganic chemical vapor deposition (MOCVD) at 750C using the two-step method. High resolution transmission electron microscopy secondary ion mass spectroscopy deep level transient spectroscopy (DLTS) and photoluminescence (PL) spectroscopy have been performed to study the initial stage of growth misfit and threading dislocations Si diffusion and the deep levels in the GaAs layer. We describe the influence of GaAs/AlAs superlattices in the buffer layer on the decrease of dislocation density and on Si diffusion from the substrate and the existence of deep electron traps induced by the heteroepitaxy. DLTS reveals hole traps attributed to Si incorporation on the basis of PL measurements which could contribute to the reduction of the minority carrier lifetime. We also show an improvement of the layer quality by the use of selective epitaxy.

  18. Variations of biomarkers response in mussels Mytilus galloprovincialis to low, moderate and high concentrations of organic chemicals and metals.

    PubMed

    Perić, Lorena; Nerlović, Vedrana; Žurga, Paula; Žilić, Luka; Ramšak, Andreja

    2017-05-01

    The changes of acetylcholinesterase activity (AChE), metallothioneins content (MTs), catalase activity (CAT) and lipid peroxidation (LPO) were assessed after 4 days exposure of mussels Mytilus galloprovincialis to a wide range of sublethal concentrations of chlorpyrifos (CHP, 0.03-100 μg/L), benzo(a)pyrene (B(a)P, 0.01-100 μg/L), cadmium (Cd, 0.2-200 μg/L) and copper (Cu, 0.2-100 μg/L). The activity of AChE in the gills decreased after exposure to CHP and Cu, whereas no change of activity was detected after exposure to B(a)P and Cd. Both induction and decrease of MTs content in digestive gland occurred after exposure to CHP and B(a)P, while a marked increase was evident at highest exposure concentrations of Cd. The content of MTs progressively decreased of MTs with increasing concentration of Cu. CAT activity and LPO in the gills did not change after exposure to any of the chemicals. The results demonstrate different response profile in relation to the type of chemical compound, and highlight the potential implications for evaluation of biological effect of contaminants in marine environment. Furthermore, the AChE activity in the gills and MTs content in the digestive gland could be modulated by CHP and Cu at environmentally relevant concentrations indicating the potential risks of short-term transient mussels exposure that may occur due to run-off from land or accidental releases.

  19. Nanoscale metal-organic materials.

    PubMed

    Carné, Arnau; Carbonell, Carlos; Imaz, Inhar; Maspoch, Daniel

    2011-01-01

    Metal-organic materials are found to be a fascinating novel class of functional nanomaterials. The limitless combinations between inorganic and organic building blocks enable researchers to synthesize 0- and 1-D metal-organic discrete nanostructures with varied compositions, morphologies and sizes, fabricate 2-D metal-organic thin films and membranes, and even structure them on surfaces at the nanometre length scale. In this tutorial review, the synthetic methodologies for preparing these miniaturized materials as well as their potential properties and future applications are discussed. This review wants to offer a panoramic view of this embryonic class of nanoscale materials that will be of interest to a cross-section of researchers working in chemistry, physics, medicine, nanotechnology, materials chemistry, etc., in the next years.

  20. "Clickable" metal-organic framework.

    PubMed

    Goto, Yuta; Sato, Hiroki; Shinkai, Seiji; Sada, Kazuki

    2008-11-05

    We demonstrated the metal-organic framework bearing the azide group in the organic linkers and in situ click reactions with some small alkynes. The XRPD patterns indicated that the click reaction proceeded without any decomposition of the original MOF network. Controlling the organic linkers and incorporation of the azide groups should provide the designer-made MOFs that have controlled molecular cavities with the desired steric dimensions and functionality.

  1. Organic metal neutron detector

    DOEpatents

    Butler, M.A.; Ginley, D.S.

    1984-11-21

    A device for detection of neutrons comprises: as an active neutron sensing element, a conductive organic polymer having an electrical conductivity and a cross-section for said neutrons whereby a detectable change in said conductivity is caused by impingement of said neutrons on the conductive organic polymer which is responsive to a property of said polymer which is altered by impingement of said neutrons on the polymer; and means for associating a change in said alterable property with the presence of neutrons at the location of said device.

  2. Control of metamorphic buffer structure and device performance of In(x)Ga(1-x)As epitaxial layers fabricated by metal organic chemical vapor deposition.

    PubMed

    Nguyen, H Q; Yu, H W; Luc, Q H; Tang, Y Z; Phan, V T H; Hsu, C H; Chang, E Y; Tseng, Y C

    2014-12-05

    Using a step-graded (SG) buffer structure via metal-organic chemical vapor deposition, we demonstrate a high suitability of In0.5Ga0.5As epitaxial layers on a GaAs substrate for electronic device application. Taking advantage of the technique's precise control, we were able to increase the number of SG layers to achieve a fairly low dislocation density (∼10(6) cm(-2)), while keeping each individual SG layer slightly exceeding the critical thickness (∼80 nm) for strain relaxation. This met the demanded but contradictory requirements, and even offered excellent scalability by lowering the whole buffer structure down to 2.3 μm. This scalability overwhelmingly excels the forefront studies. The effects of the SG misfit strain on the crystal quality and surface morphology of In0.5Ga0.5As epitaxial layers were carefully investigated, and were correlated to threading dislocation (TD) blocking mechanisms. From microstructural analyses, TDs can be blocked effectively through self-annihilation reactions, or hindered randomly by misfit dislocation mechanisms. Growth conditions for avoiding phase separation were also explored and identified. The buffer-improved, high-quality In0.5Ga0.5As epitaxial layers enabled a high-performance, metal-oxide-semiconductor capacitor on a GaAs substrate. The devices displayed remarkable capacitance-voltage responses with small frequency dispersion. A promising interface trap density of 3 × 10(12) eV(-1) cm(-2) in a conductance test was also obtained. These electrical performances are competitive to those using lattice-coherent but pricey InGaAs/InP systems.

  3. Control of metamorphic buffer structure and device performance of InxGa1-xAs epitaxial layers fabricated by metal organic chemical vapor deposition

    NASA Astrophysics Data System (ADS)

    Nguyen, H. Q.; Yu, H. W.; Luc, Q. H.; Tang, Y. Z.; Phan, V. T. H.; Hsu, C. H.; Chang, E. Y.; Tseng, Y. C.

    2014-12-01

    Using a step-graded (SG) buffer structure via metal-organic chemical vapor deposition, we demonstrate a high suitability of In0.5Ga0.5As epitaxial layers on a GaAs substrate for electronic device application. Taking advantage of the technique’s precise control, we were able to increase the number of SG layers to achieve a fairly low dislocation density (˜106 cm-2), while keeping each individual SG layer slightly exceeding the critical thickness (˜80 nm) for strain relaxation. This met the demanded but contradictory requirements, and even offered excellent scalability by lowering the whole buffer structure down to 2.3 μm. This scalability overwhelmingly excels the forefront studies. The effects of the SG misfit strain on the crystal quality and surface morphology of In0.5Ga0.5As epitaxial layers were carefully investigated, and were correlated to threading dislocation (TD) blocking mechanisms. From microstructural analyses, TDs can be blocked effectively through self-annihilation reactions, or hindered randomly by misfit dislocation mechanisms. Growth conditions for avoiding phase separation were also explored and identified. The buffer-improved, high-quality In0.5Ga0.5As epitaxial layers enabled a high-performance, metal-oxide-semiconductor capacitor on a GaAs substrate. The devices displayed remarkable capacitance-voltage responses with small frequency dispersion. A promising interface trap density of 3 × 1012 eV-1 cm-2 in a conductance test was also obtained. These electrical performances are competitive to those using lattice-coherent but pricey InGaAs/InP systems.

  4. Organic metal neutron detector

    DOEpatents

    Butler, Michael A.; Ginley, David S.

    1987-01-01

    A device for detecting neutrons comprises a layer of conductive polymer sandwiched between electrodes, which may be covered on each face with a neutron transmissive insulating material layer. Conventional electrodes are used for a non-imaging integrating total neutron fluence-measuring embodiment, while wire grids are used in an imaging version of the device. The change in conductivity of the polymer after exposure to a neutron flux is determined in either case to provide the desired data. Alternatively, the exposed conductive polymer layer may be treated with a chemical reagent which selectively binds to the sites altered by neutrons to produce an image of the flux detected.

  5. Growth and characterization of well-aligned densely-packed rutile TiO(2) nanocrystals on sapphire substrates via metal-organic chemical vapor deposition.

    PubMed

    Chen, C A; Chen, Y M; Korotcov, A; Huang, Y S; Tsai, D S; Tiong, K K

    2008-02-20

    Well-aligned densely-packed rutile TiO(2) nanocrystals (NCs) have been grown on sapphire (SA) (100) and (012) substrates via metal-organic chemical vapor deposition (MOCVD), using titanium-tetraisopropoxide (TTIP, Ti(OC(3)H(7))(4)) as a source reagent. The surface morphology as well as structural and spectroscopic properties of the as-deposited NCs were characterized using field-emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM), selected-area electron diffractometry (SAED), x-ray diffraction (XRD) and micro-Raman spectroscopy. FESEM micrographs reveal that vertically aligned NCs were grown on SA(100), whereas the NCs on the SA(012) were grown with a tilt angle of ∼33° from the normal to substrates. TEM and SAED measurements showed that the TiO(2) NCs on SA(100) with square cross section have their long axis directed along the [001] direction. The XRD results reveal TiO(2) NCs with either (002) orientation on SA(100) substrate or (101) orientation on SA(012) substrate. A strong substrate effect on the alignment of the growth of TiO(2) NCs has been demonstrated and the probable mechanism for the formation of these NCs has been discussed.

  6. Demonstration of InAlN/AlGaN high electron mobility transistors with an enhanced breakdown voltage by pulsed metal organic chemical vapor deposition

    SciTech Connect

    Xue, JunShuai Zhang, JinCheng; Hao, Yue

    2016-01-04

    In this work, InAlN/AlGaN heterostructures employing wider bandgap AlGaN instead of conventional GaN channel were grown on sapphire substrate by pulsed metal organic chemical vapor deposition, where the nominal Al composition in InAlN barrier and AlGaN channel were chosen to be 83% and 5%, respectively, to achieve close lattice-matched condition. An electron mobility of 511 cm{sup 2}/V s along with a sheet carrier density of 1.88 × 10{sup 13 }cm{sup −2} were revealed in the prepared heterostructures, both of which were lower compared with lattice-matched InAlN/GaN due to increased intrinsic alloy disorder scattering resulting from AlGaN channel and compressively piezoelectric polarization in barrier, respectively. While the high electron mobility transistor (HEMT) processed on these structures not only exhibited a sufficiently high drain output current density of 854 mA/mm but also demonstrated a significantly enhanced breakdown voltage of 87 V, which is twice higher than that of reported InAlN/GaN HEMT with the same device dimension, potential characteristics for high-voltage operation of GaN-based electronic devices.

  7. Ultrathin barrier AlN/GaN high electron mobility transistors grown at a dramatically reduced growth temperature by pulsed metal organic chemical vapor deposition

    SciTech Connect

    Xue, JunShuai Zhang, JinCheng Hao, Yue

    2015-07-27

    Ultrathin-barrier AlN/GaN heterostructures were grown on sapphire substrates by pulsed metal organic chemical vapor deposition (PMOCVD) using indium as a surfactant at a dramatically reduced growth temperature of 830 °C. Upon optimization of growth parameters, an electron mobility of 1398 cm{sup 2}/V s together with a two-dimensional-electron-gas density of 1.3 × 10{sup 13 }cm{sup −2} was obtained for a 4 nm thick AlN barrier. The grown structures featured well-ordered parallel atomic steps with a root-mean-square roughness of 0.15 nm in a 5 × 5 μm{sup 2} area revealed by atomic-force-microscopic image. Finally, the potential of such structures for device application was demonstrated by fabricating and testing under dc operation AlN/GaN high-electron-mobility transistors. These results indicate that this low temperature PMOCVD growth technique is promising for the fabrication of GaN-based electronic devices.

  8. Optical and structural properties of microcrystalline GaN on an amorphous substrate prepared by a combination of molecular beam epitaxy and metal-organic chemical vapor deposition

    NASA Astrophysics Data System (ADS)

    Min, Jung-Wook; Hwang, Hyeong-Yong; Kang, Eun-Kyu; Park, Kwangwook; Kim, Ci-Hyun; Lee, Dong-Seon; Jho, Young-Dahl; Bae, Si-Young; Lee, Yong-Tak

    2016-05-01

    Microscale platelet-shaped GaN grains were grown on amorphous substrates by a combined epitaxial growth method of molecular beam epitaxy (MBE) and metal-organic chemical vapor deposition (MOCVD). First, MBE GaN was grown on an amorphous substrate as a pre-orienting layer and its structural properties were investigated. Second, MOCVD grown GaN samples using the different growth techniques of planar and selective area growth (SAG) were comparatively investigated by transmission electron microscopy (TEM), cathodoluminescence (CL), and photoluminescence (PL). In MOCVD planar GaN, strong bound exciton peaks dominated despite the high density of the threading dislocations (TDs). In MOCVD SAG GaN, on the other hand, TDs were clearly reduced with bending, but basal stacking fault (BSF) PL peaks were observed at 3.42 eV. The combined epitaxial method not only provides a deep understanding of the growth behavior but also suggests an alternative approach for the growth of GaN on amorphous substances.

  9. Phosphor-free white-light emitters using in-situ GaN nanostructures grown by metal organic chemical vapor deposition

    PubMed Central

    Min, Daehong; Park, Donghwy; Jang, Jongjin; Lee, Kyuseung; Nam, Okhyun

    2015-01-01

    Realization of phosphor-free white-light emitters is becoming an important milestone on the road to achieve high quality and reliability in high-power white-light-emitting diodes (LEDs). However, most of reported methods have not been applied to practical use because of their difficulties and complexity. In this study we demonstrated a novel and practical growth method for phosphor-free white-light emitters without any external processing, using only in-situ high-density GaN nanostructures that were formed by overgrowth on a silicon nitride (SiNx) interlayer deposited by metal organic chemical vapor deposition. The nano-sized facets produced variations in the InGaN thickness and the indium concentration when an InGaN/GaN double heterostructure was monolithically grown on them, leading to white-color light emission. It is important to note that the in-situ SiNx interlayer not only facilitated the GaN nano-facet structure, but also blocked the propagation of dislocations. PMID:26626890

  10. Effects of growth temperature on the properties of InGaN channel heterostructures grown by pulsed metal organic chemical vapor deposition

    SciTech Connect

    Zhang, Yachao; Zhou, Xiaowei; Xu, Shengrui; Wang, Zhizhe; Chen, Zhibin; Zhang, Jinfeng; Zhang, Jincheng E-mail: xd-zhangyachao@163.com; Hao, Yue E-mail: xd-zhangyachao@163.com

    2015-12-15

    Pulsed metal organic chemical vapor deposition (P-MOCVD) is introduced into the growth of high quality InGaN channel heterostructures. The effects of InGaN channel growth temperature on the structural and transport properties of the heterostructures are investigated in detail. High resolution x-ray diffraction (HRXRD) and Photoluminescence (PL) spectra indicate that the quality of InGaN channel strongly depends on the growth temperature. Meanwhile, the atomic force microscopy (AFM) results show that the interface morphology between the InGaN channel and the barrier layer also relies on the growth temperature. Since the variation of material properties of InGaN channel has a significant influence on the electrical properties of InAlN/InGaN heterostructures, the optimal transport properties can be achieved by adjusting the growth temperature. A very high two dimension electron gas (2DEG) density of 1.92 × 10{sup 13} cm{sup −2} and Hall electron mobility of 1025 cm{sup 2}/(V⋅s) at room temperature are obtained at the optimal growth temperature around 740 °C. The excellent transport properties in our work indicate that the heterostructure with InGaN channel is a promising candidate for the microwave power devices, and the results in this paper will be instructive for further study of the InGaN channel heterostructures.

  11. Ground state lasing at 1.30 microm from InAs/GaAs quantum dot lasers grown by metal-organic chemical vapor deposition.

    PubMed

    Guimard, Denis; Ishida, Mitsuru; Bordel, Damien; Li, Lin; Nishioka, Masao; Tanaka, Yu; Ekawa, Mitsuru; Sudo, Hisao; Yamamoto, Tsuyoshi; Kondo, Hayato; Sugawara, Mitsuru; Arakawa, Yasuhiko

    2010-03-12

    We investigated the effects of post-growth annealing on the photoluminescence (PL) characteristics of InAs/GaAs quantum dots (QDs) grown by metal-organic chemical vapor deposition (MOCVD). The onset temperature at which both the peak linewidth and the PL intensity degraded and the blueshift of the ground state emission wavelength occurred was found to depend on both the QD density and the In composition of the capping layer. This behavior is particularly important in view of QD integration in photonic devices. From the knowledge of the dependences of the PL characteristics after annealing on the QD and capping growth conditions, ground state lasing at 1.30 microm could be demonstrated from InAs/GaAs QDs grown by MOCVD. Finally, we compared the laser characteristics of InAs/GaAs QDs with those of InAs/Sb:GaAs QDs, grown according to the antimony-mediated growth technique, and showed that InAs/Sb:GaAs QDs are more appropriate for laser fabrication at 1.3 microm by MOCVD.

  12. As-grown deep-level defects in n-GaN grown by metal-organic chemical vapor deposition on freestanding GaN

    SciTech Connect

    Chen Shang; Ishikawa, Kenji; Hori, Masaru; Honda, Unhi; Shibata, Tatsunari; Matsumura, Toshiya; Tokuda, Yutaka; Ueda, Hiroyuki; Uesugi, Tsutomu; Kachi, Tetsu

    2012-09-01

    Traps of energy levels E{sub c}-0.26 and E{sub c}-0.61 eV have been identified as as-grown traps in n-GaN grown by metal-organic chemical vapor deposition by using deep level transient spectroscopy of the Schottky contacts fabricated by resistive evaporation. The additional traps of E{sub c}-0.13 and E{sub c}-0.65 eV have been observed in samples whose contacts are deposited by electron-beam evaporation. An increase in concentration of the E{sub c}-0.13 and E{sub c}-0.65 eV traps when approaching the interface between the contact and the GaN film supports our argument that these traps are induced by electron-beam irradiation. Conversely, the depth profiles of as-grown traps show different profiles between several samples with increased or uniform distribution in the near surface below 50 nm. Similar profiles are observed in GaN grown on a sapphire substrate. We conclude that the growth process causes these large concentrations of as-grown traps in the near-surface region. It is speculated that the finishing step in the growth process should be an essential issue in the investigation of the surface state of GaN.

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

    SciTech Connect

    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.

  14. Growth and characterization of well-aligned densely-packed rutile TiO2 nanocrystals on sapphire substrates via metal organic chemical vapor deposition

    NASA Astrophysics Data System (ADS)

    Chen, C. A.; Chen, Y. M.; Korotcov, A.; Huang, Y. S.; Tsai, D. S.; Tiong, K. K.

    2008-02-01

    Well-aligned densely-packed rutile TiO2 nanocrystals (NCs) have been grown on sapphire (SA) (100) and (012) substrates via metal-organic chemical vapor deposition (MOCVD), using titanium-tetraisopropoxide (TTIP, Ti(OC3H7)4) as a source reagent. The surface morphology as well as structural and spectroscopic properties of the as-deposited NCs were characterized using field-emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM), selected-area electron diffractometry (SAED), x-ray diffraction (XRD) and micro-Raman spectroscopy. FESEM micrographs reveal that vertically aligned NCs were grown on SA(100), whereas the NCs on the SA(012) were grown with a tilt angle of ~33° from the normal to substrates. TEM and SAED measurements showed that the TiO2 NCs on SA(100) with square cross section have their long axis directed along the [001] direction. The XRD results reveal TiO2 NCs with either (002) orientation on SA(100) substrate or (101) orientation on SA(012) substrate. A strong substrate effect on the alignment of the growth of TiO2 NCs has been demonstrated and the probable mechanism for the formation of these NCs has been discussed.

  15. Optical and Structural Properties of Microcrystalline GaN on an Amorphous Substrate Prepared by a Combination of Molecular Beam Epitaxy and Metal-Organic Chemical Vapor Deposition

    SciTech Connect

    Min, Jung-Wook; Hwang, Hyeong-Yong; Kang, Eun-Kyu; Park, Kwangwook; Kim, Ci-Hyun; Lee, Dong-Seon; Jho, Young-Dahl; Bae, Si-Young; Lee, Yong-Tak

    2016-05-01

    Microscale platelet-shaped GaN grains were grown on amorphous substrates by a combined epitaxial growth method of molecular beam epitaxy (MBE) and metal-organic chemical vapor deposition (MOCVD). First, MBE GaN was grown on an amorphous substrate as a pre-orienting layer and its structural properties were investigated. Second, MOCVD grown GaN samples using the different growth techniques of planar and selective area growth (SAG) were comparatively investigated by transmission electron microscopy (TEM), cathodoluminescence (CL), and photoluminescence (PL). In MOCVD planar GaN, strong bound exciton peaks dominated despite the high density of the threading dislocations (TDs). In MOCVD SAG GaN, on the other hand, TDs were clearly reduced with bending, but basal stacking fault (BSF) PL peaks were observed at 3.42 eV. The combined epitaxial method not only provides a deep understanding of the growth behavior but also suggests an alternative approach for the growth of GaN on amorphous substances.

  16. Arsenic antisite defects in p-GaAs grown by metal-organic chemical-vapor deposition and the EL2 defect

    NASA Astrophysics Data System (ADS)

    Naz, Nazir A.; Qurashi, Umar S.; Iqbal, M. Zafar

    2009-11-01

    Epitaxial layers of p-GaAs grown on p+-GaAs substrates by low-pressure metal organic chemical vapor deposition have been investigated using deep level transient spectroscopy (DLTS). One dominant peak and other relatively small peak, corresponding to deep levels at Ev+0.55 eV and Ev+0.96 (low field energies), respectively, have been observed in the lower half of the band gap. Investigation with double-correlation DLTS reveals that the measured thermal emission rate of holes from the dominant level is strongly dependent on the junction electric field. Detailed data on this field enhancement have been analyzed in terms of different available theoretical models. The hole capture cross section for the dominant deep level has been found to be temperature dependent. Detailed data on the temperature dependence of the hole capture cross section have been interpreted in terms of the multiphonon carrier capture mechanism, yielding a capture barrier of 0.11 eV. In order to get deeper insight into the nature and origin of these inadvertent (intrinsic) defects, thermal annealing behavior of these levels has also been studied. Analyses of field dependence and hole capture data, in combination with the annealing study, suggest that the dominant level is associated with an arsenic-antisite (AsGa) defect. Probable association of this dominant level with the doubly charged state of the well-known EL2 defect has been discussed in detail.

  17. Chemical and structural stability of zirconium-based metal-organic frameworks with large three-dimensional pores by linker engineering.

    PubMed

    Kalidindi, Suresh B; Nayak, Sanjit; Briggs, Michael E; Jansat, Susanna; Katsoulidis, Alexandros P; Miller, Gary J; Warren, John E; Antypov, Dmytro; Corà, Furio; Slater, Ben; Prestly, Mark R; Martí-Gastaldo, Carlos; Rosseinsky, Matthew J

    2015-01-02

    The synthesis of metal-organic frameworks with large three-dimensional channels that are permanently porous and chemically stable offers new opportunities in areas such as catalysis and separation. Two linkers (L1=4,4',4'',4'''-([1,1'-biphenyl]-3,3',5,5'-tetrayltetrakis(ethyne-2,1-diyl)) tetrabenzoic acid, L2=4,4',4'',4'''-(pyrene-1,3,6,8-tetrayltetrakis(ethyne-2,1-diyl))tetrabenzoic acid) were used that have equivalent connectivity and dimensions but quite distinct torsional flexibility. With these, a solid solution material, [Zr6 O4 (OH)4 (L1)2.6 (L2)0.4 ]⋅(solvent)x , was formed that has three-dimensional crystalline permanent porosity with a surface area of over 4000 m(2)  g(-1) that persists after immersion in water. These properties are not accessible for the isostructural phases made from the separate single linkers.

  18. Low-temperature growth and characterization of single crystalline ZnO nanorod arrays using a catalyst-free inductively coupled plasma-metal organic chemical vapor deposition.

    PubMed

    Jeong, Sang-Hun; Lee, Chang-Bae; Moon, Won-Jin; Song, Ho-Jun

    2008-10-01

    Vertically aligned ZnO nanorod arrays have been synthesized on c-plane sapphires at a low temperature of 400 degrees C using catalyst-free inductively coupled plasma (ICP) metal organic chemical vapor deposition (MOCVD) technique by varying the ICP powers. Diameters of the ZnO nanorods changed from 200 nm to 400 nm as the ICP power increased from 200 to 400 Watt. TEM and XRD investigations indicated that the ZnO nanorod arrays grown at ICP powers above 200 Watt had a homogeneous in-plane alignment and single crystalline nature. PL study at room temperature (RT) and 6 K confirmed that the ZnO nanorod arrays in the present study are of high optical quality as well as good crystalline quality, showing only exciton-related emission peaks without any trace of defect-related deep level emissions in visible range. The blueshift of exciton emission peak in RTPL spectra was also found as rod diameter decreased and it is deduced that this shift in emission energy may be due to the surface resonance effect resulted from the increased surface-to-volume ratio, based on the observation and behavior of the surface exciton (SX) emission in the high-resolution 6 K PL spectra.

  19. The growth of InAsSb/InGaAs strained-layer superlattices by metal-organic chemical vapor deposition

    SciTech Connect

    Biefeld, R.M.; Baucom, K.C.; Kurtz, S.R.; Follstaedt, D.M.

    1993-12-31

    We have grown InAs{sub l-x}Sb{sub x}/In{sub 1-y}Ga{sub y}As strained-layer superlattice (SLS) semiconductors lattice matched to InAs using a variety of conditions by metal-organic chemical vapor deposition. The V/III ratio was varied from 2.5 to 10 at 475 C, at pressures of 200 to 660 torr and growth rates of 3 {minus} 5 {angstrom}/s and layer thicknesses ranging from 55 to 152 {angstrom}. Composition of InAsSb ternary can be predicted from the input gas molar flow rates using a thermodynamic model. At lower temperatures, the thermodynamic model must be modified to take account of the incomplete decomposition of arsine and trimethylantimony. Diodes have been prepared using Zn as the p-type dopant and undoped SLS as the n-type material. The diode was found to emit at 3.56 {mu}m. These layers have been characterized by optical microscopy, SIMS, x-ray diffraction, and transmission electron diffraction. The optical properties of these SLS`s were determined by infrared photoluminescence and absorption measurements.

  20. InGaAs/InP Avalanche Photodiode for Single Photon Detection with Zinc Diffusion Process Using Metal Organic Chemical Vapor Deposition.

    PubMed

    Lee, In Joon; Lee, Min Soo; Kim, Min Su; Jun, Dong-Hwan; Jeong, Hae Yong; Kim, Sangin; Han, Sang-wook; Moon, Sung

    2016-05-01

    In this paper, we describe a design, simulation, and fabrication of an InGaAs/InP single photon avalanche photodiode (SPAD), which requires a much higher gain, compared to APD's for conventional optical communications. To achieve a higher gain, an efficient multiplication width control is essential because it significantly affects the overall performance including not only gain but also noise characteristics. Normally, the multiplication layer width is controlled by the Zinc diffusion process. For the reliable and controllable diffusion process, we used metal organic chemical vapor deposition (MOCVD). The controllability of the proposed diffusion process is proved by the diffusion depth measurement of the fabricated devices which show the proportional dependence on the square root of the diffusion time. As a result, we successfully implemented the SPAD that exhibits a high gain enough to detect single photons and a very low dark current level of about 0.1 nA with 0.95 breakdown voltage. The single photon detection efficiency of 15% was measured at the 100 kHz gate pulse rate and the temperature of 230 K.

  1. Growth of self-aligned Ga2O3 nanostructures deposited on r-plane sapphire by using metal-organic chemical vapor deposition

    NASA Astrophysics Data System (ADS)

    Lee, Seoyoung; Lee, Seunghyun; Jo, Hyunjin; Bae, Sangki; Kim, Kimin; Song, Jiho; Cho, Younghwan; Kim, Jinsung; Ahn, Hyungsoo; Yang, Min

    2016-11-01

    The growth temperature dependence of self-aligned β-Ga2O3 nanostructures grown on an r-plane sapphire substrate by using metal-organic chemical vapor deposition is reported. Periodic self-alignment of the β-Ga2O3 grains was observed for certain growth temperature windows and the grain size of the β-Ga2O3 structure varied in response to the growth temperature. At temperatures under 800 °C, self-alignment of the β-Ga2O3 structures was not observed. The self-alignment tendency began to appear at 900 °C, and obvious self-alignment characteristics in a certain direction were observed at approximately 950 °C. However, as the growth temperature was increased to more than 900 °C the growth mode of the β-Ga2O3 structure gradually deviated from the self-alignment mode, finally exhibiting a two-dimensional thin film mode at 1100 °C. We surmise that the driving force of β-Ga2O3 grain self-alignment is the surface-potential difference between the planar and the step regions of the substrate on an atomic scale, which originates from misorientation occurring during the r-plane sapphire cutting process.

  2. Preparation of MgO Films by Atmospheric Metal-Organic Chemical Vapor Deposition as a Protective Layer in AC Plasma Display Panels

    NASA Astrophysics Data System (ADS)

    Okada, Takeru; Komaki, Toshihiro

    2008-03-01

    MgO thin films were fabricated by atmospheric metal-organic chemical vapor deposition as a protective layer of AC plasma display panels. The deposition conditions and the discharge properties of the films were evaluated. Among four Mg precursors tested, Mg(C11H19O2)2 [Mg(DPM)2] was the most suitable source material in film growth properties and discharge characteristics. The deposition rate increased with increasing vaporizing temperature and substrate temperature, and the maximum deposition rate reached 3.3 nm/s (5.1 min/µm). The films had (200) main orientations, and highly crystalline square-pyramid structures were observed in high deposition-rate films. Under the high-rate deposition condition, the firing voltage and the discharge delay of the film were comparable to those of conventional vacuum-evaporated MgO film. The discharge delay was shorter when the crystal size was larger, the work function was smaller, and the concentrations of impurities were lower.

  3. Metal-doped organic foam

    DOEpatents

    Rinde, James A.

    1982-01-01

    Organic foams having a low density and very small cell size and method for producing same in either a metal-loaded or unloaded (nonmetal loaded) form are described. Metal-doped foams are produced by soaking a polymer gel in an aqueous solution of desired metal salt, soaking the gel successively in a solvent series of decreasing polarity to remove water from the gel and replace it with a solvent of lower polarity with each successive solvent in the series being miscible with the solvents on each side and being saturated with the desired metal salt, and removing the last of the solvents from the gel to produce the desired metal-doped foam having desired density cell size, and metal loading. The unloaded or metal-doped foams can be utilized in a variety of applications requiring low density, small cell size foam. For example, rubidium-doped foam made in accordance with the invention has utility in special applications, such as in x-ray lasers.

  4. Heavy metal pollutants and chemical ecology: exploring new frontiers.

    PubMed

    Boyd, Robert S

    2010-01-01

    Heavy metals are an important class of pollutants with both lethal and sublethal effects on organisms. The latter are receiving increased attention, as these may have harmful ecological outcomes. For example, recent explorations of heavy metals in freshwater habitats reveal that they can modify chemical communication between individuals, resulting in "info-disruption" that can impact ecological relationships within and between species. Info-disruption can affect animal behavior and social structure, which in turn can modify both intraspecies and interspecies interactions. In terrestrial habitats, info-disruption by metals is not well studied, but recent demonstrations of chemical signaling between plants via both roots and volatile organic molecules provide potential opportunities for info-disruption. Metals in terrestrial habitats also can form elemental plant defenses, in which they can defend a plant against natural enemies. For example, hyperaccumulation of metals by terrestrial plants has been shown to provide defensive benefits, although in almost all known cases the metals are not anthropogenic pollutants but are naturally present in soils inhabited by these plants. Info-disruption among microbes is another arena in which metal pollutants may have ecological effects, as recent discoveries regarding quorum sensing in bacteria provide an avenue for metals to affect interactions among bacteria or between bacteria and other organisms. Metal pollutants also may influence immune responses of organisms, and thus affect pathogen/host relationships. Immunomodulation (modification of immune system function) has been tied to some metal pollutants, although specific metals may boost or reduce immune system function depending on dose. Finally, the study of metal pollutants is complicated by their frequent occurrence as mixtures, either with other metals or with organic pollutants. Most studies of metal pollutants focus on single metals and therefore oversimplify complex

  5. Nitride passivation reduces interfacial traps in atomic-layer-deposited Al{sub 2}O{sub 3}/GaAs (001) metal-oxide-semiconductor capacitors using atmospheric metal-organic chemical vapor deposition

    SciTech Connect

    Aoki, T. Fukuhara, N.; Osada, T.; Sazawa, H.; Hata, M.; Inoue, T.

    2014-07-21

    Using an atmospheric metal-organic chemical vapor deposition system, we passivated GaAs with AlN prior to atomic layer deposition of Al{sub 2}O{sub 3}. This AlN passivation incorporated nitrogen at the Al{sub 2}O{sub 3}/GaAs interface, improving the capacitance-voltage (C–V) characteristics of the resultant metal-oxide-semiconductor capacitors (MOSCAPs). The C–V curves of these devices showed a remarkable reduction in the frequency dispersion of the accumulation capacitance. Using the conductance method at various temperatures, we extracted the interfacial density of states (D{sub it}). The D{sub it} was reduced over the entire GaAs band gap. In particular, these devices exhibited D{sub it} around the midgap of less than 4 × 10{sup 12} cm{sup −2}eV{sup −1}, showing that AlN passivation effectively reduced interfacial traps in the MOS structure.

  6. Resonant and nonresonant vibrational excitation of ammonia molecules in the growth of gallium nitride using laser-assisted metal organic chemical vapour deposition

    NASA Astrophysics Data System (ADS)

    Golgir, Hossein Rabiee; Zhou, Yun Shen; Li, Dawei; Keramatnejad, Kamran; Xiong, Wei; Wang, Mengmeng; Jiang, Li Jia; Huang, Xi; Jiang, Lan; Silvain, Jean Francois; Lu, Yong Feng

    2016-09-01

    The influence of exciting ammonia (NH3) molecular vibration in the growth of gallium nitride (GaN) was investigated by using an infrared laser-assisted metal organic chemical vapor deposition method. A wavelength tunable CO2 laser was used to selectively excite the individual vibrational modes. Resonantly exciting the NH-wagging mode (v2) of NH3 molecules at 9.219 μm led to a GaN growth rate of 84 μm/h, which is much higher than the reported results. The difference between the resonantly excited and conventional thermally populated vibrational states was studied via resonant and nonresonant vibrational excitations of NH3 molecules. Resonant excitation of various vibrational modes was achieved at 9.219, 10.35, and 10.719 μm, respectively. Nonresonant excitation was conducted at 9.201 and 10.591 μm, similar to conventional thermal heating. Compared to nonresonant excitation, resonant excitation noticeably promotes the GaN growth rate and crystalline quality. The full width at half maximum value of the XRD rocking curves of the GaN (0002) and GaN (10-12) diffraction peaks decreased at resonant depositions and reached its minimum value of 45 and 53 arcmin, respectively, at the laser wavelength of 9.219 μm. According to the optical emission spectroscopic studies, resonantly exciting the NH3 v2 mode leads to NH3 decomposition at room temperature, reduces the formation of the TMGa:NH3 adduct, promotes the supply of active species in GaN formation, and, therefore, results in the increased GaN growth rate.

  7. Performance of metal-organic framework MIL-101 after surfactant modification in the extraction of endocrine disrupting chemicals from environmental water samples.

    PubMed

    Huang, Zhenzhen; Lee, Hian Kee

    2015-10-01

    The research presented in this paper explored the modification and application of a metal-organic framework, MIL-101, with nonionic surfactant-Triton X-114 in dispersive solid-phase extraction for the preconcentration of four endocrine disrupting chemicals (estrone, 17α-ethynylestradiol, estriol and diethylstilbestrol) from environmental water samples. Triton X-114 molecules could be adsorbed by the hydrophobic surface of the MIL-101 crystals, and thus improved the dispersibility of MIL-101 in aqueous solution by serving as a hydrophilic coating. Cloud point phase separation from Triton X-114 accelerated the separation of extracts from the aqueous matrix. The proposed method combines the favorable attributes of strong adsorption capacity resulting from the porous structure of MIL-101 and self-assembly of Triton X-114 molecules. Post-extraction derivatization using N-methyl-N-(trimethylsilyl)trifluoroacetamide was employed to facilitate the quantitative determination of the extracts by gas chromatography-mass spectrometry. The main factors affecting the preparation of modified MIL-101, and extraction of the analytes, such as the amount of surfactant, the ultrasonic and vortex durations, solution pH and desorption conditions, were investigated in detail. Under the optimized conditions, the present method yielded low limits of detection (0.006-0.023 ng/mL), good linearity from 0.09 to 45 ng/mL (coefficients of determination higher than 0.9980) and acceptable precision (relative standard deviations of 2.2-13%). The surface modified MIL-101 was demonstrated to be effective for the extraction of the selected estrogens from aqueous samples, giving rise to markedly improved extraction performance compared to the unmodified MIL-101.

  8. Parameters study on the growth of GaAs nanowires on indium tin oxide by metal-organic chemical vapor deposition

    NASA Astrophysics Data System (ADS)

    Wu, Dan; Tang, Xiaohong; Wang, Kai; Olivier, Aurelien; Li, Xianqiang

    2016-03-01

    After successful demonstration of GaAs nanowire (NW) epitaxial growth on indium tin oxide (ITO) by metal organic chemical vapor deposition, we systematically investigate the effect of growth parameters' effect on the GaAs NW, including temperature, precursor molar flow rates, growth time, and Au catalyst size. 40 nm induced GaAs NWs are observed with zinc-blende structure. Based on vapor-liquid-solid mechanism, a kinetic model is used to deepen our understanding of the incorporation of growth species and the role of various growth parameters in tuning the GaAs NW growth rate. Thermally activated behavior has been investigated by variation of growth temperature. Activation energies of 40 nm Au catalyst induced NWs are calculated at different trimethylgallium (TMGa) molar flow rates about 65 kJ/mol. The GaAs NWs growth rates increase with TMGa molar flow rates whereas the growth rates are almost independent of growth time. Due to Gibbs-Thomson effect, the GaAs NW growth rates increase with Au nanoparticle size at different temperatures. Critical radius is calculated as 2.14 nm at the growth condition of 430 °C and 1.36 μmol/s TMGa flow rate. It is also proved experimentally that Au nanoparticle below the critical radius such as 2 nm cannot initiate the growth of NWs on ITO. This theoretical and experimental growth parameters investigation enables great controllability over GaAs NWs grown on transparent conductive substrate where the methodology can be expanded to other III-V material NWs and is critical for potential hybrid solar cell application.

  9. Nanostructured surface morphology of ZnO grown on p-type GaN and Si by metal organic chemical vapor deposition

    NASA Astrophysics Data System (ADS)

    Hung, S. C.; Huang, P. J.; Chan, C. E.; Uen, W. Y.; Ren, F.; Pearton, S. J.; Yang, T. N.; Chiang, C. C.; Lan, S. M.; Chi, G. C.

    2008-12-01

    The surface morphology of ZnO grown on p-GaN templates and p-Si (1 1 1) substrates at various temperatures by metal organic chemical vapor deposition (MOCVD) in a vertical reactor at atmospheric pressure is reported. A low temperature ZnO buffer was deposited initially at 200 °C for 15 min as a nucleation layer. Epitaxial ZnO was grown at 500 °C, 550 °C, 600 °C for 40 min, respectively. Uniformly distributed and well-aligned ZnO nanorods with diameter in the range 80-120 nm and length ˜0.7 μm were observed for deposition on p-GaN template. By contrast, the morphology of ZnO epilayers grown on p-Si (1 1 1) transitioned from 2D to 3D with increasing growth temperature. X-ray diffraction (XRD) spectra showed all the ZnO epilayers had the hexagonal wurtzite structure but different preferred orientation. PL spectra showed only free-exciton emission at 378 nm (˜3.28 eV) with a full width at half maximum of 13 nm without defect-related green emission in the epitaxial ZnO grown at 550 °C and 600 °C. The epitaxial ZnO layers grown on p-GaN and p-Si at the same temperature have similar PL spectra. The PL measurement also exhibits strong exciton-related emission without defect peak, which showed that the ZnO nanostructures grown at 550 °C and 600 °C have good optical properties with excellent crystal quality.

  10. New rht-Type Metal-Organic Frameworks Decorated with Acylamide Groups for Efficient Carbon Dioxide Capture and Chemical Fixation from Raw Power Plant Flue Gas.

    PubMed

    Guo, Xiangyang; Zhou, Zhen; Chen, Cong; Bai, Junfeng; He, Cheng; Duan, Chunying

    2016-11-23

    The combination of carbon dioxide capture and chemical fixation in a one-pot process is attractive for both chemists and governments. The cycloaddition of carbon dioxide with epoxides to produce cyclic carbonates is an atomic economical reaction without any side products. By incorporating acylamide to enhance the binding affinity toward CO2, new rht-type metal-organic frameworks (MOFs) with (3, 28) and (3, 24) connected units were constructed. Zn-NTTA with two types of dinuclear paddlewheel building blocks-{Zn2(OOC(-))4} and {Zn2(OOC(-))3}. The high uptake of CO2 (115.6 cm(3)·g(-1)) and selectivity over N2 (30:1) at 273 K indicated that these MOFs are excellent candidates for postcombustion CO2 isolation and capture. The MOFs feature high catalytic activity, rapid dynamics of transformation and excellent stability with turnover number (TON) values up to 110 000 per paddlewheel unit after 5 × 6 rounds of recyclability, demonstrating that they are promising heterogeneous catalysts for CO2 cyclo-addition to value-added cyclic carbonates. The cycloaddition of epoxides with wet gases demonstrated that the catalyst activity was not affected by moisture, and the indices of the PXRD patterns of the bulk samples filtered from the catalytic reaction revealed that the crystallinities were maintained. The combination of the selective capture and catalytic transformation in one-pot enables the use of a negative-cost feedstock-raw power plant flue gas without any separation and purification-revealing the broad prospects of such MOFs for practical CO2 fixation in industry.

  11. Thermal stability of an InAlN/GaN heterostructure grown on silicon by metal-organic chemical vapor deposition

    SciTech Connect

    Watanabe, Arata Freedsman, Joseph J.; Urayama, Yuya; Christy, Dennis; Egawa, Takashi

    2015-12-21

    The thermal stabilities of metal-organic chemical vapor deposition-grown lattice-matched InAlN/GaN/Si heterostructures have been reported by using slower and faster growth rates for the InAlN barrier layer in particular. The temperature-dependent surface and two-dimensional electron gas (2-DEG) properties of these heterostructures were investigated by means of atomic force microscopy, photoluminescence excitation spectroscopy, and electrical characterization. Even at the annealing temperature of 850 °C, the InAlN layer grown with a slower growth rate exhibited a smooth surface morphology that resulted in excellent 2-DEG properties for the InAlN/GaN heterostructure. As a result, maximum values for the drain current density (I{sub DS,max}) and transconductance (g{sub m,max}) of 1.5 A/mm and 346 mS/mm, respectively, were achieved for the high-electron-mobility transistor (HEMT) fabricated on this heterostructure. The InAlN layer grown with a faster growth rate, however, exhibited degradation of the surface morphology at an annealing temperature of 850 °C, which caused compositional in-homogeneities and impacted the 2-DEG properties of the InAlN/GaN heterostructure. Additionally, an HEMT fabricated on this heterostructure yielded lower I{sub DS,max} and g{sub m,max} values of 1 A/mm and 210 mS/mm, respectively.

  12. Organic-coated nanoparticulate zero valent iron for remediation of chemical oxygen demand (COD) and dissolved metals from tropical landfill leachate.

    PubMed

    Wijesekara, S S R M D H R; Basnayake, B F A; Vithanage, Meththika

    2014-01-01

    The use of nanoparticulate zero valent iron (NZVI) in the treatment of inorganic contaminants in landfill leachate and polluted plumes has been the subject of many studies, especially in temperate, developed countries. However, NZVI's potential for reduction of chemical oxygen demand (COD) and treatment of metal ion mixtures has not been explored in detail. We investigated the efficiency of NZVI synthesized in the presence of starch, mercaptoacetic, mercaptosuccinic, or mercaptopropenoic acid for the reduction of COD, nutrients, and metal ions from landfill leachate in tropical Sri Lanka. Synthesized NZVI were characterized with X-ray diffraction (XRD), transmission electron microscopy, X-ray photoelectron spectroscopy, scanning electron microscopy (SEM), thermal gravimetric analysis, Fourier transform infrared spectroscopy (FTIR) and Brunauer-Emmett-Teller. Of the samples tested, Starch-NZVI (S-NZVI) and mercaptoacetic-NZVI (MA-NZVI) performed well for treatment both COD and metal mixture. The removal percentages for COD, nitrate-nitrogen, and phosphate from S-NZVI were 50, 88, and 99 %, respectively. Heavy metal removal was higher in S-NZVI (>95 %) than others. MA-NZVI, its oxidation products, and functional groups of its coating showed the maximum removal amounts for both Cu (56.27 mg g(-1)) and Zn (28.38 mg g(-1)). All mercapto-NZVI showed well-stabilized nature under FTIR and XRD investigations. Therefore, we suggest mercapto acids as better agents to enhance the air stability for NZVI since chemically bonded thiol and carbonyl groups actively participation for stabilization process.

  13. Effect of the misorientation of the 4H-SiC substrate on the open volume defects in GaN grown by metal-organic chemical vapor deposition

    SciTech Connect

    Tengborn, E.; Rummukainen, M.; Tuomisto, F.; Saarinen, K.; Rudzinski, M.; Hageman, P. R.; Larsen, P. K.; Nordlund, A.

    2006-08-28

    Positron annihilation spectroscopy has been used to study GaN grown by metal-organic chemical vapor deposition on misoriented 4H-SiC substrates. Two kinds of vacancy defects are observed: Ga vacancies and larger vacancy clusters in all the studied layers. In addition to vacancies, positrons annihilate at shallow traps that are likely to be dislocations. The results show that the vacancy concentration increases and the shallow positron trap concentration decreases with the increasing substrate misorientation.

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

    NASA Astrophysics Data System (ADS)

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

    2016-08-01

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

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

    PubMed

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

    2016-08-30

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

  16. Metal-organic frameworks in chromatography.

    PubMed

    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.

  17. Chemical sensing and imaging with metallic nanorods.

    PubMed

    Murphy, Catherine J; Gole, Anand M; Hunyadi, Simona E; Stone, John W; Sisco, Patrick N; Alkilany, Alaaldin; Kinard, Brian E; Hankins, Patrick

    2008-02-07

    In this Feature Article, we examine recent advances in chemical analyte detection and optical imaging applications using gold and silver nanoparticles, with a primary focus on our own work. Noble metal nanoparticles have exciting physical and chemical properties that are entirely different from the bulk. For chemical sensing and imaging, the optical properties of metallic nanoparticles provide a wide range of opportunities, all of which ultimately arise from the collective oscillations of conduction band electrons ("plasmons") in response to external electromagnetic radiation. Nanorods have multiple plasmon bands compared to nanospheres. We identify four optical sensing and imaging modalities for metallic nanoparticles: (1) aggregation-dependent shifts in plasmon frequency; (2) local refractive index-dependent shifts in plasmon frequency; (3) inelastic (surface-enhanced Raman) light scattering; and (4) elastic (Rayleigh) light scattering. The surface chemistry of the nanoparticles must be tunable to create chemical specificity, and is a key requirement for successful sensing and imaging platforms.

  18. Cascade reactions catalyzed by metal organic frameworks.

    PubMed

    Dhakshinamoorthy, Amarajothi; Garcia, Hermenegildo

    2014-09-01

    Cascade or tandem reactions where two or more individual reactions are carried out in one pot constitute a clear example of process intensification, targeting the maximization of spatial and temporal productivity with mobilization of minimum resources. In the case of catalytic reactions, cascade processes require bi-/multifunctional catalysts that contain different classes of active sites. Herein, we show that the features and properties of metal-organic frameworks (MOFs) make these solids very appropriate materials for the development of catalysts for cascade reactions. Due to composition and structure, MOFs can incorporate different types of sites at the metal nodes, organic linkers, or at the empty internal pores, allowing the flexible design and synthesis of multifunctional catalysts. After some introductory sections on the relevance of cascade reactions from the point of view of competitiveness, sustainability, and environmental friendliness, the main part of the text provides a comprehensive review of the literature reporting the use of MOFs as heterogeneous catalysts for cascade reactions including those that combine in different ways acid/base, oxidation/reduction, and metal-organic centers. The final section summarizes the current state of the art, indicating that the development of a first commercial synthesis of a high-added-value fine chemical will be a crucial milestone in this area.

  19. Chemical and biological properties of toxic metals and use of chelating agents for the pharmacological treatment of metal poisoning.

    PubMed

    Sinicropi, Maria Stefania; Amantea, Diana; Caruso, Anna; Saturnino, Carmela

    2010-07-01

    Exposure to toxic metals is a well-known problem in industrialized countries. Metals interfere with a number of physiological processes, including central nervous system (CNS), haematopoietic, hepatic and renal functions. In the evaluation of the toxicity of a particular metal it is crucial to consider many parameters: chemical forms (elemental, organic or inorganic), binding capability, presence of specific proteins that selectively bind metals, etc. Medical treatment of acute and chronic metal toxicity is provided by chelating agents, namely organic compounds capable of interacting with metal ions to form structures called chelates. The present review attempts to provide updated information about the mechanisms, the cellular targets and the effects of toxic metals.

  20. Thermodynamics of metal-organic frameworks

    SciTech Connect

    Wu, Di; Navrotsky, Alexandra

    2015-03-15

    Although there have been extensive studies over the past decade in the synthesis and application of metal-organic frameworks (MOFs), investigation of their thermodynamic stability and of the energetics of guest–host interactions has been much more limited. This review summarizes recent progress in experimental (calorimetric) determination of the thermodynamics of MOF materials. The enthalpies of MOFs relative to dense phase assemblages suggest only modest metastability, with a general increase of enthalpy with increasing molar volume, which becomes less pronounced at higher porosity. The energy landscape of nanoporous materials (inorganic and hybrid) consists of a pair of parallel patterns within a fairly narrow range of metastability of 5–30 kJ per mole of tetrahedra in zeolites and mesoporous silicas or per mole of metal in MOFs. Thus strong thermodynamic instability does not seem to limit framework formation. There are strong interactions within the chemisorption range for small molecule–MOF interactions with defined chemical binding at the metal centers or other specific locations. Coexistence of surface binding and confinement can lead to much stronger guest–host interactions. - Graphical abstract: Energy landscape of inorganic and hybrid porous materials. - Highlights: • Thermochemical data on various MOF structures were experimentally determined. • MOFs are moderately unstable relative to their dense phase assemblage. • Overall energetic landscape of porous materials was revealed. • Guest–host interactions in MOFs were evaluated directly using calorimetry. • Confinement effect and defined chemical binding lead to strong interactions.

  1. Method of stripping metals from organic solvents

    DOEpatents

    Todd, Terry A.; Law, Jack D.; Herbst, R. Scott; Romanovskiy, Valeriy N.; Smirnov, Igor V.; Babain, Vasily A.; Esimantovski, Vyatcheslav M.

    2009-02-24

    A new method to strip metals from organic solvents in a manner that allows for the recycle of the stripping agent. The method utilizes carbonate solutions of organic amines with complexants, in low concentrations, to strip metals from organic solvents. The method allows for the distillation and reuse of organic amines. The concentrated metal/complexant fraction from distillation is more amenable to immobilization than solutions resulting from current practice.

  2. An Electrically Switchable Metal-Organic Framework

    NASA Astrophysics Data System (ADS)

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

    2014-08-01

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

  3. An Electrically Switchable Metal-Organic Framework

    SciTech Connect

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

    2014-08-19

    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 5 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.

  4. An Electrically Switchable Metal-Organic Framework

    SciTech Connect

    Fernandez, CA; Martin, PC; Schaef, T; Bowden, ME; Thallapally, PK; Dang, L; Xu, W; Chen, XL; McGrail, BP

    2014-08-19

    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.

  5. An Electrically Switchable Metal-Organic Framework

    PubMed Central

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

    2014-01-01

    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. PMID:25135307

  6. Effects of irradiation and annealing on deep levels in rhodium-doped p-GaAs grown by metal-organic chemical-vapor deposition

    SciTech Connect

    Naz, Nazir A.; Qurashi, Umar S.; Iqbal, M. Zafar

    2011-06-01

    This paper reports a detailed study of the effects of irradiation and thermal annealing on deep levels in Rh-doped p-type GaAs grown by low-pressure metal-organic chemical-vapor deposition, using deep level transient spectroscopy (DLTS) technique. It is found upon irradiation with alpha particles that, in addition to the radiation-induced defect peaks, all the Rh-related peaks observed in majority, as well as minority-carrier emission DLTS scans show an increase in their respective concentrations. The usually observed {alpha}-induced defects H{alpha}1, H{alpha}2, and H{alpha}3 are found to have lower introduction rates in Rh-doped samples, as compared to reference samples (not doped with Rh). Alpha-irradiation has been found to decompose the two minority carrier emitting bands (one at low temperature {approx}150 K and the other at {approx}380 K) observed prior to irradiation into distinct peaks corresponding to deep levels Rh1 and Rh2 and EL2 and Rh3, respectively. A similar effect is also observed for the majority-carrier emitting band composed of hole emission from deep levels RhA and RhB, which separate out well upon irradiation. Further, from the double-correlation DLTS measurements, the emission rates of carriers from the radiation-enhanced peaks corresponding to deep levels Rh1, Rh2, Rh3, and RhC were found to be dependent on junction electric field. For RhC, the field dependence data have been analyzed in terms of the Poole-Frenkel model employing a 3-dimensional Coulomb potential with q = 2e (electronic charge). Temperature dependence of the hole capture cross-sections of the levels RhA and RhC was also studied quantitatively. The observed dependence of the hole capture cross-section of RhC on temperature can be interpreted in terms of multiphonon capture model, yielding a capture barrier of 0.2 eV and {sigma}({infinity}) = 2.3 x 10{sup -14} cm{sup 2}. The results of irradiation and isochronal thermal annealing study, in combination with the theoretical

  7. Effects of irradiation and annealing on deep levels in rhodium-doped p-GaAs grown by metal-organic chemical-vapor deposition

    NASA Astrophysics Data System (ADS)

    Naz, Nazir A.; Qurashi, Umar S.; Iqbal, M. Zafar

    2011-06-01

    This paper reports a detailed study of the effects of irradiation and thermal annealing on deep levels in Rh-doped p-type GaAs grown by low-pressure metal-organic chemical-vapor deposition, using deep level transient spectroscopy (DLTS) technique. It is found upon irradiation with alpha particles that, in addition to the radiation-induced defect peaks, all the Rh-related peaks observed in majority, as well as minority-carrier emission DLTS scans show an increase in their respective concentrations. The usually observed α-induced defects Hα1, Hα2, and Hα3 are found to have lower introduction rates in Rh-doped samples, as compared to reference samples (not doped with Rh). Alpha-irradiation has been found to decompose the two minority carrier emitting bands (one at low temperature ˜150 K and the other at ˜380 K) observed prior to irradiation into distinct peaks corresponding to deep levels Rh1 and Rh2 and EL2 and Rh3, respectively. A similar effect is also observed for the majority-carrier emitting band composed of hole emission from deep levels RhA and RhB, which separate out well upon irradiation. Further, from the double-correlation DLTS measurements, the emission rates of carriers from the radiation-enhanced peaks corresponding to deep levels Rh1, Rh2, Rh3, and RhC were found to be dependent on junction electric field. For RhC, the field dependence data have been analyzed in terms of the Poole-Frenkel model employing a 3-dimensional Coulomb potential with q = 2e (electronic charge). Temperature dependence of the hole capture cross-sections of the levels RhA and RhC was also studied quantitatively. The observed dependence of the hole capture cross-section of RhC on temperature can be interpreted in terms of multiphonon capture model, yielding a capture barrier of 0.2 eV and σ(∞) = 2.3 × 10-14 cm2. The results of irradiation and isochronal thermal annealing study, in combination with the theoretical analysis of the field dependence of hole emission data

  8. Chemical resistance guide for metals and alloys

    SciTech Connect

    1998-12-31

    This guide contains data for 29,000 combinations of corrodents vs. metals, metal alloys, and carbon. Features and specifications include: (1) 963 liquid or dry chemicals, gases, lubricants, household fluids, foods, atmospheres, and other environments are covered; (2) 70 chemical trade names are covered; (3) 500 synonyms of covered chemicals, gases, etc. are indexed to page numbers; (4) corrodents are listed in alphabetical order; (5) data are presented in symbolic format (A, B, C, NR); (6) where known chemical resistance varies with concentration and temperature, data are presented in descending order of concentration and temperature; (7) mechanical, physical, and electrical properties data for each metal are provided; (8) a flex thumb index is provided at the right-hand margin of the right-hand pages to facilitate quick access to the desired data; (9) an electromotive or galvanic series list covering 120 metals, alloys, and carbon is included; (10) machinability ratings for most metals, including some specific S.F.M. rates, is included; (11) creep or stress relaxation rates at various levels of stress, temperature, and time are included; and (12) printed on semigloss, 70 pound, plastic-coated bond paper that last through years of reference.

  9. Consequences of cavity size and chemical environment on the adsorption properties of isoreticular metal-organic frameworks: an inverse gas chromatography study.

    PubMed

    Gutiérrez, Inés; Díaz, Eva; Vega, Aurelio; Ordóñez, Salvador

    2013-01-25

    The role of the structure of three isoreticular metal-organic frameworks (IRMOFs) on their adsorption behavior has been studied in this work, selecting different kinds of volatile organic compounds (VOCs) as adsorbates (alkanes, alkenes, cycloalkanes, aromatics and chlorinated). For this purpose, three samples (IRMOF-1, IRMOF-8 and IRMOF-10) with cubic structure and without functionalities on the organic linkers were synthesized. Adsorption capacities at infinite dilution were derived from the adsorption isotherms, whereas thermodynamic properties have been determined from chromatographic retention volume. The capacity and the strength of adsorption were strongly influenced by the adsorbate size. This effect is especially relevant for n-alkanes adsorption, indicating the key role of the cavity size on this phenomenon, and hence the importance of the IRMOF structural properties. A different behavior has been observed for the polar compounds, where an enhancement on the specificity of the adsorption with the π-electron rich regions was observed. This fact suggests the specific interaction of these molecules with the organic linkers of the IRMOFs.

  10. Investigation of metal hydride nanoparticles templated in metal organic frameworks.

    SciTech Connect

    Jacobs, Benjamin W.; Herberg, Julie L.; Highley, Aaron M.; Grossman, Jeffrey; Wagner, Lucas; Bhakta, Raghu; Peaslee, D.; Allendorf, Mark D.; Liu, X.; Behrens, Richard, Jr.; Majzoub, Eric H.

    2010-11-01

    Hydrogen is proposed as an ideal carrier for storage, transport, and conversion of energy. However, its storage is a key problem in the development of hydrogen economy. Metal hydrides hold promise in effectively storing hydrogen. For this reason, metal hydrides have been the focus of intensive research. The chemical bonds in light metal hydrides are predominantly covalent, polar covalent or ionic. These bonds are often strong, resulting in high thermodynamic stability and low equilibrium hydrogen pressures. In addition, the directionality of the covalent/ionic bonds in these systems leads to large activation barriers for atomic motion, resulting in slow hydrogen sorption kinetics and limited reversibility. One method for enhancing reaction kinetics is to reduce the size of the metal hydrides to nano scale. This method exploits the short diffusion distances and constrained environment that exist in nanoscale hydride materials. In order to reduce the particle size of metal hydrides, mechanical ball milling is widely used. However, microscopic mechanisms responsible for the changes in kinetics resulting from ball milling are still being investigated. The objective of this work is to use metal organic frameworks (MOFs) as templates for the synthesis of nano-scale NaAlH4 particles, to measure the H2 desorption kinetics and thermodynamics, and to determine quantitative differences from corresponding bulk properties. Metal-organic frameworks (MOFs) offer an attractive alternative to traditional scaffolds because their ordered crystalline lattice provides a highly controlled and understandable environment. The present work demonstrates that MOFs are stable hosts for metal hydrides and their reactive precursors and that they can be used as templates to form metal hydride nanoclusters on the scale of their pores (1-2 nm). We find that using the MOF HKUST-1 as template, NaAlH4 nanoclusters as small as 8 formula units can be synthesized inside the pores. A detailed picture of

  11. Gas adsorption on metal-organic frameworks

    DOEpatents

    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. Chemical Dynamics at Surfaces of Metal Nanomaterials

    DTIC Science & Technology

    2014-07-23

    AFRL-OSR-VA-TR-2014-0168 Chemical Dynamics at Surfaces of Metal Nanomaterials Junrong Zheng WILLIAM MARSH RICE UNIV HOUSTON TX Final Report 07/23...Junrong Zheng Department of Chemistry, Rice University 1. Proposed summary The project was designed to develop novel spectroscopic tools for

  13. Color Coding Organic Chemicals for Inventory Control.

    ERIC Educational Resources Information Center

    Wystrach, V. P.; George, Babu

    1985-01-01

    Describes a system in which organic chemicals are recoded for inventory control and reshelving purposes. The system works well in undergraduate organic chemistry or biology laboratories but can be expanded to handle a larger and more complicated inventory. (JN)

  14. Chemical segregation in metallic glass nanowires

    SciTech Connect

    Zhang, Qi; Li, Mo; Li, Qi-Kai

    2014-11-21

    Nanowires made of metallic glass have been actively pursued recently due to the superb and unique properties over those of the crystalline materials. The amorphous nanowires are synthesized either at high temperature or via mechanical disruption using focused ion beam. These processes have potential to cause significant changes in structure and chemical concentration, as well as formation of defect or imperfection, but little is known to date about the possibilities and mechanisms. Here, we report chemical segregation to surfaces and its mechanisms in metallic glass nanowires made of binary Cu and Zr elements from molecular dynamics simulation. Strong concentration deviation are found in the nanowires under the conditions similar to these in experiment via focused ion beam processing, hot imprinting, and casting by rapid cooling from liquid state. Our analysis indicates that non-uniform internal stress distribution is a major cause for the chemical segregation, especially at low temperatures. Extension is discussed for this observation to multicomponent metallic glass nanowires as well as the potential applications and side effects of the composition modulation. The finding also points to the possibility of the mechanical-chemical process that may occur in different settings such as fracture, cavitation, and foams where strong internal stress is present in small length scales.

  15. Multiaxis sensing using metal organic frameworks

    DOEpatents

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

    2017-01-17

    A sensor device including a sensor substrate; and a thin film comprising a porous metal organic framework (MOF) on the substrate that presents more than one transduction mechanism when exposed to an analyte. A method including exposing a porous metal organic framework (MOF) on a substrate to an analyte; and identifying more than one transduction mechanism in response to the exposure to the analyte.

  16. Stimulus-responsive metal-organic frameworks.

    PubMed

    Nagarkar, Sanjog S; Desai, Aamod V; Ghosh, Sujit K

    2014-09-01

    Materials that can recognize the changes in their local environment and respond by altering their inherent physical and/or chemical properties are strong candidates for future "smart" technology materials. Metal-organic frameworks (MOFs) have attracted a great deal of attention in recent years owing to their designable architecture, host-guest chemistry, and softness as porous materials. Despite this fact, studies on the tuning of the properties of MOFs by external stimuli are still rare. This review highlights the recent developments in the field of stimulus-responsive MOFs or so-called smart MOFs. In particular, the various stimuli used and the utility of stimulus-responsive smart MOFs for various applications such as gas storage and separation, sensing, clean energy, catalysis, molecular motors, and biomedical applications are highlighted by using representative examples. Future directions in the developments of stimulus-responsive smart MOFs and their applications are proposed from a personal perspective.

  17. Minerals with metal-organic framework structures.

    PubMed

    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. Valorization of GaN based metal-organic chemical vapor deposition dust a semiconductor power device industry waste through mechanochemical oxidation and leaching: A sustainable green process.

    PubMed

    Swain, Basudev; Mishra, Chinmayee; Lee, Chan Gi; Park, Kyung-Soo; Lee, Kun-Jae

    2015-07-01

    Dust generated during metal organic vapor deposition (MOCVD) process of GaN based semiconductor power device industry contains significant amounts of gallium and indium. These semiconductor power device industry wastes contain gallium as GaN and Ga0.97N0.9O0.09 is a concern for the environment which can add value through recycling. In the present study, this waste is recycled through mechanochemical oxidation and leaching. For quantitative recovery of gallium, two different mechanochemical oxidation leaching process flow sheets are proposed. In one process, first the Ga0.97N0.9O0.09 of the MOCVD dust is leached at the optimum condition. Subsequently, the leach residue is mechanochemically treated, followed by oxidative annealing and finally re-leached. In the second process, the MOCVD waste dust is mechanochemically treated, followed by oxidative annealing and finally leached. Both of these treatment processes are competitive with each other, appropriate for gallium leaching and treatment of the waste MOCVD dust. Without mechanochemical oxidation, 40.11 and 1.86 w/w% of gallium and Indium are leached using 4M HCl, 100°C and pulp density of 100 kg/m(3,) respectively. After mechanochemical oxidation, both these processes achieved 90 w/w% of gallium and 1.86 w/w% of indium leaching at their optimum condition.

  19. Chemical vapor deposition of group IIIB metals

    DOEpatents

    Erbil, Ahmet

    1989-01-01

    Coatings of Group IIIB metals and compounds thereof are formed by chemical vapor deposition, in which a heat decomposable organometallic compound of the formula (I) ##STR1## where M is a Group IIIB metal, such as lanthanum or yttrium and R is a lower alkyl or alkenyl radical containing from 2 to about 6 carbon atoms, with a heated substrate which is above the decomposition temperature of the organometallic compound. The pure metal is obtained when the compound of the formula I is the sole heat decomposable compound present and deposition is carried out under nonoxidizing conditions. Intermetallic compounds such as lanthanum telluride can be deposited from a lanthanum compound of formula I and a heat decomposable tellurium compound under nonoxidizing conditions.

  20. Chemical vapor deposition of group IIIB metals

    DOEpatents

    Erbil, A.

    1989-11-21

    Coatings of Group IIIB metals and compounds thereof are formed by chemical vapor deposition, in which a heat decomposable organometallic compound of the formula given in the patent where M is a Group IIIB metal, such as lanthanum or yttrium and R is a lower alkyl or alkenyl radical containing from 2 to about 6 carbon atoms, with a heated substrate which is above the decomposition temperature of the organometallic compound. The pure metal is obtained when the compound of the formula 1 is the sole heat decomposable compound present and deposition is carried out under nonoxidizing conditions. Intermetallic compounds such as lanthanum telluride can be deposited from a lanthanum compound of formula 1 and a heat decomposable tellurium compound under nonoxidizing conditions.

  1. Adsorption of organic chemicals in soils.

    PubMed Central

    Calvet, R

    1989-01-01

    This paper presents a review on adsorption of organic chemicals on soils sediments and their constituents. The first part of this review deals with adsorption from gas and liquid phases and gives a discussion on the physical meaning of the shape of adsorption isotherms. Results show that no general rules can be proposed to describe univocally the relation between the shape of isotherms and the nature of adsorbate-adsorbent system. Kinetics of adsorption is discussed through the description of various models. Theoretical developments exist both for the thermodynamics and the kinetics of adsorption, but there is a strong need for experimental results. Possible adsorption mechanisms are ion exchange, interaction with metallic cations, hydrogen bonds, charge transfers, and London-van der Waals dispersion forces/hydrophobic effect. However, direct proofs of a given mechanism are rare. Several factors influence adsorption behavior. Electronic structure of adsorbed molecules, properties of adsorbents, and characteristics of the liquid phase are discussed in relation to adsorption. Such properties as water solubility, organic carbon content of adsorbing materials, and the composition of the liquid phase are particularly important. Evaluation of adsorption can be obtained through either laboratory measurements or use of several correlations. Adsorption measurements must be interpreted, taking into account treatment of adsorbent materials, experimental conditions, and secondary phenomena such as degradations. Correlations between adsorption coefficients and water-octanol partition coefficient or water solubility are numerous. They may be useful tools for prediction purposes. Relations with transport, bioavailability, and degradation are described. PMID:2695323

  2. Metal-loaded organic scintillators for neutrino physics

    NASA Astrophysics Data System (ADS)

    Buck, Christian; Yeh, Minfang

    2016-09-01

    Organic liquid scintillators are used in many neutrino physics experiments of the past and present. In particular for low energy neutrinos when realtime and energy information are required, liquid scintillators have several advantages compared to other technologies. In many cases the organic liquid needs to be loaded with metal to enhance the neutrino signal over background events. Several metal loaded scintillators of the past suffered from chemical and optical instabilities, limiting the performance of these neutrino detectors. Different ways of metal loading are described in the article with a focus on recent techniques providing metal loaded scintillators that can be used under stable conditions for many years even in ton scale experiments. Applications of metal loaded scintillators in neutrino experiments are reviewed and the performance as well as the prospects of different scintillator types are compared.

  3. A metal-organic framework-derived bifunctional oxygen electrocatalyst

    NASA Astrophysics Data System (ADS)

    Xia, Bao Yu; Yan, Ya; Li, Nan; Wu, Hao Bin; Lou, Xiong Wen (David); Wang, Xin

    2016-01-01

    Oxygen electrocatalysis is of great importance for many energy storage and conversion technologies, including fuel cells, metal-air batteries and water electrolysis. Replacing noble metal-based electrocatalysts with highly efficient and inexpensive non-noble metal-based oxygen electrocatalysts is critical for the practical applications of these technologies. Here we report a general approach for the synthesis of hollow frameworks of nitrogen-doped carbon nanotubes derived from metal-organic frameworks, which exhibit higher electrocatalytic activity and stability for oxygen reduction and evolution than commercial Pt/C electrocatalysts. The remarkable electrochemical properties are mainly attributed to the synergistic effect from chemical compositions and the robust hollow structure composed of interconnected crystalline nitrogen-doped carbon nanotubes. The presented strategy for controlled design and synthesis of metal-organic framework-derived functional nanomaterials offers prospects in developing highly active electrocatalysts in electrochemical energy devices.

  4. Metal-loaded organic scintillators for neutrino physics

    DOE PAGES

    Buck, Christian; Yeh, Minfang

    2016-08-03

    Organic liquid scintillators are used in many neutrino physics experiments of the past and present. In particular for low energy neutrinos when realtime and energy information are required, liquid scintillators have several advantages compared to other technologies. In many cases the organic liquid needs to be loaded with metal to enhance the neutrino signal over background events. Several metal loaded scintillators of the past suffered from chemical and optical instabilities, limiting the performance of these neutrino detectors. Different ways of metal loading are described in the article with a focus on recent techniques providing metal loaded scintillators that can bemore » used under stable conditions for many years even in ton scale experiments. Lastly, we review applications of metal loaded scintillators in neutrino experiments and compare the performance as well as the prospects of different scintillator types.« less

  5. Metal-loaded organic scintillators for neutrino physics

    SciTech Connect

    Buck, Christian; Yeh, Minfang

    2016-08-03

    Organic liquid scintillators are used in many neutrino physics experiments of the past and present. In particular for low energy neutrinos when realtime and energy information are required, liquid scintillators have several advantages compared to other technologies. In many cases the organic liquid needs to be loaded with metal to enhance the neutrino signal over background events. Several metal loaded scintillators of the past suffered from chemical and optical instabilities, limiting the performance of these neutrino detectors. Different ways of metal loading are described in the article with a focus on recent techniques providing metal loaded scintillators that can be used under stable conditions for many years even in ton scale experiments. Lastly, we review applications of metal loaded scintillators in neutrino experiments and compare the performance as well as the prospects of different scintillator types.

  6. Benchmarking density functional theory predictions of framework structures and properties in a chemically diverse test set of metal-organic frameworks

    SciTech Connect

    Nazarian, Dalar; Ganesh, P.; Sholl, David S.

    2015-01-01

    We compiled a test set of chemically and topologically diverse Metal–Organic Frameworks (MOFs) with high accuracy experimentally derived crystallographic structure data. The test set was used to benchmark the performance of Density Functional Theory (DFT) functionals (M06L, PBE, PW91, PBE-D2, PBE-D3, and vdW-DF2) for predicting lattice parameters, unit cell volume, bonded parameters and pore descriptors. On average PBE-D2, PBE-D3, and vdW-DF2 predict more accurate structures, but all functionals predicted pore diameters within 0.5 Å of the experimental diameter for every MOF in the test set. The test set was also used to assess the variance in performance of DFT functionals for elastic properties and atomic partial charges. The DFT predicted elastic properties such as minimum shear modulus and Young's modulus can differ by an average of 3 and 9 GPa for rigid MOFs such as those in the test set. Moreover, we calculated the partial charges by vdW-DF2 deviate the most from other functionals while there is no significant difference between the partial charges calculated by M06L, PBE, PW91, PBE-D2 and PBE-D3 for the MOFs in the test set. We find that while there are differences in the magnitude of the properties predicted by the various functionals, these discrepancies are small compared to the accuracy necessary for most practical applications.

  7. COSOLVENCY AND SOPRTION OF HYDROPHOBIC ORGANIC CHEMICALS

    EPA Science Inventory

    Sorption of hydrophobic organic chemicals (HOCs) by two soils was measured from mixed solvents containing water plus completely miscible organic solvents (CMOSs) and partially miscible organic solvents (PMOSs). The utility of the log-linear cosolvency model for predicting HOC sor...

  8. Thermodynamics of Metal-Organic Frameworks

    NASA Astrophysics Data System (ADS)

    Hughes, James Thomas

    Metal-Organic Frameworks (MOF) are crystalline nanoporous lattices constructed from the combination of cation and multi-dentate organic molecules. MOFs can display both chemical and thermal robustness while having large surface areas and pore volumes. In addition the modular composition of MOFs allows a degree of design and control of MOF structures. These unique physical properties have attracted wide interest and position MOFs to make meaningful contributions towards many applications, such as adsorption, catalysis, separation, and sensing. Despite the extensive investigative work over the last decade on MOF materials, the initial synthesis is still done by trial and error. Of the identified structures some MOFs are robust while others are fragile. It is unclear what role thermodynamics plays in the formation energies of MOFs and guest molecules interactions within the pores. Better understanding of thermochemical properties of MOFs is critical if MOF synthesis is to obtain true predictive design. To address these questions aqueous solution calorimetry was performed on ten different frameworks in both the as-synthesized and activated state. To understand the structural energetics of MOFs, the heat of formation from dense states (metal oxide and protonated organic linkers) to the open MOF framework was measured. Chapter 2 discusses the new aqueous calorimetry methodology developed to measure the enthalpy of solution for hybrid materials. Chapters 3, 4 and 5 detail the enthalpies of formation from their dense states of the frameworks: (MOF-5, ZIF-zni, ZIF-1, ZIF-3, ZIF-4, ZIF-7, ZIF-8, ZIF-9 and Cu-HKUST-1). These chapters also compare the MOF heat of formation energetics to those of zeolites, zeotypes and mesoporous silica materials. Finding that MOFs are metastable with respect to their dense states (metal oxide and protonated organic), following the current destabilization trend of the main group porous materials. The thermochemical effect of solvent on the MOF

  9. Benchmarking density functional theory predictions of framework structures and properties in a chemically diverse test set of metal-organic frameworks

    DOE PAGES

    Nazarian, Dalar; Ganesh, P.; Sholl, David S.

    2015-01-01

    We compiled a test set of chemically and topologically diverse Metal–Organic Frameworks (MOFs) with high accuracy experimentally derived crystallographic structure data. The test set was used to benchmark the performance of Density Functional Theory (DFT) functionals (M06L, PBE, PW91, PBE-D2, PBE-D3, and vdW-DF2) for predicting lattice parameters, unit cell volume, bonded parameters and pore descriptors. On average PBE-D2, PBE-D3, and vdW-DF2 predict more accurate structures, but all functionals predicted pore diameters within 0.5 Å of the experimental diameter for every MOF in the test set. The test set was also used to assess the variance in performance of DFT functionalsmore » for elastic properties and atomic partial charges. The DFT predicted elastic properties such as minimum shear modulus and Young's modulus can differ by an average of 3 and 9 GPa for rigid MOFs such as those in the test set. Moreover, we calculated the partial charges by vdW-DF2 deviate the most from other functionals while there is no significant difference between the partial charges calculated by M06L, PBE, PW91, PBE-D2 and PBE-D3 for the MOFs in the test set. We find that while there are differences in the magnitude of the properties predicted by the various functionals, these discrepancies are small compared to the accuracy necessary for most practical applications.« less

  10. Magnetism in metal-organic capsules

    SciTech Connect

    Atwood, Jerry L.; Brechin, Euan K; Dalgarno, Scott J.; Inglis, Ross; Jones, Leigh F.; Mossine, Andrew; Paterson, Martin J.; Power, Nicholas P.; Teat, Simon J.

    2010-01-07

    Nickel and cobalt seamed metal-organic capsules have been isolated and studied using structural, magnetic and computational approaches. Antiferromagnetic exchange in the Ni capsule results from coordination environments enforced by the capsule framework.

  11. Valorization of GaN based metal-organic chemical vapor deposition dust a semiconductor power device industry waste through mechanochemical oxidation and leaching: A sustainable green process

    SciTech Connect

    Swain, Basudev; Mishra, Chinmayee; Lee, Chan Gi; Park, Kyung-Soo; Lee, Kun-Jae

    2015-07-15

    Dust generated during metal organic vapor deposition (MOCVD) process of GaN based semiconductor power device industry contains significant amounts of gallium and indium. These semiconductor power device industry wastes contain gallium as GaN and Ga{sub 0.97}N{sub 0.9}O{sub 0.09} is a concern for the environment which can add value through recycling. In the present study, this waste is recycled through mechanochemical oxidation and leaching. For quantitative recovery of gallium, two different mechanochemical oxidation leaching process flow sheets are proposed. In one process, first the Ga{sub 0.97}N{sub 0.9}O{sub 0.09} of the MOCVD dust is leached at the optimum condition. Subsequently, the leach residue is mechanochemically treated, followed by oxidative annealing and finally re-leached. In the second process, the MOCVD waste dust is mechanochemically treated, followed by oxidative annealing and finally leached. Both of these treatment processes are competitive with each other, appropriate for gallium leaching and treatment of the waste MOCVD dust. Without mechanochemical oxidation, 40.11 and 1.86 w/w% of gallium and Indium are leached using 4 M HCl, 100 °C and pulp density of 100 kg/m{sup 3,} respectively. After mechanochemical oxidation, both these processes achieved 90 w/w% of gallium and 1.86 w/w% of indium leaching at their optimum condition. - Highlights: • Waste MOCVD dust is treated through mechanochemical leaching. • GaN is hardly leached, and converted to NaGaO{sub 2} through ball milling and annealing. • Process for gallium recovery from waste MOCVD dust has been developed. • Thermal analysis and phase properties of GaN to Ga{sub 2}O{sub 3} and GaN to NaGaO{sub 2} is revealed. • Solid-state chemistry involved in this process is reported.

  12. Nanostructured Metal Oxides for Stoichiometric Degradation of Chemical Warfare Agents.

    PubMed

    Štengl, Václav; Henych, Jiří; Janoš, Pavel; Skoumal, Miroslav

    2016-01-01

    Metal oxides have very important applications in many areas of chemistry, physics and materials science; their properties are dependent on the method of preparation, the morphology and texture. Nanostructured metal oxides can exhibit unique characteristics unlike those of the bulk form depending on their morphology, with a high density of edges, corners and defect surfaces. In recent years, methods have been developed for the preparation of metal oxide powders with tunable control of the primary particle size as well as of a secondary particle size: the size of agglomerates of crystallites. One of the many ways to take advantage of unique properties of nanostructured oxide materials is stoichiometric degradation of chemical warfare agents (CWAs) and volatile organic compounds (VOC) pollutants on their surfaces.

  13. Decontamination of metals using chemical etching

    DOEpatents

    Lerch, Ronald E.; Partridge, Jerry A.

    1980-01-01

    The invention relates to chemical etching process for reclaiming contaminated equipment wherein a reduction-oxidation system is included in a solution of nitric acid to contact the metal to be decontaminated and effect reduction of the reduction-oxidation system, and includes disposing a pair of electrodes in the reduced solution to permit passage of an electrical current between said electrodes and effect oxidation of the reduction-oxidation system to thereby regenerate the solution and provide decontaminated equipment that is essentially radioactive contamination-free.

  14. Asymmetric organic/metal(oxide) hybrid nanoparticles: synthesis and applications

    NASA Astrophysics Data System (ADS)

    He, Jie; Liu, Yijing; Hood, Taylor C.; Zhang, Peng; Gong, Jinlong; Nie, Zhihong

    2013-05-01

    Asymmetric particles (APs) with broken centrosymmetry are of great interest, due to the asymmetric surface properties and diverse functionalities. In particular, organic/metal(oxide) APs naturally combine the significantly different and complementary properties of organic and inorganic species, leading to their unique applications in various fields. In this review article, we highlighted recent advances in the synthesis and applications of organic/metal(oxide) APs. This type of APs is grounded on chemical or physical interactions between metal(oxide) NPs and organic small molecular or polymeric ligands. The synthetic methodologies were summarized in three categories, including the selective surface modifications, phase separation of mixed ligands on the surface of metal(oxide) NPs, and direct synthesis of APs. We further discussed the unique applications of organic/metal(oxide) APs in self-assembly, sensors, catalysis, and biomedicine, as a result of the distinctions between asymmetrically distributed organic and inorganic components. Finally, challenges and future directions are discussed in an outlook section.

  15. Asymmetric organic/metal(oxide) hybrid nanoparticles: synthesis and applications.

    PubMed

    He, Jie; Liu, Yijing; Hood, Taylor C; Zhang, Peng; Gong, Jinlong; Nie, Zhihong

    2013-06-21

    Asymmetric particles (APs) with broken centrosymmetry are of great interest, due to the asymmetric surface properties and diverse functionalities. In particular, organic/metal(oxide) APs naturally combine the significantly different and complementary properties of organic and inorganic species, leading to their unique applications in various fields. In this review article, we highlighted recent advances in the synthesis and applications of organic/metal(oxide) APs. This type of APs is grounded on chemical or physical interactions between metal(oxide) NPs and organic small molecular or polymeric ligands. The synthetic methodologies were summarized in three categories, including the selective surface modifications, phase separation of mixed ligands on the surface of metal(oxide) NPs, and direct synthesis of APs. We further discussed the unique applications of organic/metal(oxide) APs in self-assembly, sensors, catalysis, and biomedicine, as a result of the distinctions between asymmetrically distributed organic and inorganic components. Finally, challenges and future directions are discussed in an outlook section.

  16. A Novel Permeable Reactive Barrier (PRB) for Simultaneous and Rapid Removal of Heavy Metal and Organic Matter - A Systematic Chemical Speciation Approach on Sustainable Technique for Pallikarani Marshland Remediation

    NASA Astrophysics Data System (ADS)

    Selvaraj, A.; Nambi, I. M.

    2014-12-01

    In this study, an innovative technique of ZVI mediated 'coupling of Fenton like oxidation of phenol and Cr(VI) reduction technique' was attempted. The hypothesis is that Fe3+ generated from Cr(VI) reduction process acts as electron acceptor and catalyst for Fenton's Phenol oxidation process. The Fe2+ formed from Fenton reactions can be reused for Cr(VI) reduction. Thus iron can be made to recycle between two reactions, changing back and forth between Fe2+ and Fe3+ forms, makes treatment sustainable.(Fig 1) This approach advances current Fenton like oxidation process by (i)single system removal of heavy metal and organic matter (ii)recycling of iron species; hence no additional iron required (iii)more contaminant removal to ZVI ratio (iv)eliminating sludge related issues. Preliminary batch studies were conducted at different modes i) concurrent removal ii) sequential removal. The sequential removal was found better for in-situ PRB applications. PRB was designed based on kinetic rate slope and half-life time, obtained from primary column study. This PRB has two segments (i)ZVI segment[Cr(VI)] (ii)iron species segment[phenol]. This makes treatment sustainable by (i) having no iron ions in outlet stream (ii)meeting hypothesis and elongates the life span of PRB. Sequential removal of contaminates were tested in pilot scale PRB(Fig 2) and its life span was calculated based on the exhaustion of filling material. Aqueous, sand and iron aliquots were collected at various segments of PRB and analyzed for precipitation and chemical speciation thoroughly (UV spectrometer, XRD, FTIR, electron microscope). Chemical speciation profile eliminates the uncertainties over in-situ PRB's long term performance. Based on the pilot scale PRB study, 'field level PRB wall construction' was suggested to remove heavy metal and organic compounds from Pallikaranai marshland(Fig 3)., which is contaminated with leachate coming from nearby Perungudi dumpsite. This research provides (i

  17. Metal-Organic Frameworks as Platforms for Functional Materials.

    PubMed

    Cui, Yuanjing; Li, Bin; He, Huajun; Zhou, Wei; Chen, Banglin; Qian, Guodong

    2016-03-15

    Discoveries of novel functional materials have played very important roles to the development of science and technologies and thus to benefit our daily life. Among the diverse materials, metal-organic framework (MOF) materials are rapidly emerging as a unique type of porous and organic/inorganic hybrid materials which can be simply self-assembled from their corresponding inorganic metal ions/clusters with organic linkers, and can be straightforwardly characterized by various analytical methods. In terms of porosity, they are superior to other well-known porous materials such as zeolites and carbon materials; exhibiting extremely high porosity with surface area up to 7000 m(2)/g, tunable pore sizes, and metrics through the interplay of both organic and inorganic components with the pore sizes ranging from 3 to 100 Å, and lowest framework density down to 0.13 g/cm(3). Such unique features have enabled metal-organic frameworks to exhibit great potentials for a broad range of applications in gas storage, gas separations, enantioselective separations, heterogeneous catalysis, chemical sensing and drug delivery. On the other hand, metal-organic frameworks can be also considered as organic/inorganic self-assembled hybrid materials, we can take advantages of the physical and chemical properties of both organic and inorganic components to develop their functional optical, photonic, and magnetic materials. Furthermore, the pores within MOFs can also be utilized to encapsulate a large number of different species of diverse functions, so a variety of functional MOF/composite materials can be readily synthesized. In this Account, we describe our recent research progress on pore and function engineering to develop functional MOF materials. We have been able to tune and optimize pore spaces, immobilize specific functional groups, and introduce chiral pore environments to target MOF materials for methane storage, light hydrocarbon separations, enantioselective recognitions

  18. Minerals with metal-organic framework structures

    PubMed Central

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

    2016-01-01

    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. PMID:27532051

  19. EFFECT OF NON-TARGET ORGANICS ON ORGANIC CHEMICAL TRANSPORT

    EPA Science Inventory

    To improve our standard of living, man has synthesized organic compounds for use in products considered essential for life. These compounds are having and will continue to have a significant impact on the terrestrial environment. Understanding organic chemical transport through s...

  20. Low defect InGaAs quantum well selectively grown by metal organic chemical vapor deposition on Si(100) 300 mm wafers for next generation non planar devices

    SciTech Connect

    Cipro, R.; Gorbenko, V.; Baron, T. Martin, M.; Moeyaert, J.; David, S.; Bassani, F.; Bogumilowicz, Y.; Barnes, J. P.; Rochat, N.; Loup, V.; Vizioz, C.; Allouti, N.; Chauvin, N.; Bao, X. Y.; Ye, Z.; Pin, J. B.; Sanchez, E.

    2014-06-30

    Metal organic chemical vapor deposition of GaAs, InGaAs, and AlGaAs on nominal 300 mm Si(100) at temperatures below 550 °C was studied using the selective aspect ratio trapping method. We clearly show that growing directly GaAs on a flat Si surface in a SiO{sub 2} cavity with an aspect ratio as low as 1.3 is efficient to completely annihilate the anti-phase boundary domains. InGaAs quantum wells were grown on a GaAs buffer and exhibit room temperature micro-photoluminescence. Cathodoluminescence reveals the presence of dark spots which could be associated with the presence of emerging dislocation in a direction parallel to the cavity. The InGaAs layers obtained with no antiphase boundaries are perfect candidates for being integrated as channels in n-type metal oxide semiconductor field effect transistor (MOSFET), while the low temperatures used allow the co-integration of p-type MOSFET.

  1. POLAR ORGANIC CHEMICAL INTEGRATIVE SAMPLING ...

    EPA Pesticide Factsheets

    The purpose of the research presented in this paper is two-fold: (1) to demonstrate the 4 coupling of two state-of-the-art techniques: a time-weighted polar organic integrative sampler (POCIS) and micro-liquid chromatography-electrospray/ion trap mass spectrometry (u-LC-6 ES/ITMS); and (2) the assessment of these methodologies in a real-world environment -wastewater effluent - for detecting six drugs (four prescription and two illicit). In the effluent from three wastewater treatment plants (WWTP), azithromycin was detected at concentrations ranging from 15ng/L to 66ng/L, equivalent to the total annual release of 0.4 -4 kg into the receiving waters. Detected and confirmed in the effluent from two WWTPs were two illicit drugs methamphetamine and methylenedioxymethamphetamine (MDMA), at 2ng/L and 0.5ng/L, respectively. While the ecotoxicological significance of drugs in environmental matrices, particularly water, has not been closely examined, it can only be surmised that these substances have the potential to adversely affect biota that are continuously exposed to them even at very low levels. The potential for chronic affects on human health is also unknown, but of increasing concern due to the multi use character of water, particularly in densely populated arid areas. The research focused on in the subtasks is the development and application of state-of the-art technologies to meet the needs of the public, Office of Water, and ORD in the area of Water Quality

  2. Metal-Organic Chemical Vapor Deposition (MOCVD) Synthesis of Heteroepitaxial Pr0.7Ca0.3MnO3 Films: Effects of Processing Conditions on Structural/Morphological and Functional Properties

    PubMed Central

    Catalano, Maria R; Cucinotta, Giuseppe; Schilirò, Emanuela; Mannini, Matteo; Caneschi, Andrea; Lo Nigro, Raffaella; Smecca, Emanuele; Condorelli, Guglielmo G; Malandrino, Graziella

    2015-01-01

    Calcium-doped praseodymium manganite films (Pr0.7Ca0.3MnO3, PCMO) were prepared by metal-organic chemical vapor deposition (MOCVD) on SrTiO3 (001) and SrTiO3 (110) single-crystal substrates. Structural characterization through X-ray diffraction (XRD) measurements and transmission electron microscopy (TEM) analyses confirmed the formation of epitaxial PCMO phase films. Energy dispersive X-ray (EDX) and X-ray photoelectron spectroscopy (XPS) characterization was used to confirm lateral and vertical composition and the purity of the deposited films. Magnetic measurements, obtained in zero-field-cooling (ZFC) and field-cooling (FC) modes, provided evidence of the presence of a ferromagnetic (FM) transition temperature, which was correlated to the transport properties of the film. The functional properties of the deposited films, combined with the structural and chemical characterization collected data, indicate that the MOCVD approach represents a suitable route for the growth of pure, good quality PCMO for the fabrication of novel spintronic devices. PMID:26478849

  3. Influences of group-III source preflow on the polarity, optical, and structural properties of GaN grown on nitridated sapphire substrates by metal-organic chemical vapor deposition

    SciTech Connect

    Li, Chengguo; Liu, Hongfei; Chua, Soo Jin

    2015-03-28

    We report the influences of group-III source preflow, which were introduced prior to the growth of the low temperature GaN on the polarity, photoluminescence (PL), and crystallographic properties of GaN epilayers grown on nitridated c-plane sapphire substrates by metal-organic chemical vapor deposition. By studying the surface morphology evolutions under chemical etching in KOH, we found that with increasing the trimethyl-gallium (TMGa) preflow duration (t), the polarity of the GaN film can be changed from a complete N-polarity to a mixture of N- and Ga-polarity and further to a complete Ga-polarity. PL and high-resolution X-ray diffraction studies revealed that the impurity incorporation and the edge- and screw-type threading dislocations are strongly polarity dependent. A further study at the optimized t (i.e., 30 s for TMGa) shows that the polarity inversion of GaN can be realized not only by TMGa preflow but also by trimethyl-aluminium preflow and by trimethyl-indium preflow. A two-monolayer model was employed to explain the polarity inversion mechanism.

  4. Transparent Conducting ZnO:B Thin Films Grown by Ultraviolet Light Assisted Metal Organic Chemical Vapor Deposition Using Triethylboron for Cu(In,Ga)Se2 Solar Cells

    NASA Astrophysics Data System (ADS)

    Kobayashi, Taizo; Yamauchi, Kotaro; Mise, Takahiro; Nakada, Tokio

    2012-10-01

    High-efficiency cadmium-free Cu(In,Ga)Se2 (CIGS) thin-film solar cells have been fabricated using a zinc compound buffer layer deposited by the chemical bath deposition (CBD) process. However, the zinc compound buffer layers such as ZnS(O,OH) are prone to plasma-induced damage during the subsequent ZnO sputtering process. A process causing less damage such as metal-organic chemical vapor deposition (MOCVD) is thus required for ZnO-based transparent conducting oxide (TCO) layers. In the present work, the boron-doped zinc oxide (ZnO:B) films were grown by MOCVD using diethyl zinc (DEZ), H2O, and low-toxicity triethylboron (TEB). An UV-assisted MOCVD process was developed in order to reduce the resistivity of ZnO:B films. As a result, the resisitivity significantly decreased together with the increased electron mobility and carrier concentration. The comparison of performance was also carried out for the ZnS(O,OH)/CIGS solar cells with MOCVD-deposited ZnO:B and sputter-deposited ZnO:Al window layers.

  5. Chemical Sensors Based on Metal Oxide Nanostructures

    NASA Technical Reports Server (NTRS)

    Hunter, Gary W.; Xu, Jennifer C.; Evans, Laura J.; VanderWal, Randy L.; Berger, Gordon M.; Kulis, Mike J.; Liu, Chung-Chiun

    2006-01-01

    This paper is an overview of sensor development based on metal oxide nanostructures. While nanostructures such as nanorods show significan t potential as enabling materials for chemical sensors, a number of s ignificant technical challenges remain. The major issues addressed in this work revolve around the ability to make workable sensors. This paper discusses efforts to address three technical barriers related t o the application of nanostructures into sensor systems: 1) Improving contact of the nanostructured materials with electrodes in a microse nsor structure; 2) Controling nanostructure crystallinity to allow co ntrol of the detection mechanism; and 3) Widening the range of gases that can be detected by using different nanostructured materials. It is concluded that while this work demonstrates useful tools for furt her development, these are just the beginning steps towards realizati on of repeatable, controlled sensor systems using oxide based nanostr uctures.

  6. Self-exfoliated metal organic nanosheets via hydrolytic unfolding of metal organic polyhedra.

    PubMed

    Banerjee, Rahul; Garai, Bikash; Mallick, Arjit; Das, Anuja; Mukherjee, Rabibrata

    2017-04-04

    Few layer thick metal-organic nanosheets have been synthesized using water-assisted solid state transformation through a combined top-down and bottom-up approach. The metal-organic polyhedra (MOPs) convert into metal-organic frameworks (MOFs) which subsequently self-exfoliate into few layered metal-organic nanosheets. These MOP crystals experience a hydrophobicity gradient with the inner surface during contact with water because of the existence of hydrophobic spikes on their outer surface. When the amount of water available for interaction is higher, the resultant layers are not stacked to form bulk materials; instead few layered nanosheets with high uniformity were obtained in high yield. The phenomenon has resulted high yield production of uniformly distributed layered metal-organic nanosheets from three different MOPs, showing its general adaptability.

  7. Effect of metal spiking on different chemical pools and chemically extractable fractions of heavy metals in sewage sludge.

    PubMed

    Kandpal, Geeta; Ram, Bali; Srivastava, P C; Singh, S K

    2004-01-30

    A laboratory experiment was conducted to study the effect of metal spiking and incubation on some properties and sequentially extractable chemical pools of some heavy metals (F1, two extractions with 0.1 M Sr(NO3)2; F2, one extraction with 1 M NaOAc (pH 5.0); F3, three extractions with 5% NaOCl (pH 8.5) at 90-95 degrees C; F4, three extractions with 0.2 M oxalic acid + 0.2 M ammonium oxalate + 0.1 M ascorbic acid (pH 3.0); and F5, dissolution of sample residue in HF-HClO4 (residual fraction,) and also 1 M CaCl2 and 0.005 M DTPA extractable heavy metals in sewage sludge. Metal spiking and incubation decreased pH and easily oxidizable organic C content of sludge but increased electrical conductivity. Metal spiking and incubation increased F1 fraction of all heavy metals, F2 fraction of Ni, Pb, Cu, and Cd, F3 fraction of Pb, Cu, and Cd, F4 or reducible fraction of Ni, Cu, and Cd and residual fraction of Zn and Pb, but decreased F2 fraction of Zn, F3 of Zn and Ni, F4 fraction of Zn and F5 fraction of Ni, Cu, and Cd. Metal spiking and incubation increased 1 M CaCl2 and 0.005 M DTPA extractable amounts of all heavy metals in sludge except for 0.005 M DTPA extractable Zn, which registered only very marginal decrease.

  8. Effects of Pelletization Pressure on the Physical and Chemical Properties of the Metal-Organic Frameworks Cu3(BTC)2 and UiO-66

    DTIC Science & Technology

    2013-02-26

    testing was conducted with CuBTC against ammonia , which probes the reactive sites, and UiO-66 against octane, which probes physical adsorption capacity...Even with the decrease in surface area, the CuBTC materials had consistent ammonia removal capacities, while the UiO-66 pressed materials showed a...21010, USA cGeorgia Institute of Technology, School of Chemical & Biomolecular Engineering, Atlanta, GA 30332, USA a r t i c l e i n f o Article history

  9. Methane storage in metal-organic frameworks.

    PubMed

    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.

  10. Preparation of AlGaN/GaN Heterostructures on Sapphire Using Light Radiation Heating Metal-Organic Chemical Vapor Deposition at Low Pressure

    NASA Astrophysics Data System (ADS)

    Zhou, Yu-Gang; Shen, Bo; Zhang, Rong; Li, Wei-Ping; Chen, Peng; Chen, Zhi-Zhong; Gu, Shu-Lin; Shi, Yi; Z, Huang C.; Zheng, You-Dou

    2000-08-01

    AlGaN/GaN heterostructures on sapphire substrate were fabricated by using light radiation heating metalorganic chemical vapor deposition. Photoluminescence excitation spectra show that there are two abrupt slopes corresponding to the absorption edges of AlGaN and GaN, respectively. X-ray diffraction spectra clearly exhibit the GaN (0002), (0004), and AlGaN (0002), (0004) diffraction peaks, and no diffraction peak other than those from the GaN {0001} and AlGaN {0001} planes is found. Reciprocal space mapping indicates that there is no tilt between the AlGaN layer and the GaN layer. All results also indicate that the sample is of sound quality and the Al composition in the AlGaN layer is of high uniformity.

  11. Phase-change InSbTe nanowires grown in situ at low temperature by metal-organic chemical vapor deposition.

    PubMed

    Ahn, Jun-Ku; Park, Kyoung-Woo; Jung, Hyun-June; Yoon, Soon-Gil

    2010-02-10

    Phase-change InSbTe (IST) single crystalline nanowires were successfully synthesized at a low temperature of 250 degrees C by metalorganic chemical vapor deposition (MOCVD). The growth of IST nanowires by MOCVD, at very high working pressure, was governed by supersaturation. The growth mechanism of the IST nanowires by MOCVD is addressed in this paper. Under high working pressure, the InTe phase was preferentially formed on the TiAlN electrode, and the InTe protrusions were nucleated on the InTe films under high supersaturation. The Sb was continuously incorporated into the InTe protrusions, which was grown as an IST nanowire. Phase-change-induced memory switching was realized in IST nanowires with a threshold voltage of about 1.6 V. The ability to grow IST nanowires at low temperature by MOCVD should open opportunities for investigation of the nanoscale phase-transition phenomena.

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

    PubMed

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

    2017-02-08

    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

  13. Organically modified silicas on metal nanowires.

    PubMed

    Dean, Stacey L; Stapleton, Joshua J; Keating, Christine D

    2010-09-21

    Organically modified silica coatings were prepared on metal nanowires using a variety of silicon alkoxides with different functional groups (i.e., carboxyl groups, polyethylene oxide, cyano, dihydroimidazole, and hexyl linkers). Organically modified silicas were deposited onto the surface of 6-μm-long, ∼300-nm-wide, cylindrical metal nanowires in suspension by the hydrolysis and polycondensation of silicon alkoxides. Syntheses were performed at several ratios of tetraethoxysilane to an organically modified silicon alkoxide to incorporate desired functional groups into thin organosilica shells on the nanowires. These coatings were characterized using transmission electron microscopy, X-ray photoelectron spectroscopy, and infrared spectroscopy. All of the organically modified silicas prepared here were sufficiently porous to allow the removal of the metal nanowire cores by acid etching to form organically modified silica nanotubes. Additional functionality provided to the modified silicas as compared to unmodified silica prepared using only tetraethoxysilane precursors was demonstrated by chromate adsorption on imidazole-containing silicas and resistance to protein adsorption on polyethyleneoxide-containing silicas. Organically modified silica coatings on nanowires and other nano- and microparticles have potential application in fields such as biosensing or nanoscale therapeutics due to the enhanced properties of the silica coatings, for example, the prevention of biofouling.

  14. Superhydrophobic perfluorinated metal-organic frameworks.

    PubMed

    Chen, Teng-Hao; Popov, Ilya; Zenasni, Oussama; Daugulis, Olafs; Miljanić, Ognjen Š

    2013-08-07

    Three perfluorinated Cu-based metal-organic frameworks (MOFs) were prepared starting from extensively fluorinated biphenyl-based ligands accessed via C-H functionalization. These new materials are highly hydrophobic: with water contact angles of up to 151 ± 1°, they are among the most water-repellent MOFs ever reported.

  15. Mechanism of metal cationization in organic SIMS

    NASA Astrophysics Data System (ADS)

    Wojciechowski, I.; Delcorte, A.; Gonze, X.; Bertrand, P.

    2001-09-01

    A mechanism for metal cationization of phenyl group containing hydrocarbons is discussed. Intact molecules and their fragments are emitted from a thin organic layer covering a metal surface bombarded by fast ions. It is shown that the process of associative ionization of a neutral hydrocarbon molecule and a neutral excited metal atom, occurring above the surface, may contribute to the yield of cationized molecules. To demonstrate this we have calculated the potential energy curves for the model system C 6H 6+Me (Me=Ag, Cu, Au) making use of the density functional theory. The initial states of the metal atoms approaching the benzene ring along the C 6 symmetry axis were set as the ground, ionic, and excited in ( n-1)d 9ns 2 electronic configuration.

  16. Effect of fly ash, organic wastes and chemical fertilizers on yield, nutrient uptake, heavy metal content and residual fertility in a rice-mustard cropping sequence under acid lateritic soils.

    PubMed

    Rautaray, S K; Ghosh, B C; Mittra, B N

    2003-12-01

    A field experiment was conducted for two years in sandy loam acid lateritic soil to study the direct effect of fly ash, organic wastes and chemical fertilizers on rice (Oryza sativa) and their residual effect on mustard (Brassica napus var glauca) grown in sequence. Rice yields were higher when fly ash, organic wastes and chemical fertilizers were used in an integrated manner as compared to sole application of chemical fertilizers. Yields of mustard were also higher under the residual effect of the former rather than the latter. However, this beneficial residual effect under integrated nutrient sources was inadequate for the mustard crop in the low fertility test soil. Hence, direct application of fertilizers was needed, in addition to residual fertility. The effect of fly ash on mean rice equivalent yield of the rice-mustard cropping sequence was highest (up to 14%) when it was used in combination with organic wastes and chemical fertilizers. While the yield increase was 10% when it was used in combination with only chemical fertilizers. The minimum yield advantage, 3%, occurred when fly ash was applied alone. The equivalent yield of the rice-mustard cropping sequence was equally influenced by either of the organic wastes. Cadmium and Ni content in rice grain and straw were less under the direct effect of fly ash. The residual effect on mustard was similar for Ni content in seed and stover; however, Cd content was increased. Beneficial residual soil chemical properties in terms of pH, organic carbon and available N, P and K were noted for integrated nutrient treatments involved fly ash, organic wastes and chemical fertilizers as compared to continuous use of only chemical fertilizers. Application of fly ash alone was effective in raising soil available P. Thus, integrated use of fly ash, organic wastes and chemical fertilizers was beneficial in improving crop yield, soil pH, organic carbon and available N, P and K in sandy loam acid lateritic soil.

  17. ESTIMATING DISSOLVED ORGANIC CARBON PARTITION COEFFICIENTS FOR NONIONIC ORGANIC CHEMICALS

    EPA Science Inventory

    A literature search was performed for dissolved organic carbon/water partition coefficients for nonionic chemicals (Kdoc) and Kdoc data was taken from more than sixty references. The Kdoc data were evaluated as a function of the n-octanol/water partition coefficients (Kow). A pre...

  18. TSCA Chemical Data Reporting Fact Sheet: Reporting Manufactured Chemical Substances from Metal Mining and Related Activities

    EPA Pesticide Factsheets

    This fact sheet provides guidance on the Chemical Data Reporting (CDR) rule requirements related to the reporting of mined metals, intermediates, and byproducts manufactured during metal mining and related activities.

  19. Self-organized nanoporous materials for chemical separations and chemical sensing

    NASA Astrophysics Data System (ADS)

    Pandey, Bipin

    Self-organized nanoporous materials have drawn a lot of attention because the uniform, highly dense, and ordered cylindrical nanopores in these materials provide a unique platform for chemical separations and chemical sensing applications. Here, we explore self-organized nanopores of PS-b-PMMA diblock copolymer thin films and anodic gallium oxide for chemical separations and sensing applications. In the first study, cyclic voltammograms of cytochrome c on recessed nanodisk-array electrodes (RNEs) based on nanoporous films (11, 14 or 24 nm in average pore diameter; 30 nm thick) derived from polystyrene-poly(methylmethacrylate) diblock copolymers were measured. The faradic current of cytochrome c was observed on RNEs, indicating the penetration of cytochrome c (hydrodynamic diameter ≈ 4 nm) through the nanopores to the underlying electrodes. Compared to the 24-nm pores, the diffusion of cytochrome c molecules through the 11- and 14-nm pores suffered significantly larger hindrance. The results reported in this study will provide guidance in designing RNEs for size-based chemical sensing and also for controlled immobilization of biomolecules within nanoporous media for biosensors and bioreactors. In another study, conditions for the formation of self-organized nanopores of a metal oxide film were investigated. Self-organized nanopores aligned perpendicular to the film surface were obtained upon anodization of gallium films in ice-cooled 4 and 6 M aqueous H2SO4 at 10 V and 15 V. The average pore diameter was in the range of 18 ~ 40 nm, and the anodic gallium oxide was ca. 2 microm thick. In addition, anodic formation of self-organized nanopores was demonstrated for a solid gallium monolith incorporated at the end of a glass capillary. Nanoporous anodic oxide monoliths formed from a fusible metal will lead to future development of unique devices for chemical sensing and catalysis. In the final study, surface chemical property of self-organized nanoporous anodic gallium

  20. Metal hybrid nanoparticles for catalytic organic and photochemical transformations.

    PubMed

    Song, Hyunjoon

    2015-03-17

    In order to understand heterogeneous catalytic reactions, model catalysts such as a single crystalline surface have been widely studied for many decades. However, catalytic systems that actually advance the reactions are three-dimensional and commonly have multiple components including active metal nanoparticles and metal oxide supports. On the other hand, as nanochemistry has rapidly been developed and been applied to various fields, many researchers have begun to discuss the impact of nanochemistry on heterogeneous catalysis. Metal hybrid nanoparticles bearing multiple components are structurally very close to the actual catalysts, and their uniform and controllable morphology is suitable for investigating the relationship between the structure and the catalytic properties in detail. In this Account, we introduce four typical structures of metal hybrid nanoparticles that can be used to conduct catalytic organic and photochemical reactions. Metal@silica (or metal oxide) yolk-shell nanoparticles, in which metal cores exist in internal voids surrounded by thin silica (or metal oxide) shells, exhibited extremely high thermal and chemical stability due to the geometrical protection of the silica layers against the metal cores. The morphology of the metal cores and the pore density of the hollow shells were precisely adjusted to optimize the reaction activity and diffusion rates of the reactants. Metal@metal oxide core-shell nanoparticles and inverted structures, where the cores supported the shells serving an active surface, exhibited high activity with no diffusion barriers for the reactants and products. These nanostructures were used as effective catalysts for various organic and gas-phase reactions, including hydrogen transfer, Suzuki coupling, and steam methane reforming. In contrast to the yolk- and core-shell structures, an asymmetric arrangement of distinct domains generated acentric dumbbells and tipped rods. A large domain of each component added multiple

  1. Chemical Evolution of Presolar Organics in Astromaterials

    NASA Technical Reports Server (NTRS)

    Nakamura-Messenger, K.; Clemett, S. J.; Messenger, Scott; Keller, L. P.

    2010-01-01

    Sub-micron, hollow organic globules reported from several carbonaceous chondrites, interplanetary dust particles, and comet Wild-2 samples returned by NASA?s Stardust mission are enriched in N-15/N-14 and D/H compared with terrestrial materials and the parent materials [1-4]. These anomalies are ascribed to the preservation of presolar cold molecular cloud material from where H, C, and N isotopic constraints point to chemical fractionation near 10 K [5]. An origin well beyond the planet forming region and their survival in meteorites suggests submicrometer organic globules were once prevalent throughout the solar nebula. The survival of the membrane structures indicates primitive meteorites and cometary dust particles would have delivered these organic precursors to the early Earth as well as other planets and satellites. The physical, chemical, and isotopic properties of the organic globules varies to its meteorite types and its lithologies. For example, organic globules in the Tagish Lake meteorite are always embedded in fined grained (poorly crystallized) saponite, and hardly encapsulated in coarse grained serpentine, even though saponite and serpentine are both main components of phyllosilicate matrix of the Tagish Lake meteorite. The organic globules are commonly observed in the carbonate-poor lithology but not in the carbonate-rich one. In Tagish Lake, isolated single globules are common, but in the Bells (CM2) meteorite, globules are mostly aggregated. We will review the evolutions of the organic globules from its birth to alteration in the parent bodies in terms of its own physical and chemical properties as well as its associated minerals.

  2. Effect of a Ti capping layer on thermal stability of NiSi formed from Ni thin films deposited by metal-organic chemical vapor deposition using a Ni(iPr-DAD)2 precursor

    NASA Astrophysics Data System (ADS)

    Park, Jingyu; Jeon, Heeyoung; Kim, Hyunjung; Jang, Woochool; Kang, Chunho; Yuh, Junhan; Jeon, Hyeongtag

    2015-02-01

    Ni films were deposited by metal-organic chemical vapor deposition (MOCVD) using a novel Ni precursor, bis(1,4-di-isopropyl-1,3-diazabutadienyl)nickel [Ni(iPr-DAD)2], and NH3 gas. To optimize process conditions, the deposition temperature and reactant partial pressure were varied from 200 to 350 °C and from 0.2 to 0.99 Torr, respectively. Ni films deposited at 300 °C with a reactant pressure of 0.8 Torr exhibited excellent quality, and had a low carbon impurity concentration of around 4%. In addition, a sacrificial Ti capping layer was deposited by an in situ e-beam evaporator on top of the Ni films to enhance the thermal stability of the subsequently formed NiSi films. Both the Ti-capped and uncapped Ni films were annealed by a two-step method, with a first annealing conducted at 500 °C, followed by wet etching and then a second annealing carried out from 500 to 900 °C. The Ti capping layer did not affect the silicidation kinetic process, but by acting as an oxygen scavenger, it did enhance the morphological stability of the NiSi films and thus improve their electrical properties.

  3. Enhanced optical properties of InAs/InAlGaAs/InP quantum dots grown by metal-organic chemical vapor deposition using a double-cap technique

    NASA Astrophysics Data System (ADS)

    Shi, Bei; Lau, Kei May

    2016-01-01

    The effects of a double-cap procedure on the optical properties of an InAs/InAlGaAs quantum dots (QDs) system grown by metal-organic chemical vapor deposition (MOCVD) have been investigated by atomic force microscopy (AFM) and room temperature photoluminescence (RT-PL) spectroscopy. An optimized QD growth condition has been achieved, with an areal density of 4.6×1010 cm-2. It was found that the thickness and lattice constant of the high temperature second cap layer (SCL) were crucial for improving the integrated PL intensity and line-width of the 1.55 μm emission from the InAs/InAlGaAs QD system grown on a semi-insulating InP (100) substrate. With fine-tuned SCL thickness and lattice constant, the optical performance of the five-stack QDs was enhanced. The improvements can be attributed to the smooth growth front, observed from the AFM images, and the well-balanced stress engineering.

  4. Metal-assisted chemical etching of silicon: a review.

    PubMed

    Huang, Zhipeng; Geyer, Nadine; Werner, Peter; de Boor, Johannes; Gösele, Ulrich

    2011-01-11

    This article presents an overview of the essential aspects in the fabrication of silicon and some silicon/germanium nanostructures by metal-assisted chemical etching. First, the basic process and mechanism of metal-assisted chemical etching is introduced. Then, the various influences of the noble metal, the etchant, temperature, illumination, and intrinsic properties of the silicon substrate (e.g., orientation, doping type, doping level) are presented. The anisotropic and the isotropic etching behaviors of silicon under various conditions are presented. Template-based metal-assisted chemical etching methods are introduced, including templates based on nanosphere lithography, anodic aluminum oxide masks, interference lithography, and block-copolymer masks. The metal-assisted chemical etching of other semiconductors is also introduced. A brief introduction to the application of Si nanostructures obtained by metal-assisted chemical etching is given, demonstrating the promising potential applications of metal-assisted chemical etching. Finally, some open questions in the understanding of metal-assisted chemical etching are compiled.

  5. Mechanical Alloying of Metal-Organic Frameworks.

    PubMed

    Panda, Tamas; Horike, Satoshi; Hagi, Keisuke; Ogiwara, Naoki; Kadota, Kentaro; Itakura, Tomoya; Tsujimoto, Masahiko; Kitagawa, Susumu

    2017-02-20

    The solvent-free mechanical milling process for two distinct metal-organic framework (MOF) crystals induced the formation of a solid solution, which is not feasible by conventional solution-based syntheses. X-ray and STEM-EDX studies revealed that performing mechanical milling under an Ar atmosphere promotes the high diffusivity of each metal ion in an amorphous solid matrix; the amorphous state turns into the porous crystalline structure by vapor exposure treatment to form a new phase of a MOF solid solution.

  6. Metal and metal oxide nanoparticle synthesis from metal organic frameworks (MOFs): finding the border of metal and metal oxides.

    PubMed

    Das, Raja; Pachfule, Pradip; Banerjee, Rahul; Poddar, Pankaj

    2012-01-21

    Herein, for the first time, we report a generalized strategy for the successful synthesis of highly crystalline metal and metal oxide nanoparticles embedded in a carbon matrix by the controlled thermolysis of metal organic frameworks (MOFs). The rationalized synthesis strategy of a broad range of metal and metal oxides nanoparticles, such as Cu/CuO, Co/Co(3)O(4), ZnO, Mn(2)O(3), MgO and CdS/CdO, by thermolysis of MOFs demonstrates for the first time that metal ions with a reduction potential of -0.27 volts or higher present in MOFs always form pure metal nanoparticles during thermolysis in N(2), whereas metal ions with a reduction potential lower than -0.27 volts form metal oxide nanoparticles during thermolysis in N(2). Another point of interest is the fact that we have found a unique relationship between the nanoparticle size and the distance between the secondary building units inside the MOF precursors. Interestingly, the crystallinity of the carbon matrix was also found to be greatly influenced by the environment (N(2) and air) during thermolysis. Moreover, these nanoparticles dispersed in a carbon matrix showed promising H(2) and CO(2) adsorption properties depending on the environment used for the thermolysis of MOFs.

  7. Metallization with generic metallo-organic inks

    NASA Technical Reports Server (NTRS)

    Vest, G. M.

    1983-01-01

    The use and fabrication of metallo-organic films are discussed. Metallo-organic compounds are ones in which a metal is linked to a long chain carbon ligand through a hetero atom such as O, S, N, P or As. Films formed by the thermal decomposition of these metallo-organics are called MOD films. In order that the products of decomposition contain only CO2, H2O, and in rare cases nitrogen compounds, and to avoid S containing products, the use of a set of metallo-organic compounds for ink fabrication where the linking hetero atom was oxygen was pioneered. These links were made from commercially available carboxylates, or synthesized from commonly available reagents. The processing is described and the molecular design criteria are given. The particular carboxylates or amine carboxylates selected were the octoates or neodecanoates, and they are described.

  8. Purification of metal-organic framework materials

    SciTech Connect

    Farha, Omar K.; Hupp, Joseph T.

    2012-12-04

    A method of purification of a solid mixture of a metal-organic framework (MOF) material and an unwanted second material by disposing the solid mixture in a liquid separation medium having a density that lies between those of the wanted MOF material and the unwanted material, whereby the solid mixture separates by density differences into a fraction of wanted MOF material and another fraction of unwanted material.

  9. Porosity in metal-organic framework glasses.

    PubMed

    Thornton, A W; Jelfs, K E; Konstas, K; Doherty, C M; Hill, A J; Cheetham, A K; Bennett, T D

    2016-03-07

    The porosity of a glass formed by melt-quenching a metal-organic framework, has been characterized by positron annihilation lifetime spectroscopy. The results reveal porosity intermediate between the related open and dense crystalline frameworks ZIF-4 and ZIF-zni. A structural model for the glass was constructed using an amorphous polymerization algorithm, providing additional insight into the gas-inaccessible nature of porosity and the possible applications of hybrid glasses.

  10. Purification of metal-organic framework materials

    DOEpatents

    Farha, Omar K.; Hupp, Joseph T.

    2015-06-30

    A method of purification of a solid mixture of a metal-organic framework (MOF) material and an unwanted second material by disposing the solid mixture in a liquid separation medium having a density that lies between those of the wanted MOF material and the unwanted material, whereby the solid mixture separates by density differences into a fraction of wanted MOF material and another fraction of unwanted material.

  11. Metal Vinylidenes as Catalytic Species in Organic Reactions

    PubMed Central

    McClory, Andrew

    2008-01-01

    Organic vinylidene species have found limited use in organic synthesis due to their inaccessibility. In contrast, metal vinylidenes are much more stable, and may be readily accessed through transition metal activation of terminal alkynes. These electrophilic species may be trapped by a number of nucleophiles. Additionally, metal vinylidenes can participate in pericyclic reactions and processes involving migration of a metal ligand to the vinylidene species. This review addresses the reactions and applications of metal vinylidenes in organic synthesis. PMID:18172846

  12. Non-essential metals in chemical biology.

    PubMed

    Dyson, Paul J

    2011-01-01

    Metal ions and compounds are essential to life and many people routinely take them as food supplements in the form of vitamin and mineral pills. Most non-essential metals are considered to be toxic, nevertheless, many are widely used in imaging, diagnostics and medicine. This short review provides an overview from selected examples of the on-going research within my laboratory that uses metal compounds to either understand biological processes or that exhibit therapeutic properties overcoming the limitations of existing chemotherapies.

  13. Chemical characterization and metal abundance in Sri Lankan serpentine soils

    NASA Astrophysics Data System (ADS)

    Vithanage, M. S.; Rajapaksha, A. U.; Ok, Y. S.; Oze, C.

    2012-12-01

    Chemical weathering of ultramafic rocks and their related soils provide localized sources of metal contamination. In Sri Lanka, rural communities live in close proximity to these rocks and soils and utilize associated groundwaters where human intake of these high metal sources may have adverse human health effects. This study investigates metal abundances and variations in Sri Lankan serpentine soils to begin evaluating potential human health hazards. Specifically, we examine serpentinite occurrences at Ussangoda, Wasgamuwa, Ginigalpelessa, and Indikolapelessa located at the geological boundary between the Highland and Vijayan Complexes. The pH of the soils are near neutral (6.26 to 7.69) with soil electrical conductivities (EC) ranging from 33.5 to 129.9 μS cm-1, a range indicative of relatively few dissolved salts and/or major dissolved inorganic solutes. The highest EC is from the Ussangoda soil which may be due to the atmospheric deposition of salt spray from the sea. Organic carbon contents of the soils range from 1.09% to 2.58%. The highest organic carbon percentage is from the Wasgamuwa soil which is located in a protected preserve. X-ray fluorescence (XRF) spectrometry and total metal digestion results show that all serpentine soils are Fe-, Cr-, and Ni-rich with abundant aluminosilicate minerals. Nickel is highest in the Ussangoda soil (6,459 mg kg-1), while Cr (>10,000 mg kg-1), Co (441 mg kg-1) and Mn (2,263 mg kg-1) are highest in the Wasgamuwa serpentine soil. Additionally, Mn (2,200 mg kg-1) and Co (400 mg kg-1) are present at high concentrations in the Wasgamuwa and Ginigalpelessa soils respectively. Electron microprobe mapping demonstrates that these heavy metals are not homogeneously distributed where Cr is specifically associated with Al and Fe phases. Metal speciation of these serpentine soils are currently being investigated using X-ray absorption spectroscopy (XAS) to provide better constraints with regards to their mobility and toxicity.

  14. Spectroscopical properties of organic/metal nanohybrids.

    PubMed

    Dellepiane, Giovanna; Cuniberti, Carla; Alloisio, Marina; Demartini, Anna

    2010-03-28

    The aim of our work was to prepare stable nanohybrids of controlled size and shape consisting of a noble metal core decorated with polydiacetylenes (PDAs). Due to the combination of the outstanding linear and nonlinear optical properties of the polydiacetylenic chains with the electromagnetic field-enhancing capability of metal nanostructures, these novel composites can find potential application in different fields. In particular, the different colours exhibited by PDAs in relation to the chemical nature of the monomer and the polymerization procedure, as well as in response to environmental perturbations, make them excellent materials for the fabrication of sensing devices. On the basis of our previous work on PDA self-assembled monolayers on flat metal surfaces, the results of which are briefly reported, we prepared differently-shaped gold and silver nanocores (spheres, cages) coated with various diacetylenic monomers having end-groups able to firmly anchor to the metal surface. These nanohybrids exhibit in aqueous colloidal solution an enhanced photochemical polymerization monitored step by step with UV-Vis and SERS techniques. It is shown that in these stable assemblies an intra-particle polymerization takes place and that the dominant PDA form is conditioned by the core size and geometry. While the nanoparticles are SERS active in the visible, the nanocages should be excellent SERS substrates from the visible to the near infrared regions.

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

    SciTech Connect

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

    2016-08-30

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

  16. Capturing snapshots of post-synthetic metallation chemistry in metal-organic frameworks

    NASA Astrophysics Data System (ADS)

    Bloch, Witold M.; Burgun, Alexandre; Coghlan, Campbell J.; Lee, Richmond; Coote, Michelle L.; Doonan, Christian J.; Sumby, Christopher J.

    2014-10-01

    Post-synthetic metallation is employed strategically to imbue metal-organic frameworks (MOFs) with enhanced performance characteristics. However, obtaining precise structural information for metal-centred reactions that take place within the pores of these materials has remained an elusive goal, because of issues with high symmetry in certain MOFs, lower initial crystallinity for some chemically robust MOFs, and the reduction in crystallinity that can result from carrying out post-synthetic reactions on parent crystals. Here, we report a new three-dimensional MOF possessing pore cavities that are lined with vacant di-pyrazole groups poised for post-synthetic metallation. These metallations occur quantitatively without appreciable loss of crystallinity, thereby enabling examination of the products by single-crystal X-ray diffraction. To illustrate the potential of this platform to garner fundamental insight into metal-catalysed reactions in porous solids we use single-crystal X-ray diffraction studies to structurally elucidate the reaction products of consecutive oxidative addition and methyl migration steps that occur within the pores of the Rh-metallated MOF, 1·[Rh(CO)2][Rh(CO)2Cl2].

  17. Impact of metals on the biodegradation of organic pollutants.

    PubMed Central

    Sandrin, Todd R; Maier, Raina M

    2003-01-01

    Forty percent of hazardous waste sites in the United States are co-contaminated with organic and metal pollutants. Data from both aerobic and anaerobic systems demonstrate that biodegradation of the organic component can be reduced by metal toxicity. Metal bioavailability, determined primarily by medium composition/soil type and pH, governs the extent to which metals affect biodegradation. Failure to consider bioavailability rather than total metal likely accounts for much of the enormous variability among reports of inhibitory concentrations of metals. Metals appear to affect organic biodegradation through impacting both the physiology and ecology of organic degrading microorganisms. Recent approaches to increasing organic biodegradation in the presence of metals involve reduction of metal bioavailability and include the use of metal-resistant bacteria, treatment additives, and clay minerals. The addition of divalent cations and adjustment of pH are additional strategies currently under investigation. PMID:12826480

  18. Microporous Metal Organic Materials for Hydrogen Storage

    SciTech Connect

    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.

  19. Structural and optical properties of AlxGa1-xN (0.33 ≤ x ≤ 0.79) layers on high-temperature AlN interlayer grown by metal organic chemical vapor deposition

    NASA Astrophysics Data System (ADS)

    Xu, Qingjun; Liu, Bin; Zhang, Shiying; Tao, Tao; Dai, Jiangping; He, Guotang; Xie, Zili; Xiu, Xiangqian; Chen, Dunjun; Chen, Peng; Han, Ping; Zhang, Rong

    2017-01-01

    High-Al-content AlxGa1-xN films with x varying from 0.33 to 0.79 were grown on GaN templates with the high temperature AlN (HT-AlN) interlayer by metal organic chemical vapor deposition (MOCVD). The best crystalline quality, among these AlxGa1-xN alloys, can be obtained for an AlN mole fraction x = 0.55, where the full-width at half-maximum of the Al0.55Ga0.45N (0002) diffraction peak was measured to be 259 arcsec by high resolution X-ray diffraction (HRXRD). The screw threading dislocation (TDs) density was 2 × 108 cm-2 evaluated by transmission electron microscope (TEM), which agreed with the calculations from Williamson-Hall plots. Moreover, cross-sectional TEM indicated that the HT-AlN interlayer could sufficiently reduce the threading dislocations (TDs) through generation of V trenches in the HT-AlN interlayer, since the TDs propagated along the V trenches, then bent into basal planes and annihilated with other dislocations. The study of optical properties indicated that obvious S-shape of temperature dependence on emission energy was observed for Al0.55Ga0.45N layers, which was attributed to exciton localization with energy (Eloc) ∼14.95 meV at 10 K resulting from potential fluctuation and band tail states. The time-resolved photoluminescence (TRPL) curves showed a bi-exponential decay at low temperature. The fast decay time implied the presence of the localized excitons enhancing radiative recombination, while the quite slow one was due to the dominance of trapping mechanisms originating from cation vacancy complexes and the VIII-related complexes.

  20. High-quality uniaxial In(x)Ga(1-x)N/GaN multiple quantum well (MQW) nanowires (NWs) on Si(111) grown by metal-organic chemical vapor deposition (MOCVD) and light-emitting diode (LED) fabrication.

    PubMed

    Ra, Yong-Ho; Navamathavan, R; Park, Ji-Hyeon; Lee, Cheul-Ro

    2013-03-01

    This article describes the growth and device characteristics of vertically aligned high-quality uniaxial p-GaN/InxGa1-xN/GaN multiple quantum wells (MQW)/n-GaN nanowires (NWs) on Si(111) substrates grown by metal-organic chemical vapor deposition (MOCVD) technique. The resultant nanowires (NWs), with a diameter of 200-250 nm, have an average length of 2 μm. The feasibility of growing high-quality NWs with well-controlled indium composition MQW structure is demonstrated. These resultant NWs grown on Si(111) substrates were utilized for fabricating vertical-type light-emitting diodes (LEDs). The steep and intense photoluminescence (PL) and cathodoluminescence (CL) spectra are observed, based on the strain-free NWs on Si(111) substrates. High-resolution transmission electron microscopy (HR-TEM) analysis revealed that the MQW NWs are grown along the c-plane with uniform thickness. The current-voltage (I-V) characteristics of these NWs exhibited typical p-n junction LEDs and showed a sharp onset voltage at 2.75 V in the forward bias. The output power is linearly increased with increasing current. The result indicates that the pulsed MOCVD technique is an effective method to grow uniaxial p-GaN/InxGa1-xN/GaN MQW/n-GaN NWs on Si(111), which is more advantageous than other growth techniques, such as molecular beam epitaxy. These results suggest the uniaxial NWs are promising to allow flat-band quantum structures, which can enhance the efficiency of LEDs.

  1. The compositional, structural, and magnetic properties of a Fe3O4/Ga2O3/GaN spin injecting hetero-structure grown by metal-organic chemical vapor deposition

    NASA Astrophysics Data System (ADS)

    Xu, Zhonghua; Huang, Shimin; Tang, Kun; Gu, Shulin; Zhu, Shunming; Ye, Jiandong; Xu, Mingxiang; Wang, Wei; Zheng, Youdou

    2016-12-01

    In this article, the authors have designed and fabricated a Fe3O4/Ga2O3/GaN spin injecting hetero-structure by metal-organic chemical vapor deposition. The compositional, structural, and magnetic properties of the hetero-structure have been characterized and discussed. From the characterizations, the hetero-structure has been successfully grown generally. However, due to the unintentional diffusion of Ga ions from Ga2O3/GaN layers, the most part of the nominal Fe3O4 layer is actually in the form of GaxFe3-xO4 with gradually decreased x values from the Fe3O4/Ga2O3 interface to the Fe3O4 surface. Post-annealing process can further aggravate the diffusion. Due to the similar ionic radius of Ga and Fe, the structural configuration of the GaxFe3-xO4 does not differ from that of pure Fe3O4. However, the ferromagnetism has been reduced with the incorporation of Ga into Fe3O4, which has been explained by the increased Yafet-Kittel angles in presence of considerable amount of Ga incorporation. A different behavior of the magnetoresistance has been found on the as-grown and annealed samples, which could be modelled and explained by the competition between the spin-dependent and spin-independent conduction channels. This work has provided detailed information on the interfacial properties of the Fe3O4/Ga2O3/GaN spin injecting hetero-structure, which is the solid basis for further improvement and application of the structure.

  2. Complexed metals in hazardous waste: Limitations of conventional chemical oxidation

    SciTech Connect

    Diel, B.N.; Kuchynka, D.J.; Borchert, J.

    1994-12-31

    In the management of hazardous waste, more is known regarding the treatment of metals than about the fixation, destruction and/or immobilization of any other hazardous constituent group. Metals are the only hazardous constituents which cannot be destroyed, and so must be converted to their least soluble and/or reactive form to prevent reentry into the environment. The occurrence of complexed metals, e.g., metallocyanides, and/or chelated metals, e.g., M{center_dot}EDTA in hazardous waste streams presents formidable challenges to conventional waste treatment practices. This paper presents the results of extensive research into the destruction (chemical oxidation) of metallocyanides and metal-chelates, defines the utility and limitations of conventional chemical oxidation approaches, illustrates some of the waste management difficulties presented by such species, and presents preliminary data on the UV/H{sub 2}O{sub 2} photodecomposition of chelated metals.

  3. Advanced Organic Ligands for Protecting Metal Nanoparticles

    NASA Astrophysics Data System (ADS)

    Yu, Jonathan Ka-Wing

    Organic monolayer protected metal nanoparticles have been utilized in many different fields such as catalysis, drug delivery, and sensor chemistry. However, these nanomaterials are prone to increase in size consequently losing its function at the nanoscale. The stability these nanoparticles have been a great interest of research. This thesis focuses on the synthesis of a novel cross-linkable ligand for the protection of metal nanoparticles. Chapter 1 reviews key concepts of nanoparticles, its usefulness in applications, some of the stabilizing strategies employed, and the scope of the thesis project. Chapter 2 describes the synthetic attempts and optimization of the novel cross-linkable ligand. In addition, its characterization data is also included. Section 2.8 also highlights another fully synthesized novel hydrophobic ligand. Chapter 3 contains the summary of the work and closing remarks. Future works is also included to describe the prospects of the synthesis of the novel ligand. Chapter 4 entails the experimental data and supplementary information.

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

    NASA Astrophysics Data System (ADS)

    Gao, Fei; Ding, Zijing; Meng, Sheng

    2013-05-01

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

  5. Electronic and chemical structure of metal-silicon interfaces

    NASA Technical Reports Server (NTRS)

    Grunthaner, P. J.; Grunthaner, F. J.

    1984-01-01

    This paper reviews our current understanding of the near-noble metal silicides and the interfaces formed with Si(100). Using X-ray photoemission spectroscopy, we compare the chemical composition and electronic structure of the room temperature metal-silicon and reacted silicide-silicon interfaces. The relationship between the interfacial chemistry and the Schottky barrier heights for this class of metals on silicon is explored.

  6. Increasing the Stability of Metal-Organic Frameworks

    DOE PAGES

    Bosch, Mathieu; Zhang, Muwei; Zhou, Hong-Cai

    2014-01-01

    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 collapsemore » 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.« less

  7. Metal-doped organic gels and method thereof

    DOEpatents

    Satcher, Jr., Joe H.; Baumann, Theodore F.

    2003-09-02

    Disclosed herein is a sol-gel polymerization process for synthesizing metal-doped organic gels. The process polymerizes metal salts of hydroxylated benzenes or hydroxylated benzene derivatives with alkyl or aryl aldehydes to form metal-doped, wet, organic gels. The gels can then be dried by supercritical solvent extraction to form metal-doped aerogels or by evaporation to form metal-doped xerogels. The aerogels and xerogels can then be pyrolyzed.

  8. Metal-doped organic gels and method thereof

    DOEpatents

    Satcher, Jr., Joe H.; Baumann, Theodore F.

    2007-10-23

    Disclosed herein is a sol-gel polymerization process for synthesizing metal-doped organic gels. The process polymerizes metal salts of hydroxylated benzenes or hydroxylated benzene derivatives with alkyl or aryl aldehydes to form metal-doped, wet, organic gels. The gels can then be dried by supercritical solvent extraction to form metal-doped aerogels or by evaporation to form metal-doped xerogels. The aerogels and xerogels can then be pyrolyzed.

  9. Hydrogen storage in metal-organic frameworks.

    PubMed

    Hu, Yun Hang; Zhang, Lei

    2010-05-25

    Metal-organic frameworks (MOFs) are highly attractive materials because of their ultra-high surface areas, simple preparation approaches, designable structures, and potential applications. In the past several years, MOFs have attracted worldwide attention in the area of hydrogen energy, particularly for hydrogen storage. In this review, the recent progress of hydrogen storage in MOFs is presented. The relationships between hydrogen capacities and structures of MOFs are evaluated, with emphasis on the roles of surface area and pore size. The interaction mechanism between H(2) and MOFs is discussed. The challenges to obtain a high hydrogen capacity at ambient temperature are explored.

  10. Biomimicry in metal-organic materials

    SciTech Connect

    Zhang, MW; Gu, ZY; Bosch, M; Perry, Z; Zhou, HC

    2015-06-15

    Nature has evolved a great number of biological molecules which serve as excellent constructional or functional units for metal-organic materials (MOMs). Even though the study of biomimetic MOMs is still at its embryonic stage, considerable progress has been made in the past few years. In this critical review, we will highlight the recent advances in the design, development and application of biomimetic MOMs, and illustrate how the incorporation of biological components into MOMs could further enrich their structural and functional diversity. More importantly, this review will provide a systematic overview of different methods for rational design of MOMs with biomimetic features. Published by Elsevier B.V.

  11. Chemically diverse and multifunctional hybrid organic-inorganic perovskites

    NASA Astrophysics Data System (ADS)

    Li, Wei; Wang, Zheming; Deschler, Felix; Gao, Song; Friend, Richard H.; Cheetham, Anthony K.

    2017-02-01

    Hybrid organic-inorganic perovskites (HOIPs) can have a diverse range of compositions including halides, azides, formates, dicyanamides, cyanides and dicyanometallates. These materials have several common features, including their classical ABX3 perovskite architecture and the presence of organic amine cations that occupy the A-sites. Current research in HOIPs tends to focus on metal halide HOIPs, which show promise for use in solar cells and optoelectronic devices; however, the other subclasses also exhibit a diverse range of physical properties. In this Review, we summarize the chemical variability and structural diversity of all known HOIP subclasses. We also present a comprehensive account of their intriguing physical properties, including photovoltaic and optoelectronic properties, dielectricity, magnetism, ferroelectricity, ferroelasticity and multiferroicity. Moreover, we discuss the current challenges and future opportunities in this exciting field.

  12. Chemical alteration of extraterrestrial organics during atmospheric entry of micrometeorites

    NASA Astrophysics Data System (ADS)

    Kress, M.; Brownlee, D.

    Most of the extraterrestrial carbon accreted by Earth is carried by the 40,000 tons of ~0.2 mm micrometeorites that enter the atmosphere every year. Particles in this size range would have supplied an enormous amount of carbon to the inchoate biosphere since the exogenous influx at ~4 Ga would have been much higher than today. However, these particles undergo strong drag heating to ~1500 K for several seconds upon atmospheric entry, ostensibly burning away all the organics as CO. Ironically, particles of this size seemed to contribute no organic carbon to Earth despite the fact that they constitute the bulk of the total incoming mass. Conventional wisdom has thus held that organics survive only in smaller cosmic dust grains and in >~cm-sized meteorites, which account for only a tiny fraction of the total exogenous mass flux. However, carbon has been found in several smaller, yet still strongly-heated particles in the form of a refractory, char-like material imbedded with tiny FeNi metal beads, motivating us to study the pyrolysis of complex organic matter. We will present results from experiments and chemical models of the transient drag heating of micrometeorites. We predict that small aromatics, light hydrocarbons, and other organics, as well as CO and char, are formed, indicating that strongly-heated micrometeorites may have indeed been a significant source of organic carbon during the origin of life on Earth.

  13. Hydrogen Storage in Metal-Organic Frameworks

    SciTech Connect

    Omar M. Yaghi

    2012-04-26

    Conventional storage of large amounts of hydrogen in its molecular form is difficult and expensive because it requires employing either extremely high pressure gas or very low temperature liquid. Because of the importance of hydrogen as a fuel, the DOE has set system targets for hydrogen storage of gravimetric (5.5 wt%) and volumetric (40 g L-1) densities to be achieved by 2015. Given that these are system goals, a practical material will need to have higher capacity when the weight of the tank and associated cooling or regeneration system is considered. The size and weight of these components will vary substantially depending on whether the material operates by a chemisorption or physisorption mechanism. In the latter case, metal-organic frameworks (MOFs) have recently been identified as promising adsorbents for hydrogen storage, although little data is available for their sorption behavior. This grant was focused on the study of MOFs with these specific objectives. (1) To examine the effects of functionalization, catenation, and variation of the metal oxide and organic linkers on the low-pressure hydrogen adsorption properties of MOFs. (2) To develop a strategy for producing MOFs with high surface area and porosity to reduce the dead space and increase the hydrogen storage capacity per unit volume. (3) To functionalize MOFs by post synthetic functionalization with metals to improve the adsorption enthalpy of hydrogen for the room temperature hydrogen storage. This effort demonstrated the importance of open metal sites to improve the adsorption enthalpy by the systematic study, and this is also the origin of the new strategy, which termed isoreticular functionalization and metalation. However, a large pore volume is still a prerequisite feature. Based on our principle to design highly porous MOFs, guest-free MOFs with ultrahigh porosity have been experimentally synthesized. MOF-210, whose BET surface area is 6240 m2 g-1 (the highest among porous solids), takes up

  14. Stepwise Synthesis of Metal-Organic Frameworks.

    PubMed

    Bosch, Mathieu; Yuan, Shuai; Rutledge, William; Zhou, Hong-Cai

    2017-03-28

    Metal-organic frameworks (MOFs) are a category of porous materials that offer unparalleled control over their surface areas (demonstrated as higher than for any other material), pore characteristics, and functionalization. This allows them to be customized for exceptional performance in a wide variety of applications, most commonly including gas storage and separation, drug delivery, luminescence, or heterogeneous catalysis. In order to optimize biomimicry, controlled separations and storage of small molecules, and detailed testing of structure-property relationships, one major goal of MOF research is "rational design" or "pore engineering", or precise control of the placement of multiple functional groups in pores of chosen sizes and shapes. MOF crystal growth can be controlled through judicious design of stepwise synthetic routes, which can also allow functionalization of MOFs in ways that were previously synthetically inaccessible. Organic chemists have developed a library of powerful techniques over the last century, allowing the total synthesis and detailed customization of complex molecules. Our hypothesis is that total synthesis is also possible for customized porous materials, through the development of similar multistep techniques. This will enable the rational design of MOFs, which is a major goal of many researchers in the field. We have begun developing a library of stepwise synthetic techniques for MOFs, allowing the synthesis of ultrastable MOFs with multiple crystallographically ordered and customizable functional groups at controlled locations within the pores. In order to design MOFs with precise control over pore size and shape, stability, and the placement of multiple different functional groups within the pores at tunable distances from one another, we have concentrated on methods which allow us to circumvent the lack of control inherent to one-pot MOF crystallization. Kinetically tuned dimensional augmentation (KTDA) is an approach using

  15. Transition metal complexes supported on metal-organic frameworks for heterogeneous catalysts

    DOEpatents

    Farha, Omar K.; Hupp, Joseph T.; Delferro, Massimiliano; Klet, Rachel C.

    2017-02-07

    A robust mesoporous metal-organic framework comprising a hafnium-based metal-organic framework and a single-site zirconium-benzyl species is provided. The hafnium, zirconium-benzyl metal-organic framework is useful as a catalyst for the polymerization of an alkene.

  16. Metal-organic framework materials with ultrahigh surface areas

    DOEpatents

    Farha, Omar K.; Hupp, Joseph T.; Wilmer, Christopher E.; Eryazici, Ibrahim; Snurr, Randall Q.; Gomez-Gualdron, Diego A.; Borah, Bhaskarjyoti

    2015-12-22

    A metal organic framework (MOF) material including a Brunauer-Emmett-Teller (BET) surface area greater than 7,010 m.sup.2/g. Also a metal organic framework (MOF) material including hexa-carboxylated linkers including alkyne bond. Also a metal organic framework (MOF) material including three types of cuboctahedron cages fused to provide continuous channels. Also a method of making a metal organic framework (MOF) material including saponifying hexaester precursors having alkyne bonds to form a plurality of hexa-carboxylated linkers including alkyne bonds and performing a solvothermal reaction with the plurality of hexa-carboxylated linkers and one or more metal containing compounds to form the MOF material.

  17. Comparison of rapid screening assays using organic chemicals

    SciTech Connect

    Beach, S.A.; Robideau, R.R.

    1994-12-31

    In a continuation of a study presented last year using metals, the sensitivity of short term toxicity tests is examined using common organic chemicals. In toxicity testing, the focus has shifted from the traditional long-term studies utilizing the mortality of complex, multicellular eukaryotic organisms as the endpoint towards short-term studies in which transformation of biochemical pathways are monitored. The relative sensitivity of aquatic screening techniques are compared to the standardized 48-hr Daphnia magna and Ceriodaphnia dubia, 96-hr fathead minnow and 96-hr algal acute assays. The short-term test procedures investigated are: dehydrogenase enzyme activity assays utilizing triphenyltetrazolium chloride (TTC) and resazurin as the calorimetric indicators; TOXI-Chromotest, inhibition of {beta}-galactosidase; reduction in bioluminescence output utilizing the Microtox{reg_sign} test; nitrification inhibition assays with a commercial preparation of nitrifying bacteria (Nitroseed{trademark}) and municipal activated sludge; respiration inhibition assays with a commercial preparation of heterotrophic bacteria (Polytox{reg_sign}) and activated sludge; inhibition of root growth in terrestrial plants; and galactosidase inhibition through the use of a fluorometrically tagged substrate with the Daphnia magna IQ{trademark} test. Toxicity values generated by this laboratory on commonly used organic chemicals are compared.

  18. Homochiral helical metal-organic frameworks of group 1 metals.

    PubMed

    Reger, Daniel L; Leitner, Andrew; Smith, Mark D; Tran, T Thao; Halasyamani, P Shiv

    2013-09-03

    The reactions of (S)-2-(1,8-naphthalimido)propanoic acid (HL(ala)) and (S)-2-(1,8-naphthalimido)-3-hydroxypropanoic acid (HL(ser)), protonated forms of ligands that contain a carboxylate donor group, an enantiopure chiral center, and a 1,8-naphthalimide π···π stacking supramolecular tecton and in the case of HL(ser) an alcohol functional group, with the appropriate alkali metal hydroxide followed by a variety of crystallization methods leads to the formation of crystalline K(L(ala))(MeOH) (1), K(L(ala))(H2O) (2), Na(L(ala))(H2O) (3), KL(ser) (4), CsL(ser) (5), and CsL(ala) (6). Each of these new complexes has a solid state structure based on six-coordinate metals linked into homochiral helical rod secondary building unit (SBU) central cores. In addition to the bonding of the carboxylate and solvent (in the case of L(ser) the ligand alcohol) to the metals, both oxygens on the 1,8-naphthalimide act as donor groups. One naphthalimide oxygen bonds to the same helical rod SBU as the carboxylate group of that ligand forming a chelate ring. The other naphthalimide oxygen bonds to adjacent SBUs. In complexes 1-3, this inter-rod link has a square arrangement bonding four other rods forming a three-dimensional enantiopure metal-organic framework (MOF) structure, whereas in 4-6 this link has a linear arrangement bonding two other rods forming a two-dimensional, sheet structure. In the latter case, the third dimension is supported exclusively by interdigitated π···π stacking interactions of the naphthalimide supramolecular tecton, forming enantiopure supramolecular MOF solids. Compounds 1-3 lose the coordinated solvent when heating above 100 °C. For 1, the polycrystalline powder reverts to 1 only by recrystallization from methanol, whereas compounds 2 and 3 undergo gas/solid, single-crystal to single-crystal transformations to form dehydrated compounds 2* and 3*, and rehydration occurs when crystals of these new complexes are left out in air. The reversible single

  19. Hydrogen Storage in Metal-Organic Frameworks

    SciTech Connect

    Long, Jeffrey R.

    2016-04-28

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

  20. Controlling the magnetism of adsorbed metal-organic molecules

    NASA Astrophysics Data System (ADS)

    Kuch, Wolfgang; Bernien, Matthias

    2017-01-01

    Gaining control on the size or the direction of the magnetic moment of adsorbed metal-organic molecules constitutes an important step towards the realization of a surface-mounted molecular spin electronics. Such control can be gained by taking advantage of interactions of the molecule’s magnetic moment with the environment. The paramagnetic moments of adsorbed metal-organic molecules, for example, can be controlled by the interaction with magnetically ordered substrates. Metalloporphyrins and -phthalocyanines display a quasi-planar geometry, allowing the central metal ion to interact with substrate electronic states. This can lead to magnetic coupling with a ferromagnetic or even antiferromagnetic substrate. The molecule-substrate coupling can be mediated and controlled by insertion layers such as oxygen atoms, graphene, or nonmagnetic metal layers. Control on the magnetic properties of adsorbed metalloporphyrins or -phthalocyanines can also be gained by on-surface chemical modification of the molecules. The magnetic moment or the magnetic coupling to ferromagnetic substrates can be changed by adsorption and thermal desorption of small molecules that interact with the fourfold-coordinated metal center via the remaining axial coordination site. Spin-crossover molecules, which possess a metastable spin state that can be switched by external stimuli such as temperature or light, are another promising class of candidates for control of magnetic properties. However, the immobilization of such molecules on a solid surface often results in a quench of the spin transition due to the interaction with the substrate. We present examples of Fe(II) spin-crossover complexes in direct contact with a solid surface that undergo a reversible spin-crossover transition as a function of temperature, by illumination with visible light, or can be switched by the tip of a scanning tunneling microscope.

  1. Controlling the magnetism of adsorbed metal-organic molecules.

    PubMed

    Kuch, Wolfgang; Bernien, Matthias

    2017-01-18

    Gaining control on the size or the direction of the magnetic moment of adsorbed metal-organic molecules constitutes an important step towards the realization of a surface-mounted molecular spin electronics. Such control can be gained by taking advantage of interactions of the molecule's magnetic moment with the environment. The paramagnetic moments of adsorbed metal-organic molecules, for example, can be controlled by the interaction with magnetically ordered substrates. Metalloporphyrins and -phthalocyanines display a quasi-planar geometry, allowing the central metal ion to interact with substrate electronic states. This can lead to magnetic coupling with a ferromagnetic or even antiferromagnetic substrate. The molecule-substrate coupling can be mediated and controlled by insertion layers such as oxygen atoms, graphene, or nonmagnetic metal layers. Control on the magnetic properties of adsorbed metalloporphyrins or -phthalocyanines can also be gained by on-surface chemical modification of the molecules. The magnetic moment or the magnetic coupling to ferromagnetic substrates can be changed by adsorption and thermal desorption of small molecules that interact with the fourfold-coordinated metal center via the remaining axial coordination site. Spin-crossover molecules, which possess a metastable spin state that can be switched by external stimuli such as temperature or light, are another promising class of candidates for control of magnetic properties. However, the immobilization of such molecules on a solid surface often results in a quench of the spin transition due to the interaction with the substrate. We present examples of Fe(II) spin-crossover complexes in direct contact with a solid surface that undergo a reversible spin-crossover transition as a function of temperature, by illumination with visible light, or can be switched by the tip of a scanning tunneling microscope.

  2. Organic Chemicals from Bioprocesses in China

    NASA Astrophysics Data System (ADS)

    Huang, Jin; Huang, Lei; Lin, Jianping; Xu, Zhinan; Cen, Peilin

    Over the last 20 years, China has successfully established a modern biotechnology industry from almost nothing. Presently, China is a major producer of a vast array of products involving bioprocesses, for some China is even the world's top producer. The ever-increasing list of products includes organic acids, amino acids, antibiotics, solvents, chiral chemicals, biopesticides, and biopolymers. Herein, the research and development of bioprocesses in China will be reviewed briefly. We will concentrate on three categories of products: small molecules produced via fermentation, biopolymers produced via fermentation and small chemicals produced by enzyme-catalyzed reactions. In comparison with the traditional chemical process, in which, nonrenewable mineral resources are generally used, products in the first and second categories noted above can use renewable bioresources as raw materials. The bioprocesses are generally energy saving and environmentally benign. For products developed via the third category, although the raw materials still need to be obtained from mineral resources, the biocatalysts are more effective with higher selectivity and productivity, and the bioprocesses occur under ambient temperature and pressure, therefore, these are "green processes." Most of the products such as citric acid, xanthan and acrylamide etc., discussed in this paper have been in large-scale commercial production in China. Also introduced herein are three scientists, Prof. Shen Yinchu, Prof. Ouyang Pingkai and Prof. Chen Guoqiang, and six enterprises, Anhui Fengyuan Biochemical Co. Ltd., Shandong Hiland Biotechnology Co. Ltd., Shandong Fufeng Fermentation Co. Ltd., Shandong Bausch & Lomb-Freda Pharmaceutical Co. Ltd., Zhejiang Hangzhou Xinfu Pharmaceutical Co. Ltd., and Changzhou Changmao Biochemical Engineering Co. Ltd.; they have all contributed a great deal to research and development in the commercialization of bioprocesses.

  3. Organic chemicals from bioprocesses in China.

    PubMed

    Huang, Jin; Huang, Lei; Lin, Jianping; Xu, Zhinan; Cen, Peilin

    2010-01-01

    Over the last 20 years, China has successfully established a modern biotechnology industry from almost nothing. Presently, China is a major producer of a vast array of products involving bioprocesses, for some China is even the world's top producer. The ever-increasing list of products includes organic acids, amino acids, antibiotics, solvents, chiral chemicals, biopesticides, and biopolymers. Herein, the research and development of bioprocesses in China will be reviewed briefly. We will concentrate on three categories of products: small molecules produced via fermentation, biopolymers produced via fermentation and small chemicals produced by enzyme-catalyzed reactions. In comparison with the traditional chemical process, in which, nonrenewable mineral resources are generally used, products in the first and second categories noted above can use renewable bioresources as raw materials. The bioprocesses are generally energy saving and environmentally benign. For products developed via the third category, although the raw materials still need to be obtained from mineral resources, the biocatalysts are more effective with higher selectivity and productivity, and the bioprocesses occur under ambient temperature and pressure, therefore, these are "green processes." Most of the products such as citric acid, xanthan and acrylamide etc., discussed in this paper have been in large-scale commercial production in China. Also introduced herein are three scientists, Prof. Shen Yinchu, Prof. Ouyang Pingkai and Prof. Chen Guoqiang, and six enterprises, Anhui Fengyuan Biochemical Co. Ltd., Shandong Hiland Biotechnology Co. Ltd., Shandong Fufeng Fermentation Co. Ltd., Shandong Bausch & Lomb-Freda Pharmaceutical Co. Ltd., Zhejiang Hangzhou Xinfu Pharmaceutical Co. Ltd., and Changzhou Changmao Biochemical Engineering Co. Ltd.; they have all contributed a great deal to research and development in the commercialization of bioprocesses.

  4. Kinetically tuned dimensional augmentation as a versatile synthetic route towards robust metal-organic frameworks.

    PubMed

    Feng, Dawei; Wang, Kecheng; Wei, Zhangwen; Chen, Ying-Pin; Simon, Cory M; Arvapally, Ravi K; Martin, Richard L; Bosch, Mathieu; Liu, Tian-Fu; Fordham, Stephen; Yuan, Daqiang; Omary, Mohammad A; Haranczyk, Maciej; Smit, Berend; Zhou, Hong-Cai

    2014-12-04

    Metal-organic frameworks with high stability have been pursued for many years due to the sustainability requirement for practical applications. However, researchers have had great difficulty synthesizing chemically ultra-stable, highly porous metal-organic frameworks in the form of crystalline solids, especially as single crystals. Here we present a kinetically tuned dimensional augmentation synthetic route for the preparation of highly crystalline and extremely robust metal-organic frameworks with a preserved metal cluster core. Through this versatile synthetic route, we obtain large single crystals of 34 different iron-containing metal-organic frameworks. Among them, PCN-250(Fe2Co) exhibits high volumetric uptake of hydrogen and methane, and is also stable in water and aqueous solutions with a wide range of pH values.

  5. Proton-Conducting Metal-Organic Frameworks

    NASA Astrophysics Data System (ADS)

    Ford, Jamie; Simmons, Jason; Yildirim, Taner

    2010-03-01

    Vehicles powered by polymer electrolyte membrane (PEM) fuel cells are an exciting alternative to current fossil fuel technology. The membranes in these cells serve as both charge transporter, ferrying protons from the anode to the cathode, and gas diffusion barrier, preventing the backflow of oxygen to the anode. Currently, hydrated sulfonated polymers are the preferred material for these membranes. The presence of water, however, limits the operating temperature to 100 C, reducing the electrode kinetics and CO tolerance of the entire system. In an effort to increase the efficiency and operating temperature of these fuel cells, we are investigating the proton conductivity of new host/guest materials based on metal-organic frameworks (MOFs) loaded with imidazole. These thermally stable frameworks provide well-defined pores that accommodate imidazole networks and form proton-conducting pathways. Here, we will present the structure and proton dynamics of these materials as elucidated by elastic and inelastic neutron scattering measurements.

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

    PubMed

    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)).

  7. Chemical abundances in metal-poor stars in Dwarf Galaxies

    NASA Astrophysics Data System (ADS)

    Venn, Kim; Norris, John; Shetrone, Matthew

    2015-08-01

    Stars in low-mass dwarf galaxies show a larger range in their chemical properties than those in the Milky Way halo. Not only are alpha-poor stars found at lower metallicities, but also r-process challenged stars, and a disparate fraction of carbon-enhanced metal-poor stars. A more pristine and chemically inhomogeneous interstellar medium, combined with stoichastic star formation in a metal-poor environment, is thought to cause these detectable differences in the early SN II contributions. We are also now finding stars in dwarf galaxies that appear to be iron-enhanced, i.e., stars that have formed in pockets of SN Ia enriched gas. A comparison of their chemical abundances with individual SN Ia models can provide unique constraints on the SN Ia progenitors.

  8. Metal-organic frameworks: structure, properties, methods of synthesis and characterization

    NASA Astrophysics Data System (ADS)

    Butova, V. V.; Soldatov, M. A.; Guda, A. A.; Lomachenko, K. A.; Lamberti, C.

    2016-03-01

    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.

  9. Heterogeneous processes affecting metal ion transport in the presence of organic ligands: Reactive transport modeling

    NASA Astrophysics Data System (ADS)

    Kantar, Cetin

    2007-04-01

    The development of models to accurately simulate metal ion transport through saturated systems under variable chemical conditions, e.g., in systems containing organic ligands (L) such as natural organic matter (NOM), has two essential aspects: (1) establishing the ability to simulate metal ion sorption to aquifer solids over a range of metal/ligand ratios; and (2) to incorporate this ability to simulate metal speciation over a range in chemical conditions (e.g., pH, ligand activity) into mass transport models. Modeling approaches to evaluate metal ion sorption and transport in the presence of NOM include: (1) isotherm-based transport models, and (2) multicomponent (MC) transport models. The accuracy of transport models depends on how well the chemical interactions affecting metal ion transport in the presence of organic ligands (e.g., metal/ligand complexation) are described in transport equations. The isotherm-based transport models often fail to accurately describe metal ion transport in the presence of NOM since these models treat NOM as a single solute despite the fact that NOM is a multicomponent mixture of subcomponents with different chemical and polyfunctional behavior. On the other hand, the calculations presented in this study suggest that a multicomponent reactive transport model, in conjunction with a mechanistic modeling approach for the description of metal ion binding by NOM in a manner conducive to the application of surface complexation modeling (SCM), can effectively be used as an important predictive tool in simulating metal ion sorption and transport under variable chemical conditions in the presence of NOM.

  10. Preparation, Characterization, and Postsynthetic Modification of Metal-Organic Frameworks: Synthetic Experiments for an Undergraduate Laboratory Course in Inorganic Chemistry

    ERIC Educational Resources Information Center

    Sumida, Kenji; Arnold, John

    2011-01-01

    Metal-organic frameworks (MOFs) are crystalline materials that are composed of an infinite array of metal nodes (single ions or clusters) linked to one another by polyfunctional organic compounds. Because of their extraordinary surface areas and high degree of control over the physical and chemical properties, these materials have received much…

  11. Chemical compatibility of structural materials in alkali metals

    SciTech Connect

    Natesan, K.; Rink, D.L.; Haglund, R.

    1995-04-01

    The objectives of this task are to (a) evaluate the chemical compatibility of structural alloys such as V-5 wt.%Cr-5 wt.%Ti alloy and Type 316 stainless steel for application in liquid alkali metals such as lithium and sodium-78 wt.% potassium (NaK) at temperatures in the range that are of interest for International Thermonuclear Experimental Reactor (ITER); (b) evaluate the transfer of nonmetallic elements such as oxygen, nitrogen, carbon, and hydrogen between structural materials and liquid metals; and (c) evaluate the effects of such transfers on the mechanical and microstructural characteristics of the materials for long-term service in liquid-metal-environments.

  12. Metal-Organic Frameworks: Bimetallic Metal-Organic Frameworks: Probing the Lewis Acid Site for CO2 Conversion (Small 17/2016).

    PubMed

    Zou, Ruyi; Li, Pei-Zhou; Zeng, Yong-Fei; Liu, Jia; Zhao, Ruo; Duan, Hui; Luo, Zhong; Wang, Jin-Gui; Zou, Ruqiang; Zhao, Yanli

    2016-05-01

    On page 2334, R. Q. Zou, Y. L. Zhao, and co-workers present a porous metal-organic framework (MOF) that serves as a platform for studying the metal exchange effect on both CO2 adsorption and catalytic fixation. The effect is demonstrated by catalytic CO2 cycloaddition with propylene oxide to produce propylene carbonate. Molecular dynamic simulations are carried out to further confirm the catalytic performance of these MOFs on chemical fixation of CO2 to carbonates. This research sheds light on how metal exchange could influence the intrinsic properties of MOFs.

  13. Metal accumulation by stream bryophytes, related to chemical speciation.

    PubMed

    Tipping, E; Vincent, C D; Lawlor, A J; Lofts, S

    2008-12-01

    Metal accumulation by aquatic bryophytes was investigated using data for headwater streams of differing chemistry. The Windermere Humic Aqueous Model (WHAM) was applied to calculate chemical speciation, including competitive proton and metal interactions with external binding sites on the plants. The speciation modelling approach gives smaller deviations between observed and predicted bryophyte contents of Cu, Zn, Cd and Pb than regressions based on total filtered metal concentrations. If all four metals, and Ni, are considered together, the WHAM predictions are superior at the 1% level. Optimised constants for bryophyte binding by the trace metals are similar to those for humic substances and simple carboxylate ligands. Bryophyte contents of Na, Mg and Ca are approximately explained by binding at external sites, while most of the K is intracellular. Oxide phases account for some of the Al, and most of the Mn, Fe and Co.

  14. CHEMICAL DYNAMICS OF HYDROPHOBIC ORGANIC CONTAMINANTS DURING RESUSPENSION

    EPA Science Inventory

    Laboratory experiments were designed to study the chemical-particle dynamics of toxic hydrophobic organics during resuspension episodes using a particle entrainment simulator (PES). The purpose was to obtain insight into chemical transport mechanisms during resuspension. Informat...

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

    PubMed

    Huskinson, Brian; Marshak, Michael P; Suh, Changwon; Er, Süleyman; Gerhardt, Michael R; Galvin, Cooper J; Chen, Xudong; Aspuru-Guzik, Alán; Gordon, Roy G; Aziz, Michael J

    2014-01-09

    As the fraction of electricity generation from intermittent renewable sources--such as solar or wind--grows, the ability to store large amounts of electrical energy is of increasing importance. Solid-electrode batteries maintain discharge at peak power for far too short a time to fully regulate wind or solar power output. In contrast, flow batteries can independently scale the power (electrode area) and energy (arbitrarily large storage volume) components of the system by maintaining all of the electro-active species in fluid form. Wide-scale utilization of flow batteries is, however, limited by the abundance and cost of these materials, particularly those using redox-active metals and precious-metal electrocatalysts. Here we describe a class of energy storage materials that exploits the favourable chemical and electrochemical properties of a family of molecules known as quinones. The example we demonstrate is a metal-free flow battery based on the redox chemistry of 9,10-anthraquinone-2,7-disulphonic acid (AQDS). AQDS undergoes extremely rapid and reversible two-electron two-proton reduction on a glassy carbon electrode in sulphuric acid. An aqueous flow battery with inexpensive carbon electrodes, combining the quinone/hydroquinone couple with the Br2/Br(-) redox couple, yields a peak galvanic power density exceeding 0.6 W cm(-2) at 1.3 A cm(-2). Cycling of this quinone-bromide flow battery showed >99 per cent storage capacity retention per cycle. The organic anthraquinone species can be synthesized from inexpensive commodity chemicals. This organic approach permits tuning of important properties such as the reduction potential and solubility by adding functional groups: for example, we demonstrate that the addition of two hydroxy groups to AQDS increases the open circuit potential of the cell by 11% and we describe a pathway for further increases in cell voltage. The use of π-aromatic redox-active organic molecules instead of redox-active metals

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

    SciTech Connect

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

    2014-01-08

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

  17. Metal ion sorption by untreated and chemically treated biomass

    SciTech Connect

    Kilbane, J.J.; Xie, J.

    1992-12-31

    The metal-binding ability of biosorbents is well known; however, in comparison with commercial ion-exchange resins the capacity of biosorbents is low. The purpose of this research was to examine chemically modified biosorbents and biosorbents prepared from microorganisms isolated from extreme environments to determine if significant improvements in metal-binding capacity or biosorbents with unique capabilities could be produced. Chemical treatments examined included acid, alkali, carbon disulfide, phosphorus oxychloride, anhydrous formamide, sodium thiosulfate, sodium chloroacetic acid, and phenylsulfonate. Biosorbents were prepared from microorganisms isolated from pristine and acid mine drainage impacted sites and included heterotrophs, methanotrophs, algae, and sulfate reducers. Chemical modification with carbon disulfide, phosphorous oxychloride, and sodium thiosulfate yielded biosorbents with such as much as 74%, 133%, and 155% improvements, respectively, in metal-binding capacity, but the performance of these chemically modified biosorbents deteriorated upon repeated use. A culture isolated from an acid mine drainage impacted site, IGTM17, exhibits about 3-fold higher metal-binding capacity in comparison with other biosorbents examined in this study. IGTM17 also exhibits superior metal-binding ability at decreased pH or in the presence of interfering common cations in comparison with other biosorbents or some commercially available cation exchange resins. Some biosorbents, such as IGTM5, can bind anions. To our knowledge this is the first demonstration of the ability of biosorbents to bind anions. Moreover, preliminary data indicate that the chemical modification of biosorbents may be capable of imparting the ability to selectively bind certain anions. Further research is needed to optimize conditions for the chemical modification and stabilization of biosorbents.

  18. GaN nanowire arrays by a patterned metal-assisted chemical etching

    NASA Astrophysics Data System (ADS)

    Wang, K. C.; Yuan, G. D.; Wu, R. W.; Lu, H. X.; Liu, Z. Q.; Wei, T. B.; Wang, J. X.; Li, J. M.; Zhang, W. J.

    2016-04-01

    We developed an one-step and two-step metal-assisted chemical etching method to produce self-organized GaN nanowire arrays. In one-step approach, GaN nanowire arrays are synthesized uniformly on GaN thin film surface. However, in a two-step etching processes, GaN nanowires are formed only in metal uncovered regions, and GaN regions with metal-covering show nano-porous sidewalls. We propose that nanowires and porous nanostructures are tuned by sufficient and limited etch rate, respectively. PL spectra shows a red-shift of band edge emission in GaN nanostructures. The formation mechanism of nanowires was illustrated by two separated electrochemical reactions occur simultaneously. The function of metals and UV light was illustrated by the scheme of potential relationship between energy bands in Si, GaN and standard hydrogen electrode potential of solution and metals.

  19. Highly mesoporous metal-organic framework assembled in a switchable solvent

    NASA Astrophysics Data System (ADS)

    Peng, Li; Zhang, Jianling; Xue, Zhimin; Han, Buxing; Sang, Xinxin; Liu, Chengcheng; Yang, Guanying

    2014-07-01

    The mesoporous metal-organic frameworks are a family of materials that have pore sizes ranging from 2 to 50 nm, which have shown promising applications in catalysis, adsorption, chemical sensing and so on. The preparation of mesoporous metal-organic frameworks usually needs the supramolecular or cooperative template strategy. Here we report the template-free assembly of mesoporous metal-organic frameworks by using CO2-expanded liquids as switchable solvents. The mesocellular metal-organic frameworks with large mesopores (13-23 nm) are formed, and their porosity properties can be easily adjusted by controlling CO2 pressure. Moreover, the use of CO2 can accelerate the reaction for metal-organic framework formation from metal salt and organic linker due to the viscosity-lowering effect of CO2, and the product can be recovered through CO2 extraction. The as-synthesized mesocellular metal-organic frameworks are highly active in catalysing the aerobic oxidation of benzylic alcohols under mild temperature at atmospheric pressure.

  20. Highly mesoporous metal-organic framework assembled in a switchable solvent.

    PubMed

    Peng, Li; Zhang, Jianling; Xue, Zhimin; Han, Buxing; Sang, Xinxin; Liu, Chengcheng; Yang, Guanying

    2014-07-22

    The mesoporous metal-organic frameworks are a family of materials that have pore sizes ranging from 2 to 50 nm, which have shown promising applications in catalysis, adsorption, chemical sensing and so on. The preparation of mesoporous metal-organic frameworks usually needs the supramolecular or cooperative template strategy. Here we report the template-free assembly of mesoporous metal-organic frameworks by using CO2-expanded liquids as switchable solvents. The mesocellular metal-organic frameworks with large mesopores (13-23 nm) are formed, and their porosity properties can be easily adjusted by controlling CO2 pressure. Moreover, the use of CO2 can accelerate the reaction for metal-organic framework formation from metal salt and organic linker due to the viscosity-lowering effect of CO2, and the product can be recovered through CO2 extraction. The as-synthesized mesocellular metal-organic frameworks are highly active in catalysing the aerobic oxidation of benzylic alcohols under mild temperature at atmospheric pressure.

  1. Metal-organic framework composites: from fundamentals to applications

    NASA Astrophysics Data System (ADS)

    Li, Shaozhou; Huo, Fengwei

    2015-04-01

    Metal-organic frameworks (MOFs) are a class of crystallized porous polymeric materials consisting of metal ions or clusters linked together by organic bridging ligands. Due to their permanent porosity, rich surface chemistry and tuneable pore sizes, MOFs have emerged as one type of important porous solid and have attracted intensive interests in catalysis, gas adsorption, separation and storage over the past two decades. When compared with pure MOFs, the combination of MOFs with functional species or matrix materials not only shows enhanced properties, but also broadens the applications of MOFs in new fields, such as bio-imaging, drug delivery and electrical catalysis, owing to the interactions of the functional species/matrix with the MOF structures. Although the synthesis, chemical modification and potential applications of MOFs have been reviewed previously, there is an increasing awareness on the synthesis and applications of their composites, which have rarely been reviewed. This review aims to fill this gap and discuss the fabrication, properties, and applications of MOF composites. The remaining challenges and future opportunities in this field, in terms of processing techniques, maximizing composite properties, and prospects for applications, have also been indicated.

  2. The chemical form of metallic debris in tissues surrounding metal-on-metal hips with unexplained failure.

    PubMed

    Hart, Alister J; Quinn, Paul D; Sampson, Barry; Sandison, Ann; Atkinson, Kirk D; Skinner, John A; Powell, Jonathan J; Mosselmans, J Fred W

    2010-11-01

    Implant-derived material from metal-on-metal (MOM) hip arthroplasties may be responsible for an unexplained tissue inflammatory response. The chemical form of the metal species in the tissues is predominantly chromium (Cr), but the currently used techniques have not been able to determine whether this is Cr(III) phosphate or Cr(III) oxide. The analytical challenge must overcome the fact that the metal in the tissues is at a relatively low concentration and tissue preparation or the microscopy beam used can affect the results. Microfocus X-ray spectroscopy using a synchrotron beam is useful in addressing both these issues. Using this technique we compared tissue from failed MOM hips with: (1) tissue from metal-on-polyethylene (MOP) hips; (2) chemical standards; (3) metal discs cut from MOM hips. The most abundant implant-related species in all MOM hip tissues contained Cr. Comparison with standards revealed the chemical form was Cr(III) phosphate, which did not vary with manufacturer type (four types analysed) or level of blood metal ions. Cobalt (Co) and molybdenum (Mo) were occasionally present in areas of high Cr. Co was normally found in a metallic state in the tissue, while Mo was found in an oxidized state. The variety of metallic species may have arisen from corrosion, wear or a combination of both. No evidence of Cr(VI) was seen in the tissues examined.

  3. Metal-organic chemical vapor deposition of indium oxide based transparent conducting oxide thin films: Precursor synthesis, film growth and characterization, and their application in polymer light-emitting diode devices

    NASA Astrophysics Data System (ADS)

    Ni, Jun

    2005-07-01

    Four novel diamine adducts of bis(hexafluoroacetylacetonato)zinc [Zn(hfa)2·(diamine)] can be synthesized in a single step reaction. Single crystal x-ray diffraction studies reveal monomeric, six-coordinate structures. The thermal stabilities and vapor phase transport properties of these complexes are considerably greater than those of conventional solid/liquid zinc metal-organic chemical vapor deposition (MOCVD) precursors. Of the four complexes, bis(1,1,1,5,5,5-hexafluoro-2,4-pentadionato)(N,N '-diethylethylenediamine)zinc [Zn(hfa)2 ( N,N'-DEA)], is particularly effective in the growth of thin films of the transparent conducting oxide Zn- and Sn-doped In2O3 (ZITO) due to its superior volatility and low melting point of 64°C. ZITO (ZnInxSnyOz, 1.5 < x < 4.0, 0.5 < y < 2.5) thin films with In contents ranging from 40--70 cation % (a metastable phase) were grown by low pressure MOCVD using volatile precursors tris(2,2,6,6-tetramethyl-3,5-heptanedionato)indium [In(dpm) 3], bis(2,4-pentanedionato)tin [Sn(acac)2], and Zn(hfa) 2(N,N'-DEA). These films exhibit conductivity as high as 2900 S/cm and optical transparency comparable to or greater than that of commercial ITO (Sn-doped indium oxide) films. They are more stable under acidic conditions than commercial ITO films as evidenced by XPS studies. Polymer light emitting diode (PLED) devices based on ZnIn 2.00Sn1.50Oz anode exhibit maximum light output of 4500 cd/m2 and current efficiency of 0.85 cd/A, which are 70% and 80% higher than those of PLED devices based on commercial ITO anode, respectively. The increased performance of ZITO based devices is attributed to the decreased reactivity of ZITO anode towards the acidic PEDOT-PSS hole injection layer compared to ITO anode. MITO (MgInxSnyOz, 6.0 < x < 16.0; 3.0 < y < 8.0, a metastable phase) thin films were grown by low-pressure MOCVD using volatile precursors In(dpm)3, Sn(acac)2, and bis(2,2,6,6-tetramethyl-3,5-heptanedionato)(tetramethylmethylenediamine)magnesium [Mg

  4. Probing buried organic-organic and metal-organic heterointerfaces by hard x-ray photoelectron spectroscopy

    NASA Astrophysics Data System (ADS)

    Shibuta, Masahiro; Eguchi, Toyoaki; Watanabe, Yoshio; Son, Jin-Young; Oji, Hiroshi; Nakajima, Atsushi

    2012-11-01

    We present a nondestructive characterization method for buried hetero-interfaces for organic/organic and metal/organic systems using hard x-ray photoelectron spectroscopy (HAXPES) which can probe electronic states at depths deeper than ˜10 nm. A significant interface-derived signal showing a strong chemical interaction is observed for Au deposited onto a C60 film, while there is no such additional feature for copper phthalocyanine deposited onto a C60 film reflecting the weak interaction between the molecules in the latter case. A depth analysis with HAXPES reveals that a Au-C60 intermixed layer with a thickness of 5.1 nm is formed at the interface.

  5. Structure and properties of an amorphous metal-organic framework.

    PubMed

    Bennett, Thomas D; Goodwin, Andrew L; Dove, Martin T; Keen, David A; Tucker, Matthew G; Barney, Emma R; Soper, Alan K; Bithell, Erica G; Tan, Jin-Chong; Cheetham, Anthony K

    2010-03-19

    ZIF-4, a metal-organic framework (MOF) with a zeolitic structure, undergoes a crystal-amorphous transition on heating to 300 degrees C. The amorphous form, which we term a-ZIF, is recoverable to ambient conditions or may be converted to a dense crystalline phase of the same composition by heating to 400 degrees C. Neutron and x-ray total scattering data collected during the amorphization process are used as a basis for reverse Monte Carlo refinement of an atomistic model of the structure of a-ZIF. The structure is best understood in terms of a continuous random network analogous to that of a-SiO2. Optical microscopy, electron diffraction and nanoindentation measurements reveal a-ZIF to be an isotropic glasslike phase capable of plastic flow on its formation. Our results suggest an avenue for designing broad new families of amorphous and glasslike materials that exploit the chemical and structural diversity of MOFs.

  6. Structure and Properties of an Amorphous Metal-Organic Framework

    NASA Astrophysics Data System (ADS)

    Bennett, Thomas D.; Goodwin, Andrew L.; Dove, Martin T.; Keen, David A.; Tucker, Matthew G.; Barney, Emma R.; Soper, Alan K.; Bithell, Erica G.; Tan, Jin-Chong; Cheetham, Anthony K.

    2010-03-01

    ZIF-4, a metal-organic framework (MOF) with a zeolitic structure, undergoes a crystal-amorphous transition on heating to 300°C. The amorphous form, which we term a-ZIF, is recoverable to ambient conditions or may be converted to a dense crystalline phase of the same composition by heating to 400°C. Neutron and x-ray total scattering data collected during the amorphization process are used as a basis for reverse Monte Carlo refinement of an atomistic model of the structure of a-ZIF. The structure is best understood in terms of a continuous random network analogous to that of a-SiO2. Optical microscopy, electron diffraction and nanoindentation measurements reveal a-ZIF to be an isotropic glasslike phase capable of plastic flow on its formation. Our results suggest an avenue for designing broad new families of amorphous and glasslike materials that exploit the chemical and structural diversity of MOFs.

  7. Metal-organic frameworks for membrane-based separations

    NASA Astrophysics Data System (ADS)

    Denny, Michael S.; Moreton, Jessica C.; Benz, Lauren; Cohen, Seth M.

    2016-12-01

    As research into metal-organic frameworks (MOFs) enters its third decade, efforts are naturally shifting from fundamental studies to applications, utilizing the unique features of these materials. Engineered forms of MOFs, such as membranes and films, are being investigated to transform laboratory-synthesized MOF powders to industrially viable products for separations, chemical sensors and catalysts. Following encouraging demonstrations of gas separations using MOF-based membranes, liquid-phase separations are now being explored in an effort to build effective membranes for these settings. In this Review, we highlight MOF applications that are in their nascent stages, specifically liquid-phase separations using MOF-based mixed-matrix membranes. We also highlight the analytical techniques that provide important insights into these materials, particularly at surfaces and interfaces, to better understand MOFs and their interactions with other materials, which will ultimately lead to their use in advanced technologies.

  8. Metal oxide charge transport material doped with organic molecules

    DOEpatents

    Forrest, Stephen R.; Lassiter, Brian E.

    2016-08-30

    Doping metal oxide charge transport material with an organic molecule lowers electrical resistance while maintaining transparency and thus is optimal for use as charge transport materials in various organic optoelectronic devices such as organic photovoltaic devices and organic light emitting devices.

  9. 40 CFR Table 1 to Subpart F of... - Synthetic Organic Chemical Manufacturing Industry Chemicals

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 9 2010-07-01 2010-07-01 false Synthetic Organic Chemical... POLLUTANTS FOR SOURCE CATEGORIES National Emission Standards for Organic Hazardous Air Pollutants From the Synthetic Organic Chemical Manufacturing Industry Pt. 63, Subpt. F, Table 1 Table 1 to Subpart F of Part...

  10. 40 CFR Table 1 to Subpart F of... - Synthetic Organic Chemical Manufacturing Industry Chemicals

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 10 2012-07-01 2012-07-01 false Synthetic Organic Chemical... POLLUTANTS FOR SOURCE CATEGORIES National Emission Standards for Organic Hazardous Air Pollutants From the Synthetic Organic Chemical Manufacturing Industry Pt. 63, Subpt. F, Table 1 Table 1 to Subpart F of Part...

  11. 40 CFR Table 1 to Subpart F of... - Synthetic Organic Chemical Manufacturing Industry Chemicals

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 9 2011-07-01 2011-07-01 false Synthetic Organic Chemical... POLLUTANTS FOR SOURCE CATEGORIES National Emission Standards for Organic Hazardous Air Pollutants From the Synthetic Organic Chemical Manufacturing Industry Pt. 63, Subpt. F, Table 1 Table 1 to Subpart F of Part...

  12. 40 CFR Table 1 to Subpart F of... - Synthetic Organic Chemical Manufacturing Industry Chemicals

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 10 2014-07-01 2014-07-01 false Synthetic Organic Chemical... POLLUTANTS FOR SOURCE CATEGORIES National Emission Standards for Organic Hazardous Air Pollutants From the Synthetic Organic Chemical Manufacturing Industry Pt. 63, Subpt. F, Table 1 Table 1 to Subpart F of Part...

  13. 40 CFR Table 1 to Subpart F of... - Synthetic Organic Chemical Manufacturing Industry Chemicals

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 10 2013-07-01 2013-07-01 false Synthetic Organic Chemical... POLLUTANTS FOR SOURCE CATEGORIES National Emission Standards for Organic Hazardous Air Pollutants From the Synthetic Organic Chemical Manufacturing Industry Pt. 63, Subpt. F, Table 1 Table 1 to Subpart F of Part...

  14. Single crystalline hollow metal-organic frameworks: a metal-organic polyhedron single crystal as a sacrificial template.

    PubMed

    Kim, Hyehyun; Oh, Minhak; Kim, Dongwook; Park, Jeongin; Seong, Junmo; Kwak, Sang Kyu; Lah, Myoung Soo

    2015-02-28

    Single crystalline hollow metal-organic frameworks (MOFs) with cavity dimensions on the order of several micrometers and hundreds of micrometers were prepared using a metal-organic polyhedron single crystal as a sacrificial hard template. The hollow nature of the MOF crystal was confirmed by scanning electron microscopy of the crystal sliced using a focused ion beam.

  15. COSOLVENCY OF PARTIALLY MISCIBLE ORGANIC SOLVENTS ON THE SOLUBILITY OF HYDROPHOBIC ORGANIC CHEMICALS

    EPA Science Inventory

    The cosolvency of completely miscible organic solvents (CMOSs) and partially miscible organic solvents (PMOSs) on the solubility of hydrophobic organic chemicals (HOCs) was examined, with an emphasis on PMOSs. Measured solubilities were compared with predictions from the log- lin...

  16. LOSS OF ORGANIC CHEMICALS IN SOIL: PURE COMPOUND TREATABILITY STUDIES

    EPA Science Inventory

    Comprehensive screening data on the treatability of 32 organic chemicals in soil were developed. Of the evaluated chemicals, 22 were phenolic compounds. Aerobic batch laboratory microcosm experiments were conducted using two soils: an acidic clay soil with <1% organic matter and ...

  17. Synthetic Organic Chemicals: United States Production and Sales, 1976.

    ERIC Educational Resources Information Center

    Adams, Roger; And Others

    This is the sixth annual report of the U.S. Trade Commission on domestic production and sales of synthetic organic chemicals and the raw materials from which they are made. The report consists of 15 sections, each covering a specified group (based primarily on use) of organic chemicals as follows: tar and tar crudes; primary products from…

  18. Uptake, Metabolism, and Tissue Distribution of Chemicals in Organisms

    EPA Science Inventory

    This talk will explain how chemicals get into aquatic species, what tissues and organs the chemicals move into, and what can happen to the chemicals once they get there. This will be presented using examples from recent studies conducted using state-of-the-art microscopy with em...

  19. Metal-assisted chemical etch porous silicon formation method

    DOEpatents

    Li, Xiuling; Bohn, Paul W.; Sweedler, Jonathan V.

    2004-09-14

    A thin discontinuous layer of metal such as Au, Pt, or Au/Pd is deposited on a silicon surface. The surface is then etched in a solution including HF and an oxidant for a brief period, as little as a couple seconds to one hour. A preferred oxidant is H.sub.2 O.sub.2. Morphology and light emitting properties of porous silicon can be selectively controlled as a function of the type of metal deposited, Si doping type, silicon doping level, and/or etch time. Electrical assistance is unnecessary during the chemical etching of the invention, which may be conducted in the presence or absence of illumination.

  20. Metal-organic scintillator crystals for X-ray, gamma ray, and neutron detection

    DOEpatents

    Boatner, Lynn A [Oak Ridge, TN; Kolopus, James A [Clinton, TN; Neal, John S [Knoxville, TN; Ramey, Joanne Oxendine [Knoxville, TN; Wisniewski, Dariusz J [Torun, PL

    2012-01-03

    New metal-organic materials are useful as scintillators and have the chemical formula LX.sub.3(CH.sub.3OH).sub.4 where L is Y, Sc, or a lanthanide element, and X is a halogen element. An example of the scintillator materials is CeCl.sub.3(CH.sub.3OH).sub.4.

  1. Lipase-supported metal-organic framework bioreactor catalyzes warfarin synthesis.

    PubMed

    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.

  2. Modelling of trace metal uptake by roots taking into account complexation by exogenous organic ligands

    NASA Astrophysics Data System (ADS)

    Jean-Marc, Custos; Christian, Moyne; Sterckeman, Thibault

    2010-05-01

    The context of this study is phytoextraction of soil trace metals such as Cd, Pb or Zn. Trace metal transfer from soil to plant depends on physical and chemical processes such as minerals alteration, transport, adsorption/desorption, reactions in solution and biological processes including the action of plant roots and of associated micro-flora. Complexation of metal ions by organic ligands is considered to play a role on the availability of trace metals for roots in particular in the event that synthetic ligands (EDTA, NTA, etc.) are added to the soil to increase the solubility of the contaminants. As this role is not clearly understood, we wanted to simulate it in order to quantify the effect of organic ligands on root uptake of trace metals and produce a tool which could help in optimizing the conditions of phytoextraction.We studied the effect of an aminocarboxilate ligand on the absorption of the metal ion by roots, both in hydroponic solution and in soil solution, for which we had to formalize the buffer power for the metal. We assumed that the hydrated metal ion is the only form which can be absorbed by the plants. Transport and reaction processes were modelled for a system made up of the metal M, a ligand L and the metal complex ML. The Tinker-Nye-Barber model was adapted to describe the transport of solutes M, L and ML in the soil and absorption of M by the roots. This allowed to represent the interactions between transport, chelating reactions, absorption of the solutes at the root surface, root growth with time, in order to simulate metal uptake by a whole root system.Several assumptions were tested such as i) absorption of the metal by an infinite sink and according to a Michaelis-Menten kinetics, solutes transport by diffusion with and without ii) mass flow and iii) soil buffer power for the ligand L. In hydroponic solution (without soil buffer power), ligands decreased the trace metal flux towards roots, as they reduced the concentration of hydrated

  3. Aerosol chemical vapor deposition of metal oxide films

    DOEpatents

    Ott, Kevin C.; Kodas, Toivo T.

    1994-01-01

    A process of preparing a film of a multicomponent metal oxide including: forming an aerosol from a solution comprised of a suitable solvent and at least two precursor compounds capable of volatilizing at temperatures lower than the decomposition temperature of said precursor compounds; passing said aerosol in combination with a suitable oxygen-containing carrier gas into a heated zone, said heated zone having a temperature sufficient to evaporate the solvent and volatilize said precursor compounds; and passing said volatilized precursor compounds against the surface of a substrate, said substrate having a sufficient temperature to decompose said volatilized precursor compounds whereby metal atoms contained within said volatilized precursor compounds are deposited as a metal oxide film upon the substrate is disclosed. In addition, a coated article comprising a multicomponent metal oxide film conforming to the surface of a substrate selected from the group consisting of silicon, magnesium oxide, yttrium-stabilized zirconium oxide, sapphire, or lanthanum gallate, said multicomponent metal oxide film characterized as having a substantially uniform thickness upon said FIELD OF THE INVENTION The present invention relates to the field of film coating deposition techniques, and more particularly to the deposition of multicomponent metal oxide films by aerosol chemical vapor deposition. This invention is the result of a contract with the Department of Energy (Contract No. W-7405-ENG-36).

  4. Silicon nanowire photodetectors made by metal-assisted chemical etching

    NASA Astrophysics Data System (ADS)

    Xu, Ying; Ni, Chuan; Sarangan, Andrew

    2016-09-01

    Silicon nanowires have unique optical effects, and have potential applications in photodetectors. They can exhibit simple optical effects such as anti-reflection, but can also produce quantum confined effects. In this work, we have fabricated silicon photodetectors, and then post-processed them by etching nanowires on the incident surface. These nanowires were produced by a wet-chemical etching process known as the metal-assisted-chemical etching, abbreviated as MACE. N-type silicon substrates were doped by thermal diffusion from a solid ceramic source, followed by etching, patterning and contact metallization. The detectors were first tested for functionality and optical performance. The nanowires were then made by depositing an ultra-thin film of gold below its percolation thickness to produce an interconnected porous film. This was then used as a template to etch high aspect ratio nanowires into the face of the detectors with a HF:H2O2 mixture.

  5. A pH-responsive cleavage route based on a metal-organic coordination bond.

    PubMed

    Xing, Lei; Zheng, Haoquan; Che, Shunai

    2011-06-20

    The physical or chemical event that generally causes stimuli responses is limited to the formation or destruction of secondary forces, such as hydrogen bonding, hydrophobic effects, electrostatic interactions, and simple reactions. Here, pH-responsive behavior of metal-organic coordination bonding, which is intrinsic to natural systems (e.g., transferrin recycling in cells), is becoming a strong candidate for a new stimulus-responsive route. We have designed a simple pH-responsive release system by integrating a metal ion and ligand or self-assembling these species with biodegradable host molecules to form nanoparticles with "metal-ligand" or "host-metal-ligand" architectures. The cleavage of either or both the "metal-ligand" or the "host-metal" coordination bond in response to pH variations causes significant damage to the nanoparticles and the subsequent release of ligand molecules under designated pH conditions.

  6. Influence of Filler Metals in Welding Wires on the Phase and Chemical Composition of Weld Metal

    NASA Astrophysics Data System (ADS)

    Kozyrev, N. A.; Osetkovskiy, I. V.; Kozyreva, O. A.; Zernin, E. A.; Kartsev, D. S.

    2016-04-01

    The influence of filler metals used in welding wires on the phase and chemical composition of the metal, which is surfaced to mining equipment exposed to abrasive wear, has been investigated. Under a laboratory environment, samples of Mo-V-B and Cr-Mn-Mo-V wires were made. The performed experiments have revealed that fillers of the Cr-Mn-Mo-V system used in powder wire show better wear resistance of the weld metal than that of the Mn-Mo-V-B system; the absence of boron, which promotes grain refinement in the Mn-Mo-V-B system, significantly reduces wear resistance; the Mn-Mo-V-B weld metal has a finer structure than the Cr-Mn-Mo-V weld metal.

  7. Tattoo inks: legislation, pigments, metals and chemical analysis.

    PubMed

    Prior, Gerald

    2015-01-01

    Legal limits for chemical substances require that they are linked to clearly defined analytical methods. Present limits for certain chemicals in tattoo and permanent make-up inks do not mention analytical methods for the detection of metals, polycyclic aromatic hydrocarbons or forbidden colourants. There is, therefore, no established method for the determination of the quantities of these chemicals in tattoo and permanent make-up inks. Failing to provide an appropriate method may lead to unqualified and questionable results which often cause legal disputes that are ultimately resolved by a judge with regard to the method that should have been applied. Analytical methods are tuned to exactly what is to be found and what causes the health problems. They are extremely specific. Irrespective of which is the correct method for detecting metals in tattoo inks, the focus should be on the actual amounts of ink in the skin. CTL® has conducted experiments to determine these amounts and these experiments are crucial for toxicological evaluations and for setting legal limits. When setting legal limits, it is essential to also incorporate factors such as daily consumption, total uptake and frequency of use. A tattoo lasts for several decades; therefore, the limits that have been established for heavy metals used in drinking water or soap are not relevant. Drinking water is consumed on a daily basis and soap is used several times per week, while tattooing only occurs once.

  8. Organic matter in hydrothermal metal ores and hydrothermal fluids

    USGS Publications Warehouse

    Orem, W.H.; Spiker, E. C.; Kotra, R.K.

    1990-01-01

    Massive polymetallic sulfides are currently being deposited around active submarine hydrothermal vents associated with spreading centers. Chemoautolithotrophic bacteria are responsible for the high production of organic matter also associated with modern submarine hydrothermal activity. Thus, there is a significant potential for organic matter/metal interactions in these systems. We have studied modern and ancient hydrothermal metal ores and modern hydrothermal fluids in order to establish the amounts and origin of the organic matter associated with the metal ores. Twenty-six samples from modern and ancient hydrothermal systems were surveyed for their total organic C contents. Organic C values ranged from 0.01% to nearly 4.0% in these samples. Metal ores from modern and ancient sediment-covered hydrothermal systems had higher organic C values than those from modern and ancient hydrothermal systems lacking appreciable sedimentary cover. One massive pyrite sample from the Galapagos spreading center (3% organic C) had stable isotope values of -27.4% (??13C) and 2.1% (??15N), similar to those in benthic siphonophors from active vents and distinct from seep sea sedimentary organic matter. This result coupled with other analyses (e.g. 13C NMR, pyrolysis/GC, SEM) of this and other samples suggests that much of the organic matter may originate from chemoautolithotrophic bacteria at the vents. However, the organic matter in hydrothermal metal ores from sediment covered vents probably arises from complex sedimentary organic matter by hydrothermal pyrolysis. The dissolved organic C concentrations of hydrothermal fluids from one site (Juan de Fuca Ridge) were found to be the same as that of background seawater. This result may indicate that dissolved organic C is effectively scavenged from hydrothermal fluids by biological activity or by co-precipitation with metal ores. ?? 1990.

  9. Quantification of Stereochemical Communication in Metal-Organic Assemblies.

    PubMed

    Castilla, Ana M; Miller, Mark A; Nitschke, Jonathan R; Smulders, Maarten M J

    2016-08-26

    The derivation and application of a statistical mechanical model to quantify stereochemical communication in metal-organic assemblies is reported. The factors affecting the stereochemical communication within and between the metal stereocenters of the assemblies were experimentally studied by optical spectroscopy and analyzed in terms of a free energy penalty per "incorrect" amine enantiomer incorporated, and a free energy of coupling between stereocenters. These intra- and inter-vertex coupling constants are used to track the degree of stereochemical communication across a range of metal-organic assemblies (employing different ligands, peripheral amines, and metals); temperature-dependent equilibria between diastereomeric cages are also quantified. The model thus provides a unified understanding of the factors that shape the chirotopic void spaces enclosed by metal-organic container molecules.

  10. Safety in the Chemical Laboratory. Organic Peroxides.

    ERIC Educational Resources Information Center

    Shanley, Edward S.

    1990-01-01

    Discussed is the thermodynamic instability of organic peroxides. The process of autoxidation which results in peroxide formation is described. Precautions necessary to prevent autoxidation hazards associated with these reagents are suggested. (CW)

  11. Heavy metal content in sediments along the Calore river: relationships with physical-chemical characteristics.

    PubMed

    Bartoli, G; Papa, S; Sagnella, E; Fioretto, A

    2012-03-01

    In the present study, trace metals contents (V, Cr, Mn, Fe, Ni, Cu, Zn, Cd and Pb) and physico-chemical parameters (nitrogen, organic and inorganic carbon, pH and particle size) in sediments samples along the Calore river were analyzed in two seasons. Sediment samples were collected in ten sites upstream and downstream of the city of Benevento and its industrial area, the confluence of Sabato and Tammaro tributaries, and the confluence of Calore and Volturno rivers. The highest contents of trace metals were found, generally, in the sites immediately downstream of industrial area and of Benevento city. The sites on the Tammaro and Sabato also showed relatively high contents of Ni and, only for Sabato sites, of Cr, and Fe. With the exception of Cd, the heavy metal contents were highest in the last site of Calore river, which therefore is a source of pollution to the Volturno river. Besides the sites downstream of Benevento city showed the higher pH values and also the highest contents of fine particles size and organic matter. Positive correlations among trace metals, organic substance, particle size sediments were found. The data obtained in this study were analyzed with reference to Interim Sediment Quality Guidelines and indicated moderate-to-high pollution by some trace metals (V, Cr, Mn, Fe, Ni, Cu).

  12. USING ZERO-VALENT METAL NANOPARTICLES TO REMEDIATE ORGANIC CONTAMINANTS

    EPA Science Inventory

    The transport of organic contaminants down the soil profile constitutes a serious threat to the quality of ground water. Zero-valent metals are considered innocuous abiotic agents capable of mediating decontamination processes in terrestrial systems. In this investigation, ze...

  13. Applications of metal-organic frameworks in heterogeneous supramolecular catalysis.

    PubMed

    Liu, Jiewei; Chen, Lianfen; Cui, Hao; Zhang, Jianyong; Zhang, Li; Su, Cheng-Yong

    2014-08-21

    This review summarizes the use of metal-organic frameworks (MOFs) as a versatile supramolecular platform to develop heterogeneous catalysts for a variety of organic reactions, especially for liquid-phase reactions. Following a background introduction about catalytic relevance to various metal-organic materials, crystal engineering of MOFs, characterization and evaluation methods of MOF catalysis, we categorize catalytic MOFs based on the types of active sites, including coordinatively unsaturated metal sites (CUMs), metalloligands, functional organic sites (FOS), as well as metal nanoparticles (MNPs) embedded in the cavities. Throughout the review, we emphasize the incidental or deliberate formation of active sites, the stability, heterogeneity and shape/size selectivity for MOF catalysis. Finally, we briefly introduce their relevance into photo- and biomimetic catalysis, and compare MOFs with other typical porous solids such as zeolites and mesoporous silica with regard to their different attributes, and provide our view on future trends and developments in MOF-based catalysis.

  14. Porous materials: Lining up metal-organic frameworks

    NASA Astrophysics Data System (ADS)

    Champness, Neil R.

    2017-02-01

    A new report demonstrates an innovative approach to aligning crystallites of metal-organic frameworks such that thin films are created with oriented channels -- potentially overcoming one of the major barriers to application of these highly topical materials.

  15. From metal-organic framework to intrinsically fluorescent carbon nanodots.

    PubMed

    Amali, Arlin Jose; Hoshino, Hideto; Wu, Chun; Ando, Masanori; Xu, Qiang

    2014-07-01

    Highly photoluminescent carbon nanodots (CNDs) were synthesized for the first time from metal-organic framework (MOF, ZIF-8) nanoparticles. Coupled with fluorescence and non-toxic characteristics, these carbon nanodots could potentially be used in biosafe color patterning.

  16. Metal-organic framework for the separation of alkane isomers

    DOEpatents

    Long, Jeffrey R.; Herm, Zoey R.; Wiers, Brian M.; Krishna, Rajamani

    2017-01-10

    A metal organic framework Fe.sub.2(bdp).sub.3 (BDP.sup.2-=1,4-benzenedipyrazolate) with triangular channels is particularly suited for C5-C7 separations of alkanes according to the number of branches in the molecule rather than by carbon number. The metal-organic framework can offer pore geometries that is unavailable in zeolites or other porous media, facilitating distinct types of shape-based molecular separations.

  17. Chemical vapor deposition of ceramic coatings on metals and ceramic fibers

    NASA Astrophysics Data System (ADS)

    Nable, Jun Co

    2005-07-01

    The research presented in this study consists of two major parts. The first part is about the development of ceramic coatings on metals by chemical vapor deposition (CVD) and metal-organic chemical vapor deposition (MOCVD). Ceramics such as Al2O3 and Cr2O3, are used as protective coatings for materials used at elevated temperatures (>700°C). These metal oxides either exhibit oxidation resistance or have been used as environmental bond coats. Conventional methods of coating by chemical vapor deposition requires deposition temperatures of >950°C which could damage the substrate material during the coating process. Lower deposition temperatures (400 to 600°C) by MOCVD of these metal oxides were successful on Ni metal substrates. Surface modification such as pre-oxidation and etching were also investigated. In addition, a novel approach for the CVD of TiN on metals was developed. This new approach utilizes ambient pressure conditions which lead to deposition temperatures of 800°C or lower compared to conventional CVD of TiN at 1000°C. Titanium nitride can be used as an abrasive and wear coating on cutting and grinding tools. This nitride can also serve as a diffusion coating in metals. The second major part of this research involves the synthesis of interfacial coatings on ceramic reinforcing fibers for ceramic matrix composites. Aluminum and chromium oxides were deposited onto SiC, and Al2O3-SiO 2 fibers by MOCVD. The effects of the interface coatings on the tensile strength of ceramic fibers are also discussed. New duplex interface coatings consisting of BN or TiN together with Al2O3 or ZrO 2 were also successfully deposited and evaluated on SiC fibers.

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

    DOEpatents

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

    2017-01-10

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

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

    PubMed Central

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

    2016-01-01

    Earth-abundant metal catalysts are critically needed for sustainable chemical synthesis. Here we report a simple, cheap and effective strategy of producing novel earth-abundant metal catalysts at metal–organic framework (MOF) nodes for broad-scope organic transformations. The straightforward metalation of MOF secondary building units (SBUs) with cobalt and iron salts affords highly active and reusable single-site solid catalysts for a range of organic reactions, including chemoselective borylation, silylation and amination of benzylic C–H bonds, as well as hydrogenation and hydroboration of alkenes and ketones. Our structural, spectroscopic and kinetic studies suggest that chemoselective organic transformations occur on site-isolated, electron-deficient and coordinatively unsaturated metal centres at the SBUs via σ-bond metathesis pathways and as a result of the steric environment around the catalytic site. MOFs thus provide a novel platform for the development of highly active and affordable base metal catalysts for the sustainable synthesis of fine chemicals. PMID:27574182

  20. COSOLVENT EFFECTS ON ORGANIC CHEMICAL PARTITIONING TO SEDIMENT ORGANIC CARBON

    EPA Science Inventory

    Sorption-desorption hysteresis, slow desorption kinetics and resultant bioavailability, and other nonideal phenomena have been attributed to the differing sorptive characteristics of the natural organic polymers associated with soils and sediments. The objectives of this study we...

  1. CHEMICAL ACTIVATION OF MOLECULES BY METALS: EXPERIMENTAL STUDIES OF ELECTRON DISTRIBUTIONS AND BONDING

    SciTech Connect

    LICHTENBERGER, DENNIS L.

    2002-03-26

    This research program is directed at obtaining detailed experimental information on the electronic interactions between metals and organic molecules. These interactions provide low energy pathways for many important chemical and catalytic processes. A major feature of the program is the continued development and application of our special high-resolution valence photoelectron spectroscopy (UPS), and high-precision X-ray core photoelectron spectroscopy (XPS) instrumentation for study of organometallic molecules in the gas phase. The study involves a systematic approach towards understanding the interactions and activation of bound carbonyls, C-H bonds, methylenes, vinylidenes, acetylides, alkenes, alkynes, carbenes, carbynes, alkylidenes, alkylidynes, and others with various monometal, dimetal, and cluster metal species. Supporting ligands include -aryls, alkoxides, oxides, and phosphines. We are expanding our studies of both early and late transition metal species and electron-rich and electron-poor environments in order to more completely understand the electronic factors that serve to stabilize particular organic fragments and intermediates on metals. Additional new directions for this program are being taken in ultra-high vacuum surface UPS, XPS, scanning tunneling microscopy (STM) and atomic force microscopy (AFM) experiments on both physisorbed and chemisorbed organometallic thin films. The combination of these methods provides additional electronic structure information on surface-molecule and molecule-molecule interactions. A very important general result emerging from this program is the identification of a close relationship between the ionization energies of the species and the thermodynamics of the chemical and catalytic reactions of these systems.

  2. BASIC CHEMICAL RESEARCH PROGRAM. ELECTRICAL PROPERTIES OF ORGANIC COMPOUNDS

    DTIC Science & Technology

    BENZENE, *CYANIDES, *HYDROXIDES, *ORGANIC COMPOUNDS, ACETYLENES, ALKYL RADICALS, AMIDES, ANILINES , BENZALDEHYDES, CHEMICAL REACTIONS , CONDENSATION... REACTIONS , ELECTRICAL CONDUCTIVITY, MATERIALS, MEASUREMENT, MONOCYCLIC COMPOUNDS, PHENOLS, PHENYL RADICALS, QUINONES, SOLID STATE PHYSICS, SYNTHESIS.

  3. Chemiluminescent chemical sensors for inorganic and organic vapors

    SciTech Connect

    Collins, G.E.; Rose-Pehrsson, S.L.

    1995-12-31

    Chemiluminescent, chemical sensors for inorganic and organic vapors are being investigated via the immobilization of 3-aminophthalhydrazide (luminol) within hydrogels and polymeric, sorbent coatings. The films are supported behind a teflon membrane and positioned in front of a photomultiplier tube, permitting the sensitive detection of numerous toxic vapors. Some selectivity has been tailored into these devices by careful selection of the polymer type, pH and metal catalyst incorporated within the film. The incorporation of luminol and Fe(3) within a polyvinylalcohol hydrogel gave a film with superior sensitivity toward NO{sub 2} (detection limit of 0.46 ppb and a response time on the order of seconds). The use of the hydrogel matrix helped eliminate humidity problems associated with other polymeric films. Other chemiluminescent thin films prepared have demonstrated the detection of ppb levels of SO{sub 2}(g) and hydrazine, N{sub 2}H{sub 4}(g). Recently, the authors have begun investigating the incorporation of a heated Pt filament into the inlet line as a pre-oxidative step prior to passage of the gas stream across the teflon membrane. This has permitted the sensitive detection of ppm levels of CCl{sub 4}(g), CHCl{sub 3}(g) and CH{sub 2}Cl{sub 2}(g).

  4. Chemical reactions of organic compounds on clay surfaces.

    PubMed Central

    Soma, Y; Soma, M

    1989-01-01

    Chemical reactions of organic compounds including pesticides at the interlayer and exterior surfaces of clay minerals and with soil organic matter are reviewed. Representative reactions under moderate conditions possibly occurring in natural soils are described. Attempts have been made to clarify the importance of the chemical nature of molecules, their structures and their functional groups, and the Brönsted or Lewis acidity of clay minerals. PMID:2533556

  5. Distribution of volatile organic chemicals in outdoor and indoor air

    NASA Technical Reports Server (NTRS)

    Shah, Jitendra J.; Singh, Hanwant B.

    1988-01-01

    The EPA volatile organic chemistry (VOC) national ambient data base (Shah, 1988) is discussed. The 320 chemicals included in the VOC data base are listed. The methods used to obtain the data are reviewed and the availability, accessibility, and operation of the data base are examined. Tables of the daily outdoor concentrations for 66 chemicals and the daily indoor concentrations for 35 chemicals are presented.

  6. CTEPP NC DATA ANALYTICAL RESULTS ORGANIZED BY CHEMICAL AND MEDIA

    EPA Science Inventory

    This data set contains the field sample data by chemical and matrix. The data are organized at the sample, chemical level.

    The Children’s Total Exposure to Persistent Pesticides and Other Persistent Pollutant (CTEPP) study was one of the largest aggregate exposure studies of y...

  7. Modeling organic chemical fate in aquatic systems: Significance of bioaccumulation and relevant time-space scales

    SciTech Connect

    Thomann, R.V.

    1995-06-01

    The importance of aquatic food chain bioaccumulation of organic chemicals in contributing to human dose is derived. It is shown that for chemicals with log octanol water partition coefficients greater than about 3, the role of food chain transfer to fish consumed by humans becomes the more dominant route over drinking water. Modeling of aquatic food chain bioaccumulation then becomes necessary to accurately estimate dose of such chemicals to humans. The relevant time and space scales for groundwater and surface water also indicate a division of organic chemicals at a log octanol water partition coefficient of about 3. For chemicals greater than that level, groundwater transport is minimal, while for chemicals with log octanol water coefficients of less than about 3, detention times are long relative to surface water and biodegradation processes become more significant. An illustration is given of modeling the groundwater transport of two organic chemicals (BCEE and benzene) and a metal (chromium) at a Superfund site. The model indicates that after 10 years only a relatively small fraction of the chemicals had traveled in the groundwater about 300 m to the point of release from the site to surface water. On the other hand, steady state in the adjacent stream and lake is reached rapidly over a distance of 2000 m, illustrating the difference in spatial and temporal scales for the groundwater and surface water. 15 refs., 8 figs., 1 tab.

  8. Residual metallic contamination of transferred chemical vapor deposited graphene.

    PubMed

    Lupina, Grzegorz; Kitzmann, Julia; Costina, Ioan; Lukosius, Mindaugas; Wenger, Christian; Wolff, Andre; Vaziri, Sam; Östling, Mikael; Pasternak, Iwona; Krajewska, Aleksandra; Strupinski, Wlodek; Kataria, Satender; Gahoi, Amit; Lemme, Max C; Ruhl, Guenther; Zoth, Guenther; Luxenhofer, Oliver; Mehr, Wolfgang

    2015-05-26

    Integration of graphene with Si microelectronics is very appealing by offering a potentially broad range of new functionalities. New materials to be integrated with the Si platform must conform to stringent purity standards. Here, we investigate graphene layers grown on copper foils by chemical vapor deposition and transferred to silicon wafers by wet etching and electrochemical delamination methods with respect to residual submonolayer metallic contaminations. Regardless of the transfer method and associated cleaning scheme, time-of-flight secondary ion mass spectrometry and total reflection X-ray fluorescence measurements indicate that the graphene sheets are contaminated with residual metals (copper, iron) with a concentration exceeding 10(13) atoms/cm(2). These metal impurities appear to be partially mobile upon thermal treatment, as shown by depth profiling and reduction of the minority charge carrier diffusion length in the silicon substrate. As residual metallic impurities can significantly alter electronic and electrochemical properties of graphene and can severely impede the process of integration with silicon microelectronics, these results reveal that further progress in synthesis, handling, and cleaning of graphene is required to advance electronic and optoelectronic applications.

  9. Molecular Properties and Fate of Organic Chemicals

    DTIC Science & Technology

    1990-08-14

    Monsen, R.M. Water Sci. Technol. 1989, 21, ?????-????? (7) Haber, F .; Weiss, J.J. Proc. Roy. Soc. London, Ser. A 1934, 147, 332-???? (8) Lindsay Smith...366. (30) Tejedor , I., personal comm. Table 1: Products from oxidation of chlorobenzene with Fenton’s Reagent Concentrations, (mM) atmosphere Fe÷3...Complete mineralization of organic compounds was not observed dluring the oxidation o) f 4-chhorophenol is most observed because some of the ring-cleavage

  10. Separating of organic and inorganic forms of metals in sediments

    SciTech Connect

    Hsieh, Yuch Ping

    1995-12-31

    Separating organic forms of trace metals from their pyritic forms is a difficult problem one constantly faced when studying trace metals in a reduced soil. It is known that pyritic forms and organic forms of metals can be separated by solubilizing pyritic forms in a reducing agent while leaving the organic forms intact. The problem is that the reducing agents used in those procedures are also metals such as Cr or Sn that makes the study of trace metals impossible. If oxidation procedure is used, both pyritic anorganic forms oxidize almost at the same rate which resulted in hardly any separation. Reported here is a new procedure that oxidizes > 95% of pyritic forms and < 5% of organic forms of heavy metal using a modified hydrogen peroxide solution. The procedure is examined using mixtures of standards and salt marsh sediments. Using this procedure, we prove that rarely any added Cu retained in salt marshes is in organic form, a result has been repeatedly mistakenly reported.

  11. Biomimetic mineralization of metal-organic frameworks as protective coatings for biomacromolecules

    PubMed Central

    Liang, Kang; Ricco, Raffaele; Doherty, Cara M.; Styles, Mark J.; Bell, Stephen; Kirby, Nigel; Mudie, Stephen; Haylock, David; Hill, Anita J.; Doonan, Christian J.; Falcaro, Paolo

    2015-01-01

    Enhancing the robustness of functional biomacromolecules is a critical challenge in biotechnology, which if addressed would enhance their use in pharmaceuticals, chemical processing and biostorage. Here we report a novel method, inspired by natural biomineralization processes, which provides unprecedented protection of biomacromolecules by encapsulating them within a class of porous materials termed metal-organic frameworks. We show that proteins, enzymes and DNA rapidly induce the formation of protective metal-organic framework coatings under physiological conditions by concentrating the framework building blocks and facilitating crystallization around the biomacromolecules. The resulting biocomposite is stable under conditions that would normally decompose many biological macromolecules. For example, urease and horseradish peroxidase protected within a metal-organic framework shell are found to retain bioactivity after being treated at 80 °C and boiled in dimethylformamide (153 °C), respectively. This rapid, low-cost biomimetic mineralization process gives rise to new possibilities for the exploitation of biomacromolecules. PMID:26041070

  12. Chemical speciation of sulfur and metals in biogas reactors - Implications for cobalt and nickel bio-uptake processes.

    PubMed

    Yekta, Sepehr Shakeri; Skyllberg, Ulf; Danielsson, Åsa; Björn, Annika; Svensson, Bo H

    2017-02-15

    This article deals with the interrelationship between overall chemical speciation of S, Fe, Co, and Ni in relation to metals bio-uptake processes in continuous stirred tank biogas reactors (CSTBR). To address this topic, laboratory CSTBRs digesting sulfur(S)-rich stillage, as well as full-scale CSTBRs treating sewage sludge and various combinations of organic wastes, termed co-digestion, were targeted. Sulfur speciation was evaluated using acid volatile sulfide extraction and X-ray absorption spectroscopy. Metal speciation was evaluated by chemical fractionation, kinetic and thermodynamic analyses. Relative Fe to S content is identified as a critical factor for chemical speciation and bio-uptake of metals. In reactors treating sewage sludge, quantity of Fe exceeds that of S, inducing Fe-dominated conditions, while sulfide dominates in laboratory and co-digestion reactors due to an excess of S over Fe. Under sulfide-dominated conditions, metals availability for microorganisms is restricted due to formation of metal-sulfide precipitates. However, aqueous concentrations of different Co and Ni species were shown to be sufficient to support metal acquisition by microorganisms under sulfidic conditions. Concentrations of free metal ions and labile metal complexes in aqueous phase, which directly participate in bio-uptake processes, are higher under Fe-dominated conditions. This in turn enhances metal adsorption on cell surfaces and bio-uptake rates.

  13. A new metalation complex for organic synthesis and polymerization reactions

    NASA Technical Reports Server (NTRS)

    Hirshfield, S. M.

    1971-01-01

    Organometallic complex of N,N,N',N' tetramethyl ethylene diamine /TMEDA/ and lithium acts as metalation intermediate for controlled systhesis of aromatic organic compounds and polymer formation. Complex of TMEDA and lithium aids in preparation of various organic lithium compounds.

  14. Thin films of metal oxides grown by chemical vapor deposition from volatile transition metal and lanthanide metal complexes

    NASA Astrophysics Data System (ADS)

    Pollard, Kimberly Dona

    1998-08-01

    This thesis describes the synthesis and characterization of novel volatile metal-organic complexes for the chemical vapor deposition (CVD) of metal oxides. Monomeric tantalum complexes, lbrack Ta(OEt)sb4(beta-diketonate)) are prepared by the acid-base reaction of lbrack Tasb2(OEt)sb{10}rbrack with a beta-diketone, (RC(O)CHsb2C(O)Rsp' for R = CHsb3, Rsp' = CFsb3; R = Rsp'=C(CHsb3)sb3; R = Csb3Fsb7,\\ Rsp'=C(CHsb3)sb3;\\ R=Rsp'=CFsb3; and R = Rsp' = CHsb3). The products are characterized spectroscopically. Thermal CVD using these complexes as precursors gave good quality Tasb2Osb5 thin films which are characterized by XPS, SEM, electrical measurements, and XRD. Factors affecting the film deposition such as the type of carrier gas and the temperature of the substrate were considered. Catalyst-enhanced CVD reactions with each of the precursors and a palladium catalyst, ((2-methylallyl)Pd(acac)), were studied as a lower temperature route to good quality Tasb2Osb5 films. The decomposition mechanism at the hot substrate surface was studied. Precursors for the formation of yttria by CVD were examined. New complexes of the form (Y(hfac)sb3(glyme)), (hfac = \\{CFsb3C(O)CHC(O)CFsb3\\}sp-,\\ glyme=CHsb3O(CHsb2CHsb2O)sb{n}CHsb3 for n = 1-4) were synthesized and characterized spectroscopically. X-ray structural determinations of three new complexes were obtained. CVD reaction conditions were determined which give YOF films and, with catalyst-enhanced CVD, reaction conditions which give selective formation of Ysb2Osb3, YOF, or YFsb3. The films were studied by XPS, SEM, and XRD. Decomposition mechanisms which lead to film formation, together with a possible route for fluorine atom transfer from the ligand to the metal resulting in fluorine incorporation, were studied by analysis of exhaust products using GC-MS. Novel precursors of the form lbrack Ce(hfac)sb3(glyme)rbrack,\\ (hfac=\\{CFsb3C(O)CHC(O)CFsb3\\}sp-,\\ glyme=CHsb3O(CHsb2CHsb2O)sb{n}CHsb3, n = 1-4) for CVD of ceria were

  15. Metal-Organic Frameworks for Highly Selective Separations

    SciTech Connect

    Omar M. Yaghi

    2009-09-28

    This grant was focused on the study of metal-organic frameworks with these specific objectives. (1) To examine the use of MOFs with well-defined open metal sites for binding of gases and small organics. (2) To develop a strategy for producing MOFs that combine large pore size with high surface area for their use in gas adsorption and separation of polycyclic organic compounds. (3) To functionalize MOFs for the storage of inert gases such as methane. A brief outline of our progress towards these objectives is presented here as it forms part of the basis for the ideas to be developed under the present proposal.

  16. CHEMICAL TRANSPORT FACILITATED BY COLLOIDAL-SIZED ORGANIC MOLECULES

    EPA Science Inventory

    The fluid passing through the pores of soils and geologic materials is not just water with dissolved inorganic chemicals, but a complex mixture of organic and inorganic molecules. Large organic molecules such as humic and fulvic materials may impact the movement of contaminants. ...

  17. Chemically Modified Metal Oxide Nanostructure for Photoelectrochemical Water Splitting

    NASA Astrophysics Data System (ADS)

    Wang, Gongming

    Hydrogen gas is chemical fuel with high energy density, and represents a clean, renewable and carbon-free burning fuel, which has the potential to solve the more and more urgent energy crisis in today's society. Inspired by natural photosynthesis, artificial photosynthesis to generate hydrogen energy has attracted a lot of attentions in the field of chemistry, physics and material. Photoelectrochemical water splitting based on semiconductors represents a green and low cost method to generate hydrogen fuel. However, the current overall efficiency of solar to hydrogen is quite low, due to some intrinsic limitations such as bandgap, diffusion distance, carrier lifetime and photostability of semiconductors. Although nanostructured semiconductors can improve their photoelectrochemical water splitting performance to some extent, by increasing electrolyte accessible area and shortening minority carrier diffusion distance, nanostructure engineering cannot change their intrinsic electronic properties. Recent development in chemically modified nanostructures such as surface catalyst decoration, element doping, plasmonic modification and interfacial hetero-junction design have led to significant advancement in the photoelectrochemical water splitting, by improving surface reaction kinetics and charge separation, transportation and collection efficiency. In this thesis, I will give a detailed discussion on the chemically modified metal oxide nanostructures for photoelectrocemical hydrogen generation, with a focus on the element doping, hydrogen treatment and catalyst modification. I have demonstrated nitrogen doping on ZnO and Ti doping on hematite can improve their photoelectrochemical performance. In addition, we found hydrogen treatment is a general and effective method to improve the photocatalytic performance, by increasing their carrier desities. Hydrogen treatment has been demonstrated on TiO2, WO3 and BiVO4. In the end, we also used electrochemical catalyt to modify

  18. Copper Benzenetricarboxylate Metal-Organic Framework Nucleation Mechanisms on Metal Oxide Powders and Thin Films formed by Atomic Layer Deposition.

    PubMed

    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.

  19. Membrane-Organized Chemical Photoredox Systems

    SciTech Connect

    Hurst, James K.

    2014-09-18

    This project has three interrelated goals relevant to solar water photolysis, which are to develop: (1) vesicle-organized assemblies for H2 photoproduction that utilize pyrylium and structurally related compounds as combined photosensitizers and cyclic electroneutral transmembrane electron carriers; (2) transmembrane redox systems whose reaction rates can be modulated by light; and (3) homogeneous catalysts for water oxidation. . In area (1), initial efforts to photogenerate H2 from vectorially-organized vesicles containing occluded colloidal Pt and commonly available pyrylium ions as transmembrane redox mediators were unsuccessful. New pyrylium compounds with significantly lower reduction potentials have been synthesized to address this problem, their apparent redox potentials in functioning systems have been now evaluated by using a series of occluded viologens, and H2 photoproduction has been demonstrated in continuous illumination experiments. In area (2), spirooxazine-quinone dyads have been synthesized and their capacity to function as redox mediators across bilayer membranes has been evaluated through continuous photolysis and transient spectrophotometric measurements. Photoisomerization of the spiro moiety to the ring-open mero form caused net quantum yields to decrease significantly, providing a basis for photoregulation of transmembrane redox. Research on water oxidation (area 3) has been directed at understanding mechanisms of catalysis by cis,cis-[(bpy)2Ru(OH2)]2O4+ and related polyimine complexes. Using a variety of physical techniques, we have: (i) identified the redox state of the complex ion that is catalytically active; (ii) shown using 18O isotopic labeling that there are two reaction pathways, both of which involve participation of solvent H2O; and (iii) detected and characterized by EPR and resonance Raman spectroscopies new species which may be key intermediates in the catalytic cycle.

  20. Synthesis and Characterization of Functionalized Metal-organic Frameworks

    PubMed Central

    Karagiaridi, Olga; Bury, Wojciech; Sarjeant, Amy A.; Hupp, Joseph T.; Farha, Omar K.

    2014-01-01

    Metal-organic frameworks have attracted extraordinary amounts of research attention, as they are attractive candidates for numerous industrial and technological applications. Their signature property is their ultrahigh porosity, which however imparts a series of challenges when it comes to both constructing them and working with them. Securing desired MOF chemical and physical functionality by linker/node assembly into a highly porous framework of choice can pose difficulties, as less porous and more thermodynamically stable congeners (e.g., other crystalline polymorphs, catenated analogues) are often preferentially obtained by conventional synthesis methods. Once the desired product is obtained, its characterization often requires specialized techniques that address complications potentially arising from, for example, guest-molecule loss or preferential orientation of microcrystallites. Finally, accessing the large voids inside the MOFs for use in applications that involve gases can be problematic, as frameworks may be subject to collapse during removal of solvent molecules (remnants of solvothermal synthesis). In this paper, we describe synthesis and characterization methods routinely utilized in our lab either to solve or circumvent these issues. The methods include solvent-assisted linker exchange, powder X-ray diffraction in capillaries, and materials activation (cavity evacuation) by supercritical CO2 drying. Finally, we provide a protocol for determining a suitable pressure region for applying the Brunauer-Emmett-Teller analysis to nitrogen isotherms, so as to estimate surface area of MOFs with good accuracy. PMID:25225784

  1. Synthesis and characterization of functionalized metal-organic frameworks.

    PubMed

    Karagiaridi, Olga; Bury, Wojciech; Sarjeant, Amy A; Hupp, Joseph T; Farha, Omar K

    2014-09-05

    Metal-organic frameworks have attracted extraordinary amounts of research attention, as they are attractive candidates for numerous industrial and technological applications. Their signature property is their ultrahigh porosity, which however imparts a series of challenges when it comes to both constructing them and working with them. Securing desired MOF chemical and physical functionality by linker/node assembly into a highly porous framework of choice can pose difficulties, as less porous and more thermodynamically stable congeners (e.g., other crystalline polymorphs, catenated analogues) are often preferentially obtained by conventional synthesis methods. Once the desired product is obtained, its characterization often requires specialized techniques that address complications potentially arising from, for example, guest-molecule loss or preferential orientation of microcrystallites. Finally, accessing the large voids inside the MOFs for use in applications that involve gases can be problematic, as frameworks may be subject to collapse during removal of solvent molecules (remnants of solvothermal synthesis). In this paper, we describe synthesis and characterization methods routinely utilized in our lab either to solve or circumvent these issues. The methods include solvent-assisted linker exchange, powder X-ray diffraction in capillaries, and materials activation (cavity evacuation) by supercritical CO2 drying. Finally, we provide a protocol for determining a suitable pressure region for applying the Brunauer-Emmett-Teller analysis to nitrogen isotherms, so as to estimate surface area of MOFs with good accuracy.

  2. Organic thin-film transistors for chemical and biological sensing.

    PubMed

    Lin, Peng; Yan, Feng

    2012-01-03

    Organic thin-film transistors (OTFTs) show promising applications in various chemical and biological sensors. The advantages of OTFT-based sensors include high sensitivity, low cost, easy fabrication, flexibility and biocompatibility. In this paper, we review the chemical sensors and biosensors based on two types of OTFTs, including organic field-effect transistors (OFETs) and organic electrochemical transistors (OECTs), mainly focusing on the papers published in the past 10 years. Various types of OTFT-based sensors, including pH, ion, glucose, DNA, enzyme, antibody-antigen, cell-based sensors, dopamine sensor, etc., are classified and described in the paper in sequence. The sensing mechanisms and the detection limits of the devices are described in details. It is expected that OTFTs may have more important applications in chemical and biological sensing with the development of organic electronics.

  3. Chemical methods and phytoremediation of soil contaminated with heavy metals.

    PubMed

    Chen, H M; Zheng, C R; Tu, C; Shen, Z G

    2000-07-01

    The effects of chemical amendments (calcium carbonate (CC), steel sludge (SS) and furnace slag (FS)) on the growth and uptake of cadmium (Cd) by wetland rice, Chinese cabbage and wheat grown in a red soil contaminated with Cd were investigated using a pot experiment. The phytoremediation of heavy metal contaminated soil with vetiver grass was also studied in a field plot experiment. Results showed that treatments with CC, SS and FS decreased Cd uptake by wetland rice, Chinese cabbage and wheat by 23-95% compared with the unamended control. Among the three amendments, FS was the most efficient at suppressing Cd uptake by the plants, probably due to its higher content of available silicon (Si). The concentrations of zinc (Zn), lead (Pb) and Cd in the shoots of vetiver grass were 42-67%, 500-1200% and 120-260% higher in contaminated plots than in control, respectively. Cadmium accumulation by vetiver shoots was 218 g Cd/ha at a soil Cd concentration of 0.33 mg Cd/kg. It is suggested that heavy metal-contaminated soil could be remediated with a combination of chemical treatments and plants.

  4. Metal-Organic Frameworks Stabilize Solution-Inaccessible Cobalt Catalysts for Highly Efficient Broad-Scope Organic Transformations.

    PubMed

    Zhang, Teng; Manna, Kuntal; Lin, Wenbin

    2016-03-09

    New and active earth-abundant metal catalysts are critically needed to replace precious metal-based catalysts for sustainable production of commodity and fine chemicals. We report here the design of highly robust, active, and reusable cobalt-bipyridine- and cobalt-phenanthroline-based metal-organic framework (MOF) catalysts for alkene hydrogenation and hydroboration, aldehyde/ketone hydroboration, and arene C-H borylation. In alkene hydrogenation, the MOF catalysts tolerated a variety of functional groups and displayed unprecedentedly high turnover numbers of ∼2.5 × 10(6) and turnover frequencies of ∼1.1 × 10(5) h(-1). Structural, computational, and spectroscopic studies show that site isolation of the highly reactive (bpy)Co(THF)2 species in the MOFs prevents intermolecular deactivation and stabilizes solution-inaccessible catalysts for broad-scope organic transformations. Computational, spectroscopic, and kinetic evidence further support a hitherto unknown (bpy(•-))Co(I)(THF)2 ground state that coordinates to alkene and dihydrogen and then undergoing σ-complex-assisted metathesis to form (bpy)Co(alkyl)(H). Reductive elimination of alkane followed by alkene binding completes the catalytic cycle. MOFs thus provide a novel platform for discovering new base-metal molecular catalysts and exhibit enormous potential in sustainable chemical catalysis.

  5. Baade's window and APOGEE. Metallicities, ages, and chemical abundances

    NASA Astrophysics Data System (ADS)

    Schultheis, M.; Rojas-Arriagada, A.; García Pérez, A. E.; Jönsson, H.; Hayden, M.; Nandakumar, G.; Cunha, K.; Allende Prieto, C.; Holtzman, J. A.; Beers, T. C.; Bizyaev, D.; Brinkmann, J.; Carrera, R.; Cohen, R. E.; Geisler, D.; Hearty, F. R.; Fernandez-Tricado, J. G.; Maraston, C.; Minnitti, D.; Nitschelm, C.; Roman-Lopes, A.; Schneider, D. P.; Tang, B.; Villanova, S.; Zasowski, G.; Majewski, S. R.

    2017-03-01

    Context. Baade's window (BW) is one of the most observed Galactic bulge fields in terms of chemical abundances. Owing to its low and homogeneous interstellar absorption it is considered the perfect calibration field for Galactic bulge studies. Aims: In the era of large spectroscopic surveys, calibration fields such as BW are necessary for cross calibrating the stellar parameters and individual abundances of the APOGEE survey. Methods: We use the APOGEE BW stars to derive the metallicity distribution function (MDF) and individual abundances for α- and iron-peak elements of the APOGEE ASPCAP pipeline (DR13), as well as the age distribution for stars in BW. Results: We determine the MDF of APOGEE stars in BW and find a remarkable agreement with that of the Gaia-ESO survey (GES). Both exhibit a clear bimodal distribution. We also find that the Mg-metallicity planes of the two surveys agree well, except for the metal-rich part ([Fe/H] > 0.1), where APOGEE finds systematically higher Mg abundances with respect to the GES. The ages based on the [C/N] ratio reveal a bimodal age distribution, with a major old population at 10 Gyr, with a decreasing tail towards younger stars. A comparison of stellar parameters determined by APOGEE and those determined by other sources reveals detectable systematic offsets, in particular for spectroscopic surface gravity estimates. In general, we find a good agreement between individual abundances of O, Na, Mg, Al, Si, K, Ca, Cr, Mn, Co, and Ni from APOGEE with that of literature values. Conclusions: We have shown that in general APOGEE data show a good agreement in terms of MDF and individual chemical abundances with respect to literature works. Using the [C/N] ratio we found a significant fraction of young stars in BW.

  6. Metallacarboranes: Towards promising hydrogen storage metal organic framework

    NASA Astrophysics Data System (ADS)

    Singh, Abhishek; Sadrzadeh, Arta; Yakobson, Boris

    2011-03-01

    Using first principles calculations we show the high hydrogen storage capacity of metallacarboranes, where the transition metal (TM) atoms bind hydrogen via Kubas interaction. The average binding energy of ~ 0.3 eV/H favorably lies within the reversible adsorption range The Sc and Ti are found to be the optimum metal atoms maximizing the number of stored H2 molecules. Depending upon the structure, metallacarboranes can adsorb up to 8 wt% of hydrogen, which exceeds DOE goal for 2015. Being integral part of the cage, TMs do not suffer from the aggregation problem. Furthermore, the presence of carbon atom in the cages permits linking the metallacarboranes to form metal organic frameworks (MOF), thus able to adsorb hydrogen via Kubas interaction, in addition to van der Waals physisorption. A. K. Singh, A. Sadrzadeh, and B. I. Yakobson, Metallacarboranes: Toward Promising Hydrogen Storage Metal Organic Frameworks, JACS 132,14126 (2010).

  7. Highly Efficient Luminescent Metal-Organic Framework for the Simultaneous Detection and Removal of Heavy Metals from Water.

    PubMed

    Rudd, Nathan D; Wang, Hao; Fuentes-Fernandez, Erika M A; Teat, Simon J; Chen, Feng; Hall, Gene; Chabal, Yves J; Li, Jing

    2016-11-09

    We have designed and synthesized an isoreticular series of luminescent metal-organic frameworks (LMOFs) by incorporating a strongly emissive molecular fluorophore and functionally diverse colinkers into Zn-based structures. The three-dimensional porous networks of LMOF-261, -262, and -263 represent a unique/new type of nets, classified as a 2-nodal, (4,4)-c net (mot-e type) with 4-fold, class IIIa interpenetration. All compounds crystallize in a body-centered tetragonal crystal system (space group I41/a). A systematic study has been implemented to analyze their interactions with heavy metals. LMOF-263 exhibits impressive water stability, high porosity, and strong luminescence, making it an excellent candidate as a fluorescent chemical sensor and adsorbent for aqueous contaminants. It is extremely responsive to toxic heavy metals at a parts per billion level (3.3 ppb Hg(2+), 19.7 ppb Pb(2+)) and demonstrates high selectivity for heavy metals over light metals, with detection ratios of 167.4 and 209.5 for Hg(2+)/Ca(2+) and Hg(2+)/Mg(2+), respectively. Mixed-metal adsorption experiments also show that LMOF-263 selectively adsorbs Hg(2+) over other heavy metal ions in addition to light metals. The Pb(2+) KSV value for LMOF-263 (55,017 M(-1)) is the highest among LMOFs reported to date, and the Hg(2+) KSV value is the second highest (459,446 M(-1)). LMOF-263 exhibits a maximum adsorption capacity of 380 mg Hg(2+)/g. The Hg(2+) adsorption process follows pseudo-second-order kinetics, removing 99.1% of the metal within 30 min. An in situ XPS study provides insight to help understand the interaction mechanism between Hg(2+) and LMOF-263. No other MOFs have demonstrated such a high performance in both the detection and the capture of Hg(2+) from aqueous solution.

  8. Mechanochemical synthesis of an yttrium based metal-organic framework.

    PubMed

    Singh, Niraj K; Hardi, Meenakshi; Balema, Viktor P

    2013-02-01

    For the first time a metal hydride has been used for the preparation of a metal-organic framework. MIL-78 has been synthesized by the solid-state mechanochemical reaction between yttrium hydride and trimesic acid. The process does not involve solvents and does not generate liquid by-products, thus proving the viability of the solid-state approach to the synthesis of MOFs.

  9. Metal speciation in landfill leachates with a focus on the influence of organic matter

    SciTech Connect

    Claret, Francis; Tournassat, Christophe; Crouzet, Catherine; Gaucher, Eric C.; Schaefer, Thorsten; Braibant, Gilles; Guyonnet, Dominique

    2011-09-15

    Highlights: > This study characterises the heavy-metal content in leachates collected from eight landfills in France. > Most of the metals are concentrated in the <30 kDa fraction, while Pb, Cu and Cd are associated with larger particles. > Metal complexation with OM is not sufficient to explain apparent supersaturation of metals with sulphide minerals. - Abstract: This study characterises the heavy-metal content in leachates collected from eight landfills in France. In order to identify heavy metal occurrence in the different size fractions of leachates, a cascade filtration protocol was applied directly in the field, under a nitrogen gas atmosphere to avoid metal oxidation. The results of analyses performed on the leachates suggest that most of the metals are concentrated in the <30 kDa fraction, while lead, copper and cadmium show an association with larger particles. Initial speciation calculations, without considering metal association with organic matter, suggest that leachate concentrations in lead, copper, nickel and zinc are super-saturated with respect to sulphur phases. Speciation calculations that account for metal complexation with organic matter, considered as fulvic acids based on C1(s) NEXAFS spectroscopy, show that this mechanism is not sufficient to explain such deviation from equilibrium conditions. It is therefore hypothesized that the deviation results also from the influence of biological activity on the kinetics of mineral phase precipitation and dissolution, thus providing a dynamic system. The results of chemical analyses of sampled fluids are compared with speciation calculations and some implications for the assessment of metal mobility and natural attenuation in a context of landfill risk assessment are discussed.

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

    DOEpatents

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

    2004-11-16

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

  11. Bioavailability of heavy metals in soil: impact on microbial biodegradation of organic compounds and possible improvement strategies.

    PubMed

    Olaniran, Ademola O; Balgobind, Adhika; Pillay, Balakrishna

    2013-05-15

    Co-contamination of the environment with toxic chlorinated organic and heavy metal pollutants is one of the major problems facing industrialized nations today. Heavy metals may inhibit biodegradation of chlorinated organics by interacting with enzymes directly involved in biodegradation or those involved in general metabolism. Predictions of metal toxicity effects on organic pollutant biodegradation in co-contaminated soil and water environments is difficult since heavy metals may be present in a variety of chemical and physical forms. Recent advances in bioremediation of co-contaminated environments have focussed on the use of metal-resistant bacteria (cell and gene bioaugmentation), treatment amendments, clay minerals and chelating agents to reduce bioavailable heavy metal concentrations. Phytoremediation has also shown promise as an emerging alternative clean-up technology for co-contaminated environments. However, despite various investigations, in both aerobic and anaerobic systems, demonstrating that metal toxicity hampers the biodegradation of the organic component, a paucity of information exists in this area of research. Therefore, in this review, we discuss the problems associated with the degradation of chlorinated organics in co-contaminated environments, owing to metal toxicity and shed light on possible improvement strategies for effective bioremediation of sites co-contaminated with chlorinated organic compounds and heavy metals.

  12. Bioavailability of Heavy Metals in Soil: Impact on Microbial Biodegradation of Organic Compounds and Possible Improvement Strategies

    PubMed Central

    Olaniran, Ademola O.; Balgobind, Adhika; Pillay, Balakrishna

    2013-01-01

    Co-contamination of the environment with toxic chlorinated organic and heavy metal pollutants is one of the major problems facing industrialized nations today. Heavy metals may inhibit biodegradation of chlorinated organics by interacting with enzymes directly involved in biodegradation or those involved in general metabolism. Predictions of metal toxicity effects on organic pollutant biodegradation in co-contaminated soil and water environments is difficult since heavy metals may be present in a variety of chemical and physical forms. Recent advances in bioremediation of co-contaminated environments have focussed on the use of metal-resistant bacteria (cell and gene bioaugmentation), treatment amendments, clay minerals and chelating agents to reduce bioavailable heavy metal concentrations. Phytoremediation has also shown promise as an emerging alternative clean-up technology for co-contaminated environments. However, despite various investigations, in both aerobic and anaerobic systems, demonstrating that metal toxicity hampers the biodegradation of the organic component, a paucity of information exists in this area of research. Therefore, in this review, we discuss the problems associated with the degradation of chlorinated organics in co-contaminated environments, owing to metal toxicity and shed light on possible improvement strategies for effective bioremediation of sites co-contaminated with chlorinated organic compounds and heavy metals. PMID:23676353

  13. Microporous metal-organic framework with potential for carbon dioxide capture at ambient conditions.

    PubMed

    Xiang, Shengchang; He, Yabing; Zhang, Zhangjing; Wu, Hui; Zhou, Wei; Krishna, Rajamani; Chen, Banglin

    2012-07-17

    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 such separations and to replace current technologies, which use aqueous solvents to chemically absorb carbon dioxide. Here we show that a metal-organic frameworks (UTSA-16) displays high uptake (160 cm(3) cm(-3)) of CO(2) at ambient conditions, making it a potentially useful adsorbent material for post-combustion carbon dioxide capture and biogas stream purification. This has been further confirmed by simulated breakthrough experiments. The high storage capacities and selectivities of UTSA-16 for carbon dioxide capture are attributed to the optimal pore cages and the strong binding sites to carbon dioxide, which have been demonstrated by neutron diffraction studies.

  14. Interplay between defects, disorder and flexibility in metal-organic frameworks

    NASA Astrophysics Data System (ADS)

    Bennett, Thomas D.; Cheetham, Anthony K.; Fuchs, Alain H.; Coudert, François-Xavier

    2017-01-01

    Metal-organic frameworks are a novel family of chemically diverse materials, which are of interest across engineering, physics, chemistry, biology and medicine-based disciplines. Since the development of the field in its current form more than two decades ago, priority has been placed on the synthesis of new structures. However, more recently, a clear trend has emerged in shifting the emphasis from material design to exploring the chemical and physical properties of structures already known. In particular, although such nanoporous materials were traditionally seen as rigid crystalline structures, there is growing evidence that large-scale flexibility, the presence of defects and long-range disorder are not the exception in metal-organic frameworks, but the rule. Here we offer some perspective into how these concepts are perhaps inescapably intertwined, highlight recent advances in our understanding and discuss how a consideration of the interfaces between them may lead to enhancements of the materials' functionalities.

  15. Metal Speciation in Landfill Leachates with a Focus on the Influence of Organic Matter

    SciTech Connect

    F Claret; C Tournassat; C Crouzet; E Gaucher; T Schäfer; G Braibant; D Guyonnet

    2011-12-31

    This study characterizes the heavy-metal content in leachates collected from eight landfills in France. In order to identify heavy metal occurrence in the different size fractions of leachates, a cascade filtration protocol was applied directly in the field, under a nitrogen gas atmosphere to avoid metal oxidation. The results of analyses performed on the leachates suggest that most of the metals are concentrated in the <30 kDa fraction, while lead, copper and cadmium show an association with larger particles. Initial speciation calculations, without considering metal association with organic matter, suggest that leachate concentrations in lead, copper, nickel and zinc are super-saturated with respect to sulphur phases. Speciation calculations that account for metal complexation with organic matter, considered as fulvic acids based on C1(s) NEXAFS spectroscopy, show that this mechanism is not sufficient to explain such deviation from equilibrium conditions. It is therefore hypothesized that the deviation results also from the influence of biological activity on the kinetics of mineral phase precipitation and dissolution, thus providing a dynamic system. The results of chemical analyses of sampled fluids are compared with speciation calculations and some implications for the assessment of metal mobility and natural attenuation in a context of landfill risk assessment are discussed.

  16. From Bioavailability Science to Regulation of Organic Chemicals.

    PubMed

    Ortega-Calvo, Jose-J; Harmsen, Joop; Parsons, John R; Semple, Kirk T; Aitken, Michael D; Ajao, Charmaine; Eadsforth, Charles; Galay-Burgos, Malyka; Naidu, Ravi; Oliver, Robin; Peijnenburg, Willie J G M; Römbke, Jörg; Streck, Georg; Versonnen, Bram

    2015-09-01

    The bioavailability of organic chemicals in soil and sediment is an important area of scientific investigation for environmental scientists, although this area of study remains only partially recognized by regulators and industries working in the environmental sector. Regulators have recently started to consider bioavailability within retrospective risk assessment frameworks for organic chemicals; by doing so, realistic decision-making with regard to polluted environments can be achieved, rather than relying on the traditional approach of using total-extractable concentrations. However, implementation remains difficult because scientific developments on bioavailability are not always translated into ready-to-use approaches for regulators. Similarly, bioavailability remains largely unexplored within prospective regulatory frameworks that address the approval and regulation of organic chemicals. This article discusses bioavailability concepts and methods, as well as possible pathways for the implementation of bioavailability into risk assessment and regulation; in addition, this article offers a simple, pragmatic and justifiable approach for use within retrospective and prospective risk assessment.

  17. Microporous metal-organic frameworks for storage and separation of small hydrocarbons.

    PubMed

    He, Yabing; Zhou, Wei; Krishna, Rajamani; Chen, Banglin

    2012-12-18

    Hydrocarbons are very important energy resources and raw materials for some industrially important products and fine chemicals. There is a need for the discovery of better materials that offer enhanced capacities for safe storage of hydrocarbons. Furthermore, the development of improved separation technologies will lead to significant reduction in energy requirements and costs. In this feature article, we provide an overview of the current status of the emerging microporous metal-organic frameworks for the storage and separation of small hydrocarbons.

  18. Corrosion Control through a Better Understanding of the Metallic Substrate/Organic Coating/Interface.

    DTIC Science & Technology

    1984-12-13

    Delamination Process at the Organic Coating/Metal Substrate Interface," Wendy, Ching-Yung Wang, Ph.D. Thesis, Chemical Engineer- ing, January 1984... Process ," Jeffrey M. Parks, Ph.D. Thesis, Physical Chemistry, January 1985. -4- * S Papers Submitted, Accepted or in Fres "A Mathematical Model for the...ferric oxide. 47 -26- "" levels in the bed can be obtained by pump-down through the evaporative cooling process , and even lower moisture levels can be

  19. Chemical Characterization of Organisms Isolated from Leprosy Patients

    PubMed Central

    Beaman, Blain L.; Kim, Kwang-Shin; Lanéelle, Marie A.; Barksdale, Lane

    1974-01-01

    Chemical analyses of the cell walls of organisms isolated in various parts of the world from cases of lepromatous and tuberculoid leprosy make possible their assignment to one of the three genera: Corynebacterium, Mycobacterium, or Propionibacterium. One, bacterium 22M, remains unassigned. The combined chemical and enzymatic properties attributed to leprosy bacilli freshly harvested from lepromata are found collectively, but not individually, in these three genera. Images PMID:4813897

  20. Synthesis of magnetic metal-organic framework (MOF) for efficient removal of organic dyes from water

    PubMed Central

    Zhao, Xiaoli; Liu, Shuangliu; Tang, Zhi; Niu, Hongyun; Cai, Yaqi; Meng, Wei; Wu, Fengchang; Giesy, John P.

    2015-01-01

    A novel, simple and efficient strategy for fabricating a magnetic metal-organic framework (MOF) as sorbent to remove organic compounds from simulated water samples is presented and tested for removal of methylene blue (MB) as an example. The novel adsorbents combine advantages of MOFs and magnetic nanoparticles and possess large capacity, low cost, rapid removal and easy separation of the solid phase, which makes it an excellent sorbent for treatment of wastewaters. The resulting magnetic MOFs composites (also known as MFCs) have large surface areas (79.52 m2 g−1), excellent magnetic response (14.89 emu g−1), and large mesopore volume (0.09 cm3 g−1), as well as good chemical inertness and mechanical stability. Adsorption was not drastically affected by pH, suggesting π–π stacking interaction and/or hydrophobic interactions between MB and MFCs. Kinetic parameters followed pseudo-second-order kinetics and adsorption was described by the Freundlich isotherm. Adsorption capacity was 84 mg MB g−1 at an initial MB concentration of 30 mg L−1, which increased to 245 mg g−1 when the initial MB concentration was 300 mg L−1. This capacity was much greater than most other adsorbents reported in the literature. In addition, MFC adsorbents possess excellent reusability, being effective after at least five consecutive cycles. PMID:26149818

  1. Rational design of metal-organic electronic devices: A computational perspective

    NASA Astrophysics Data System (ADS)

    Chilukuri, Bhaskar

    Organic and organometallic electronic materials continue to attract considerable attention among researchers due to their cost effectiveness, high flexibility, low temperature processing conditions and the continuous emergence of new semiconducting materials with tailored electronic properties. In addition, organic semiconductors can be used in a variety of important technological devices such as solar cells, field-effect transistors (FETs), flash memory, radio frequency identification (RFID) tags, light emitting diodes (LEDs), etc. However, organic materials have thus far not achieved the reliability and carrier mobility obtainable with inorganic silicon-based devices. Hence, there is a need for finding alternative electronic materials other than organic semiconductors to overcome the problems of inferior stability and performance. In this dissertation, I research the development of new transition metal based electronic materials which due to the presence of metal-metal, metal-pi, and pi-pi interactions may give rise to superior electronic and chemical properties versus their organic counterparts. Specifically, I performed computational modeling studies on platinum based charge transfer complexes and d 10 cyclo-[M(mu-L)]3 trimers (M = Ag, Au and L = monoanionic bidentate bridging (C/N~C/N) ligand). The research done is aimed to guide experimental chemists to make rational choices of metals, ligands, substituents in synthesizing novel organometallic electronic materials. Furthermore, the calculations presented here propose novel ways to tune the geometric, electronic, spectroscopic, and conduction properties in semiconducting materials. In addition to novel material development, electronic device performance can be improved by making a judicious choice of device components. I have studied the interfaces of a p-type metal-organic semiconductor viz cyclo-[Au(mu-Pz)] 3 trimer with metal electrodes at atomic and surface levels. This work was aimed to guide the device

  2. Metals in sediments and benthic organisms in the Mersey estuary

    NASA Astrophysics Data System (ADS)

    Langston, W. J.

    1986-08-01

    Concentrations of twelve metals were determined in sediments, seaweed ( Fucus vesiculosus), winkles ( Littorina littorea), polychaetes ( Nereis diversicolor), suspension feeding bivalves ( Mytilus edulis, Cerastoderma edule) and deposit feeding bivalves ( Macoma balthica, Scrobicularia plana) collected from the Mersey estuary between April 1980 and June 1984. Sediments and organisms in the Mersey are moderately contaminated with most of the metals measured, but mercury concentrations are consistently higher than in other United Kingdom estuaries. Comparisons with other sites in the North West of England indicate that mercury residues in organisms, though primarily dependent on sediment concentrations, are also influenced by complexation with particulate organic matter which reduces the availability of mercury. The biological availability of arsenic in Mersey sediments is similarly influenced by complexation with iron oxyhydroxides. Nereis diversicolor and Macoma balthica are the most suitable indicator species in terms of abundance and widespread distribution along the estuary, and, for the majority of metals, tissue concentrations increase upstream, reflecting corresponding gradients in sediment contamination. However mid-estuarine peaks for tin, chromium copper and nickel in Nereis indicate more localised inputs to the estuary. Correlations between lead in sediments and organisms are poor; it is suggested that hydrophilic alkyl lead compounds may be the predominant biologically available forms. Progressive reductions in mercury contamination in sediments and mercury and lead in organisms have occurred in recent years, which coincide with efforts to reduce inputs of these metals to teh Mersey estuary.

  3. Species sensitivity analysis of heavy metals to freshwater organisms.

    PubMed

    Xin, Zheng; Wenchao, Zang; Zhenguang, Yan; Yiguo, Hong; Zhengtao, Liu; Xianliang, Yi; Xiaonan, Wang; Tingting, Liu; Liming, Zhou

    2015-10-01

    Acute toxicity data of six heavy metals [Cu, Hg, Cd, Cr(VI), Pb, Zn] to aquatic organisms were collected and screened. Species sensitivity distributions (SSD) curves of vertebrate and invertebrate were constructed by log-logistic model separately. The comprehensive comparisons of the sensitivities of different trophic species to six typical heavy metals were performed. The results indicated invertebrate taxa to each heavy metal exhibited higher sensitivity than vertebrates. However, with respect to the same taxa species, Cu had the most adverse effect on vertebrate, followed by Hg, Cd, Zn and Cr. When datasets from all species were included, Cu and Hg were still more toxic than the others. In particular, the toxicities of Pb to vertebrate and fish were complicated as the SSD curves of Pb intersected with those of other heavy metals, while the SSD curves of Pb constructed by total species no longer crossed with others. The hazardous concentrations for 5 % of the species (HC5) affected were derived to determine the concentration protecting 95 % of species. The HC5 values of the six heavy metals were in the descending order: Zn > Pb > Cr > Cd > Hg > Cu, indicating toxicities in opposite order. Moreover, potential affected fractions were calculated to assess the ecological risks of different heavy metals at certain concentrations of the selected heavy metals. Evaluations of sensitivities of the species at various trophic levels and toxicity analysis of heavy metals are necessary prior to derivation of water quality criteria and the further environmental protection.

  4. Textbook Errors: 137. Physical and Chemical Properties and Bonding of Metallic Elements.

    ERIC Educational Resources Information Center

    Myers, R. Thomas

    1979-01-01

    Focuses attention on the almost universal practice of discussing all metals as malleable. The author points out that some are brittle and then he presents the variation in chemical properties of metals. (SA)

  5. Humic acid metal cation interaction studied by spectromicroscopy techniques in combination with quantum chemical calculations.

    PubMed

    Plaschke, M; Rothe, J; Armbruster, M K; Denecke, M A; Naber, A; Geckeis, H

    2010-03-01

    Humic acids (HA) have a high binding capacity towards traces of toxic metal cations, thus affecting their transport in aquatic systems. Eu(III)-HA aggregates are studied by synchrotron-based scanning transmission X-ray microscopy (STXM) at the carbon K-edge and laser scanning luminescence microscopy (LSLM) at the (5)D(0) --> (7)F(1,2) fluorescence emission lines. Both methods provide the necessary spatial resolution in the sub-micrometre range to resolve characteristic aggregate morphologies: optically dense zones embedded in a matrix of less dense material in STXM images correspond to areas with increased Eu(III) luminescence yield in the LSLM micrographs. In the C 1s-NEXAFS of metal-loaded polyacrylic acid (PAA), used as a HA model compound, a distinct complexation effect is identified. This effect is similar to trends observed in the dense fraction of HA/metal cation aggregates. The strongest complexation effect is observed for the Zr(IV)-HA/PAA system. This effect is confirmed by quantum chemical calculations performed at the ab initio level for model complexes with different metal centres and complex geometries. Without the high spatial resolution of STXM and LSLM and without the combination of molecular modelling with experimental results, the different zones indicating a ;pseudo'-phase separation into strong complexing domains and weaker complexing domains of HA would never have been identified. This type of strategy can be used to study metal interaction with other organic material.

  6. Introduction: Self-organization in nonequilibrium chemical systems.

    PubMed

    Epstein, Irving R; Pojman, John A; Steinbock, Oliver

    2006-09-01

    The field of self-organization in nonequilibrium chemical systems comprises the study of dynamical phenomena in chemically reacting systems far from equilibrium. Systematic exploration of this area began with investigations of the temporal behavior of the Belousov-Zhabotinsky oscillating reaction, discovered accidentally in the former Soviet Union in the 1950s. The field soon advanced into chemical waves in excitable media and propagating fronts. With the systematic design of oscillating reactions in the 1980s and the discovery of Turing patterns in the 1990s, the scope of these studies expanded dramatically. The articles in this Focus Issue provide an overview of the development and current state of the field.

  7. Encoding of Fundamental Chemical Entities of Organic Reactivity Interest using chemical ontology and XML.

    PubMed

    Durairaj, Vijayasarathi; Punnaivanam, Sankar

    2015-09-01

    Fundamental chemical entities are identified in the context of organic reactivity and classified as appropriate concept classes namely ElectronEntity, AtomEntity, AtomGroupEntity, FunctionalGroupEntity and MolecularEntity. The entity classes and their subclasses are organized into a chemical ontology named "ChemEnt" for the purpose of assertion, restriction and modification of properties through entity relations. Individual instances of entity classes are defined and encoded as a library of chemical entities in XML. The instances of entity classes are distinguished with a unique notation and identification values in order to map them with the ontology definitions. A model GUI named Entity Table is created to view graphical representations of all the entity instances. The detection of chemical entities in chemical structures is achieved through suitable algorithms. The possibility of asserting properties to the entities at different levels and the mechanism of property flow within the hierarchical entity levels is outlined.

  8. Inorganic metal oxide/organic polymer nanocomposites and method thereof

    DOEpatents

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

    2004-03-30

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

  9. Predicting the bioconcentration factor of highly hydrophobic organic chemicals.

    PubMed

    Garg, Rajni; Smith, Carr J

    2014-07-01

    Bioconcentration refers to the process of uptake and buildup of chemicals in living organisms. Experimental measurement of bioconcentration factor (BCF) is time-consuming and expensive, and is not feasible for a large number of chemicals of regulatory concern. Quantitative structure-activity relationship (QSAR) models are used for estimating BCF values to help in risk assessment of a chemical. This paper presents the results of a QSAR study conducted to address an important problem encountered in the prediction of the BCF of highly hydrophobic chemicals. A new QSAR model is derived using a dataset of diverse organic chemicals previously tested in a United States Environmental Protection Agency laboratory. It is noted that the linear relationship between the BCF and hydrophobic parameter, i.e., calculated octanol-water partition coefficient (ClogP), breaks down for highly hydrophobic chemicals. The parabolic QSAR equation, log BCF=3.036 ClogP-0.197 ClogP(2)-0.808 MgVol (n=28, r(2)=0.817, q(2)=0.761, s=0.558) (experimental log BCF range=0.44-5.29, ClogP range=3.16-11.27), suggests that a non-linear relationship between BCF and the hydrophobic parameter, along with inclusion of additional molecular size, weight and/or volume parameters, should be considered while developing a QSAR model for more reliable prediction of the BCF of highly hydrophobic chemicals.

  10. Precursors for chemical and photochemical vapor deposition of copper metal

    NASA Astrophysics Data System (ADS)

    James, Alicia Marie

    The colorless square-planar cluster [CuN(SiMe3)2] 4, which contains four Cu(I) ions with four bridging amide groups, was studied as a precursor for chemical and photochemical vapor deposition of Cu metal. The cluster phosphoresces in CH2Cl2 solution and in the solid state at room temperature. Its electronic spectrum in CH 2Cl2 consists of two intense bands which are assigned to symmetry-allowed 3d → 4p transitions; the phosphorescence is also likely to be metal-centered. Solid [CuN(SiMe3)2]4 luminesces with approximately the same spectrum as that of the CH2Cl2 solutions. At 77 K, the solid-state luminescence red-shifts slightly. The emission lifetime in glassy Et2O solution is 690 mus. [CuN(SiMe3) 2]4 deposits Cu metal via chemical vapor deposition under H2 carrier gas at substrate temperatures of 145--200°C. Deposition also occurs photochemically beginning at 136--138°C under near-UV irradiation. The preparation of monomeric derivatives of [CuN(SiMe3) 2]4 was attempted by using neutral donor ligands L (e.g. LnCuN(SiMe3)2; L = CO, PR3, CN-t-Bu; n = 1--3). The target compounds were expected to be more volatile than the copper cluster and still maintain photosensitivity. CuCl and [Cu(CH 3CN)4]PF6 were used as starting materials. Even in the presence of L, [CuN(SiMe3)2] 4 is a major product in reactions using CuCl and NaN(SiCH3) 2- [Cu(CH3CN)4]PF6 was a promising route for the monomeric Cu(I) complexes because of ready dissociation of its acetonitrile ligands. However, the characterization of these complexes was unsuccessful. Other Cu(I) amide clusters have been prepared; they may also be suitable for chemical and photochemical vapor deposition of Cu. [CuNEt2] 4, [CuN(i-Pr)2]4, and [CuN(t-Bu)(SiMe 3)]4 are phosphorescent though they are very air sensitive. They should be more volatile and produce Cu metal films more readily than [CuN(SiMe3)2]4 Cu(hfac)2 is a versatile Lewis acid, forming adducts with a variety of bases. The bases that were used were ethylene

  11. The Development of Metal Oxide Chemical Sensing Nanostructures

    NASA Technical Reports Server (NTRS)

    Hunter, G. W.; VanderWal,R. L.; Xu, J. C.; Evans, L. J.; Berger, G. M.; Kulis, M. J.

    2008-01-01

    This paper discusses sensor development based on metal oxide nanostructures and microsystems technology. While nanostructures such as nanowires show significant potential as enabling materials for chemical sensors, a number of significant technical challenges remain. This paper discusses development to address each of these technical barriers: 1) Improved contact and integration of the nanostructured materials with microsystems in a sensor structure; 2) Control of nanostructure crystallinity to allow control of the detection mechanism; and 3) Widening the range of gases that can be detected by fabricating multiple nanostructured materials. A sensor structure composed of three nanostructured oxides aligned on a single microsensor has been fabricated and tested. Results of this testing are discussed and future development approaches are suggested. It is concluded that while this work lays the foundation for further development, these are the beginning steps towards realization of repeatable, controlled sensor systems using oxide based nanostructures.

  12. Chemical vapour deposition: Transition metal carbides go 2D

    DOE PAGES

    Gogotsi, Yury

    2015-08-17

    Here, the research community has been steadily expanding the family of few-atom-thick crystals beyond graphene, discovering new materials or producing known materials in a 2D state and demonstrating their unique properties1, 2. Recently, nanometre-thin 2D transition metal carbides have also joined this family3. Writing in Nature Materials, Chuan Xu and colleagues now report a significant advance in the field, showing the synthesis of large-area, high-quality, nanometre-thin crystals of molybdenum carbide that demonstrate low-temperature 2D superconductivity4. Moreover, they also show that other ultrathin carbide crystals, such as tungsten and tantalum carbides, can be grown by chemical vapour deposition with a highmore » crystallinity and very low defect concentration.« less

  13. Chemical vapour deposition: Transition metal carbides go 2D

    SciTech Connect

    Gogotsi, Yury

    2015-08-17

    Here, the research community has been steadily expanding the family of few-atom-thick crystals beyond graphene, discovering new materials or producing known materials in a 2D state and demonstrating their unique properties1, 2. Recently, nanometre-thin 2D transition metal carbides have also joined this family3. Writing in Nature Materials, Chuan Xu and colleagues now report a significant advance in the field, showing the synthesis of large-area, high-quality, nanometre-thin crystals of molybdenum carbide that demonstrate low-temperature 2D superconductivity4. Moreover, they also show that other ultrathin carbide crystals, such as tungsten and tantalum carbides, can be grown by chemical vapour deposition with a high crystallinity and very low defect concentration.

  14. Chemical and Biological Sensors Based on Organic Electrochemical Transistors

    NASA Astrophysics Data System (ADS)

    Lin, Peng

    Organic thin film transistors (OTFTs) have been explored for sensing applications for several decades due to their many advantages like easy fabrication, low cost, flexibility, and biocompatibility. Among these OTFTs, organic electrochemical transistors (OECTs) have attracted a great deal of interest in recent years since the devices can operate stably in aqueous environment with relatively low working voltages and are suitable for applications in chemical and biological sensing. In this thesis, ion-sensitive properties of OECTs based on poly(3,4- ethylenedioxythiophene):poly(styrene sulfonic acid) (PEDOT:PSS) have been systematically studied. It was found that the gate electrode played an important role on the ion-sensitive properties of OECTs. For the devices with Ag/AgCl gate electrode, Nernstian relationships between the shift of gate voltage and the concentrations of cations were obtained. For the devices with Pt and Au gate electrodes, the ion sensitivities were higher than that given by Nernst equation, which could be attributed to the interface between the metal gate electrode and the electrolyte. Moreover, OECTs based on PEDOT:PSS were integrated into flexible microfluidic systems. Then a novel label-free DNA sensor was developed, in which single-stranded DNA probes were immobilized on the surface of Au gate electrode. These devices successfully detected complementary DNA targets at concentrations as low as 1 nM. The detection limit was also extended to 10 pM by pulse-enhanced hybridization process of DNA. OECTs based on PEDOT:PSS were also exploited as cell-based biosensors. Human esophageal squamous epithelial cancer cell lines (KYSE30) and fibroblast cell lines (HFFI) were successfully grown on the surface of PEDOT:PSS film. Then the devices were used for in-vitro monitoring cell activities when the living cells were treated by trypsin and an anti-cancer drug, retinoic acid. It was found that the devices were sensitive to the change of surface charge

  15. Ambient air monitoring for organic compounds, acids, and metals at Los Alamos National Laboratory, January 1991

    SciTech Connect

    Williams, C.H.; Eberhart, C.F.

    1992-10-01

    Los Alamos National Laboratory (LANL) contracted Radian Corporation (Radian) to conduct a short-term, intensive air monitoring program whose goal was to estimate the impact of chemical emissions from LANL on the ambient air environment. A comprehensive emission inventory had identified more than 600 potential air contaminants in LANL`s emissions. A subset of specific target chemicals was selected for monitoring: 20 organic vapors, 6 metals and 5 inorganic acid vapors. These were measured at 5 ground level sampling sites around LANL over seven consecutive days in January 1991. The sampling and analytical strategy used a combination of EPA and NIOSH methods modified for ambient air applications.

  16. Ambient air monitoring for organic compounds, acids, and metals at Los Alamos National Laboratory, January 1991

    SciTech Connect

    Williams, C.H. ); Eberhart, C.F. )

    1992-01-01

    Los Alamos National Laboratory (LANL) contracted Radian Corporation (Radian) to conduct a short-term, intensive air monitoring program whose goal was to estimate the impact of chemical emissions from LANL on the ambient air environment. A comprehensive emission inventory had identified more than 600 potential air contaminants in LANL's emissions. A subset of specific target chemicals was selected for monitoring: 20 organic vapors, 6 metals and 5 inorganic acid vapors. These were measured at 5 ground level sampling sites around LANL over seven consecutive days in January 1991. The sampling and analytical strategy used a combination of EPA and NIOSH methods modified for ambient air applications.

  17. Time-Resolved In Situ X-ray Diffraction Reveals Metal-Dependent Metal-Organic Framework Formation.

    PubMed

    Wu, Yue; Henke, Sebastian; Kieslich, Gregor; Schwedler, Inke; Yang, Miaosen; Fraser, Duncan A X; O'Hare, Dermot

    2016-11-02

    Versatility in metal substitution is one of the key aspects of metal-organic framework (MOF) chemistry, allowing properties to be tuned in a rational way. As a result, it important to understand why MOF syntheses involving different metals arrive at or fail to produce the same topological outcome. Frequently, conditions are tuned by trial-and-error to make MOFs with different metal species. We ask: is it possible to adjust synthetic conditions in a systematic way in order to design routes to desired phases? We have used in situ X-ray powder diffraction to study the solvothermal formation of isostructural M2 (bdc)2 dabco (M=Zn, Co, Ni) pillared-paddlewheel MOFs in real time. The metal ion strongly influences both kinetics and intermediates observed, leading in some cases to multiphase reaction profiles of unprecedented complexity. The standard models used for MOF crystallization break down in these cases; we show that a simple kinetic model describes the data and provides important chemical insights on phase selection.

  18. Self-templated chemically stable hollow spherical covalent organic framework

    NASA Astrophysics Data System (ADS)

    Kandambeth, Sharath; Venkatesh, V.; Shinde, Digambar B.; Kumari, Sushma; Halder, Arjun; Verma, Sandeep; Banerjee, Rahul

    2015-04-01

    Covalent organic frameworks are a family of crystalline porous materials with promising applications. Although active research on the design and synthesis of covalent organic frameworks has been ongoing for almost a decade, the mechanisms of formation of covalent organic frameworks crystallites remain poorly understood. Here we report the synthesis of a hollow spherical covalent organic framework with mesoporous walls in a single-step template-free method. A detailed time-dependent study of hollow sphere formation reveals that an inside-out Ostwald ripening process is responsible for the hollow sphere formation. The synthesized covalent organic framework hollow spheres are highly porous (surface area ~1,500 m2 g-1), crystalline and chemically stable, due to the presence of strong intramolecular hydrogen bonding. These mesoporous hollow sphere covalent organic frameworks are used for a trypsin immobilization study, which shows an uptake of 15.5 μmol g-1 of trypsin.

  19. Self-templated chemically stable hollow spherical covalent organic framework.

    PubMed

    Kandambeth, Sharath; Venkatesh, V; Shinde, Digambar B; Kumari, Sushma; Halder, Arjun; Verma, Sandeep; Banerjee, Rahul

    2015-04-10

    Covalent organic frameworks are a family of crystalline porous materials with promising applications. Although active research on the design and synthesis of covalent organic frameworks has been ongoing for almost a decade, the mechanisms of formation of covalent organic frameworks crystallites remain poorly understood. Here we report the synthesis of a hollow spherical covalent organic framework with mesoporous walls in a single-step template-free method. A detailed time-dependent study of hollow sphere formation reveals that an inside-out Ostwald ripening process is responsible for the hollow sphere formation. The synthesized covalent organic framework hollow spheres are highly porous (surface area ∼1,500 m(2 )g(-1)), crystalline and chemically stable, due to the presence of strong intramolecular hydrogen bonding. These mesoporous hollow sphere covalent organic frameworks are used for a trypsin immobilization study, which shows an uptake of 15.5 μmol g(-1) of trypsin.

  20. Pore Space Partition in Metal-Organic Frameworks.

    PubMed

    Zhai, Quan-Guo; Bu, Xianhui; Zhao, Xiang; Li, Dong-Sheng; Feng, Pingyun

    2017-02-21

    Metal-organic framework (MOF) materials have emerged as one of the favorite crystalline porous materials (CPM) because of their compositional and geometric tunability and many possible applications. In efforts to develop better MOFs for gas storage and separation, a number of strategies including creation of open metal sites and implantation of Lewis base sites have been used to tune host-guest interactions. In addition to these chemical factors, the geometric features such as pore size and shape, surface area, and pore volume also play important roles in sorption energetics and uptake capacity. For efficient capture of small gas molecules such as carbon dioxide under ambient conditions, large surface area or high pore volume are often not needed. Instead, maximizing host-guest interactions or the density of binding sites by encaging gas molecules in snug pockets of pore space can be a fruitful approach. To put this concept into practice, the pore space partition (PSP) concept has been proposed and has achieved a great experimental success. In this account, we will highlight many efforts to implement PSP in MOFs and impact of PSP on gas uptake performance. In the synthetic design of PSP, it is helpful to distinguish between factors that contribute to the framework formation and factors that serve the purpose of PSP. Because of the need for complementary structural roles, the synthesis of MOFs with PSP often involves multicomponent systems including mixed ligands, mixed inorganic nodes, or both. It is possible to accomplish both framework formation and PSP with a single type of polyfunctional ligands that use some functional groups (called framework-forming group) for framework formation and the remaining functional groups (called pore-partition group) for PSP. Alternatively, framework formation and PSP can be shouldered by different chemical species. For example, in a mixed-ligand system, one ligand (called framework-forming agent) can play the role of the

  1. Intrinsic electrical conductivity of nanostructured metal-organic polymer chains

    PubMed Central

    Hermosa, Cristina; Vicente Álvarez, Jose; Azani, Mohammad-Reza; Gómez-García, Carlos J.; Fritz, Michelle; Soler, Jose M.; Gómez-Herrero, Julio; Gómez-Navarro, Cristina; Zamora, Félix

    2013-01-01

    One-dimensional conductive polymers are attractive materials because of their potential in flexible and transparent electronics. Despite years of research, on the macro- and nano-scale, structural disorder represents the major hurdle in achieving high conductivities. Here we report measurements of highly ordered metal-organic nanoribbons, whose intrinsic (defect-free) conductivity is found to be 104 S m−1, three orders of magnitude higher than that of our macroscopic crystals. This magnitude is preserved for distances as large as 300 nm. Above this length, the presence of structural defects (~ 0.5%) gives rise to an inter-fibre-mediated charge transport similar to that of macroscopic crystals. We provide the first direct experimental evidence of the gapless electronic structure predicted for these compounds. Our results postulate metal-organic molecular wires as good metallic interconnectors in nanodevices. PMID:23591876

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

    SciTech Connect

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

    2007-05-10

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

  3. Metal-organic frameworks: Shuttling in the solid state

    NASA Astrophysics Data System (ADS)

    Olson, Mark A.

    2015-06-01

    Incorporating mechanically interlocked molecular shuttles within a metal-organic framework that has enough free space in the crystal lattice to permit volume-conserving translational motion sets the stage for defect-free molecular-electronic device fabrication and more.

  4. Omar Yaghi on Chemistry and Metal Organic Frameworks

    SciTech Connect

    Omar Yaghi

    2012-07-23

    In this edited version of the hour long talk, Omar Yaghi, director of the Molecular Foundry, sat down in conversation with Jeff Miller, head of Public Affairs, on July 11th, 2012 to discuss his fascination with the hidden world of chemistry and his work on Metal Organic Frameworks.

  5. Omar Yaghi on Chemistry and Metal Organic Frameworks

    ScienceCinema

    Omar Yaghi

    2016-07-12

    In this edited version of the hour long talk, Omar Yaghi, director of the Molecular Foundry, sat down in conversation with Jeff Miller, head of Public Affairs, on July 11th, 2012 to discuss his fascination with the hidden world of chemistry and his work on Metal Organic Frameworks.

  6. Method of making metal-doped organic foam products

    DOEpatents

    Rinde, James A.

    1981-01-01

    Organic foams having a low density and very small cell size and method for roducing same in either a metal-loaded or unloaded (nonmetal loaded) form are described. Metal-doped foams are produced by soaking a polymer gel in an aqueous solution of desired metal salt, soaking the gel successively in a solvent series of decreasing polarity to remove water from the gel and replace it with a solvent of lower polarity with each successive solvent in the series being miscible with the solvents on each side and being saturated with the desired metal salt, and removing the last of the solvents from the gel to produce the desired metal-doped foam having desired density cell size, and metal loading. The unloaded or metal-doped foams can be utilized in a variety of applications requiring low density, small cell size foam. For example, rubidium-doped foam made in accordance with the invention has utility in special applications, such as in x-ray lasers.

  7. Target organs in chronic bioassays of 533 chemical carcinogens.

    PubMed Central

    Gold, L S; Slone, T H; Manley, N B; Bernstein, L

    1991-01-01

    A compendium of carcinogenesis bioassay results organized by target organ is presented for 533 chemicals that are carcinogenic in at least one species. This compendium is based primarily on experiments in rats or mice; results in hamsters, nonhuman primates, and dogs are also reported. The compendium can be used to identify chemicals that induce tumors at particular sites, and to determine whether target sites are the same for chemicals positive in more than one species. The Carcinogenic Potency Database (CPDB), which includes results of 3969 experiments, is used in the analysis. The published CPDB includes details on each test, and literature references. Chemical carcinogens are reported for 35 different target organs in rats or mice. More than 80% of the carcinogens in each of these species are positive in at least one of the 8 most frequent target sites: liver, lung, mammary gland, stomach, vascular system, kidney, hematopoietic system, and urinary bladder. An analysis is presented of how well one can predict the carcinogenic response in mice from results in rats, or vice versa. Among chemicals tested in both species, 76% of rat carcinogens are positive in mice, and 71% of mouse carcinogens are positive in rats. Prediction is less accurate to the same target site: 52% of rat carcinogens are positive in the same site in mice, and 48% of mouse carcinogens are positive in the same site in rats. The liver is the most frequent site in common between rats and mice. PMID:1773795

  8. Metallic nanoparticle deposition techniques for enhanced organic photovoltaic cells

    NASA Astrophysics Data System (ADS)

    Cacha, Brian Joseph Gonda

    Energy generation via organic photovoltaic (OPV) cells provide many advantages over alternative processes including flexibility and price. However, more efficient OPVs are required in order to be competitive for applications. One way to enhance efficiency is through manipulation of exciton mechanisms within the OPV, for example by inserting a thin film of bathocuproine (BCP) and gold nanoparticles between the C60/Al and ZnPc/ITO interfaces, respectively. We find that BCP increases efficiencies by 330% due to gains of open circuit voltage (Voc) by 160% and short circuit current (Jsc) by 130%. However, these gains are complicated by the anomalous photovoltaic effect and an internal chemical potential. Exploration in the tuning of metallic nanoparticle deposition on ITO was done through four techniques. Drop casting Ag nanoparticle solution showed arduous control on deposited morphology. Spin-coating deposited very low densities of nanoparticles. Drop casting and spin-coating methods showed arduous control on Ag nanoparticle morphology due to clustering and low deposition density, respectively. Sputtered gold on glass was initially created to aid the adherence of Ag nanoparticles but instead showed a quick way to deposit aggregated gold nanoparticles. Electrodeposition of gold nanoparticles (AuNP) proved a quick method to tune nanoparticle morphology on ITO substrates. Control of deposition parameters affected AuNP size and distribution. AFM images of electrodeposited AuNPs showed sizes ranging from 39 to 58 nm. UV-Vis spectroscopy showed the presence of localized plasmon resonance through absorption peaks ranging from 503 to 614 nm. A linear correlation between electrodeposited AuNP size and peak absorbance was seen with a slope of 3.26 wavelength(nm)/diameter(nm).

  9. Physico-chemical changes in dissolved organic matters in the rhizosphere of plants grown in soil amended with organic wastes: an in-situ investigation.

    NASA Astrophysics Data System (ADS)

    Djae, Tanalou; Bravin, Matthieu; Garnier, Cédric; Mayen, Jean-Fabien; Doelsch, Emmanuel

    2014-05-01

    In agricultural context, prerequisite condition to forecast trace metal phytodisponibility is to evaluate trace metal speciation in the rhizosphere solution, especially in soil amended with organic wastes. The most advanced trace metal speciation models (e.g. WHAM, NICA-DONNAN) take into account dissolved organic matter (DOM) reactivity toward trace metals. Generally, the scientific community uses, a fixed percentage of DOM reactivity, usually of 40 % to 80 %, to predict trace metal speciation. However, recent studies have demonstrated that the binding capacity of DOM towards trace metals is much larger than expected. The aim of our study was to investigate the mechanisms supporting the variability in DOM reactivity by assessing the physico-chemical changes of DOM in the bulk-soil and rhizosphere in context of agricultural recycling of organic wastes. An in-situ experiment was conducted in Reunion Island (Indian Ocean). Two plant species, i.e. a graminaceous species the fescue (Festuca rubra) and a dicotyledonous species the tomato (Lycopersicon esculentum), were grown on a soil where we applied two types of organic wastes (pig manure compost and poultry manure compost) at three rates and a mineral fertilizer. Following this experiment, the soil either adhering to the roots (i.e. rhizosphere) or not (i.e. bulk-soil) was sampled and the soil solution was recovered by chemical extraction. DOM concentration, total acidity and DOM fluorescence were measured. Root activities and organic wastes induced variations in the physico-chemical parameters of DOM. DOM concentration tended to increase in bulk-soil with increasing organic waste application rate. DOM concentrations measured in rhizosphere are significantly greater than those in the bulk-soil especially when organic wastes were applied to soil. Preliminary results allow us to observe a decrease in the density of carboxylic-like (pKa

  10. In Situ Chemical Reduction for Organic Explosives in Soil

    DTIC Science & Technology

    2009-05-01

    Amendment • Combines solid controlled-release carbon and nutrients (aerobic) or with micro-scale ZVI (anaerobic) • Stimulates indigenous bacteria by...herbicides • organic explosives • chlorinated solvents Aerobic • wood treatment chemicals ( PAHs & PCP) • manufactured gas plant PAHs • phthalates

  11. Dynamic exposure of organisms and passive samplers to hydrophobic chemicals.

    PubMed

    Bayen, Stéphane; Ter Laak, Thomas L; Buffle, Jacques; Hermens, Joop L M

    2009-04-01

    An insight into the dynamic aspects of the accumulation process is essential for understanding bioaccumulation as well as effect studies of hydrophobic organic chemicals. This review presents an overview of kinetic studies with organisms (fish, bivalve, crustacean, insect, worm, algae, and protozoan) as well as passive samplers (solid and liquid phase microextraction, semipermeable membrane device, polymer sheet, solid-phase extraction, Chemcatcher, etc.) for the uptake of neutral nonpolar chemicals from the aqueous phase. Information about uptake rates, elimination rates, and 95% equilibration times was collected and analyzed with diffusion based models. The present literature review suggests that the surface to volume ratio appears to be a critical parameter for the uptake rate of the more hydrophobic chemicals both for samplers and organisms. In addition, as a very first approximation, the combination of the first-order kinetic model with the assumption that diffusion through the aqueous boundary layers is rate limiting, gives a reasonable description of the experimental kinetic data. In this way, the presented model might be used to estimate uptake and elimination rate constants of chemicals by organisms or passive samplers.

  12. Influence of organic matter transformations on the bioavailability of heavy metals in a sludge based compost.

    PubMed

    Ingelmo, Florencio; Molina, Maria José; Soriano, Maria Desamparados; Gallardo, Antonio; Lapeña, Leonor

    2012-03-01

    The agricultural use of anaerobically digested sewage sludge (ADSS) as stable, mature compost implies knowing its total content in heavy metals and their bioavailability. This depends not only on the initial characteristics of the composted substrates but also on the organic matter transformations during composting which may influence the chemical form of the metals and their bioavailability. The objective of this work was to examine the relationships between the changes in the organic matter content and humus fractions, and the bioavailability of heavy metals. A detailed sampling at 0, 14, 84, and 140 days of the composting process was performed to measure C contents in humic acids (HAs), fulvic acids, (FAs) and humin, the total content of Zn, Pb, Cu, Ni, and Cd, and also their distribution into mobile and mobilisable (MB), and low bioavailability (LB) forms. Significant changes of C contents in HA, FA, and Humin, and in the FA/HA, HA/Humin and C(humus)/TOC ratios were observed during composting. The MB and LB fractions of each metal also varied significantly during composting. The MB fraction increased for Zn, Cu, Ni, and Cd, and the LB fraction increased for Pb. Stepwise linear regressions and quadratic curve estimation conducted on the MB and LB fractions of each metal as dependent on the measured organic variables suggested that Zn bioavailability was mainly associated to percentage of C in FAs. Bioavailability of Cu, Ni and Cd during composting was associated to humin and HAs. Pb concentration increased in the LB form, and its variations followed a quadratic function with the C(humus)/TOC ratio. Our results suggest that the composting process renders the metals in more available forms. The main forms of metal binding in the sludge and their availability in the final compost may be better described when metal fractionation obtained in sequential extraction and humus fractionation during composting are considered together.

  13. Metal-organic framework templated inorganic sorbents for rapid and efficient extraction of heavy metals.

    PubMed

    Abney, C W; Gilhula, J C; Lu, K; Lin, W

    2014-12-17

    An innovative wet-treatment with Na2 S transforms two indium metal-organic frameworks (MOFs) into a series of porous inorganic sorbents. These MOF-templated materials display remarkable affinity for heavy metals with saturation occurring in less than 1 h. The saturation capacity for Hg(II) exceeds 2 g g(-1) , more than doubling the best thiol-functionalized sorbents in the literature.

  14. Multifunctional polymer-metal nanocomposites via direct chemical reduction by conjugated polymers.

    PubMed

    Xu, Ping; Han, Xijiang; Zhang, Bin; Du, Yunchen; Wang, Hsing-Lin

    2014-03-07

    Noble metal nanoparticles (MNPs) have attracted continuous attention due to their promising applications in chemistry, physics, bioscience, medicine and materials science. As an alternative to conventional solution chemistry routes, MNPs can be directly synthesized through a conjugated polymer (CP) mediated technique utilizing the redox chemistry of CPs to chemically reduce the metal ions and modulate the size, morphology, and structure of the MNPs. The as-prepared multifunctional CP-MNP nanocomposites have shown application potentials as highly sensitive surface enhanced Raman spectroscopy (SERS) substrates, effective heterogeneous catalysts for organic synthesis and electrochemistry, and key components for electronic and sensing devices. In this tutorial review, we begin with a brief introduction to the chemical nature and redox properties of CPs that enable the spontaneous reduction of noble metal ions to form MNPs. We then focus on recent progress in control over the size, morphology and structure of MNPs during the conjugated polymer mediated syntheses of CP-MNP nanocomposites. Finally, we highlight the multifunctional CP-MNP nanocomposites toward their applications in sensing, catalysis, and electronic devices.

  15. Recent Developments of Metal and Metal Oxide Nanocatalysts in Organic Synthesis.

    PubMed

    Makawana, Jigar A; Sangani, Chetan B; Yao, Yong-Fang; Duan, Yong-Tao; Lv, Peng-Cheng; Zhu, Hai-Liang

    2016-01-01

    Recently, various nanomaterials have been used in many organic transformations as efficient catalysts. The development of new catalysts by nanoscale design has emerged as a fertile field for research and innovation. The ability of nanotechnology to enhance catalytic activity opens the potential to replace expensive catalysts with lower amounts of inexpensive nanocatalysts. Besides, development of efficient and environmentally friendly synthetic methodologies for the synthesis of compound libraries of medicinal scaffolds is an attractive area of research in both academic and pharmaceutical industry. According to above reports and needs, this review deals with applications of nanoparticles as catalysts in various organic syntheses. We detail the topic of organic transformations using nanoparticles: Metal Nanoparticles and Metal Oxide Nanoparticles. In the latter part, different Metal Oxide Nanoparticles, such as ZnO Nanoparticle, TiO2 Nanoparticle, and CuO Nanoparticle are discussed.

  16. A Green Strategy to Prepare Metal Oxide Superstructure from Metal-Organic Frameworks

    PubMed Central

    Song, Yonghai; Li, Xia; Wei, Changting; Fu, Jinying; Xu, Fugang; Tan, Hongliang; Tang, Juan; Wang, Li

    2015-01-01

    Metal or metal oxides with diverse superstructures have become one of the most promising functional materials in sensor, catalysis, energy conversion, etc. In this work, a novel metal-organic frameworks (MOFs)-directed method to prepare metal or metal oxide superstructure was proposed. In this strategy, nodes (metal ions) in MOFs as precursors to form ordered building blocks which are spatially separated by organic linkers were transformed into metal oxide micro/nanostructure by a green method. Two kinds of Cu-MOFs which could reciprocally transform by changing solvent were prepared as a model to test the method. Two kinds of novel CuO with three-dimensional (3D) urchin-like and 3D rods-like superstructures composed of nanoparticles, nanowires and nanosheets were both obtained by immersing the corresponding Cu-MOFs into a NaOH solution. Based on the as-formed CuO superstructures, a novel and sensitive nonenzymatic glucose sensor was developed. The small size, hierarchical superstructures and large surface area of the resulted CuO superstructures eventually contribute to good electrocatalytic activity of the prepared sensor towards the oxidation of glucose. The proposed method of hierarchical superstructures preparation is simple, efficient, cheap and easy to mass production, which is obviously superior to pyrolysis. It might open up a new way for hierarchical superstructures preparation. PMID:25669731

  17. The metal/organic interface in cobalt/vinylidene fluoride heterostructures

    NASA Astrophysics Data System (ADS)

    Foreman, K.; Echeverria, E.; Koten, M. A.; Lindsay, R. M.; Hong, N.; Shield, J.; Adenwalla, S.

    2016-11-01

    Organic-based electronic devices are rapidly increasing in popularity, making it essential to understand and characterize the interface between organic materials and metallic electrodes. This work reports on the characterization of the interface between thin films of an emerging organic ferroelectric, vinylidene fluoride (VDF) oligomer, and Co, an important high Curie temperature ferromagnet. Using a wide battery of experimental techniques, it is shown that VDF oligomer thin films as thin as 15 nm can halt, or prevent, Co oxidization in atmospheric conditions, a necessary condition for device applications. Selectivity of magnetic properties, such as remanent magnetization, is enabled by the clarification of the time scale of Co oxidation, a topic on which there are many conflicting reports. Furthermore, this work shows evidence of chemical bonding at the interface between VDF oligomer and Co, a result with important implications for organic spintronic devices. These results establish the suitability of VDF oligomer for organic-based electronic devices.

  18. 40 CFR 414.70 - Applicability; description of the bulk organic chemicals subcategory.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... organic chemicals subcategory. 414.70 Section 414.70 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) EFFLUENT GUIDELINES AND STANDARDS ORGANIC CHEMICALS, PLASTICS, AND SYNTHETIC FIBERS Bulk Organic Chemicals § 414.70 Applicability; description of the bulk organic chemicals...

  19. 40 CFR 414.70 - Applicability; description of the bulk organic chemicals subcategory.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... organic chemicals subcategory. 414.70 Section 414.70 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) EFFLUENT GUIDELINES AND STANDARDS ORGANIC CHEMICALS, PLASTICS, AND SYNTHETIC FIBERS Bulk Organic Chemicals § 414.70 Applicability; description of the bulk organic chemicals...

  20. 40 CFR 414.70 - Applicability; description of the bulk organic chemicals subcategory.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... organic chemicals subcategory. 414.70 Section 414.70 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) EFFLUENT GUIDELINES AND STANDARDS ORGANIC CHEMICALS, PLASTICS, AND SYNTHETIC FIBERS Bulk Organic Chemicals § 414.70 Applicability; description of the bulk organic chemicals...

  1. 40 CFR 414.70 - Applicability; description of the bulk organic chemicals subcategory.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... organic chemicals subcategory. 414.70 Section 414.70 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) EFFLUENT GUIDELINES AND STANDARDS ORGANIC CHEMICALS, PLASTICS, AND SYNTHETIC FIBERS Bulk Organic Chemicals § 414.70 Applicability; description of the bulk organic chemicals...

  2. Approaches to Establishing the Chemical Structure of Extraterrestrial Organic Solids

    NASA Technical Reports Server (NTRS)

    Cody, G. D.; Alexander, C. M. OD.; Wirick, Susan

    2003-01-01

    The majority of extraterrestrial organic matter in carbonaceous chondrites resides in a chemically complex, insoluble and perhaps macromolecular phase. We have been applying a series of independent solid state NMR experiments that are designed to provide a self consistent chemical characterization of this complex material. To date we have thoroughly analyzed 8 organic residues from different meteorites, including a CR2 (EET92042), CIl(Orgueil), CM2 (Murchison), Tagish Lake, CM2 (AlH83100), CM2 (Cold Bokkefeld), CM2 (Mighei), CM3 (Y86720). In fig 1. (1)H to (13)C cross polarization NMR spectra of four of these are shown. Note that there exists an enormous range in chemistry exhibited in organic solid [evident by the breadth of the spectral features both in the aliphatic region (sp(sup 3)) and the aromatic region (sp(sup 2))]. There is also considerable differences in the carbon chemistry across the meteorite groups.

  3. Optical Detection of Organic Chemical Biosignatures at Hydrothermal Vents

    NASA Technical Reports Server (NTRS)

    Conrad, P. G.; Lane, A. L.; Bhartia, R.; Hug, W. H.

    2004-01-01

    We have developed a non-contact, optical life detection instrument that can detect organic chemical biosignatures in a number of different environments, including dry land, shallow aqueous, deep marine or in ice. Hence, the instrument is appropriate as a biosignature survey tool both for Mars exploration or in situ experiments in an ice-covered ocean such as one might wish to explore on Europa. Here, we report the results we obtained on an expedition aboard the Russian oceanographic vessel Akademik Mstislav Keldysh to hydrothermal vent sites in the Pacific Ocean using our life detection instrument MCDUVE, a multichannel, deep ultraviolet excitation fluorescence detector. MCDUVE detected organic material distribution on rocks near the vent, as well as direct detection of organisms, both microbial and microscopic. We also were able to detect organic material issuing directly from vent chimneys, measure the organic signature of the water column as we ascended, and passively observe the emission of light directly from some vents.

  4. Effect of organic substituents on the adsorption of carbon dioxide on a metal-organic framework

    NASA Astrophysics Data System (ADS)

    Thu Ha, Nguyen Thi; Lefedova, O. V.; Ha, Nguyen Ngoc

    2017-01-01

    The adsorption of carbon dioxide on the MOF-5 metal-organic framework and modifications of it obtained by replacing the hydrogen atoms in the organic ligands with electron donor (-CH3,-OCH3) or electron acceptor groups (-CN,-NO2) is investigated using the grand canonical Monte Carlo (GCMC) method and density functional theory (DFT). It is shown that the adsorption of carbon dioxide molecules on the structures of metal-organic frameworks is most likely on Zn4O clusters, and that the adsorption of carbon dioxide is of a physical nature. The presence of substituents-CH3,-OCH3,-CN in metal-organic frameworks increases their capacity to adsorb carbon dioxide, while that of nitro groups (-NO2) has the opposite effect.

  5. Combinations of Aminocatalysts and Metal Catalysts: A Powerful Cooperative Approach in Selective Organic Synthesis.

    PubMed

    Afewerki, Samson; Córdova, Armando

    2016-11-23

    The cooperation and interplay between organic and metal catalyst systems is of utmost importance in nature and chemical synthesis. Here innovative and selective cooperative catalyst systems can be designed by combining two catalysts that complement rather than inhibit one another. This refined strategy can permit chemical transformations unmanageable by either of the catalysts alone. This review summarizes innovations and developments in selective organic synthesis that have used cooperative dual catalysis by combining simple aminocatalysts with metal catalysts. Considerable efforts have been devoted to this fruitful field. This emerging area employs the different activation modes of amine and metal catalysts as a platform to address challenging reactions. Here, aminocatalysis (e.g., enamine activation catalysis, iminium activation catalysis, single occupied molecular orbital (SOMO) activation catalysis, and photoredox activation catalysis) is employed to activate unreactive carbonyl substrates. The transition metal catalyst complements by activating a variety of substrates through a range of interactions (e.g., electrophilic π-allyl complex formation, Lewis acid activation, allenylidene complex formation, photoredox activation, C-H activation, etc.), and thereby novel concepts within catalysis are created. The inclusion of heterogeneous catalysis strategies allows for "green" chemistry development, catalyst recyclability, and the more eco-friendly synthesis of valuable compounds.

  6. Organic molecules on metal and oxide semiconductor substrates: Adsorption behavior and electronic energy level alignment

    NASA Astrophysics Data System (ADS)

    Ruggieri, Charles M.

    (110), which exhibits chemical hybridization accompanied by molecular distortion, as well as extreme charge transfer resulting in the development of a space charge layer in the oxide. Thus, we present a broad experimental and theoretical perspective on the study of organic/metal and organic/oxide interfaces, elucidating fundamental physical interactions that govern molecular organization and energy level alignment.

  7. INFLUENCE OF ORGANIC COSOLVENTS ON THE SORPTION KINETICS OF HYDROPHOBIC ORGANIC CHEMICALS

    EPA Science Inventory

    A quantitative examination of the kinetics of sorption of hydrophobic organic chemicals by soils from mixed solvents reveals that the reverse sorption rate constant (k2) increases log-linearly with increasing volume fraction of organic cosolvent (fc). This relationship was expec...

  8. Role of chemical and ecological factors in trophic transfer of organic chemicals in aquatic food webs

    SciTech Connect

    Russell, R.W.; Gobas, F.A.P.C. . School of Resource and Environmental Management); Haffner, G.D. )

    1999-06-01

    Trophic transfer of chlorinated organic contaminants was investigated in an aquatic community composed of zooplankton, benthic invertebrates, and fish. Biomagnification, measured as the increase in lipid-based chemical concentrations in predator over that in prey, was observed for high-K[sub OW] chemicals (log K[sub OW] > 6.3). Low-K[sub OW] chemicals (log K[sub OW] < 5.5) did not biomagnify in the food web, and chemicals with log K[sub OW] between 5.5 and 6.3 showed some evidence of biomagnification. Trophic level differences in chemical accumulation in the food web could not be attributed to bioconcentration into increasing trophic levels with increasing lipid levels, as no relationship was observed between trophic position and lipid content of organisms. Plots of contaminant-ordinated principal component scores in component space predicted the detailed diets of the species examined. It is concluded that (1) trophic interactions play a crucial role in the distribution of high-K[sub OW] chemicals but not for low-K[sub OW] chemicals and that (2) contaminant distributions provide a means to determine structure in aquatic communities.

  9. Chemical Control of Plasmons in Metal Chalcogenide and Metal Oxide Nanostructures.

    PubMed

    Mattox, Tracy M; Ye, Xingchen; Manthiram, Karthish; Schuck, P James; Alivisatos, A Paul; Urban, Jeffrey J

    2015-10-14

    The field of plasmonics has grown to impact a diverse set of scientific disciplines ranging from quantum optics and photovoltaics to metamaterials and medicine. Plasmonics research has traditionally focused on noble metals; however, any material with a sufficiently high carrier density can support surface plasmon modes. Recently, researchers have made great gains in the synthetic (both intrinsic and extrinsic) control over the morphology and doping of nanoscale oxides, pnictides, sulfides, and selenides. These synthetic advances have, collectively, blossomed into a new, emerging class of plasmonic metal chalcogenides that complement traditional metallic materials. Chalcogenide and oxide nanostructures expand plasmonic properties into new spectral domains and also provide a rich suite of chemical controls available to manipulate plasmons, such as particle doping, shape, and composition. New opportunities in plasmonic chalcogenide nanomaterials are highlighted in this article, showing how they may be used to fundamentally tune the interaction and localization of electromagnetic fields on semiconductor surfaces in a way that enables new horizons in basic research and energy-relevant applications.

  10. Tracing the migration history of metal catalysts in metal-assisted chemically etched silicon.

    PubMed

    Güder, Firat; Yang, Yang; Küçükbayrak, Umut M; Zacharias, Margit

    2013-02-26

    Three-dimensional (3D) visualization of complex embedded nanopore networks in silicon requires expensive machinery and tedious sample preparation procedures such as electron tomography, also known as 3D transmission electron microscopy. In this article, we report a new, fast, powerful, and low-cost three-dimensional imaging technique with sub-5 nm resolution. This new imaging method is applied to metal-assisted chemically etched monocrystalline Si to demonstrate its capabilities. The AFEI (atomic layer deposition-fill-etch-imaging) technique consists of three simple process steps that are available in most material research settings. First the porous substrate is conformally coated with an atomic layer deposition (ALD) metal oxide layer. ALD is able to penetrate deep into complex, high aspect ratio pores, as it is a sequential gas-phase deposition process. Next, the cross-section of the ALD-filled porous Si substrate is etched with high-density fluorine-based plasma processing, which yields very high selectivity toward Si (e.g., >400:1 for Si:ZnO). This step removes the bulk Si and exposes the metal oxide structures grown inside the pores. In the last step, the sample cross-section is examined using a standard scanning electron microscope at various angles, which allows precise imaging of hidden features and reconstruction of a 3D model of the embedded pore network.

  11. Seamless metal-clad fiber-reinforced organic matrix composite structures and process for their manufacture

    NASA Technical Reports Server (NTRS)

    Bluck, Raymond M. (Inventor); Bush, Harold G. (Inventor); Johnson, Robert R. (Inventor)

    1990-01-01

    A metallic outer sleeve is provided which is capable of enveloping a hollow metallic inner member having continuous reinforcing fibers attached to the distal end thereof. The inner member is then introduced into outer sleeve until inner member is completely enveloped by outer sleeve. A liquid matrix member is then injected into space between inner member and outer sleeve. A pressurized heat transfer medium is flowed through the inside of inner member, thereby forming a fiber reinforced matrix composite material. The wall thicknesses of both inner member and outer sleeve are then reduced to the appropriate size by chemical etching, to adjust the thermal expansion coefficient of the metal-clad composite structure to the desired value. thereby forming a fiber reinforced matrix composite material. The wall thicknesses of both inner member and outer sleeve are then reduced to the appropriate size by chemical etching, to adjust the thermal expansion coefficient of the metal-clad composite structure to the desired value. The novelty of this invention resides in the development of a efficient method of producing seamless metal clad fiber reinforced organic matrix composite structures.

  12. When hole extraction determines charge transfer across metal-organic-metal structure

    NASA Astrophysics Data System (ADS)

    Govor, L. V.; Reiter, G.; Parisi, J.

    2016-03-01

    We examined the charge transfer in metal-organic-metal structure, where the contact resistance of the extracting interface is larger than the resistance of the organic crystalline material and the resistance of the injecting interface. If direct tunneling (low voltage) and Fowler-Nordheim tunnelling (high voltage) across both interfaces take place, part of the injected holes remains located in the organic crystal because of the blocking action of the extracting interface, but not because of traps within the organic crystalline material (which was negligible). If Fowler-Nordheim tunneling across the injecting interface and direct tunneling across the extracting interface take place for high voltages, the latter leads to the deviation of the total current-voltage characteristic from the power law I∼ Vγ with γ>2 to Ohm's law with γ≃1.0 .

  13. Chemical evolution and the preservation of organic compounds on Mars

    NASA Technical Reports Server (NTRS)

    Kanavarioti, Anastassia; Mancinelli, Rocco L.

    1989-01-01

    Several lines of evidence suggest that the environment on early Mars and early Earth were very similar. Since life is abundant on Earth, it seems likely that conditions on early Earth were conducive to chemical evolution and the origin of life. The similarity between early Mars and early Earth encourages the hypothesis that chemical evolution might have also occurred on Mars, but that decreasing temperatures and the loss of its atmosphere brought the evolution to a halt. The possibility of finding on Mars remnants of organic material dating back to this early clement period is addressed.

  14. Chemically and temperature-induced phase transformations of metal vanadates

    NASA Astrophysics Data System (ADS)

    Patridge, Christopher James

    different individual beta'-Cu xV2O5 nanowires vary widely. Using scanning transmission X-ray microspectroscopy of individual beta'-CuxV2O 5 nanowires, correlations appear to exist between MIT characteristics and the markedly different orbital hybridization of vanadium and oxygen at the O K and V L absorption edges. These comprehensive nanostructure studies hint at the possibility of approaching the incredibly important realm of single-domain measurements which are needed to understand and exploit the intrinsic physical properties of materials. In addition to the bronze MIT studies, the classical MIT material vanadium dioxide, VO2, also shows new properties when scaling down to nanoscale dimensions as well as incorporation of substitutional dopants such as tungsten. X-ray absorption spectroscopy of the dopant local structure suggests an increased symmetry and depairing of V4+-V 4+, which is critical for transition to the lower temperature insulating phase thereby super-cooling the metallic phase to temperatures as low as 254 K. Mechanistic insight and structural changes associated with the intercalation of Li+ are key aspects in understanding and designing useful secondary Li ion batteries. In similarity to the MxV2O 5 studies, another metal vanadate, Ag2VO2PO 4, undergoes phase transformations due to introduction of Li and the vacancy of Ag ions. Employing a comprehensive study on Ag2VO 2PO4 using X-ray absorption spectroscopy, information about chemical state changes and rehybridization of frontier orbitals allows for a more precise understanding of how the material discharges, what, if any, intermediate phases exist during the process, and provides evidence for the posited structural stability at high depths of discharge.

  15. Structures of alkali metals in silica gel nanopores: new materials for chemical reductions and hydrogen production.

    PubMed

    Shatnawi, Mouath; Paglia, Gianluca; Dye, James L; Cram, Kevin C; Lefenfeld, Michael; Billinge, Simon J L

    2007-02-07

    Alkali metals and their alloys can be protected from spontaneous reaction with dry air by intercalation (with subsequent heating) into the pores of silica gel (SG) at loadings up to 40 wt %. The resulting loose, black powders are convenient materials for chemical reduction of organic compounds and the production of clean hydrogen. The problem addressed in this paper is the nature of the reducing species present in these amorphous materials. The atomic pair distribution function (PDF), which considers both Bragg and diffuse scattering components, was used to examine their structures. Liquid Na-K alloys added to silica gel at room temperature (stage 0) or heated to 150 degrees C (stage I) as well as stage I Na-SG, retain the overall pattern of pure silica gel. Broad oscillations in the PDF show that added alkali metals remain in the pores as nanoscale metal clusters. 23Na MAS NMR studies confirm the presence of Na(0) and demonstrate that Na+ ions are formed as well. The relative amounts of Na(0) and Na(+) depend on both the overall metal loading and the average pore size. The results suggest that ionization occurs near or in the SiO2 walls, with neutral metal present in the larger cavities. The fate of the electrons released by ionization is uncertain, but they may add to the silica gel lattice, or form an "electride-like plasma" near the silica gel walls. A remaining mystery is why the stage I material does not show a melting endotherm of the encapsulated metal and does not react with dry oxygen. Na-SG when heated to 400 degrees C (stage II) yields a dual-phase reaction product that consists of Na(4)Si(4) and Na(2)SiO(3).

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

    USGS Publications Warehouse

    Lovely, Derek R.; Anderson, Robert T.

    2000-01-01

    Geobacter become dominant members of the microbial community when Fe(III)-reducing conditions develop as the result of organic contamination, or when Fe(III) reduction is artificially stimulated. These results suggest that further understanding of the ecophysiology of Geobacter species would aid in better prediction of the natural attenuation of organic contaminants under anaerobic conditions and in the design of strategies for the bioremediation of subsurface metal contamination.

  17. Early holocene trace metal enrichment in organic lake sediments, Baffin Island, Arctic Canada

    SciTech Connect

    Wolfe, A.P.; Haertling, J.W.

    1997-02-01

    Trace metals having accumulated in preindustrial ({sup 14}C dated) sediments from two small, acid-sensitive, arctic lakes show unexpected stratigraphic trends. Concentrations of Cu, Cr, Pb, Ni, and Zn have successive maxima in early to mid-Holocene sediments, of amplitudes comparable to lakes affected by loading from industrial atmospheric fallout. These profiles contrast sharply the concentrations of elements primarily associated with catchment erosion (Ti, V, Zr), and are attributed to the enhanced transport of organic-bound trace metals from the catchments to the lakes in the early Holocene. Paleoliminological conditions conferred effective sedimentary sinks for each of the enriched elements, although a certain degree of diagenetic mobilization is also observed. The study verifies that natural conditions may, under specific circumstances, produce sediment chemical signatures of potentially toxic metals that bear similarities to those reported from lakes adversely impacted by atmospheric pollution. 31 refs., 4 figs., 1 tab.

  18. Using blood samples to estimate persistent organic pollutants and metals in green sea turtles (Chelonia mydas).

    PubMed

    van de Merwe, Jason P; Hodge, Mary; Olszowy, Henry A; Whittier, Joan M; Lee, Shing Y

    2010-04-01

    Persistent organic pollutants (POPs) and heavy metals have been reported in a number of green turtle (Chelonia mydas) populations worldwide. However, due to ethical considerations, these studies have generally been on tissues from deceased and stranded animals. The purpose of this study was to investigate the use of blood samples to estimate the tissue contamination of live C. mydas populations. This study analysed 125 POP compounds and eight heavy metals in the blood, liver, kidney and muscle of 16 C. mydas from the Sea World Sea Turtle Rehabilitation Program, Gold Coast, Australia. Strong correlations were observed between blood and tissue concentrations for a number of POPs and metals. Furthermore, these correlations were observed over large ranges of turtle size, sex and condition. These results indicate that blood samples are a reliable non-lethal method for predicting chemical contamination in C. mydas.

  19. Adsorption of volatile organic compounds in porous metal-organic frameworks functionalized by polyoxometalates

    NASA Astrophysics Data System (ADS)

    Ma, Feng-Ji; Liu, Shu-Xia; Liang, Da-Dong; Ren, Guo-Jian; Wei, Feng; Chen, Ya-Guang; Su, Zhong-Min

    2011-11-01

    The functionalization of porous metal-organic frameworks (Cu 3( BTC) 2) was achieved by incorporating Keggin-type polyoxometalates (POMs), and further optimized via alkali metal ion-exchange. In addition to thermal gravimetric analysis, IR, single-crystal X-ray diffraction, and powder X-ray diffraction, the adsorption properties were characterized by N 2 and volatile organic compounds (VOCs) adsorption measurements, including short-chain alcohols ( C<4), cyclohexane, benzene, and toluene. The adsorption enthalpies estimated by the modified Clausius-Clapeyron equation provided insight into the impact of POMs and alkali metal cations on the adsorption of VOCs. The introduction of POMs not only improved the stability, but also brought the increase of adsorption capacity by strengthening the interaction with gas molecules. Furthermore, the exchanged alkali metal cations acted as active sites to interact with adsorbates and enhanced the adsorption of VOCs.

  20. Metal-Organic Frameworks as Catalysts for Oxidation Reactions.

    PubMed

    Dhakshinamoorthy, Amarajothi; Asiri, Abdullah M; Garcia, Hermenegildo

    2016-06-06

    This Concept is aimed at describing the current state of the art in metal-organic frameworks (MOFs) as heterogeneous catalysts for liquid-phase oxidations, focusing on three important substrates, namely, alkenes, alkanes and alcohols. Emphases are on the nature of active sites that have been incorporated within MOFs and on future targets to be set in this area. Thus, selective alkene epoxidation with peroxides or oxygen catalyzed by constitutional metal nodes of MOFs as active sites are still to be developed. Moreover, no noble metal-free MOF has been reported to date that can act as a general catalyst for the aerobic oxidation of primary and secondary aliphatic alcohols. In contrast, in the case of alkanes, a target should be to tune the polarity of MOF internal pores to control the outcome of the autooxidation process, resulting in the selective formation of alcohol/ketone mixtures at high conversion.

  1. Metalation of a Mesoporous Three-Dimensional Covalent Organic Framework.

    PubMed

    Baldwin, Luke A; Crowe, Jonathan W; Pyles, David A; McGrier, Psaras L

    2016-11-23

    Constructing metalated three-dimensional (3D) covalent organic frameworks is a challenging synthetic task. Herein, we report the synthesis and characterization of a highly porous (SABET = 5083 m(2) g(-1)) 3D COF with a record low density (0.13 g cm(-3)) containing π-electron conjugated dehydrobenzoannulene (DBA) units. Metalation of DBA-3D-COF 1 with Ni to produce Ni-DBA-3D-COF results in a minimal reduction in the surface area (SABET = 4763 m(2) g(-1)) of the material due to the incorporation of the metal within the cavity of the DBA units, and retention of crystallinity. Both 3D DBA-COFs also display great uptake capacities for ethane and ethylene gas.

  2. Chemical preparation of graphene materials results in extensive unintentional doping with heteroatoms and metals.

    PubMed

    Chua, Chun Kiang; Ambrosi, Adriano; Sofer, Zdeněk; Macková, Anna; Havránek, Vladimír; Tomandl, Ivo; Pumera, Martin

    2014-11-24

    Chemical synthesis of graphene relies on the usage of various chemical reagents. The initial synthesis step, in which graphite is oxidized to graphite oxide, is achieved by a combination of chemical oxidants and acids. A subsequent chemical reduction step eliminates/reduces most oxygen functionalities to yield graphene. We demonstrate here that these chemical treatments significantly contaminate graphene with heteroatoms/metals, depending on the procedures followed. Contaminations with heteroatoms (N, B, Cl, S) or metals (Mn, Al) were present at relatively high concentrations (up to 3 at%), with their chemical states dependent on the procedures. Such unintentional contaminations (unwanted doping) during chemical synthesis are rarely anticipated and reported, although the heteroatoms/metals may alter the electronic and catalytic properties of graphene. In fact, the levels of unintentionally introduced contaminants on graphene are often higher than typical levels found on intentionally doped graphene. Our findings are important for scientists applying chemical methods to prepare graphene.

  3. Using risk-ranking of metals to identify which poses the greatest threat to freshwater organisms in the UK.

    PubMed

    Donnachie, Rachel L; Johnson, Andrew C; Moeckel, Claudia; Pereira, M Glória; Sumpter, John P

    2014-11-01

    Freshwater aquatic organisms face the challenge of being exposed to a multitude of chemicals discharged by the human population. The objective of this study was to rank metals according to the threat they pose to aquatic organisms. This will contribute to a wider Chemical Strategy for freshwater which will risk-rank all chemicals based on their potential risk to wildlife in a UK setting. The method involved comparing information on ecotoxicological thresholds with measured concentrations in rivers. The bioconcentration factor was also considered as a ranking method. The metals; Ag, Al, As, Cd, Cr, Cu, Fe, Hg, Mn, Ni, Pb and Zn, were analysed using this approach. Triclosan and lindane were used as comparative organic pollutants. Using a range of ranking techniques, Cu, Al and Zn came top of the list of concern, with Cu coming first.

  4. Metal hydride/chemical heat pump development project

    NASA Astrophysics Data System (ADS)

    Madariaga, H. A.; Rohy, D. A.

    1982-02-01

    A mental hydride heat pump (MHHP) is a chemical heat pump containing two different hydrides and using hydrogen as a working fluid for the storage and/or recovery of thermal energy. It utilizes the heat of reaction of hydrogen with specific metal alloys. The MHHP design can be tailored to provide heating and cooling or temperature upgrading over a wide range of input and ambient temperatures. This system can be used with a variety of heat sources including industrial waste heat, solar energy or a fossil fuel. Temperature as low as 130 F can drive the MHHP when a suitable sink is provided. A project is currently underway to develop this unique heat pump for a specific application. The goals of the project include the development of cost effective hydride containers with high heat transfer and low mass; design and fabrication of a laboratory evaluation model; and design and fabrication of a demonstration unit. Extensive component and system test will provide the data for the design processes.

  5. Gas uptake and chemical aging of semisolid organic aerosol particles.

    PubMed

    Shiraiwa, Manabu; Ammann, Markus; Koop, Thomas; Pöschl, Ulrich

    2011-07-05

    Organic substances can adopt an amorphous solid or semisolid state, influencing the rate of heterogeneous reactions and multiphase processes in atmospheric aerosols. Here we demonstrate how molecular diffusion in the condensed phase affects the gas uptake and chemical transformation of semisolid organic particles. Flow tube experiments show that the ozone uptake and oxidative aging of amorphous protein is kinetically limited by bulk diffusion. The reactive gas uptake exhibits a pronounced increase with relative humidity, which can be explained by a decrease of viscosity and increase of diffusivity due to hygroscopic water uptake transforming the amorphous organic matrix from a glassy to a semisolid state (moisture-induced phase transition). The reaction rate depends on the condensed phase diffusion coefficients of both the oxidant and the organic reactant molecules, which can be described by a kinetic multilayer flux model but not by the traditional resistor model approach of multiphase chemistry. The chemical lifetime of reactive compounds in atmospheric particles can increase from seconds to days as the rate of diffusion in semisolid phases can decrease by multiple orders of magnitude in response to low temperature or low relative humidity. The findings demonstrate that the occurrence and properties of amorphous semisolid phases challenge traditional views and require advanced formalisms for the description of organic particle formation and transformation in atmospheric models of aerosol effects on air quality, public health, and climate.

  6. Bhasmas: unique ayurvedic metallic-herbal preparations, chemical characterization.

    PubMed

    Kumar, A; Nair, A G C; Reddy, A V R; Garg, A N

    2006-03-01

    Bhasmas are unique Ayurvedic metallic preparations with herbal juices/fruits, known in the Indian subcontinent since the seventh century BC and widely recommended for treatment of a variety of chronic ailments. Twenty bhasmas based on calcium, iron, zinc, mercury, silver, potassium, arsenic, copper, tin, and gemstones were analyzed for up to 18 elements by instrumental neutron activation analysis, including their C, H, N, and S contents. In addition to the major constituent element found at % level, several other essential elements such as Na, K, Ca, Mg, V, Mn, Fe, Cu, and Zn have also been found in microg/g amounts and ultratrace (ng/g) amounts of Au and Co. These seem to remain chelated with organic ligands derived from medicinal herbs. The bhasmas are biologically produced nanoparticles and are taken along with milk, butter, honey, or ghee (a preparation from milk); thus, this makes these elements easily assimilable, eliminating their harmful effects and enhancing their biocompatibility. Siddha Makaradhwaja, a mercury preparation is found to be stoichiometrically HgS without any traces of any other element. Similarly, Swet Parpati is stoichiometrically KNO3 but is found to have Mn, Cu, Zn, Na, P, and Cl as well. An attempt has been made to correlate the metallic contents with their medicinal importance. Na and K, the two electrolytic elements, seem to be well correlated, although K/Na varies in a wide range from 0.06 to 95, with specifically low values for Ca-, Fe-, and Zn-based bhasmas. K/P also varies in a wide range from 0.23 to 12, although for most bhasmas (n = 12), it is 2.3 +/- 1.2. Further, Fe/Mn is linearly correlated (r = 0.96) with Fe in nine noniron bhasmas.

  7. Increased Thermal Conductivity in Metal-Organic Heat Carrier Nanofluids

    PubMed Central

    Nandasiri, Manjula I.; Liu, Jian; McGrail, B. Peter; Jenks, Jeromy; Schaef, Herbert T.; Shutthanandan, Vaithiyalingam; Nie, Zimin; Martin, Paul F.; Nune, Satish K.

    2016-01-01

    Metal-organic heat carriers (MOHCs) are recently developed nanofluids containing metal-organic framework (MOF) nanoparticles dispersed in various base fluids including refrigerants (R245Fa) and methanol. Here, we report the synthesis and characterization of MOHCs containing nanoMIL-101(Cr) and graphene oxide (GO) in an effort to improve the thermo-physical properties of various base fluids. MOHC/GO nanocomposites showed enhanced surface area, porosity, and nitrogen adsorption compared with the intrinsic nanoMIL-101(Cr) and the properties depended on the amount of GO added. MIL-101(Cr)/GO in methanol exhibited a significant increase in the thermal conductivity (by approximately 50%) relative to that of the intrinsic nanoMIL-101(Cr) in methanol. The thermal conductivity of the base fluid (methanol) was increased by about 20%. The increase in the thermal conductivity of nanoMIL-101(Cr) MOHCs due to GO functionalization is explained using a classical Maxwell model. PMID:27302196

  8. Recent progress in the synthesis of metal-organic frameworks

    NASA Astrophysics Data System (ADS)

    Sun, Yujia; Zhou, Hong-Cai

    2015-10-01

    Metal-organic frameworks (MOFs) have attracted considerable attention for various applications due to their tunable structure, porosity and functionality. In general, MOFs have been synthesized from isolated metal ions and organic linkers under hydrothermal or solvothermal conditions via one-spot reactions. The emerging precursor approach and kinetically tuned dimensional augmentation strategy add more diversity to this field. In addition, to speed up the crystallization process and create uniform crystals with reduced size, many alternative synthesis routes have been explored. Recent advances in microwave-assisted synthesis and electrochemical synthesis are presented in this review. In recent years, post-synthetic approaches have been shown to be powerful tools to synthesize MOFs with modified functionality, which cannot be attained via de novo synthesis. In this review, some current accomplishments of post-synthetic modification (PSM) based on covalent transformations and coordinative interactions as well as post-synthetic exchange (PSE) in robust MOFs are provided.

  9. Increased Thermal Conductivity in Metal-Organic Heat Carrier Nanofluids

    NASA Astrophysics Data System (ADS)

    Nandasiri, Manjula I.; Liu, Jian; McGrail, B. Peter; Jenks, Jeromy; Schaef, Herbert T.; Shutthanandan, Vaithiyalingam; Nie, Zimin; Martin, Paul F.; Nune, Satish K.

    2016-06-01

    Metal-organic heat carriers (MOHCs) are recently developed nanofluids containing metal-organic framework (MOF) nanoparticles dispersed in various base fluids including refrigerants (R245Fa) and methanol. Here, we report the synthesis and characterization of MOHCs containing nanoMIL-101(Cr) and graphene oxide (GO) in an effort to improve the thermo-physical properties of various base fluids. MOHC/GO nanocomposites showed enhanced surface area, porosity, and nitrogen adsorption compared with the intrinsic nanoMIL-101(Cr) and the properties depended on the amount of GO added. MIL-101(Cr)/GO in methanol exhibited a significant increase in the thermal conductivity (by approximately 50%) relative to that of the intrinsic nanoMIL-101(Cr) in methanol. The thermal conductivity of the base fluid (methanol) was increased by about 20%. The increase in the thermal conductivity of nanoMIL-101(Cr) MOHCs due to GO functionalization is explained using a classical Maxwell model.

  10. Increased Thermal Conductivity in Metal-Organic Heat Carrier Nanofluids.

    PubMed

    Nandasiri, Manjula I; Liu, Jian; McGrail, B Peter; Jenks, Jeromy; Schaef, Herbert T; Shutthanandan, Vaithiyalingam; Nie, Zimin; Martin, Paul F; Nune, Satish K

    2016-06-15

    Metal-organic heat carriers (MOHCs) are recently developed nanofluids containing metal-organic framework (MOF) nanoparticles dispersed in various base fluids including refrigerants (R245Fa) and methanol. Here, we report the synthesis and characterization of MOHCs containing nanoMIL-101(Cr) and graphene oxide (GO) in an effort to improve the thermo-physical properties of various base fluids. MOHC/GO nanocomposites showed enhanced surface area, porosity, and nitrogen adsorption compared with the intrinsic nanoMIL-101(Cr) and the properties depended on the amount of GO added. MIL-101(Cr)/GO in methanol exhibited a significant increase in the thermal conductivity (by approximately 50%) relative to that of the intrinsic nanoMIL-101(Cr) in methanol. The thermal conductivity of the base fluid (methanol) was increased by about 20%. The increase in the thermal conductivity of nanoMIL-101(Cr) MOHCs due to GO functionalization is explained using a classical Maxwell model.

  11. Recent progress in the synthesis of metal-organic frameworks.

    PubMed

    Sun, Yujia; Zhou, Hong-Cai

    2015-10-01

    Metal-organic frameworks (MOFs) have attracted considerable attention for various applications due to their tunable structure, porosity and functionality. In general, MOFs have been synthesized from isolated metal ions and organic linkers under hydrothermal or solvothermal conditions via one-spot reactions. The emerging precursor approach and kinetically tuned dimensional augmentation strategy add more diversity to this field. In addition, to speed up the crystallization process and create uniform crystals with reduced size, many alternative synthesis routes have been explored. Recent advances in microwave-assisted synthesis and electrochemical synthesis are presented in this review. In recent years, post-synthetic approaches have been shown to be powerful tools to synthesize MOFs with modified functionality, which cannot be attained via de novo synthesis. In this review, some current accomplishments of post-synthetic modification (PSM) based on covalent transformations and coordinative interactions as well as post-synthetic exchange (PSE) in robust MOFs are provided.

  12. Heavy metal and organic contaminants in mangrove ecosystems of China: a review.

    PubMed

    Zhang, Zai-Wang; Xu, Xiang-Rong; Sun, Yu-Xin; Yu, Shen; Chen, Yong-Shan; Peng, Jia-Xi

    2014-10-01

    China's rapid economic growth has been accompanied by increasing environmental pollution. Mangrove ecosystems are now facing greater pollution pressures due to elevated chemical discharges from various land-based sources. Data on the levels of heavy metals and organic pollutants in mangrove compartments (sediments, plants, zoobenthos, and fish) in China over the past 20 years have been summarized to evaluate the current pollution status of the mangrove ecosystem. Overall, the Pearl River and Jiulong River estuaries were severely polluted spots. Concentrations of Cu, Zn, Cd, and Pb in mangrove sediments of Guangdong, Fujian, and Hong Kong were higher than those from Guangxi and Hainan. The pollution status was closely linked to industrialization and urbanization. The highest concentrations of polycyclic aromatic hydrocarbons (PAHs) were found in mangrove sediments from Hong Kong, followed by Fujian and Guangdong. Mangrove plants tend to have low-enriched ability for heavy metals and organic pollutants. Much higher levels of Pb, Cd, and Hg were observed in mollusks.

  13. Unraveling the chemical space of terrestrial and meteoritic organic matter

    NASA Astrophysics Data System (ADS)

    Schmitt-Kopplin, Philippe; Harir, Mourad; Hertkorn, Norbert; Kanawati, Basem; Ruf, Alexander; Quirico, Eric; Bonal, Lydie; Beck, Pierre; Gabelica, Zelimir

    2015-04-01

    In terrestrial environments natural organic matter (NOM) occurs in soils, freshwater and marine environments, in the atmosphere and represents an exceedingly complex mixture of organic compounds that collectively exhibits a nearly continuous range of properties (size-reactivity continuum). In these materials, the "classical" biogeosignatures of the (biogenic and geogenic) precursor molecules, like lipids, lignins, proteins and natural products have been attenuated, often beyond recognition, during a succession of biotic and abiotic (e.g. photo- and redox chemistry) reactions. Because of this loss of biochemical signature, these materials can be designated non-repetitive complex systems. The access to extra-terrestrial organic matter is given i.e. in the analysis of meteoritic materials. Numerous descriptions of organic molecules present in organic chondrites have improved our understanding of the early interstellar chemistry that operated at or just before the birth of our solar system. However, many molecular analyses are so far targeted toward selected classes of compounds with a particular emphasis on biologically active components in the context of prebiotic chemistry. Here we demonstrate that a non-targeted ultrahigh-resolution molecular analysis of the solvent-accessible organic fraction of meteorite extracted under mild conditions allows one to extend its indigenous chemical diversity to tens of thousands of different molecular compositions and likely millions of diverse structures. The description of the molecular complexity provides hints on heteroatoms chronological assembly, shock and thermal events and revealed recently new classes of thousands of novel organic, organometallic compounds uniquely found in extra-terrestrial materials and never described in terrestrial systems. This high polymolecularity suggests that the extraterrestrial chemodiversity is high compared to terrestrial relevant biological and biogeochemical-driven chemical space. (ultra

  14. Complex organic molecules at metal surfaces: bonding, organisation and chirality [review article

    NASA Astrophysics Data System (ADS)

    Barlow, S. M.; Raval, R.

    2003-08-01

    Surface science techniques have now reached a stage of maturity that has enabled their successful deployment in the study of complex adsorption systems. A particular example of this success has been the understanding that has been gained regarding the behaviour of multi-functional organic molecules at metal surfaces. These organic-metal systems show enormous diversity, starting from their local description which can vary in terms of chemical structure, orientation and bonding. Additionally, in many cases, these complex organic molecules self-organise into beautiful, ordered superstructures held together by networks of intermolecular bonds. Both these aspects enable a single organic molecule-metal system to exhibit a wide-ranging and flexible approach to its environment, leading to a variety of adsorption phases, according to the prevailing temperature and coverage conditions. In this review we have attempted to capture this complexity by constructing adsorption phase diagrams from the available literature for complex carboxylic acids, amino acids, anhydrides and ring systems, all deposited under controlled conditions onto defined metal surfaces. These provide an accessible, pictorial basis of the adsorption phases which are then discussed further in the text of the review. Finally, interest has recently focused on the property of chirality that can be bestowed at an achiral metal surface by the adsorption of these complex organic molecules. The creation of such architectures offers the opportunity for ultimate stereocontrol of reactions and responses at surfaces. We have, therefore, specifically examined the various ways in which chirality can be expressed at a surface and provide a framework for classifying chiral hierarchies that are manifested at surfaces, with particular attention being paid to the progression of chirality from a local to a global level.

  15. Influence of Organic Chemicals on Water Molecule Bridges in Soil Organic Matter of a Sapric Histosol.

    PubMed

    Ondruch, Pavel; Kučerík, Jiri; Steinmetz, Zacharias; Schaumann, Gabriele E

    2017-03-02

    Water molecules in soil organic matter (SOM) can form clusters bridging neighboring molecular segments (water molecule bridges; WaMB). WaMB are hypothesized to enhance physical entrapment of organic chemicals and to control the rigidity of the SOM supramolecular structure. However, the understanding of WaMB dynamics in SOM is still limited. We investigated the relation between WaMB stability and the physicochemical properties of their environment by treating a sapric histosol with various solvents and organic chemicals. Based on predictions from molecular modeling, we hypothesized that the stability of WaMB, measured by differential scanning calorimetry, increases with decreasing ability of a chemical to interact with water molecules of the WaMB. The interaction ability between WaMB and the chemicals was characterized by linear solvation energy relationships. WaMB stability in solvent-treated samples was found to decrease with increasing ability of a solvent to undergo H-donor/acceptor interactions. Spiking with an organic chemical stabilized (naphthalene) or destabilized (phenol) the WaMB. WaMB stability and matrix rigidity were generally reduced strongly and fast when hydrophilic chemicals entered the soil. The physicochemical aging following this destabilization is slow, but leads to a successive WaMB stabilization and matrix stiffening.

  16. Smart Metal-Organic Framework Coatings: Triggered Antibiofilm Compound Release.

    PubMed

    Claes, Birgit; Boudewijns, Tom; Muchez, Laurens; Hooyberghs, Geert; Van der Eycken, Erik V; Vanderleyden, Jozef; Steenackers, Hans P; De Vos, Dirk E

    2017-02-08

    Metal-organic frameworks (MOFs) have a large potential for delivery of active molecules. Here, a MOF coating is investigated as a smart host matrix for triggered release of antibiofilm compounds. In addition to a coating consisting of the regular Fe-terephthalate MIL-88B(Fe), a new hydrophobic MIL-88B(Fe) coating is synthesized in hydrothermal conditions using palmitic acid as a lattice terminating group. These porous materials are used as a host matrix for the antibiofilm compound 5-(4-chlorophenyl)-N-(2-isobutyl)-2-aminoimidazole, which has a specific biofilm-inhibiting effect at concentrations at which no activity against planktonic cells is detected. The stability of MIL-88B(Fe) in distilled water and tryptic soy broth medium is investigated, together with the ability of iron(III) chelators to serve as a trigger for controlled decomposition of MIL-88B(Fe) by metal complexation. Organic iron chelators are used to mimic the iron chelating function of siderophores, which are specific molecules excreted by biofilm-forming bacteria. Trisodium citrate is able to chelate metal ions from the junctions of the framework. By sequestration of these metal ions, the host matrix is partially degraded, resulting in an antibiofilm compound release. Finally, the antibiofilm properties against Salmonella Typhimurium are validated by monitoring biofilm growth on MOF layers either loaded or not with aminoimidazole. A strong proof-of-concept is shown for efficient inhibition of biofilm growth through triggered antibiofilm compound release.

  17. Identification and chemical characterization of specific organic indicators in the effluents from chemical production sites.

    PubMed

    Botalova, Oxana; Schwarzbauer, Jan; al Sandouk, Nadia

    2011-06-01

    The structural diversity of the wastewater composition was described by the use of detailed non-target screening analyses of industrial effluents from chemical production sites. Determination of the indicative organic compounds acting as potential molecular indicators for industrial emissions from chemical production industries has been possible due to (i) detailed characterisation of industrial contaminants and identification of compounds with high source specificity, (ii) quantitative determination of the organic constituents in the industrial effluents and (iii) the review of their industrial applications. The determination of potential site-specific markers and industrial molecular indicators corresponding to certain production processes (production of starting materials for manufacturing paper and printing inks, powder coatings as well as epichlorohydrin production) was performed in this work. The results of this study allowed significant contributions to the chemical characterisation of industrial contaminants and isolation of indicators that can act as representatives of industrial effluents in the aquatic environment.

  18. Apparatus for sensing volatile organic chemicals in fluids

    DOEpatents

    Hughes, Robert C.; Manginell, Ronald P.; Jenkins, Mark W.; Kottenstette, Richard; Patel, Sanjay V.

    2005-06-07

    A chemical-sensing apparatus is formed from the combination of a chemical preconcentrator which sorbs and concentrates particular volatile organic chemicals (VOCs) and one or more chemiresistors that sense the VOCs after the preconcentrator has been triggered to release them in concentrated form. Use of the preconcentrator and chemiresistor(s) in combination allows the VOCs to be detected at lower concentration than would be possible using the chemiresistor(s) alone and further allows measurements to be made in a variety of fluids, including liquids (e.g. groundwater). Additionally, the apparatus provides a new mode of operation for sensing VOCs based on the measurement of decay time constants, and a method for background correction to improve measurement precision.

  19. On the occurrence of metallic character in the periodic table of the chemical elements.

    PubMed

    Hensel, Friedrich; Slocombe, Daniel R; Edwards, Peter P

    2015-03-13

    The classification of a chemical element as either 'metal' or 'non-metal' continues to form the basis of an instantly recognizable, universal representation of the periodic table (Mendeleeff D. 1905 The principles of chemistry, vol. II, p. 23; Poliakoff M. & Tang S. 2015 Phil. Trans. R. Soc. A 373: , 20140211). Here, we review major, pre-quantum-mechanical innovations (Goldhammer DA. 1913 Dispersion und Absorption des Lichtes; Herzfeld KF. 1927 Phys. Rev. 29: , 701-705) that allow an understanding of the metallic or non-metallic status of the chemical elements under both ambient and extreme conditions. A special emphasis will be placed on recent experimental advances that investigate how the electronic properties of chemical elements vary with temperature and density, and how this invariably relates to a changing status of the chemical elements. Thus, the prototypical non-metals, hydrogen and helium, becomes metallic at high densities; and the acknowledged metals, mercury, rubidium and caesium, transform into their non-metallic forms at low elemental densities. This reflects the fundamental fact that, at temperatures above the absolute zero of temperature, there is therefore no clear dividing line between metals and non-metals. Our conventional demarcation of chemical elements as metals or non-metals within the periodic table is of course governed by our experience of the nature of the elements under ambient conditions. Examination of these other situations helps us to examine the exact divisions of the chemical elements into metals and non-metals (Mendeleeff D. 1905 The principles of chemistry, vol. II, p. 23).

  20. A multistimuli-responsive photochromic metal-organic gel.

    PubMed

    Wei, Shi-Chao; Pan, Mei; Li, Kang; Wang, Sujuan; Zhang, Jianyong; Su, Cheng-Yong

    2014-04-02

    A photochromic metal-organic gel with thermo-, photo-, and anion-responsive behavior is obtained. Unusually, heating of the Al-ligand solution leads to gel formation and cooling to room temperature reverses the process to reform the solution. The gel is sensitive to weakly coordinating anions. Additionally, reversible photochromic transformations take place both in the solution and gel states, accompanied by reversibly switched luminescence.

  1. Metal-Organic Frameworks for Thin-Layer Chromatographic Applications.

    PubMed

    Schenk, Claudia; Kutzscher, Christel; Drache, Franziska; Helten, Stella; Senkovska, Irena; Kaskel, Stefan

    2017-01-25

    Preparation of thin-layer chromatographic (TLC) plates based on metal-organic frameworks (MOFs) as porous stationary phases is described. DUT-67 (DUT = Dresden University of Technology), a zirconium based MOF, was used in combination with a fluorescent indicator as stationary phase for analyzing a small selection of a wide spectrum of relevant analytes. The successful separation of benzaldehyde from trans-cinnamaldehyde and 4-aminophenol from 2-aminotoluene is reported as a model system using optimized eluent mixtures containing acetic acid.

  2. Metal-organic gel templated synthesis of magnetic porous carbon for highly efficient removal of organic dyes.

    PubMed

    Wang, Luhuan; Ke, Fei; Zhu, Junfa

    2016-03-21

    Magnetic porous carbon composites are promising materials in various applications, such as adsorbents, supercapacitors and catalyst supports, due to their high surface area, thermal and chemical stability, and easy separation. However, despite the increasing number of reports of magnetic porous carbon composites, the preparation of these materials with environmentally friendly procedures still remains a great challenge. Herein, we report a facile method to prepare a magnetic porous carbon composite with high surface area from a Fe-based metal-organic gel (MOG) template, an extended structure of a metal-organic framework (MOF). The obtained magnetic porous carbon composite was applied to remove organic dyes from an aqueous solution by selecting methyl orange (MO) as a model molecule. It exhibits excellent adsorption capacity (182.82 mg g(-1)), fast adsorption kinetics (8.13 × 10(-3) g mg(-1) min(-1)), and a perfect magnetic separation performance for the MO removal. This study demonstrates a new way to achieve clean synthesis of magnetic porous carbon materials, and opens a new door for the application of MOGs in organic dye removal.

  3. Metal-organic frameworks as selectivity regulators for hydrogenation reactions

    NASA Astrophysics Data System (ADS)

    Zhao, Meiting; Yuan, Kuo; Wang, Yun; Li, Guodong; Guo, Jun; Gu, Lin; Hu, Wenping; Zhao, Huijun; Tang, Zhiyong

    2016-11-01

    Owing to the limited availability of natural sources, the widespread demand of the flavouring, perfume and pharmaceutical industries for unsaturated alcohols is met by producing them from α,β-unsaturated aldehydes, through the selective hydrogenation of the carbon-oxygen group (in preference to the carbon-carbon group). However, developing effective catalysts for this transformation is challenging, because hydrogenation of the carbon-carbon group is thermodynamically favoured. This difficulty is particularly relevant for one major category of heterogeneous catalyst: metal nanoparticles supported on metal oxides. These systems are generally incapable of significantly enhancing the selectivity towards thermodynamically unfavoured reactions, because only the edges of nanoparticles that are in direct contact with the metal-oxide support possess selective catalytic properties; most of the exposed nanoparticle surfaces do not. This has inspired the use of metal-organic frameworks (MOFs) to encapsulate metal nanoparticles within their layers or inside their channels, to influence the activity of the entire nanoparticle surface while maintaining efficient reactant and product transport owing to the porous nature of the material. Here we show that MOFs can also serve as effective selectivity regulators for the hydrogenation of α,β-unsaturated aldehydes. Sandwiching platinum nanoparticles between an inner core and an outer shell composed of an MOF with metal nodes of Fe3+, Cr3+ or both (known as MIL-101; refs 19, 20, 21) results in stable catalysts that convert a range of α,β-unsaturated aldehydes with high efficiency and with significantly enhanced selectivity towards unsaturated alcohols. Calculations reveal that preferential interaction of MOF metal sites with the carbon-oxygen rather than the carbon-carbon group renders hydrogenation of the former by the embedded platinum nanoparticles a thermodynamically favoured reaction. We anticipate that our basic design

  4. Evaluating metal-organic frameworks for natural gas storage

    SciTech Connect

    Mason, JA; Veenstra, M; Long, JR

    2014-01-01

    Metal-organic frameworks have received significant attention as a new class of adsorbents for natural gas storage; however, inconsistencies in reporting high-pressure adsorption data and a lack of comparative studies have made it challenging to evaluate both new and existing materials. Here, we briefly discuss high-pressure adsorption measurements and review efforts to develop metal-organic frameworks with high methane storage capacities. To illustrate the most important properties for evaluating adsorbents for natural gas storage and for designing a next generation of improved materials, six metal-organic frameworks and an activated carbon, with a range of surface areas, pore structures, and surface chemistries representative of the most promising adsorbents for methane storage, are evaluated in detail. High-pressure methane adsorption isotherms are used to compare gravimetric and volumetric capacities, isosteric heats of adsorption, and usable storage capacities. Additionally, the relative importance of increasing volumetric capacity, rather than gravimetric capacity, for extending the driving range of natural gas vehicles is highlighted. Other important systems-level factors, such as thermal management, mechanical properties, and the effects of impurities, are also considered, and potential materials synthesis contributions to improving performance in a complete adsorbed natural gas system are discussed.

  5. Evolution of form in metal-organic frameworks

    NASA Astrophysics Data System (ADS)

    Lee, Jiyoung; Kwak, Ja Hun; Choe, Wonyoung

    2017-01-01

    Self-assembly has proven to be a widely successful synthetic strategy for functional materials, especially for metal-organic materials (MOMs), an emerging class of porous materials consisting of metal-organic frameworks (MOFs) and metal-organic polyhedra (MOPs). However, there are areas in MOM synthesis in which such self-assembly has not been fully utilized, such as controlling the interior of MOM crystals. Here we demonstrate sequential self-assembly strategy for synthesizing various forms of MOM crystals, including double-shell hollow MOMs, based on single-crystal to single-crystal transformation from MOP to MOF. Moreover, this synthetic strategy also yields other forms, such as solid, core-shell, double and triple matryoshka, and single-shell hollow MOMs, thereby exhibiting form evolution in MOMs. We anticipate that this synthetic approach might open up a new direction for the development of diverse forms in MOMs, with highly advanced areas such as sequential drug delivery/release and heterogeneous cascade catalysis targeted in the foreseeable future.

  6. Fan organs of crayfish enhance chemical information flow.

    PubMed

    Breithaupt, T

    2001-04-01

    Animals as well as autonomous robots need to acquire environmental signals in order to adjust their activity in time and space. Some information is accessible to the sensors only as a result of specific behaviors for stimulus acquisition. Due to the slow rate of molecular diffusion, dispersal of chemical stimuli depends on fluid flow. Aquatic crustaceans can generate directed water currents by specialized appendages. Here I describe the crayfish fan organs, which are feathered flagella of the mouthparts, and their activity in sending and receiving chemical signals in environments with stagnant flow conditions. During the power-stroke, the fan opens and displaces water; during the return stroke, it collapses and thereby minimizes drag. These organs can create a variety of flow fields including water jets, and in many different directions. Bilateral upward fanning draws water horizontally from all directions toward the anterior chemoreceptors. Unilateral upward fanning draws water from only one side towards the body. The versatility of the crayfish fan organ makes it a candidate for biomimetic reconstruction and use in autonomous robots that can search chemical sources.

  7. REMOVAL OF ORGANIC CHEMICALS FROM WASTEWATER BY SURFACTANT SEPARATION

    SciTech Connect

    Unknown

    2002-01-01

    This research presents a novel hybrid process for removing organic chemicals from contaminated water. The process uses surfactant to carry out two unit operations (1) Extraction; (2) Foam flotation. In the first step, surfactant is used to extract most of the amounts of organic contaminants in the stream. In the second step, foam flotation is used to further reduce organic contaminants and recover surfactant from the stream. The process combines the advantages of extraction and foam flotation, which allows the process not only to handle a wide range of organic contaminants, but also to effectively treat a wide range of the concentration of organic contaminants in the stream and reduce it to a very low level. Surfactant regeneration can be done by conventional methods. This process is simple and low cost. The wastes are recoverable. The objective of this research is to develop an environmentally innocuous process for the wastewater or reclaimed water treatment with the ability to handle a wide range of organic contaminants, also to effectively treat a wide range of the concentration of organic contaminants in contaminated water and reduce it to a very low level, finally, provides simpler, less energy cost and economically-practical process design. Another purpose is to promote the environmental concern in minority students and encourage minority students to become more involved in environmental engineering research.

  8. Adsorption of gases and large polycyclic organic molecules in metal-organic frameworks

    NASA Astrophysics Data System (ADS)

    Siberio-Perez, Diana Yazmin

    Metal-organic frameworks (MOFs) are a class of porous materials with unique properties, including size tunable pores and cavities that allow for high surface areas and high levels of porosity. These properties make MOFs appealing for a number of traditional processes such as separations and catalysis, and for areas of current interest such as gas storage. The implementation of these frameworks into these areas first requires an understanding of the adsorbene-adsorbent interactions. For this reason, the adsorption behavior of CH4, N2, and CO2 (298 K, 30 bar) in a series of isoreticular MOFs (IRMOFs) was investigated by Raman spectroscopy. The data were marked by different shifts to the normal vibrational modes of the gases, depending on the IRMOF to which they were adsorbed. These shifts arise due to interactions within the framework pores, and not with the outer crystal surface. In all cases, Raman spectra at pressures up to 30 bar showed that saturation of the sorption sites does not occur. The observed shifts of the vibrational modes for each gas indicate different chemical environments within different IRMOFs, pointing to the important role the linkers play in the adsorption of gases. Despite the fact that MOFs possess surface areas that exceed those of other porous materials, no method of determining the upper limit in surface area for a material had yet been determined. Here, a general strategy is presented that has allowed for the realization of a structure that has one of the highest surface areas reported to date. The design and inclusion properties of crystalline Zn4O(1,3,5-benzenetribenzoate)2, a framework with a surface area measured to exceed 4,500 m2/g, is reported. This framework, named MOF-177, combines this exceptional level of surface area with an ordered structure that has extra-large pores capable of binding polycyclic organic guest molecules, that include C60 and several dyes. Size and isomer selectivity may also be achieved with MOF-177, as

  9. 40 CFR 455.30 - Applicability; description of the metallo-organic pesticide chemicals manufacturing subcategory.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... metallo-organic pesticide chemicals manufacturing subcategory. 455.30 Section 455.30 Protection of...) PESTICIDE CHEMICALS Metallo-Organic Pesticide Chemicals Manufacturing Subcategory § 455.30 Applicability; description of the metallo-organic pesticide chemicals manufacturing subcategory. The provisions of...

  10. 40 CFR 455.30 - Applicability; description of the metallo-organic pesticide chemicals manufacturing subcategory.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... metallo-organic pesticide chemicals manufacturing subcategory. 455.30 Section 455.30 Protection of...) PESTICIDE CHEMICALS Metallo-Organic Pesticide Chemicals Manufacturing Subcategory § 455.30 Applicability; description of the metallo-organic pesticide chemicals manufacturing subcategory. The provisions of...

  11. 40 CFR 455.30 - Applicability; description of the metallo-organic pesticide chemicals manufacturing subcategory.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... metallo-organic pesticide chemicals manufacturing subcategory. 455.30 Section 455.30 Protection of...) PESTICIDE CHEMICALS Metallo-Organic Pesticide Chemicals Manufacturing Subcategory § 455.30 Applicability; description of the metallo-organic pesticide chemicals manufacturing subcategory. The provisions of...

  12. Toxicity to Eisenia andrei and Folsomia candida of a metal mixture applied to soil directly or via an organic matrix.

    PubMed

    Natal-da-Luz, T; Ojeda, G; Pratas, J; Van Gestel, C A M; Sousa, J P

    2011-09-01

    Regulatory limits for chemicals and ecological risk assessment are usually based on the effects of single compounds, not taking into account mixture effects. The ecotoxicity of metal-contaminated sludge may, however, not only be due to its metal content. Both the sludge matrix and the presence of other toxicants may mitigate or promote metal toxicity. To test this assumption, the toxicity of soils recently amended with an industrial sludge predominantly contaminated with chromium, copper, nickel, and zinc and soils freshly spiked with the same mixture of metals was evaluated through earthworm (Eisenia andrei) and collembolan (Folsomia candida) reproduction tests. The sludge was less toxic than the spiked metal mixture for E. andrei but more toxic for F. candida. Results obtained for the earthworms suggest a decrease in metal bioavailability promoted by the high organic matter content of the sludge. The higher toxicity of the sludge for F. candida was probably due to the additive toxic effect of other pollutants.

  13. Metal-organic frameworks as competitive materials for non-linear optics.

    PubMed

    Mingabudinova, L R; Vinogradov, V V; Milichko, V A; Hey-Hawkins, E; Vinogradov, A V

    2016-09-26

    The last five years have witnessed a huge breakthrough in the creation and the study of the properties of a new class of compounds - metamaterials. The next stage of this technological revolution will be the development of active, controllable, and non-linear metamaterials, surpassing natural media as platforms for optical data processing and quantum information applications. However, scientists are constantly faced with the need to find new methods that can ensure the formation of quantum and non-linear metamaterials with higher resolution. One such method of producing metamaterials in the future, which will provide scalability and availability, is chemical synthesis. Meanwhile, the chemical synthesis of organized 3D structures with a period of a few nanometers and a size of up to a few millimeters is not an easy task and is yet to be resolved. The most promising avenue seems to be the use of highly porous structures based on metal-organic frameworks that have demonstrated their unique properties in the field of non-linear optics (NLO) over the past three years. Thus, the aim of this review is to examine current progress and the possibilities of using metal-organic frameworks in the field of non-linear optics as chemically obtained metamaterials of the future. The review begins by presenting the theoretical principles of physical phenomena represented by mathematical descriptions for clarity. Major attention is paid to the second harmonic generation (SHG) effect. In this section we compare inorganic single crystals, which are most commonly used to study the effect in question, to organic materials, which also possess the required properties. Based on these data, we present a rationale for the possibility of studying the non-linear optical properties of metal-organic structures as well as describing the use of synthetic approaches and the difficulties associated with them. The second part of the review explicitly acquaints the reader with a new class of materials

  14. Sediment Surface Areas, Organic Content, and Metal Fractionation of Point Mugu Sediments

    NASA Astrophysics Data System (ADS)

    Becerra, C. A.; Wong, N.; Khachikian, C. S.

    2002-12-01

    Point Mugu contains one of the largest coastal wetlands ecosystems in California, which includes a Naval Air station, several sewage oxidation ponds and a partly dredged lagoon. Remediation efforts include investigating the feasibility of using the present sewage pond sludge to restore a dredged area in the lagoon. A problem with this approach is the potential release and subsequent environmental impact of the toxic substances from the sludge. Contaminants may become unavailable once sorbed onto particles. In general, this process is a direct function of surface area and organic carbon sorbed onto the sediment. The goal of the current investigation is to provide insight into the biological availability of a suite of metal contaminants in Pt. Mugu marsh sediments by studying changes in the physical and chemical properties of the sediments at horizontal and vertical spatial scales. The surface area and organic carbon for eight cores were measured as well as the first three sequential extraction of a host of metals. We have found that a direct correlation exists between surface area and the organic content of sediments as a function of depth. Surface area and the amount of organic carbon decreases with depth, which could result in higher availability of metals with increasing depth into the sediments.

  15. ELECTRONIC AND CHEMICAL PROPERTIES OF PD IN BIMETALLIC SYSTEMS: HOW MUCH DO WE KNOW ABOUT HETERONUCLEAR METAL-METAL BONDING?

    SciTech Connect

    RODRIGUEZ,J.A.

    2001-09-27

    The experimental and theoretical studies described above illustrate the complex nature of the heteronuclear metal-metal bond. In many cases, bimetallic bonding induces a significant redistribution of charge around the bonded metals. This redistribution of charge is usually linked to the strength of the bimetallic bond, affects the position of the core and valence levels of the metals, and can determine the chemical reactivity of the system under study. New concepts are emerging [22,23,34,36] and eventually the coupling of experiment and theory can be useful for designing more efficient bimetallic catalysts [98,106,107].

  16. High-internal-phase emulsions stabilized by metal-organic frameworks and derivation of ultralight metal-organic aerogels

    PubMed Central

    Zhang, Bingxing; Zhang, Jianling; Liu, Chengcheng; Peng, Li; Sang, Xinxin; Han, Buxing; Ma, Xue; Luo, Tian; Tan, Xiuniang; Yang, Guanying

    2016-01-01

    To design high-internal-phase emulsion (HIPE) systems is of great interest from the viewpoints of both fundamental researches and practical applications. Here we demonstrate for the first time the utilization of metal-organic framework (MOF) for HIPE formation. By stirring the mixture of water, oil and MOF at room temperature, the HIPE stabilized by the assembly of MOF nanocrystals at oil-water interface could be formed. The MOF-stabilized HIPE provides a novel route to produce highly porous metal-organic aerogel (MOA) monolith. After removing the liquids from the MOF-stabilized HIPE, the ultralight MOA with density as low as 0.01 g·cm−3 was obtained. The HIPE approach for MOA formation has unique advantages and is versatile in producing different kinds of ultralight MOAs with tunable porosities and structures. PMID:26892258

  17. Adsorption characteristics of metal ions on chitosan chemically modified by D-galactose

    SciTech Connect

    Kondo, Kazuo; Sumi, Hisaharu; Matsumoto, Michiaki

    1996-07-01

    The adsorption characteristics of metal ions on chitosan chemically modified by D-galactose were examined. The pH dependency on the distribution ratio was found to be affected by the valency of the metal ion, and the apparent adsorption equilibrium constants of the metal ions were determined. The order of adsorption of the metal ions is Ga > In > Nd > Eu for the trivalent metal ions and Cu > Ni > Co for the divalent metal ions. It is believed that amino and hydroxyl groups in the chitosan act as a chelating ligand.

  18. 40 CFR 414.80 - Applicability; description of the specialty organic chemicals subcategory.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... specialty organic chemicals subcategory. 414.80 Section 414.80 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) EFFLUENT GUIDELINES AND STANDARDS ORGANIC CHEMICALS, PLASTICS, AND SYNTHETIC FIBERS Specialty Organic Chemicals § 414.80 Applicability; description of the specialty organic...

  19. 40 CFR 414.60 - Applicability; description of the commodity organic chemicals subcategory.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... commodity organic chemicals subcategory. 414.60 Section 414.60 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) EFFLUENT GUIDELINES AND STANDARDS ORGANIC CHEMICALS, PLASTICS, AND SYNTHETIC FIBERS Commodity Organic Chemicals § 414.60 Applicability; description of the commodity organic...

  20. 40 CFR 414.80 - Applicability; description of the specialty organic chemicals subcategory.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... specialty organic chemicals subcategory. 414.80 Section 414.80 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) EFFLUENT GUIDELINES AND STANDARDS ORGANIC CHEMICALS, PLASTICS, AND SYNTHETIC FIBERS Specialty Organic Chemicals § 414.80 Applicability; description of the specialty organic...

  1. 40 CFR 414.80 - Applicability; description of the specialty organic chemicals subcategory.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... specialty organic chemicals subcategory. 414.80 Section 414.80 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) EFFLUENT GUIDELINES AND STANDARDS ORGANIC CHEMICALS, PLASTICS, AND SYNTHETIC FIBERS Specialty Organic Chemicals § 414.80 Applicability; description of the specialty organic...

  2. 40 CFR 414.80 - Applicability; description of the specialty organic chemicals subcategory.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... specialty organic chemicals subcategory. 414.80 Section 414.80 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) EFFLUENT GUIDELINES AND STANDARDS ORGANIC CHEMICALS, PLASTICS, AND SYNTHETIC FIBERS Specialty Organic Chemicals § 414.80 Applicability; description of the specialty organic...

  3. 40 CFR 414.60 - Applicability; description of the commodity organic chemicals subcategory.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... commodity organic chemicals subcategory. 414.60 Section 414.60 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) EFFLUENT GUIDELINES AND STANDARDS ORGANIC CHEMICALS, PLASTICS, AND SYNTHETIC FIBERS Commodity Organic Chemicals § 414.60 Applicability; description of the commodity organic...

  4. 40 CFR 414.60 - Applicability; description of the commodity organic chemicals subcategory.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... commodity organic chemicals subcategory. 414.60 Section 414.60 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) EFFLUENT GUIDELINES AND STANDARDS ORGANIC CHEMICALS, PLASTICS, AND SYNTHETIC FIBERS Commodity Organic Chemicals § 414.60 Applicability; description of the commodity organic...

  5. 40 CFR 414.60 - Applicability; description of the commodity organic chemicals subcategory.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... commodity organic chemicals subcategory. 414.60 Section 414.60 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) EFFLUENT GUIDELINES AND STANDARDS ORGANIC CHEMICALS, PLASTICS, AND SYNTHETIC FIBERS Commodity Organic Chemicals § 414.60 Applicability; description of the commodity organic...

  6. 40 CFR 414.80 - Applicability; description of the specialty organic chemicals subcategory.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... specialty organic chemicals subcategory. 414.80 Section 414.80 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) EFFLUENT GUIDELINES AND STANDARDS ORGANIC CHEMICALS, PLASTICS, AND SYNTHETIC FIBERS Specialty Organic Chemicals § 414.80 Applicability; description of the specialty organic...

  7. 40 CFR 414.60 - Applicability; description of the commodity organic chemicals subcategory.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... commodity organic chemicals subcategory. 414.60 Section 414.60 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) EFFLUENT GUIDELINES AND STANDARDS ORGANIC CHEMICALS, PLASTICS, AND SYNTHETIC FIBERS Commodity Organic Chemicals § 414.60 Applicability; description of the commodity organic...

  8. Controlled Encapsulation of Functional Organic Molecules within Metal-Organic Frameworks: In Situ Crystalline Structure Transformation.

    PubMed

    Guan, Jinju; Hu, Yu; Wang, Yu; Li, Hongfeng; Xu, Zhiling; Zhang, Tao; Wu, Peng; Zhang, Suoying; Xiao, Gengwu; Ji, Wenlan; Li, Linjie; Zhang, Meixuan; Fan, Yun; Li, Lin; Zheng, Bing; Zhang, Weina; Huang, Wei; Huo, Fengwei

    2017-01-23

    Functional organic molecules/metal-organic frameworks composites can be obtained by in situ crystalline structure transformation from ZIF-L to ZIF-8-L under double solvent conditions. Interestingly, the as-prepared molecules/ZIF-8-L composites with the leaf-like morphology exhibit good fluorescence properties and size selectivity in fluorescent quenchers due to the molecular sieving effect of the well-defined microporous ZIF-8-L.

  9. Spontaneous grafting of diazonium salts: chemical mechanism on metallic surfaces.

    PubMed

    Mesnage, Alice; Lefèvre, Xavier; Jégou, Pascale; Deniau, Guy; Palacin, Serge

    2012-08-14

    The spontaneous reaction of diazonium salts on various substrates has been widely employed since it consists of a simple immersion of the substrate in the diazonium salt solution. As electrochemical processes involving the same diazonium salts, the spontaneous grafting is assumed to give covalently poly(phenylene)-like bonded films. Resistance to solvents and to ultrasonication is commonly accepted as indirect proof of the existence of a covalent bond. However, the most relevant attempts to demonstrate a metal-C interface bond have been obtained by an XPS investigation of spontaneously grafted films on copper. Similarly, our experiments give evidence of such a bond in spontaneously grafted films on nickel substrates in acetonitrile. In the case of gold substrates, the formation of a spontaneous film was unexpected but reported in the literature in parallel to our observations. Even if no interfacial bond was observed, formation of the films was explained by grafting of aryl cations or radicals on the surface arising from dediazoniation, the film growing later by azo coupling, radical addition, or cationic addition on the grafted phenyl layer. Nevertheless, none of these mechanisms fits our experimental results showing the presence of an Au-N bond. In this work, we present a fine spectroscopic analysis of the coatings obtained on gold and nickel substrates that allow us to propose a chemical structure of such films, in particular, their interface with the substrates. After testing the most probable mechanisms, we have concluded in favor of the involvement of two complementary mechanisms which are the direct reaction of diazonium salts with the gold surface that accounts for the observed Au-N interfacial bonds as well as the formation of aryl cations able to graft on the substrate through Au-C linkages.

  10. Control method for transition metal oxides as a hole-injection layer for organic light-emitting devices

    NASA Astrophysics Data System (ADS)

    Zhang, Wejiang; Zhang, Jie

    2013-12-01

    The mechanism of transition metal oxide, molybdenum oxide (MoOx), used as interlayers in organic light-emitting devices (OLEDs) are investigated. The electronic structures and interfacial chemical reactions are investigated with ultraviolet and x-ray photoelectron spectroscopy. The influence of evaporation temperatures on the electronic structures of MoOx films and the electrical properties of organic light emitting diodes are investigated.

  11. Metal-organic framework templated synthesis of ultrathin, well-aligned metallic nanowires.

    PubMed

    Volosskiy, Boris; Niwa, Kenta; Chen, Yu; Zhao, Zipeng; Weiss, Nathan O; Zhong, Xing; Ding, Mengning; Lee, Chain; Huang, Yu; Duan, Xiangfeng

    2015-03-24

    With well-defined porous structures and dimensions, metal-organic frameworks (MOFs) can function as versatile templates for the growth of metallic nanostructures with precisely controlled shapes and sizes. Using MOFs as templates, metallic nanostructures can be grown without the need of bulky surfactants and thus preserve their intrinsic surface. Additionally, the high surface area of MOFs can also ensure that the surface of the template metallic nanostructures is readily accessible, which is critical for the proper function of catalysts or sensors. The hybrid metal@MOF structures have been demonstrated to exhibit useful properties not found in either component separately. Here we report the growth of ultrafine metallic nanowires inside one-dimensional MOF pores with well-controlled shape and size. Our study shows that solvent selection plays an important role in controlling precursor loading and the reduction rate inside the MOF pores for the formation of the nanowires. The growth of the well-aligned, ultrathin nanowires was monitored and characterized by transmission electron microscopy, X-ray diffraction, UV-vis spectroscopy, fluorescence studies, and Brunauer-Emmet-Teller surface area analysis.

  12. Reusable oxidation catalysis using metal-monocatecholato species in a robust metal-organic framework.

    PubMed

    Fei, Honghan; Shin, JaeWook; Meng, Ying Shirley; Adelhardt, Mario; Sutter, Jörg; Meyer, Karsten; Cohen, Seth M

    2014-04-02

    An isolated metal-monocatecholato moiety has been achieved in a highly robust metal-organic framework (MOF) by two fundamentally different postsynthetic strategies: postsynthetic deprotection (PSD) and postsynthetic exchange (PSE). Compared with PSD, PSE proved to be a more facile and efficient functionalization approach to access MOFs that could not be directly synthesized under solvothermal conditions. Metalation of the catechol functionality residing in the MOFs resulted in unprecedented Fe-monocatecholato and Cr-monocatecholato species, which were characterized by X-ray absorption spectroscopy, X-band electron paramagnetic resonance spectroscopy, and (57)Fe Mössbauer spectroscopy. The resulting materials are among the first examples of Zr(IV)-based UiO MOFs (UiO = University of Oslo) with coordinatively unsaturated active metal centers. Importantly, the Cr-metalated MOFs are active and efficient catalysts for the oxidation of alcohols to ketones using a wide range of substrates. Catalysis could be achieved with very low metal loadings (0.5-1 mol %). Unlike zeolite-supported, Cr-exchange oxidation catalysts, the MOF-based catalysts reported here are completely recyclable and reusable, which may make them attractive catalysts for 'green' chemistry processes.

  13. Chemical extractions of heavy metals in sediments and metal uptake by Palaemonetes pugio and mercenaria merenaria. Final report

    SciTech Connect

    Rule, J.H.

    1984-08-17

    Sediments from four sites in the Hampton Roads Harbor and Elizabeth River system were subjected to solid-phase bioassays using Palaemonetes pugio (grass shrimp) and Mercenaria mercenaria (clams). A reference sediment from an offhsore potential disposal site was included. Metal levels in both organisms after exposure to the sediments varied little between sites. There was essentially no difference in metal uptake between organisms exposed to the test sediments and to the reference sediment. Based on these results, all of the test sites would be acceptable for ocean disposal with respect to the metals tested. Metal concentrations in Palaemonetes were generally greater than in Merceneria. Since there was no significant difference in the concentrations in tissue for either organism, there was no correlation of metal uptake with sediment extraction method. Out of four sites and seven metals studied with two test organisms, only four instances of bioaccumulation occurred. Using data from sediment extractable metals and metal/Fe ratios, Palaemonetes were enriched with respect to the sediment in chromium, copper, nickel, lead, and zinc; Mecenaria were enriched in lead and zinc.

  14. Elucidating triplet-sensitized photolysis mechanisms of sulfadiazine and metal ions effects by quantum chemical calculations.

    PubMed

    Wang, Se; Song, Xuedan; Hao, Ce; Gao, Zhanxian; Chen, Jingwen; Qiu, Jieshan

    2015-03-01

    Sulfadiazine (SDZ) mainly proceeds triplet-sensitized photolysis with dissolved organic matter (DOM) in the aquatic environment. However, the mechanisms underlying the triplet-sensitized photolysis of SDZ with DOM have not been fully worked out. In this study, we investigated the mechanisms of triplet-sensitized photolysis of SDZ(0) (neutral form) and SDZ(-) (anionic form) with four DOM analogues, i.e., fluorenone (FL), thioxanthone (TX), 2-acetonaphthone (2-AN), and 4-benzoylbenzoic acid (CBBP), and three metal ions (i.e., Mg(2+), Ca(2+), and Zn(2+)) effects using quantum chemical calculations. Results indicated that the triplet-sensitized photolysis mechanism of SDZ(0) with FL, TX, and 2-AN was hydrogen transfer, and with CBBP was electron transfer along with proton transfer (for complex SDZ(0)-CBBP2) and hydrogen transfer (for complex SDZ(0)-CBBP1). The triplet-sensitized photolysis mechanisms of SDZ(-) with FL, TX, and CBBP was electron transfer along with proton transfer, and with 2-AN was hydrogen transfer. The triplet-sensitized photolysis product of both SDZ(0) and SDZ(-) was a sulfur dioxide extrusion product (4-(2-iminopyrimidine-1(2H)-yl)aniline), but the formation routs of the products for SDZ(0) and SDZ(-) were different. In addition, effects of the metal ions on the triplet-sensitized photolysis of SDZ(0) and SDZ(-) were different. The metal ions promoted the triplet-sensitized photolysis of SDZ(0), but inhibited the triplet-sensitized photolysis of SDZ(-).

  15. Chemical reactions at metallic and metal/semiconductor interfaces stimulated by pulsed laser annealing

    NASA Astrophysics Data System (ADS)

    Petit, E. J.; Caudano, R.

    1992-01-01

    Multilayer Al/Sb thin films have been evaporated on GaSb single crystals in ultra-high vacuum and pulsed-laser irradiated in-situ above the energy density threshold for surface melting. Superficial and interfacial chemical reactions have been characterized in-situ by Auger electron spectroscopy; and later, by X-ray photoelectron spectroscopy profiling, Rutherford backscattering spectrometry and scanning electron microscopy. The chemical reaction between the Al and Sb films is considered as a model reaction for laser-assisted synthesis of high-purity intermetallic compounds. The observation of a strong interfacial reaction between the melted film and the substrate is also a subject of great concern for optical data recording and laser alloying of ohmic contacts on semiconductors. We show that a suitable choice of the substrate and adding a low surface tension element into the metallic film can improve its stability during melting, and prevent inhomogeneous reaction and formation of holes, cracks and particles. Finally, other solutions are suggested to improve the control of these reactions.

  16. Metal-organic frameworks with dynamic interlocked components

    NASA Astrophysics Data System (ADS)

    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.

  17. Force-induced chemical reactions on the metal centre in a single metalloprotein molecule.

    PubMed

    Zheng, Peng; Arantes, Guilherme M; Field, Martin J; Li, Hongbin

    2015-06-25

    Metalloproteins play indispensable roles in biology owing to the versatile chemical reactivity of metal centres. However, studying their reactivity in many metalloproteins is challenging, as protein three-dimensional structure encloses labile metal centres, thus limiting their access to reactants and impeding direct measurements. Here we demonstrate the use of single-molecule atomic force microscopy to induce partial unfolding to expose metal centres in metalloproteins to aqueous solution, thus allowing for studying their chemical reactivity in aqueous solution for the first time. As a proof-of-principle, we demonstrate two chemical reactions for the FeS4 centre in rubredoxin: electrophilic protonation and nucleophilic ligand substitution. Our results show that protonation and ligand substitution result in mechanical destabilization of the FeS4 centre. Quantum chemical calculations corroborated experimental results and revealed detailed reaction mechanisms. We anticipate that this novel approach will provide insights into chemical reactivity of metal centres in metalloproteins under biologically more relevant conditions.

  18. Organic/Inorganic Hybrid Nanostructures for Chemical Plasmonic Sensors

    NASA Astrophysics Data System (ADS)

    Chang, Sehoon

    2011-12-01

    The work presented in this dissertation suggests novel design of chemical plasmonic sensors which have been developed based on Localized Surface Plasmon Resonance (LSPR), and Surface-enhanced Raman scattering (SERS) phenomena. The goal of the study is to understand the SERS phenomena for 3D hybrid (organic/inorganic) templates and to design of the templates for trace-level detection of selected chemical analytes relevant to liquid explosives and hazardous chemicals. The key design criteria for the development of the SERS templates are utilizing selective polymeric nanocoatings within cylindrical nanopores for promoting selective adsorption of chemical analyte molecules, maximizing specific surface area, and optimizing concentration of hot spots with efficient light interaction inside nanochannels. The organic/inorganic hybrid templates are optimized through a comprehensive understanding of the LSPR properties of the gold nanoparticles, gold nanorods, interaction of light with highly porous alumina template, and the choice of physical and chemical attributes of the selective coating. Furthermore, novel method to assemble silver nanoparticles in 3D as the active SERS-active substrate has been demonstrated by uniform, in situ growth of silver nanoparticles from electroless deposited silver seeds excluding any adhesive polymer layer on template. This approach can be the optimal for SERS sensing applications because it is not necessary to separate the Raman bands of the polyelectrolyte binding layer from those of the desired analyte. The fabrication method is an efficient, simple and fast way to assemble nanoparticles into 3D nanostructures. Addressable Raman markers from silver nanowire crossbars with silver nanoparticles are also introduced and studied. Assembly of silver nanowire crossbar structure is achieved by simple, double-step capillary transfer lithography. The on/off SERS properties can be observed on silver nanowire crossbars with silver nanoparticles

  19. Photonic confinement in laterally structured metal-organic microcavities

    NASA Astrophysics Data System (ADS)

    Mischok, Andreas; Brückner, Robert; Sudzius, Markas; Reinhardt, Christoph; Lyssenko, Vadim G.; Fröb, Hartmut; Leo, Karl

    2014-08-01

    We investigate the formation of optical modes in organic microcavities with an incorporated perforated silver layer. The metal leads to a formation of Tamm-plasmon-polaritons and thus separates the sample into metal-free or metal-containing areas, supporting different resonances. This mode splitting is exploited to confine photons in elliptic holes and triangular cuts, forming distinctive standing wave patterns showing the strong lateral confinement. A comparison with a Maxwell-Bloch based rate equation model clearly shows the nonlinear transition into the lasing regime. The concentration of the electric field density and inhibition of lateral loss channels in turn decreases the lasing threshold by up to one order of magnitude, to 0.1 nJ. By spectroscopic investigation of such a triangular wedge, we observe the transition from the unperturbed cavity state to a strongly confined complex transversal mode. Such a structured silver layer can be utilized in future for charge carrier injection in an electrically driven organic solid state laser.

  20. Metal-organic frameworks as biosensors for luminescence-based detection and imaging

    PubMed Central

    Miller, Sophie E.; Teplensky, Michelle H.; Moghadam, Peyman Z.; Fairen-Jimenez, David

    2016-01-01

    Metal-organic frameworks (MOFs), formed by the self-assembly of metal centres or clusters and organic linkers, possess many key structural and chemical features that have enabled them to be used in sensing platforms for a variety of environmentally, chemically and biomedically relevant compounds. In particular, their high porosity, large surface area, tuneable chemical composition, high degree of crystallinity, and potential for post-synthetic modification for molecular recognition make MOFs promising candidates for biosensing applications. In this review, we separate our discussion of MOF biosensors into two categories: quantitative sensing, focusing specifically on luminescence-based sensors for the direct measurement of a specific analyte, and qualitative sensing, where we describe MOFs used for fluorescence microscopy and as magnetic resonance imaging contrast agents. We highlight several key publications in each of these areas, concluding that MOFs present an exciting, versatile new platform for biosensing applications and imaging, and we expect to see their usage grow as the field progresses. PMID:27499847

  1. Aqueous photolysis of the organic ultraviolet filter chemical octyl methoxycinnamate.

    PubMed

    MacManus-Spencer, Laura A; Tse, Monica L; Klein, Jacob L; Kracunas, Alison E

    2011-05-01

    Organic UV filter chemicals are the active ingredients in personal care products designed to protect the skin from UV radiation, and hundreds of tons are estimated to be produced annually. Despite their entrance into the aquatic environment by both direct and indirect routes and their detection in surface waters and fish, little is known about their environmental fate. UV filter chemicals are designed to be photostable, but some undergo transformation upon exposure to UV light. Octyl methoxycinnamate (OMC), a commonly used UV filter chemical, degrades rapidly by direct photolysis; previous studies have focused on its photoisomerization, and a few investigators have reported the formation of cyclodimers. Here, we present the kinetics and quantum efficiency of the direct photolysis of OMC and confirm that dimerization occurs as a result of direct photolysis in aqueous solution. Likely identities of the dimers are offered based on comparison to reported results for other cinnamate derivatives. We have identified additional products of direct photolysis that have not been previously reported and investigated their photostability, as well as the mechanism of product formation. There is also some evidence of indirect photolysis in the presence of dissolved natural organic matter.

  2. Hazardous organic chemicals in rubber recycled tire playgrounds and pavers.

    PubMed

    Llompart, Maria; Sanchez-Prado, Lucia; Pablo Lamas, J; Garcia-Jares, Carmen; Roca, Enrique; Dagnac, Thierry

    2013-01-01

    In this study, the presence of hazardous organic chemicals in surfaces containing recycled rubber tires is investigated. Direct material analyses using solvent extraction, as well as SPME analysis of the vapour phase above the sample, were carried out. Twenty-one rubber mulch samples were collected from nine different playgrounds. In addition, seven commercial samples of recycled rubber pavers were acquired in a local store of a multinational company. All samples were extracted by ultrasound energy, followed by analysis of the extract by GC-MS. The analysis confirmed the presence of a large number of hazardous substances including PAHs, phthalates, antioxidants (e.g. BHT, phenols), benzothiazole and derivatives, among other chemicals. The study evidences the high content of toxic chemicals in these recycled materials. The concentration of PAHs in the commercial pavers was extremely high, reaching values up to 1%. In addition, SPME studies of the vapour phase above the samples confirm the volatilisation of many of those organic compounds. Uses of recycled rubber tires, especially those targeting play areas and other facilities for children, should be a matter of regulatory concern.

  3. Hydrophobic interaction of organic chemicals with microtubule assembly in vitro.

    PubMed

    Stoiber, Thomas; Unger, Eberhard; Dorn, Susanne B; Degen, Gisela H; Bolt, Hermann M

    2008-09-01

    A recent concept connecting the lipophilicity of organic chemicals with their genotoxicity on a chromosomal level implies that the lipophilic character of organic chemicals determines a certain background of chromosomal genotoxicity that can be addressed as "non-specific". This is opposed to compounds with more "specific" modes of action. Such mechanisms influence the processes of karyokinesis and cytokinesis. A critical partial process for the chromosomal segregation is the dynamics of assembly and disassembly of microtubules. To broaden the present database for such interactions, chemicals were selected based on their lipophilicity (log P between -1.5 and +1.0) and on hints from the literature pointing to possibilities of interaction with the tubulin-microtubule system. Thus, acetamide, acrylamide, methylmethane sulfonate, acetonitrile, acrylonitrile and cyclohexanone were assessed as to their potencies to influence the dynamic processes of microtubule assembly and disassembly in a cell-free system in vitro. These compounds covered a range of log P between -1.5 and 1.0, complementary to compounds investigated earlier. The entire body of data supports the general concept that hydrophobic interactions are connected with non-specific processes, which contribute to a background genotoxicity on a chromosomal level. It also points to the dynamics of microtubule assembly and disassembly as a decisive partial process involved.

  4. Metal inhibition on the reactivity of manganese dioxide toward organic contaminant oxidation in relation to metal adsorption and ionic potential.

    PubMed

    Jiang, Jing; Wang, Zhuopu; Chen, Yang; He, Anfei; Li, Jianliang; Sheng, G Daniel

    2017-03-01

    Coexisting metal ions may significantly inhibit the oxidative reactivity of manganese oxides toward organic contaminants in metal-organic multi-pollutant waters. While the metal inhibition on the oxidation of organic contaminants by manganese oxides has previously been reported, the extent of the inhibition in relation to metal properties has not been established. Six alkali, alkaline, and transition metals, as well as two testing metals were evaluated for their abilities to inhibit the reactivity of birnessite. Regardless of the pathways of phenol and diuron oxidation (polymerization vs. breakdown), the extent of metal inhibition depended mainly on the metal itself and its concentration. The observed metal inhibition efficiency followed the order of Mn(2+) > Co(2+) > Cu(2+) > Al(3+) > Mg(2+) > K(+), consistent with metal adsorption on birnessite. The first-order organic oxidation rate constant (kobs) was linearly negatively correlated with metal adsorption (qe) on birnessite. These observations demonstrated that the metal inhibition efficiency was determined by metal adsorption on birnessite. The slopes of the kobs-qe varied among metals and followed the order of K(+) > Ca(2+) > Mg(2+) > Mn(2+) > Cd(2+) > Co(2+) > Cu(2+) > Al(3+). These slopes defined intrinsic inhibitory abilities of metals. As metals were adsorbed hydrated on birnessite, the intrinsic inhibitory ability was significantly linearly correlated with ionic potentials of metals, leading to a single straight line. Metals with multiple d electrons in the outermost orbit with polarizing energy that promotes hydrolysis sat slightly below the line, and vice versa.

  5. Highly effective hydrogen isotope separation in nanoporous metal-organic frameworks with open metal sites: direct measurement and theoretical analysis.

    PubMed

    Oh, Hyunchul; Savchenko, Ievgeniia; Mavrandonakis, Andreas; Heine, Thomas; Hirscher, Michael

    2014-01-28

    Separating gaseous mixtures that consist of very similar size is one of the critical issues in modern separation technology. Especially, the separation of the isotopes hydrogen and deuterium requires special efforts, even though these isotopes show a very large mass ratio. Conventionally, H/D separation can be realized through cryogenic distillation of the molecular species or the Girdler-sulfide process, which are among the most energy-intensive separation techniques in the chemical industry. However, costs can be significantly reduced by using highly mass-selective nanoporous sorbents. Here, we describe a hydrogen isotope separation strategy exploiting the strongly attractive open metal sites present in nanoporous metal-organic frameworks of the CPO-27 family (also referred to as MOF-74). A theoretical analysis predicts an outstanding hydrogen isotopologue separation at open metal sites due to isotopal effects, which has been directly observed through cryogenic thermal desorption spectroscopy. For H2/D2 separation of an equimolar mixture at 60 K, the selectivity of 12 is the highest value ever measured, and this methodology shows extremely high separation efficiencies even above 77 K. Our theoretical results imply also a high selectivity for HD/H2 separation at similar temperatures, and together with catalytically active sites, we propose a mechanism to produce D2 from HD/H2 mixtures with natural or enriched deuterium content.

  6. Regulating the spatial distribution of metal nanoparticles within metal-organic frameworks to enhance catalytic efficiency

    PubMed Central

    Yang, Qiu; Liu, Wenxian; Wang, Bingqing; Zhang, Weina; Zeng, Xiaoqiao; Zhang, Cong; Qin, Yongji; Sun, Xiaoming; Wu, Tianpin; Liu, Junfeng; Huo, Fengwei; Lu, Jun

    2017-01-01

    Composites incorporating metal nanoparticles (MNPs) within metal-organic frameworks (MOFs) have broad applications in many fields. However, the controlled spatial distribution of the MNPs within MOFs remains a challenge for addressing key issues in catalysis, for example, the efficiency of catalysts due to the limitation of molecular diffusion within MOF channels. Here we report a facile strategy that enables MNPs to be encapsulated into MOFs with controllable spatial localization by using metal oxide both as support to load MNPs and as a sacrificial template to grow MOFs. This strategy is versatile to a variety of MNPs and MOF crystals. By localizing the encapsulated MNPs closer to the surface of MOFs, the resultant MNPs@MOF composites not only exhibit effective selectivity derived from MOF cavities, but also enhanced catalytic activity due to the spatial regulation of MNPs as close as possible to the MOF surface. PMID:28195131

  7. Regulating the spatial distribution of metal nanoparticles within metal-organic frameworks to enhance catalytic efficiency

    NASA Astrophysics Data System (ADS)

    Yang, Qiu; Liu, Wenxian; Wang, Bingqing; Zhang, Weina; Zeng, Xiaoqiao; Zhang, Cong; Qin, Yongji; Sun, Xiaoming; Wu, Tianpin; Liu, Junfeng; Huo, Fengwei; Lu, Jun

    2017-02-01

    Composites incorporating metal nanoparticles (MNPs) within metal-organic frameworks (MOFs) have broad applications in many fields. However, the controlled spatial distribution of the MNPs within MOFs remains a challenge for addressing key issues in catalysis, for example, the efficiency of catalysts due to the limitation of molecular diffusion within MOF channels. Here we report a facile strategy that enables MNPs to be encapsulated into MOFs with controllable spatial localization by using metal oxide both as support to load MNPs and as a sacrificial template to grow MOFs. This strategy is versatile to a variety of MNPs and MOF crystals. By localizing the encapsulated MNPs closer to the surface of MOFs, the resultant MNPs@MOF composites not only exhibit effective selectivity derived from MOF cavities, but also enhanced catalytic activity due to the spatial regulation of MNPs as close as possible to the MOF surface.

  8. Trophic magnification of organic chemicals: A global synthesis

    USGS Publications Warehouse

    Walters, David; Jardine, T.D.; Cade, Brian S.; Kidd, K.A.; Muir, D.C.G.; Leipzig-Scott, Peter C.

    2016-01-01

    Production of organic chemicals (OCs) is increasing exponentially, and some OCs biomagnify through food webs to potentially toxic levels. Biomagnification under field conditions is best described by trophic magnification factors (TMFs; per trophic level change in log-concentration of a chemical) which have been measured for more than two decades. Syntheses of TMF behavior relative to chemical traits and ecosystem properties are lacking. We analyzed >1500 TMFs to identify OCs predisposed to biomagnify and to assess ecosystem vulnerability. The highest TMFs were for OCs that are slowly metabolized by animals (metabolic rate kM < 0.01 day–1) and are moderately hydrophobic (log KOW 6–8). TMFs were more variable in marine than freshwaters, unrelated to latitude, and highest in food webs containing endotherms. We modeled the probability that any OC would biomagnify as a combined function of KOW and kM. Probability is greatest (∼100%) for slowly metabolized compounds, regardless of KOW, and lowest for chemicals with rapid transformation rates (kM > 0.2 day–1). This probabilistic model provides a new global tool for screening existing and new OCs for their biomagnification potential.

  9. Research in the Field of Organic Photovoltaics at the Institute for Problems of Chemical Physics of Russian Academy of Sciences

    NASA Astrophysics Data System (ADS)

    Troshin, Pavel A.

    2015-08-01

    In the present review we highlight the main research activities in the field of organic photonics and photovoltaics at the Institute for Problems of Chemical Physics of Russian Academy of Sciences (IPCP RAS). Extensive investigation of optical and electrical properties of π-conjugated organic compounds performed at IPCP RAS since 1960's resulted in design of many exciting materials representing organic semiconductors, metals and superconductors. Organic Schottky barrier and p/n junction photovoltaic devices constructed at IPCP RAS in 1960's and 1970's were among the first examples of reasonably efficient organic solar cells at that time. These early discoveries inspired younger generations of the researchers to continue the work of their mentors and explore the world of organic materials and photonic devices such as molecular photonic switches, organic light emitting diodes, solar cells, photodetectors, photoswitchable organic field-effect transistors and memory elements.

  10. Transformation of metal-organic frameworks for molecular sieving membranes

    NASA Astrophysics Data System (ADS)

    Li, Wanbin; Zhang, Yufan; Zhang, Congyang; Meng, Qin; Xu, Zehai; Su, Pengcheng; Li, Qingbiao; Shen, Chong; Fan, Zheng; Qin, Lei; Zhang, Guoliang

    2016-04-01

    The development of simple, versatile strategies for the synthesis of metal-organic framework (MOF)-derived membranes are of increasing scientific interest, but challenges exist in understanding suitable fabrication mechanisms. Here we report a route for the complete transformation of a series of MOF membranes and particles, based on multivalent cation substitution. Through our approach, the effective pore size can be reduced through the immobilization of metal salt residues in the cavities, and appropriate MOF crystal facets can be exposed, to achieve competitive molecular sieving capabilities. The method can also be used more generally for the synthesis of a variety of MOF membranes and particles. Importantly, we design and synthesize promising MOF membranes candidates that are hard to achieve through conventional methods. For example, our CuBTC/MIL-100 membrane exhibits 89, 171, 241 and 336 times higher H2 permeance than that of CO2, O2, N2 and CH4, respectively.

  11. Transformation of metal-organic frameworks for molecular sieving membranes

    PubMed Central

    Li, Wanbin; Zhang, Yufan; Zhang, Congyang; Meng, Qin; Xu, Zehai; Su, Pengcheng; Li, Qingbiao; Shen, Chong; Fan, Zheng; Qin, Lei; Zhang, Guoliang

    2016-01-01

    The development of simple, versatile strategies for the synthesis of metal-organic framework (MOF)-derived membranes are of increasing scientific interest, but challenges exist in understanding suitable fabrication mechanisms. Here we report a route for the complete transformation of a series of MOF membranes and particles, based on multivalent cation substitution. Through our approach, the effective pore size can be reduced through the immobilization of metal salt residues in the cavities, and appropriate MOF crystal facets can be exposed, to achieve competitive molecular sieving capabilities. The method can also be used more generally for the synthesis of a variety of MOF membranes and particles. Importantly, we design and synthesize promising MOF membranes candidates that are hard to achieve through conventional methods. For example, our CuBTC/MIL-100 membrane exhibits 89, 171, 241 and 336 times higher H2 permeance than that of CO2, O2, N2 and CH4, respectively. PMID:27090597

  12. Functionalization of Metal-Organic Frameworks with Metalloligands and Postsynthetic Modification

    NASA Astrophysics Data System (ADS)

    Garibay, Sergio J.

    Metal-organic frameworks (MOFs) are a hybrid class of porous materials that are comprised of metal clusters and bridging organic ligands. The modular nature these materials makes them suited for chemical strategies aimed at fine-tuning their structure and function. Significant efforts have been spent on developing MOFs for novel applications through the use of functionalized ligands. However, incorporation of functional groups on the ligands can introduce steric, solubility, and metal-coordinating characteristics that can interfere with MOF formation. By targeting the organic linking component of the a prefabricated MOF one can utilize various organic reactions to transform it into a new MOF with altered functional groups and thus different physical and chemical properties. The work in this thesis explores the development of functionalized MOFs through both prefunctionalization and postsynthetic modification (PSM) approaches on a variety of MOFs. In Chapter 2, the use of chiral tris(dipyrrinato) metalloligands was examined in an attempt to introduce chiral functionality into a set MOFs with distinct topologies realized through the use of a racemic analogue. The results further exemplify the difficulties associated with the functionalized linker strategy and suggest that PSM offers a more viable functionalization route. In Chapter 3, the versatile nature of the PSM approach is demonstrated with the successful incorporation of chiral, amine protected, and free carboxylic acid groups into an amine functionalized framework through the use of anhydrides. In Chapter 4, the scope and limitation of a multi-step PSM approach termed tandem PSM is discussed. A set a diverse multifunctional amide and urea MOFs were realized through tandem PSM. While there have been many studies investigating MOFs as heterogeneous catalysts, most examples utilize unsaturated metal sites. In Chapter 5, the utilization of carboxylic acid functionalized MOFs as a solid state Bronsted acid catalyst

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

    PubMed

    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.

  14. Measurement of volatile organic chemicals at selected sites in California

    NASA Technical Reports Server (NTRS)

    Singh, Hanwant B.; Salas, L.; Viezee, W.; Sitton, B.; Ferek, R.

    1992-01-01

    Urban air concentrations of 24 selected volatile organic chemicals that may be potentially hazardous to human health and environment were measured during field experiments conducted at two California locations, at Houston, and at Denver. Chemicals measured included chlorofluorocarbons, halomethanes, haloethanes, halopropanes, chloroethylenes, and aromatic hydrocarbons. With emphasis on California sites, data from these studies are analyzed and interpreted with respect to variabilities in ambient air concentrations, diurnal changes, relation to prevailing meteorology, sources and trends. Except in a few instances, mean concentrations are typically between 0 and 5 ppb. Significant variabilities in atmospheric concentrations associated with intense sources and adverse meteorological conditions are shown to exist. In addition to short-term variability, there is evidence of systematic diurnal and seasonal trends. In some instances it is possible to detect declining trends resulting from the effectiveness of control strategies.

  15. Hydrogen storage by physisorption on Metal Organic Frameworks

    NASA Astrophysics Data System (ADS)

    Dailly, Anne

    2008-03-01

    Cryo-adsorption systems based on materials with high specific surface areas have the main advantage that they can store and release hydrogen with fast kinetics and high reversibility over multiples cycles. Recently Metal Organic Frameworks (MOFs) have been proposed as promising adsorbents for hydrogen. These crystallographically well organized hybrid solids resulting from the three dimensional connection of inorganic clusters using organic linkers show the largest specific surface areas of all known crystalline solids. The determination of the relationships between physical properties (chemistry, structure, surface area ) of the MOFs and their hydrogen storage behavior is a key step in the characterization of these materials, if they are to be designed for hydrogen storage applications. Excess hydrogen sorption measurements for different MOFs will be presented. We show that maximum hydrogen uptake at high pressure and 77K does not always scale with the specific surface area. A linear correlation trend only apply within a class of specific materials and breaks down when the surface area measurement does not represent the surface sites that are available to H2. The influence of pore size and shape will also be discussed by comparing several MOFs with different structure types. The hydrogen adsorption and binding energy at low pressure are strongly dependent on the metal ions and the pore size.

  16. In Silico Discovery of High Deliverable Capacity Metal-Organic Frameworks

    NASA Astrophysics Data System (ADS)

    Bao, Yi; Martin, Richard; Simon, Cory; Haranczyk, Maciej; Smit, Berend; Deem, Michael; Michael W. Deem Team; Maciej Haranczyk Team; Berend Smit Team

    2015-03-01

    Metal organic frameworks (MOFs) are actively being explored as potential adsorbed natural gas storage materials for small vehicles. Experimental exploration of potential materials is limited by the throughput of synthetic chemistry. We here describe a computational methodology to complement and guide these experimental efforts. The method uses known chemical transformations in silico to identify MOFs with high methane deliverable capacity. The procedure explicitly considers synthesizability with geometric requirements on organic linkers. We efficiently search the composition and conformation space of organic linkers for nine MOF networks, finding 48 materials with higher predicted deliverable capacity (at 65 bar storage, 5.8 bar depletion, and 298 K) than MOF-5 in four of the nine networks. The best material has a predicted deliverable capacity 8% higher than that of MOF-5. US Department of Energy.

  17. Protecting group and switchable pore-discriminating adsorption properties of a hydrophilic-hydrophobic metal-organic framework.

    PubMed

    Mohideen, M Infas H; Xiao, Bo; Wheatley, Paul S; McKinlay, Alistair C; Li, Yang; Slawin, Alexandra M Z; Aldous, David W; Cessford, Naomi F; Düren, Tina; Zhao, Xuebo; Gill, Rachel; Thomas, K Mark; Griffin, John M; Ashbrook, Sharon E; Morris, Russell E

    2011-04-01

    Formed by linking metals or metal clusters through organic linkers, metal-organic frameworks are a class of solids with structural and chemical properties that mark them out as candidates for many emerging gas storage, separation, catalysis and biomedical applications. Important features of these materials include their high porosity and their flexibility in response to chemical or physical stimuli. Here, a copper-based metal-organic framework has been prepared in which the starting linker (benzene-1,3,5-tricarboxylic acid) undergoes selective monoesterification during synthesis to produce a solid with two different channel systems, lined by hydrophilic and hydrophobic surfaces, respectively. The material reacts differently to gases or vapours of dissimilar chemistry, some stimulating subtle framework flexibility or showing kinetic adsorption effects. Adsorption can be switched between the two channels by judicious choice of the conditions. The monoesterified linker is recoverable in quantitative yield, demonstrating possible uses of metal-organic frameworks in molecular synthetic chemistry as 'protecting groups' to accomplish selective transformations that are difficult using standard chemistry techniques.

  18. Protecting group and switchable pore-discriminating adsorption properties of a hydrophilic-hydrophobic metal-organic framework

    NASA Astrophysics Data System (ADS)

    Mohideen, M. Infas H.; Xiao, Bo; Wheatley, Paul S.; McKinlay, Alistair C.; Li, Yang; Slawin, Alexandra M. Z.; Aldous, David W.; Cessford, Naomi F.; Düren, Tina; Zhao, Xuebo; Gill, Rachel; Thomas, K. Mark; Griffin, John M.; Ashbrook, Sharon E.; Morris, Russell E.

    2011-04-01

    Formed by linking metals or metal clusters through organic linkers, metal-organic frameworks are a class of solids with structural and chemical properties that mark them out as candidates for many emerging gas storage, separation, catalysis and biomedical applications. Important features of these materials include their high porosity and their flexibility in response to chemical or physical stimuli. Here, a copper-based metal-organic framework has been prepared in which the starting linker (benzene-1,3,5-tricarboxylic acid) undergoes selective monoesterification during synthesis to produce a solid with two different channel systems, lined by hydrophilic and hydrophobic surfaces, respectively. The material reacts differently to gases or vapours of dissimilar chemistry, some stimulating subtle framework flexibility or showing kinetic adsorption effects. Adsorption can be switched between the two channels by judicious choice of the conditions. The monoesterified linker is recoverable in quantitative yield, demonstrating possible uses of metal-organic frameworks in molecular synthetic chemistry as ‘protecting groups’ to accomplish selective transformations that are difficult using standard chemistry techniques.

  19. Bimetallic Metal-Organic Frameworks: Probing the Lewis Acid Site for CO2 Conversion.

    PubMed

    Zou, Ruyi; Li, Pei-Zhou; Zeng, Yong-Fei; Liu, Jia; Zhao, Ruo; Duan, Hui; Luo, Zhong; Wang, Jin-Gui; Zou, Ruqiang; Zhao, Yanli

    2016-05-01

    A highly porous metal-organic framework (MOF) incorporating two kinds of second building units (SBUs), i.e., dimeric paddlewheel (Zn2 (COO)4 ) and tetrameric (Zn4 (O)(CO2 )6 ), is successfully assembled by the reaction of a tricarboxylate ligand with Zn(II) ion. Subsequently, single-crystal-to-single-crystal metal cation exchange using the constructed MOF is investigated, and the results show that Cu(II) and Co(II) ions can selectively be introduced into the MOF without compromising the crystallinity of the pristine framework. This metal cation-exchangeable MOF provides a useful platform for studying the metal effect on both gas adsorption and catalytic activity of the resulted MOFs. While the gas adsorption experiments reveal that Cu(II) and Co(II) exchanged samples exhibit comparable CO2 adsorption capability to the pristine Zn(II) -based MOF under the same conditions, catalytic investigations for the cycloaddition reaction of CO2 with epoxides into related carbonates demonstrate that Zn(II) -based MOF affords the highest catalytic activity as compared with Cu(II) and Co(II) exchanged ones. Molecular dynamic simulations are carried out to further confirm the catalytic performance of these constructed MOFs on chemical fixation of CO2 to carbonates. This research sheds light on how metal exchange can influence intrinsic properties of MOFs.

  20. Composites for removing metals and volatile organic compounds and method thereof

    DOEpatents

    Coronado, Paul R.; Coleman, Sabre J.; Reynolds, John G.

    2006-12-12

    Functionalized hydrophobic aerogel/solid support structure composites have been developed to remove metals and organic compounds from aqueous and vapor media. The targeted metals and organics are removed by passing the aqueous or vapor phase through the composite which can be in molded, granular, or powder form. The composites adsorb the metals and the organics leaving a purified aqueous or vapor stream. The species-specific adsorption occurs through specific functionalization of the aerogels tailored towards specific metals and/or organics. After adsorption, the composites can be disposed of or the targeted metals and/or organics can be reclaimed or removed and the composites recycled.

  1. Nanopatterning the electronic properties of gold surfaces with self-organized superlattices of metallic nanostructures.

    PubMed

    Didiot, Clement; Pons, Stephane; Kierren, Bertrand; Fagot-Revurat, Yannick; Malterre, Daniel

    2007-10-01

    The self-organized growth of nanostructures on surfaces could offer many advantages in the development of new catalysts, electronic devices and magnetic data-storage media. The local density of electronic states on the surface at the relevant energy scale strongly influences chemical reactivity, as does the shape of the nanoparticles. The electronic properties of surfaces also influence the growth and decay of nanostructures such as dimers, chains and superlattices of atoms or noble metal islands. Controlling these properties on length scales shorter than the diffusion lengths of the electrons and spins (some tens of nanometres for metals) is a major goal in electronics and spintronics. However, to date, there have been few studies of the electronic properties of self-organized nanostructures. Here we report the self-organized growth of macroscopic superlattices of Ag or Cu nanostructures on Au vicinal surfaces, and demonstrate that the electronic properties of these systems depend on the balance between the confinement and the perturbation of the surface states caused by the steps and the nanostructures' superlattice. We also show that the local density of states can be modified in a controlled way by adjusting simple parameters such as the type of metal deposited and the degree of coverage.

  2. Formation of self-organized nanoporous anodic oxide from metallic gallium.

    PubMed

    Pandey, Bipin; Thapa, Prem S; Higgins, Daniel A; Ito, Takashi

    2012-09-25

    This paper reports the formation of self-organized nanoporous gallium oxide by anodization of solid gallium metal. Because of its low melting point (ca. 30 °C), metallic gallium can be shaped into flexible structures, permitting the fabrication of nanoporous anodic oxide monoliths within confined spaces like the inside of a microchannel. Here, solid gallium films prepared on planar substrates were employed to investigate the effects of anodization voltage (1, 5, 10, 15 V) and H(2)SO(4) concentration (1, 2, 4, 6 M) on anodic oxide morphology. Self-organized nanopores aligned perpendicular to the film surface were obtained upon anodization of gallium films in ice-cooled 4 and 6 M aqueous H(2)SO(4) at 10 and 15 V. Nanopore formation could be recognized by an increase in anodic current after a current decrease reflecting barrier oxide formation. The average pore diameter was in the range of 18-40 nm with a narrow diameter distribution (relative standard deviation ca. 10-20%), and was larger at lower H(2)SO(4) concentration and higher applied voltage. The maximum thickness of nanoporous anodic oxide was ca. 2 μm. In addition, anodic formation of self-organized nanopores was demonstrated for a solid gallium monolith incorporated at the end of a glass capillary. Nanoporous anodic oxide monoliths formed from a fusible metal will lead to future development of unique devices for chemical sensing and catalysis.

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

    SciTech Connect

    Annapureddy, Harsha V.; Motkuri, Radha K.; Nguyen, Phuong T.; Truong, T. B.; Thallapally, Praveen K.; McGrail, B. Peter; Dang, Liem X.

    2014-01-08

    In this review, we describe recent efforts in which computer simulations were used to systematically study nano-structured metal organic frameworks, with particular emphasis on their application in heating and cooling processes. These materials also are known as metal organic heat carriers. 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 and also the elemental gases Xe and Rn by the metal organic framework (i.e., Ni2(dhtp)). We also evaluated the effects of temperature and pressure on the uptake mechanism. Our computed results compared reasonably well with available experimental measurements, thus validating our potential models and approaches. In addition, we also investigated the structural, diffusive, and adsorption properties of different hydrocarbons in Ni2(dhtp). To elucidate the mechanism of nanoparticle dispersion in condensed phases, we also studied the interactions among nanoparticles in various liquids, such as n-hexane, water and methanol. This work was performed at Pacific Northwest National Laboratory (PNNL) and was supported by the Division of Chemical Sciences, Geosciences and Biosciences, Office of Basic Energy Sciences, U.S. Department of Energy (DOE). PNNL is operated by Battelle for the DOE. The authors also gratefully acknowledge support received from the National Energy Technology Laboratory of DOE's Office of Fossil Energy.

  4. Optical metal-organic framework sensor for selective discrimination of some toxic metal ions in water.

    PubMed

    Shahat, Ahmed; Hassan, Hassan M A; Azzazy, Hassan M E

    2013-09-02

    This paper reports the development of a facile and effective approach, based on the use of Zr-based metal-organic frameworks (UiO-66) sensor with micropores geometry, shape and particle morphology for the visual detection and removal of ultra-traces of some toxic metal ions such as Bi(III), Zn(II), Pb(II), Hg(II) and Cd(II). UiO-66 was used as selective carriers for accommodating hydrophobic chromophore probes such as dithizone (DZ) without coupling agent for sensitive and selective discrimination of trace level of toxic analytes. The developed UiO-66 sensor was utilized for the detection of ultra-traces of some toxic metal ions with the naked eye. The new sensor displays high sensitivity and selectivity of a wide range of detectable metals analytes up to 10(-10) mol dm(-3) in solution, in a rapid analyte uptake response (seconds). The developed sensor is stable, cost effective, easy to prepare, and would be useful for rapid detection and removal of ultra-traces of toxic metal ions in water samples.

  5. The surface chemistry of metal-organic frameworks.

    PubMed

    McGuire, Christina V; Forgan, Ross S

    2015-03-28

    Metal-organic frameworks (MOFs) have received particular attention over the last 20 years as a result of their attractive properties offering potential applications in a number of areas. Typically, these characteristics are tuned by functionalisation of the bulk of the MOF material itself. This Feature Article focuses instead on modification of MOF particles at their surfaces only, which can also offer control over the bulk properties of the material. The differing surface modification techniques available to the synthetic chemist will be discussed, with a focus on the effect of surface modification of MOFs on their fundamental properties and application in adsorption, catalysis, drug delivery and other areas.

  6. Surface functionalization of metal organic frameworks for mixed matrix membranes

    DOEpatents

    Albenze, Erik; Lartey, Michael; Li, Tao; Luebke, David R.; Nulwala, Hunaid B.; Rosi, Nathaniel L.; Venna, Surendar R.

    2017-03-21

    Mixed Matrix Membrane (MMM) are composite membranes for gas separation and comprising a quantity of inorganic filler particles, in particular metal organic framework (MOF), dispersed throughout a polymer matrix comprising one or more polymers. This disclosure is directed to MOF functionalized through addition of a pendant functional group to the MOF, in order to improve interaction with a surrounding polymer matrix in a MMM. The improved interaction aids in avoiding defects in the MMM due to incompatible interfaces between the polymer matrix and the MOF particle, in turn increasing the mechanical and gas separation properties of the MMM. The disclosure is also directed to a MMM incorporating the surface functionalized MOF.

  7. Chemical ions affect survival of avian cholera organisms in pondwater

    USGS Publications Warehouse

    Price, J.I.; Yandell, B.S.; Porter, W.P.

    1992-01-01

    Avian cholera (Pasteurella multocida) is a major disease of wild waterfowl, but its epizootiology remains little understood. Consequently, we examined whether chemical ions affected survival of avian cholera organisms in water collected from the Nebraska Rainwater Basin where avian cholera is enzootic. We tested the response of P. multocida to ammonium (NH4), calcium (Ca), magnesium (Mg), nitrate (NO3), and ortho-phosphate (PO4) ions individually and in combination using a fractional factorial design divided into 4 blocks. High concentrations of Ca and Mg, singly or in combination, increased survival of P. multocida organisms (P < 0.001). We developed a survival index to predict whether or not specific ponds could be "problem" or "nonproblem" avian cholera sites based on concentrations of these ions in the water.

  8. Chemically Delaminated Free-Standing Ultrathin Covalent Organic Nanosheets.

    PubMed

    Khayum, M Abdul; Kandambeth, Sharath; Mitra, Shouvik; Nair, Sanoop B; Das, Anuja; Nagane, Samadhan S; Mukherjee, Rabibrata; Banerjee, Rahul

    2016-12-12

    Covalent organic nanosheets (CONs) are a new class of porous thin two-dimensional (2D) nanostructures that can be easily designed and functionalized and could be useful for separation applications. Poor dispersion, layer restacking, and difficult postsynthetic modifications are the major hurdles that need to be overcome to fabricate scalable CON thin films. Herein, we present a unique approach for the chemical exfoliation of an anthracene-based covalent organic framework (COF) to N-hexylmaleimide-functionalized CONs, to yield centimeter-sized free-standing thin films through layer-by-layer CON assembly at the air-water interface. The thin-layer fabrication technique presented here is simple, scalable, and does not require any surfactants or stabilizing agents.

  9. Chemical composition of dissolved organic matter draining permafrost soils

    NASA Astrophysics Data System (ADS)

    Ward, Collin P.; Cory, Rose M.

    2015-10-01

    Northern circumpolar permafrost soils contain roughly twice the amount of carbon stored in the atmosphere today, but the majority of this soil organic carbon is perennially frozen. Climate warming in the arctic is thawing permafrost soils and mobilizing previously frozen dissolved organic matter (DOM) from deeper soil layers to nearby surface waters. Previous studies have reported that ancient DOM draining deeper layers of permafrost soils was more susceptible to degradation by aquatic bacteria compared to modern DOM draining the shallow active layer of permafrost soils, and have suggested that DOM chemical composition may be an important control for the lability of DOM to bacterial degradation. However, the compositional features that distinguish DOM drained from different depths in permafrost soils are poorly characterized. Thus, the objective of this study was to characterize the chemical composition of DOM drained from different depths in permafrost soils, and relate these compositional differences to its susceptibility to biological degradation. DOM was leached from the shallow organic mat and the deeper permafrost layer of soils within the Imnavait Creek watershed on the North Slope of Alaska. DOM draining both soil layers was characterized in triplicate by coupling ultra-high resolution mass spectrometry, 13C solid-state NMR, and optical spectroscopy methods with multi-variate statistical analyses. Reproducibility of replicate mass spectra was high, and compositional differences resulting from interfering species or isolation effects were significantly smaller than differences between DOM drained from each soil layer. All analyses indicated that DOM leached from the shallower organic mat contained higher molecular weight, more oxidized, and more unsaturated aromatic species compared to DOM leached from the deeper permafrost layer. Bacterial production rates and bacterial efficiencies were significantly higher for permafrost compared to organic mat DOM

  10. Computational screening of large molecule adsorption by metal-organic frameworks.

    SciTech Connect

    Allendorf, Mark D.; Greathouse, Jeffery A.

    2010-04-01

    Grand canonical Monte Carlo simulations were performed to investigate trends in low-pressure adsorption of a broad range of organic molecules by a set of metal-organic frameworks (MOFs). The organic analytes considered here are relevant to applications in chemical detection: small aromatics (o-, m-, and p-xylene), polycyclic aromatic hydrocarbons (naphthalene, anthracene, phenanthrene), explosives (TNT and RDX), and chemical warfare agents (GA and VM). The framework materials included several Zn-MOFs (IRMOFs 1-3, 7, 8), a Cr-MOF (CrMIL-53lp), and a Cu-MOF (HKUST-1). Many of the larger organics were significantly adsorbed by the target MOFs at low pressure, which is consistent with the exceptionally high isosteric heats of adsorption (25 kcal/mol - 60 kcal/mol) for this range of analyte. At a higher loading pressure of 101 kPa, the Zn-MOFs show a much higher volumetric uptake than either CrMIL-53-lp or HKUST-1 for all types of analyte. Within the Zn-MOF series, analyte loading is proportional to free volume, and loading decreases with increasing analyte size due to molecular packing effects. CrMIL-53lp showed the highest adsorption energy for all analytes, suggesting that this material may be suitable for low-level detection of organics.

  11. Chemical Vapor Deposition of an Organic Magnet, Vanadium Tetracyanoethylene.

    PubMed

    Harberts, Megan; Lu, Yu; Yu, Howard; Epstein, Arthur J; Johnston-Halperin, Ezekiel

    2015-07-03

    Recent progress in the field of organic materials has yielded devices such as organic light emitting diodes (OLEDs) which have advantages not found in traditional materials, including low cost and mechanical flexibility. In a similar vein, it would be advantageous to expand the use of organics into high frequency electronics and spin-based electronics. This work presents a synthetic process for the growth of thin films of the room temperature organic ferrimagnet, vanadium tetracyanoethylene (V[TCNE]x, x~2) by low temperature chemical vapor deposition (CVD). The thin film is grown at <60 °C, and can accommodate a wide variety of substrates including, but not limited to, silicon, glass, Teflon and flexible substrates. The conformal deposition is conducive to pre-patterned and three-dimensional structures as well. Additionally this technique can yield films with thicknesses ranging from 30 nm to several microns. Recent progress in optimization of film growth creates a film whose qualities, such as higher Curie temperature (600 K), improved magnetic homogeneity, and narrow ferromagnetic resonance line-width (1.5 G) show promise for a variety of applications in spintronics and microwave electronics.

  12. Webinar Presentation: Metals, Endocrine Disrupting Chemicals and Biomarkers of Metabolic Syndrome Risk in Adolescence

    EPA Pesticide Factsheets

    This presentation, Metals, Endocrine Disrupting Chemicals and Biomarkers of Metabolic Syndrome Risk in Adolescence, was given at the NIEHS/EPA Children's Centers 2015 Webinar Series held on Feb. 11, 2015.

  13. Chemical and biological extraction of metals present in E waste: A hybrid technology.

    PubMed

    Pant, Deepak; Joshi, Deepika; Upreti, Manoj K; Kotnala, Ravindra K

    2012-05-01

    Management of metal pollution associated with E-waste is widespread across the globe. Currently used techniques for the extraction of metals from E-waste by using either chemical or biological leaching have their own limitations. Chemical leaching is much rapid and efficient but has its own environmental consequences, even the future prospects of associated nanoremediation are also uncertain. Biological leaching on the other hand is comparatively a cost effective technique but at the same moment it is time consuming and the complete recovery of the metal, alone by biological leaching is not possible in most of the cases. The current review addresses the individual issues related to chemical and biological extraction techniques and proposes a hybrid-methodology which incorporates both, along with safer chemicals and compatible microbes for better and efficient extraction of metals from the E-waste.

  14. Modeling regional secondary organic aerosol using the Master Chemical Mechanism

    NASA Astrophysics Data System (ADS)

    Li, Jingyi; Cleveland, Meredith; Ziemba, Luke D.; Griffin, Robert J.; Barsanti, Kelley C.; Pankow, James F.; Ying, Qi

    2015-02-01

    A modified near-explicit Master Chemical Mechanism (MCM, version 3.2) with 5727 species and 16,930 reactions and an equilibrium partitioning module was incorporated into the Community Air Quality Model (CMAQ) to predict the regional concentrations of secondary organic aerosol (SOA) from volatile organic compounds (VOCs) in the eastern United States (US). In addition to the semi-volatile SOA from equilibrium partitioning, reactive surface uptake processes were used to simulate SOA formation due to isoprene epoxydiol, glyoxal and methylglyoxal. The CMAQ-MCM-SOA model was applied to simulate SOA formation during a two-week episode from August 28 to September 7, 2006. The southeastern US has the highest SOA, with a maximum episode-averaged concentration of ∼12 μg m-3. Primary organic aerosol (POA) and SOA concentrations predicted by CMAQ-MCM-SOA agree well with AMS-derived hydrocarbon-like organic aerosol (HOA) and oxygenated organic aerosol (OOA) urban concentrations at the Moody Tower at the University of Houston. Predicted molecular properties of SOA (O/C, H/C, N/C and OM/OC ratios) at the site are similar to those reported in other urban areas, and O/C values agree with measured O/C at the same site. Isoprene epoxydiol is predicted to be the largest contributor to total SOA concentration in the southeast US, followed by methylglyoxal and glyoxal. The semi-volatile SOA components are dominated by products from β-caryophyllene oxidation, but the major species and their concentrations are sensitive to errors in saturation vapor pressure estimation. A uniform decrease of saturation vapor pressure by a factor of 100 for all condensable compounds can lead to a 150% increase in total SOA. A sensitivity simulation with UNIFAC-calculated activity coefficients (ignoring phase separation and water molecule partitioning into the organic phase) led to a 10% change in the predicted semi-volatile SOA concentrations.

  15. Turn-on luminescence sensing and real-time detection of traces of water in organic solvents by a flexible metal-organic framework.

    PubMed

    Douvali, Antigoni; Tsipis, Athanassios C; Eliseeva, Svetlana V; Petoud, Stéphane; Papaefstathiou, Giannis S; Malliakas, Christos D; Papadas, Ioannis; Armatas, Gerasimos S; Margiolaki, Irene; Kanatzidis, Mercouri G; Lazarides, Theodore; Manos, Manolis J

    2015-01-26

    The development of efficient sensors for the determination of the water content in organic solvents is highly desirable for a number of chemical industries. Presented herein is a Mg(2+) metal-organic framework (MOF), which exhibits the remarkable capability to rapidly detect traces of water (0.05-5 % v/v) in various organic solvents through an unusual turn-on luminescence sensing mechanism. The extraordinary sensitivity and fast response of this MOF for water, and its reusability make it one of the most powerful water sensors known.

  16. "Heterogeneity within order" in metal-organic frameworks.

    PubMed

    Furukawa, Hiroyasu; Müller, Ulrich; Yaghi, Omar M

    2015-03-09

    Metal-organic frameworks (MOFs) are constructed by linking inorganic units with organic linkers to make extended networks. Though more than 20 000 MOF structures have been reported most of these are ordered and largely composed of a limited number of different kinds building units, and very few have multiple different building units (heterogeneous). Although heterogeneity and multiplicity is a fundamental characteristic of biological systems, very few synthetic materials incorporate heterogeneity without losing crystalline order. Thus, the question arises: how do we introduce heterogeneity into MOFs without losing their ordered structure? This Review outlines strategies for varying the building units within both the backbone of the MOF and its pores to produce the heterogeneity that is sought after. The impact this heterogeneity imparts on the properties of a MOF is highlighted. We also provide an update on the MOF industry as part of this themed issue for the 150th anniversary of BASF.

  17. Total concentrations and chemical speciation of heavy metals in liquefaction residues of sewage sludge.

    PubMed

    Yuan, Xingzhong; Huang, Huajun; Zeng, Guangming; Li, Hui; Wang, Jingyu; Zhou, Chunfei; Zhu, Huina; Pei, Xiaokai; Liu, Zhifeng; Liu, Zhantao

    2011-03-01

    The risk (including bioavailability and eco-toxicity) of heavy metals (Pb, Zn, Cu, Cd, Cr and Ni) in liquefaction residues (LR) of sewage sludge (SS) was estimated, according to both the speciation of heavy metals and the local environmental characteristics. The amount of organic matters in LR was lower than that in SS, resulting in a smaller calorific value, while the total content of heavy metals in LR nearly doubled. High residual rates of heavy metals (about 80%) indicated that the heavy metals in SS were concentrated into LR after liquefaction. The comparisons of sequential extraction results between SS and LR showed that after liquefaction, the mobile and easily available heavy metal fractions (acid soluble/exchangeable and reducible fractions) were mainly transformed into the relatively stable heavy metal fractions (oxidizable and residual fractions). The bioavailability and eco-toxicity of heavy metals in LR were relieved, though the total concentrations of heavy metals increased.

  18. Chemical Raman Enhancement of Organic Adsorbates on Metal Surfaces

    DTIC Science & Technology

    2011-02-25

    system with an ordered monolayer of about one BTmolecule per nm2 bonded to a flat periodic Au(111) slab. A 400 eV plane-wave cutoff and 2 2 1 Monkhorst...cm 1 width. (B) Binding geometries. Our supercell consists of 5 atomic layers of Au stacked along [111] with 16 atoms per layer, with 30 Å of vacuum... 1 ] M. Fleischman, P. J. Hendra, and A. McQuillan, Chem. Phys. Lett. 26, 163 (1974). [2] D. L. Jeanmaire and R. P. V . Duyne, J. Electroanal. Chem. 84

  19. Metal-organic Frameworks as A Tunable Platform for Designing Functional Molecular Materials

    PubMed Central

    Wang, Cheng; Liu, Demin

    2013-01-01

    Metal-organic frameworks (MOFs), also known as coordination polymers, represent an interesting class of crystalline molecular materials that are synthesized by combining metal-connecting points and bridging ligands. The modular nature of and mild conditions for MOF synthesis have permitted the rational structural design of numerous MOFs and the incorporation of various functionalities via constituent building blocks. The resulting designer MOFs have shown promise for applications in a number of areas, including gas storage/separation, nonlinear optics/ferroelectricity, catalysis, energy conversion/storage, chemical sensing, biomedical imaging, and drug delivery. The structure-property relationships of MOFs can also be readily established by taking advantage of the knowledge of their detailed atomic structures, which enables fine-tuning of their functionalities for desired applications. Through the combination of molecular synthesis and crystal engineering MOFs thus present an unprecedented opportunity for the rational and precise design of functional materials. PMID:23944646

  20. Metal-inorganic-organic matrices as efficient sorbents for hydrogen storage.

    PubMed

    Azzouz, Abdelkrim; Nousir, Saadia; Bouazizi, Nabil; Roy, René

    2015-03-01

    Stabilization of metal nanoparticles (MNPs) without re-aggregation is a major challenge. An unprecedented strategy is developed for achieving high dispersion of copper(0) or palladium(0) on montmorillonite-supported diethanolamine or thioglycerol. This results in novel metal-inorganic-organic matrices (MIOM) that readily capture hydrogen at ambient conditions, with easy release under air stream. Hydrogen retention appears to involve mainly physical interactions, slightly stronger on thioglycerol-based MIOM (S-MIOM). Thermal enhancement of desorption suggests also a contribution of chemical interactions. The increase of hydrogen uptake with prolonged contact times arises from diffusion hindrance, which appears to be beneficial by favoring hydrogen entrapment. Even with compact structures, MIOMs act as efficient sorbents with much higher efficiency factor (1.14-1.17 mmol H 2 m(-2)) than many other sophisticated adsorbents reported in the literature. This opens new prospects for hydrogen storage and potential applications in microfluidic hydrogenation reactions.